阅读说明：本技术 拒液性结构体及其制造方法、以及包装材料和剥离片 (Liquid-repellent structure, method for producing same, packaging material, and release sheet ) 是由 加藤了嗣 木下广介 铃田昌由 关川未奈 于 2019-06-12 设计创作，主要内容包括：根据本公开的一个方面的拒液性结构体具备：要赋予拒液性的表面、以及在该表面上形成的拒液层,其中,上述拒液层包含平均粒径为0.1～6μm的鳞片状填料、热塑性树脂和氟化合物,并且具有包含鳞片状填料的凝聚体,拒液层中所含的鳞片状填料的质量W_(S1)相对于拒液层中所含的热塑性树脂的质量W_P和氟化合物的质量W_(FC)的合计(W_P+W_(FC))的比率W_(S1)/(W_P+W_(FC))为0.1～10。(A liquid-repellent structure according to one aspect of the present disclosure includes: a surface to be liquid-repellent, and a liquid-repellent layer formed on the surface, wherein the liquid-repellent layer contains a scaly filler having an average particle diameter of 0.1 to 6 [ mu ] m, a thermoplastic resin, and a fluorine compound, and has an aggregate containing the scaly filler, and the mass W of the scaly filler contained in the liquid-repellent layer S1 Mass W relative to thermoplastic resin contained in liquid repellent layer P And mass W of fluorine compound FC Total (W) of P +W FC ) Ratio W of S1 /(W P +W FC ) 0.1 to 10.)

1. A liquid-repellent structure comprising: a surface to be imparted with liquid repellency, and a liquid repellent layer formed on the surface, wherein,

the liquid-repellent layer contains a scaly filler having an average particle diameter of 0.1 to 6 [ mu ] m, a thermoplastic resin, and a fluorine compound, and has an aggregate containing the scaly filler,

mass W of the scaly filler contained in the liquid-repellent layer_S1Mass W of the thermoplastic resin contained in the liquid repellent layer_PAnd the mass W of the fluorine compound_FCTotal (W) of_P+W_FC) Ratio W of_S1/(W_P+W_FC) 0.1 to 10.

2. The liquid repellent structure according to claim 1, wherein,

the liquid-repellent layer further contains a No. 2 filler having an average particle diameter of 5 to 1000nm,

mass W of the scaly filler contained in the liquid-repellent layer_S1And the mass W of the 2 nd filler_S2Total (W) of_S1+W_S2) Mass W of the thermoplastic resin contained in the liquid repellent layer_PAnd the mass W of the fluorine compound_FCTotal (W) of_P+W_FC) Ratio (W) of_S1+W_S2)/(W_P+W_FC) 0.1 to 10.

3. The liquid repellent structure according to claim 1, wherein,

the liquid-repellent layer further contains a No. 3 filler having an average particle diameter of 10 to 100 μm,

mass W of the scaly filler contained in the liquid-repellent layer_S1And the mass W of the 3 rd filler_S3Total (W) of_S1+W_S3) Mass W of the thermoplastic resin contained in the liquid repellent layer_PAnd the mass W of the fluorine compound_FCTotal (W) of_P+W_FC) Ratio (W) of_S1+W_S3)/(W_P+W_FC) 0.1 to 10.

4. The liquid repellent structure according to claim 2, wherein,

the liquid-repellent layer further contains a No. 3 filler having an average particle diameter of 10 to 100 μm,

mass W of the scaly filler contained in the liquid-repellent layer_S1And the mass W of the 2 nd filler_S2And the mass W of the 3 rd filler_S3Total (W) of_S1+W_S2+W_S3) Mass W of the thermoplastic resin contained in the liquid repellent layer_PAnd the mass W of the fluorine compound_FCTotal (W) of_P+W_FC) Ratio (W) of_S1+W_S2+W_S3)/(W_P+W_FC) 0.1 to 10.

5. The liquid-repellent structure according to any one of claims 1 to 4, wherein,

the fluorine compound does not contain a structural unit derived from pyrrolidone or a derivative thereof.

6. A liquid-repellent structure comprising: a surface to be imparted with liquid repellency, and a liquid repellent layer formed on the surface, wherein,

the liquid-repellent layer contains a scaly filler having an average particle diameter of 0.1 to 6 [ mu ] m, a No. 3 filler having an average particle diameter of 10 to 100 [ mu ] m, a thermoplastic resin, and a fluorine compound, and has an aggregate containing the scaly filler,

an area A occupied by the 3 rd filler when the liquid repellent layer is viewed from a normal direction₃Ratio A to area A of the liquid repellent layer₃the/A is 0.25 to 0.95.

7. The liquid-repellent structure according to claim 3, 4 or 6, wherein,

mass W of the scaly filler contained in the liquid-repellent layer_S1And the mass W of the 3 rd filler_S3Ratio W of_S3/W_S1Is 1.0 to 20.0.

8. The liquid repellent structure according to claim 7, wherein,

mass W of the scaly filler contained in the liquid-repellent layer_S1And the mass W of the 3 rd filler_S3Total (W) of_S1+W_S3) Mass W of the thermoplastic resin contained in the liquid repellent layer_PAnd the mass W of the fluorine compound_FCTotal (W) of_P+W_FC) Ratio (W) of_S1+W_S3)/(W_P+W_FC) 0.1 to 10.0.

9. The liquid-repellent structure according to any one of claims 6 to 8, wherein,

the liquid repellent layer further contains a No. 2 filler having an average particle diameter of 5 to 1000 nm.

10. A liquid-repellent structure comprising: a surface to be imparted with liquid repellency, and a liquid repellent layer formed on the surface, wherein,

the liquid repellent layer includes a cured product of a liquid repellent layer-forming composition containing a filler, a fluorine compound, and a crosslinking agent having a functional group reactive with the fluorine compound.

11. The liquid repellent structure according to claim 10, wherein,

the crosslinking agent has at least one group selected from the group consisting of an aziridinyl group, an isocyanate group and a carbodiimide group as the functional group.

12. The liquid-repellent structure according to claim 10 or 11, wherein,

the filler comprises flaky fillers with the average particle size of 0.1-6 mu m, and the liquid repellent layer comprises an aggregate of the flaky fillers.

13. The liquid-repellent structure according to any one of claims 10 to 12, wherein,

the filler comprises a No. 2 filler with the average particle size of 5-1000 nm.

14. The liquid-repellent structure according to any one of claims 10 to 13, wherein,

the filler comprises a No. 3 filler with the average particle size of 10-100 mu m.

15. The liquid-repellent structure according to any one of claims 10 to 14, wherein,

the liquid repellent layer-forming composition further comprises a thermoplastic resin.

16. The liquid-repellent structure according to any one of claims 10 to 15, wherein,

the mass W of the filler contained in the liquid repellent layer-forming composition_SRelative to theMass W of the fluorine compound contained in the liquid repellent layer-forming composition_FCAnd the mass W of the crosslinking agent_CTotal (W) of_FC+W_C) Ratio W of_S/(W_FC+W_C) 0.3 to 10.

17. The liquid repellent structure of claim 15, wherein,

the mass W of the filler contained in the liquid repellent layer-forming composition_SThe mass W of the thermoplastic resin contained in the liquid-repellent layer-forming composition_PAnd the mass W of the fluorine compound_FCAnd mass W of the crosslinking agent_CTotal (W) of_P+W_FC+W_C) Ratio W of_S/(W_P+W_FC+W_C) 0.3 to 10.

18. The liquid-repellent structure according to any one of claims 10 to 17, wherein,

mass W of the crosslinking agent contained in the liquid repellent layer-forming composition_CA mass W of the fluorine compound contained in the liquid repellent layer-forming composition_FCRatio W of_C/W_FC0.01 to 0.5.

19. The liquid repellent structure according to claim 15 or 17, wherein,

mass W of the crosslinking agent contained in the liquid repellent layer-forming composition_CA mass W of the thermoplastic resin contained in the liquid repellent layer-forming composition_PAnd the mass W of the fluorine compound_FCTotal (W) of_P+W_FC) Ratio W of_C/(W_P+W_FC) 0.01 to 0.5.

20. A liquid-repellent structure comprising: a surface to be imparted with liquid repellency, and a liquid repellent layer formed on the surface, wherein,

the liquid-repellent layer contains a binder resin containing a fluorine-containing resin, and a filler dispersed in the binder resin,

the mass W of fluorine contained in the fluorine-containing resin_FRelative to the mass W of the filler_SRatio W of_F/W_S0.06 to 0.90.

21. The liquid repellent structure of claim 20, wherein,

the fluorine-containing resin contains a fluorine-acrylic acid copolymer.

22. The liquid repellent structure according to claim 20 or 21, wherein,

the average primary particle size of the filler is 5 nm-30 mu m.

23. The liquid-repellent structure according to any one of claims 20 to 22, wherein,

the filler comprises flaky fillers with the average primary particle size of 0.1-6 mu m.

24. The liquid-repellent structure according to any one of claims 20 to 23, wherein,

the filler includes a No. 2 filler having an average primary particle diameter of 5 to 1000 nm.

25. The liquid-repellent structure according to any one of claims 20 to 24, wherein,

the filler contains a No. 4 filler having an average primary particle diameter of 5 to 30 [ mu ] m.

26. The liquid-repellent structure according to any one of claims 20 to 25, wherein,

the liquid repellent layer further comprises a thermoplastic resin.

27. The liquid-repellent structure of any one of claims 20 to 26, wherein,

the liquid repellent layer further comprises a cross-linking agent.

28. The liquid-repellent structure according to any one of claims 1 to 27, wherein,

the liquid repellent layer does not contain a structural unit derived from pyrrolidone or a derivative thereof.

29. The liquid-repellent structure according to any one of claims 1 to 28, further comprising a base layer disposed between the surface to be liquid-repellent and the liquid-repellent layer and comprising a thermoplastic resin.

30. The liquid repellent structure according to claim 29, wherein the base layer comprises a 5 th filler having an average primary particle diameter of 5 to 30 μm.

31. The liquid-repellent structure according to claim 30, wherein the 5 th filler has an average primary particle diameter of 10 to 20 μm.

32. A packaging material having the liquid-repellent structure of any one of claims 1 to 31 on a side that comes into contact with an article.

33. A packaging material according to claim 32, wherein the article contains moisture.

34. A packaging material according to claim 32 or 33, wherein the article comprises an oil component.

35. A packaging material according to any one of claims 32 to 34, wherein the article comprises a surfactant.

36. The packaging material of claim 32, wherein the article is one selected from the group consisting of hand soaps, shower gels, shampoos, moisturizers, creams, and cosmetics.

37. A release sheet having the liquid-repellent structure of any one of claims 1 to 31 on a side to be in contact with an article.

38. The release sheet of claim 37, wherein the article comprises moisture.

39. The release sheet according to claim 37 or 38, wherein the article contains an oil component.

40. The release sheet of any one of claims 37 to 39, wherein the article comprises a surfactant.

41. The release sheet according to claim 37, wherein the article is one selected from the group consisting of a hand soap, a bath lotion, a shampoo, a moisturizing cream, a cream, and a cosmetic.

42. A method for producing a liquid-repellent structure according to any one of claims 1 to 28, comprising:

a step of preparing a coating liquid for forming the liquid-repellent layer;

a step of forming a coating film of the coating liquid on a surface to be imparted with liquid repellency; and

and drying the coating film.

43. A method for producing a liquid-repellent structure according to any one of claims 29 to 31, comprising:

a step of forming the base layer on a surface to be imparted with liquid repellency;

a step of preparing a coating liquid for forming the liquid-repellent layer;

forming a coating film of the coating liquid on the base layer; and

and drying the coating film.

Technical Field

The present disclosure relates to a liquid-repellent structure, a method for producing the same, and a packaging material and a release sheet having the liquid-repellent structure on a side contacting an article.

Background

Various methods are known for a structure having water repellency. For example, patent document 1 discloses a water repellent structure in which a fine particle layer obtained by fixing scale-like inorganic fine particles with a binder and a water repellent film layer covering the surface of the fine particle layer are provided on the surface of a base material portion. Patent document 2 discloses a single-layer water-repellent heat-sealing film comprising a thermoplastic resin and hydrophobic particles. Patent document 3 discloses: in a water-repellent laminate for covering materials, which comprises a base material and a heat-adhesive layer on the base material, the heat-adhesive layer comprises a thermoplastic resin, water-repellent fine particles, and beads having an average particle size larger than that of the water-repellent fine particles.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2017-132055

Patent document 2: japanese patent laid-open publication No. 2017-155186

Patent document 3: international publication No. 2017/204258

Disclosure of Invention

Problems to be solved by the invention

In the inventions described in patent documents 1 to 3, the water repellency is evaluated by the contact angle with a water droplet. In the inventions described in patent documents 2 and 3, yogurt repellency (adhesion of yogurt) was also evaluated. However, in the inventions described in these documents, liquid repellency to liquid substances containing oil (for example, curry and fresh cream) has not been studied.

Disclosed is a liquid-repellent structure which has excellent liquid repellency to water and also has excellent liquid repellency to oil or a liquid substance containing oil, and a method for producing the same. In addition, the present disclosure provides a packaging material and a release sheet having the above-described liquid-repellent structure on the side in contact with an article.

Means for solving the problems

A liquid-repellent structure according to a first aspect of the present disclosure includes: a surface to be liquid-repellent (hereinafter referred to as "treated surface" in some cases), and a liquid-repellent layer formed on the treated surface, the liquid-repellent layer containing a scaly filler having an average particle diameter of 0.1 to 6 μm, a thermoplastic resin, and a fluorine compound (for example, a fluorine compound)Fluorine-containing resin) and also has an aggregate containing a flaky filler, the mass W of the flaky filler contained in the liquid-repellent layer_S1Mass W relative to thermoplastic resin contained in liquid repellent layer_PAnd mass W of fluorine compound_FCTotal (W) of_P+W_FC) Ratio W of_S1/(W_P+W_FC) 0.1 to 10.

The liquid repellent layer has excellent liquid repellency to water and yogurt, and also has excellent liquid repellency to oil or liquid substances containing oil (e.g., curry, fresh cream). The inventor finds that: by mixing the mass W of the flaky filler contained in the liquid-repellent layer_S1Mass W relative to thermoplastic resin contained in liquid repellent layer_PAnd mass W of fluorine compound_FCTotal (W) of_P+W_FC) Ratio W of_S1/(W_P+W_FC) Set to a predetermined range (0.1. ltoreq. W)_S1/(W_P+W_FC) 10 ≦ 10), whereby aggregates containing the scaly filler can be formed on the surface of the liquid-repellent layer in the process of forming the liquid-repellent layer, specifically, aggregates contributing to excellent liquid repellency by integrating a large amount of the scaly filler, the thermoplastic resin, and the fluorine compound can be formed on the surface of the liquid-repellent layer.

Since the aggregates present in the liquid-repellent layer are composed of a large amount of the scale-like filler, irregularities or voids due to the scale-like filler having a complicated and fine shape are formed on the surface of the liquid-repellent layer (see SEM images of fig. 4 and 5). Thus, even in a state where the liquid substance is in contact with the liquid repellent layer, the contact area with the liquid substance can be reduced, and liquid repellency is exhibited. Further, since the aggregate containing the fluorine compound is present on the surface of the liquid-repellent layer, the liquid repellency by the fluorine compound is also exhibited. Further, since the aggregate containing the scale-like filler contains the thermoplastic resin, the strength of the aggregate is improved, and the aggregate can be inhibited from peeling off from the liquid repellent layer.

The above ratio W is_S1/(W_P+W_FC) The value of (A) is in the range of 0.1 to 10 based on various evaluation testsThe following findings of the present inventors. That is, if the value is less than 0.1, the amount of the scaly filler is relatively small, so that unevenness cannot be sufficiently formed at the surface of the liquid-repellent layer, liquid repellency tends to become insufficient, and at the same time, complicated and fine shapes of the scaly filler are covered with the binder resin (thermoplastic resin and fluorine compound), and the exhibition of liquid repellency by the shape of the scaly filler tends to become insufficient. On the other hand, if the value exceeds 10, the amount of the scale-like filler is relatively large, so that the scale-like filler is easily dropped from the liquid repellent layer. Further, the scale-like filler is easily precipitated in the coating liquid for forming the liquid-repellent layer, and thus it tends to be difficult to stably form the liquid-repellent layer by coating.

When the liquid-repellent structure according to the first aspect is compared with the liquid-repellent structure described in patent document 1 described above, the two are significantly different in at least the following respects: in the former, the liquid substance comes into contact with the liquid repellent layer containing the scale-like filler, whereas in the latter, the fine particle layer containing the scale-like filler is coated with the water repellent film layer, and water comes into contact with the water repellent film layer, not the fine particle layer. In addition, when the liquid-repellent structure according to the first aspect is compared with the inventions described in the above patent documents 2 and 3, the two are significantly different in at least the following points: in the former, the filler contained in the liquid-repellent layer is in a flake form, and it is not necessary to have hydrophobicity, whereas in the latter, the particles used are considered to be spherical and must have hydrophobicity (water-repellency).

The liquid repellent layer of the present disclosure may further include a 2 nd filler having an average particle diameter of 5 to 1000 nm. The filler having such a size is blended in the coating liquid for forming the liquid repellent layer, whereby the filler can be interposed between the primary particles of the scale-like filler. This can prevent the primary particles of the scale-like filler from being excessively stacked (aggregated) to form an excessively large aggregate. In addition, the unevenness of the nm order can be formed more efficiently.

The liquid-repellent layer of the present disclosure may further contain a 3 rd filler (hereinafter referred to as "coarse filler" as the case may be) having an average particle diameter of 10 to 100 μm. Since the liquid repellent layer contains the filler having such a size, the surface of the liquid repellent layer can have a roughness coarser than the roughness of the aggregate of the scale-like filler. Thus, the liquid-repellent layer can exhibit particularly excellent liquid repellency even for liquid substances (for example, hand soaps, shower gels, shampoos, moisturizers, creams, cosmetics, and the like) containing surfactants and the like and having high viscosity.

In the liquid-repellent layer of the present disclosure, W represents the mass of the scale-like filler contained in the liquid-repellent layer_S1And the mass of the 3 rd filler is set as W_S3Then, the ratio W can be set_S3/W_S1The value of (b) is 1.0 to 20.0. The formation of the unevenness of the order of μm depends on the mass W of the flaky filler_S1Mass W of No. 3 filler_S3The ratio of (a) to (b) is different. I.e., if W_S3/W_S1When the value of (3) is 1.0 or more, the 3 rd filler can sufficiently form the unevenness of the order of μm, and excellent liquid repellency can be obtained. If W_S3/W_S1When the value of (b) is 20.0 or less, the nano-scale unevenness can be sufficiently formed by the scaly filler, and excellent liquid repellency can be obtained.

In the liquid-repellent layer of the present disclosure, the mass W of the flaky filler contained in the liquid-repellent layer may be set_S1And mass W of No. 3 Filler_S3Total (W) of_S1+W_S3) Mass W relative to thermoplastic resin contained in liquid repellent layer_PAnd mass W of fluorine compound_FCTotal (W) of_P+W_FC) Ratio (W) of_S1+W_S3)/(W_P+W_FC) Set to 0.1-10. If the ratio is less than 0.1, the complicated and fine shape of the scaly filler is covered with the binder resin (thermoplastic resin and fluorine compound), and the liquid repellency exhibited by the shape of the scaly filler tends to be insufficient. On the other hand, if the value exceeds 10, the amount of the scale-like filler and the coarse filler is relatively large, so that the scale-like filler or the coarse filler is easily dropped from the liquid repellent layer. Further, in the coating liquid for forming the liquid repellent layer, the amount of the fluorine compound is relatively small, and the liquid repellent property tends not to be stably obtained.

The above-mentioned fluorine compound contained in the liquid repellent layer of the present disclosure may not contain a structural unit derived from pyrrolidone or a derivative thereof (hereinafter, referred to as "pyrrolidone" as the case may be). In addition, the entire liquid repellent layer may not contain a structural unit derived from a pyrrolidone. In oil-resistant paper and the like requiring excellent oil resistance, a structural unit derived from pyrrolidones may be contained in a fluorine compound (fluorine additive) in order to improve adhesion of the fluorine compound to the underlying layer (paper and the like) or to stabilize dispersion of the fluorine compound in water, but the present inventors have found that: when the surfactant is brought into contact with a liquid substance having a high viscosity and containing the surfactant or the like, the liquid repellency may be lowered due to an interaction between the surfactant or the like and a structural unit derived from a pyrrolidone. Some of the fluorine compounds contain a structural unit derived from a pyrrolidone, and when such a fluorine compound is used, the effect of improving the liquid repellency of a liquid substance containing a surfactant or the like and having high viscosity may not be sufficiently exhibited. On the other hand, by not including a structural unit derived from a pyrrolidone in the fluorine compound even in the entire liquid-repellent layer, particularly excellent liquid repellency can be obtained for a liquid substance having high viscosity and containing a surfactant or the like.

A liquid-repellent structure according to a second aspect of the present disclosure includes: the liquid-repellent layer comprises a scale-like filler having an average particle diameter of 0.1 to 6 [ mu ] m, a 3 rd filler (coarse filler) having an average particle diameter of 10 to 100 [ mu ] m, a thermoplastic resin, and a fluorine compound, and further comprises aggregates containing the scale-like filler, and the ratio of the area occupied by the 3 rd filler to the area of the liquid-repellent layer is 0.25 to 0.95 when the liquid-repellent layer is viewed from the normal direction.

The liquid-repellent layer has excellent liquid repellency to water and yogurt, and also has excellent liquid repellency to oil or liquid substances containing oil (e.g., curry, fresh milk oil, etc.), and liquid substances containing a surfactant (e.g., hand soaps, bath lotions, shampoos, moisturizing creams, cosmetics, etc.). That is, the present inventors have found that, by adopting the above-described configuration, it is possible to integrate the nm-order unevenness due to the aggregate of the scale-like filler, the μm-order coarse unevenness due to the coarse filler occupying a predetermined area of the liquid repellent layer, the thermoplastic resin, and the fluorine compound in the process of forming the liquid repellent layer, and it is possible to form the liquid repellent layer having excellent liquid repellency to oil or a liquid substance containing oil and a liquid substance containing a surfactant and having high viscosity.

Since the aggregates present in the liquid-repellent layer are composed of a large amount of the scale-like filler, it is possible to form the nm-order unevenness on the surface of the liquid-repellent layer, which is caused by the scale-like filler having a complicated and fine shape (see fig. 10). Thereby, even in a state where the liquid substance is in contact with the liquid repellent layer, the contact area with the liquid substance can be reduced, and thus liquid repellency is exhibited. If the average particle diameter of the scaly filler is larger than 6 μm, the formed irregularities become large, and the irregularities of the nm order necessary for improving the liquid repellency cannot be sufficiently formed.

Further, coarse irregularities on the order of μm generated by coarse fillers present in the liquid-repellent layer at a predetermined occupancy rate are formed on the surface of the liquid-repellent layer (see fig. 10). Thus, a gap is formed between the liquid-repellent layer and the liquid substance contacting the liquid-repellent layer, and liquid repellency is exhibited. When the average particle diameter of the coarse filler is 10 μm or more, a sufficient gap is easily formed between the liquid repellent layer and the liquid droplets, and when it is 100 μm or less, the coarse filler can be sufficiently prevented from falling off from the liquid repellent layer.

Further, since the aggregate containing the fluorine compound is present on the surface of the liquid-repellent layer, the liquid repellency by the fluorine compound is also exhibited. Further, since the thermoplastic resin is contained, the strength of the aggregate containing the scaly filler is improved, and the aggregate of the scaly filler or the coarse filler can be suppressed from peeling off from the liquid repellent layer.

The following findings by the present inventors after various evaluation tests were made based on the following findings that the ratio of the area occupied by the coarse filler to the area of the liquid-repellent layer is in the range of 0.25 to 0.95 when the liquid-repellent layer is viewed from the normal direction. That is, the area occupied by the coarse filler (3 rd filler) is defined as A₃The area of the liquid repellent layer is defined as A and the ratio of A to A₃When A is 0.25 or moreThe rough irregularities of the order of μm can be sufficiently formed, the liquid droplets of the liquid substance can be sufficiently held, and excellent liquid repellency is exhibited. When the ratio A is₃When aa is 0.95 or less, the coarse filler is suppressed from filling the liquid repellent layer and becoming smooth, and a sufficient void for holding liquid droplets is formed, thereby exhibiting excellent liquid repellency.

When the liquid-repellent structure according to the second aspect is compared with the liquid-repellent structure described in patent document 1 described above, the two are significantly different in at least the following respects: in the former, the liquid substance contacts the liquid repellent layer containing the scale-like filler and the coarse filler, whereas in the latter, the fine particle layer containing the scale-like filler is coated with the water repellent film layer, and water contacts the water repellent film layer, not the fine particle layer. In addition, when the liquid-repellent structure according to the second aspect is compared with the inventions described in patent documents 2 and 3, the two are significantly different in at least the following points: in the former, the liquid repellent layer contains both a scale-like filler and a coarse filler, and the scale-like filler as a fine filler does not necessarily have hydrophobicity, whereas in the latter, the fine particles used are considered to be spherical and must have hydrophobicity (water repellency).

A liquid-repellent structure according to a third aspect of the present disclosure includes: the liquid repellent layer includes a cured product of a liquid repellent layer-forming composition containing a filler, a fluorine compound, and a crosslinking agent having a functional group reactive with the fluorine compound.

The liquid repellent layer has excellent liquid repellency to water and yogurt, and also has excellent liquid repellency to oil or liquid substances containing oil (e.g., curry, fresh cream). Further, the liquid repellent layer of the liquid repellent structure can maintain liquid repellency even when it is in contact with water, yogurt, oil, or a liquid substance containing oil (hereinafter, these are collectively referred to as "liquid substance" in some cases) for a long time. The present inventors consider the following reasons for obtaining the above-described effects. In the liquid repellent layer comprising the cured product of the liquid repellent layer-forming composition, the fluorine compound bleeds out to the surface to lower the surface free energy, and the filler forms irregularities on the surface, whereby even in a state where the liquid material is in contact with the liquid repellent layer, the contact area with the liquid material can be reduced, and excellent liquid repellency can be obtained. Since the fluorine compound is contained in the liquid-repellent layer-forming composition together with the filler to form the liquid-repellent layer, the filling of the irregularities with the fluorine compound can be suppressed and excellent liquid repellency can be easily exhibited, as compared with the case where the irregularities are formed by the filler and then a layer of the fluorine compound is laminated thereon.

Further, since the liquid repellent layer-forming composition contains the crosslinking agent having a functional group reactive with the fluorine compound, the crosslinking agent reacts with the fluorine compound to form a crosslinked structure in the liquid repellent layer, and the filler can be prevented from falling off from the liquid repellent layer. Further, since the crosslinking agent reacts with the fluorine compound, the reaction point (functional group such as hydroxyl group) of the fluorine compound can be reduced, and the affinity between the liquid repellent layer and the liquid substance due to the reaction point can be reduced. Further, it is considered that the formation of a crosslinked structure between the fluorine compound and the crosslinking agent makes it possible to straighten the orientation of the fluorine-containing group such as a perfluoroalkyl group (Rf group) of the fluorine compound, and to suppress the reduction in liquid repellency due to the disturbance of the orientation of the fluorine-containing group when the liquid repellent layer is brought into contact with the liquid substance for a long time. By these actions caused by the addition of the crosslinking agent, the liquid repellent layer of the liquid repellent structure can maintain excellent liquid repellency even when it is in contact with a liquid substance for a long time. In the present specification, the property of maintaining liquid repellency even when the liquid substance is brought into contact with the liquid substance for a long time is referred to as "durability" in some cases.

From the viewpoint of more sufficiently obtaining the above-described effects by adding the crosslinking agent, the crosslinking agent may have at least one group selected from the group consisting of an aziridine group, an isocyanate group and a carbodiimide group as the functional group. These groups are excellent in reactivity with the fluorine compound and a thermoplastic resin described later.

The liquid repellent layer-forming composition may further contain a thermoplastic resin. This can more sufficiently suppress the filler from falling off from the liquid-repellent layer, and can further improve the liquid repellency and durability of the liquid-repellent layer. When the liquid repellent layer-forming composition contains a thermoplastic resin, the crosslinking agent also reacts with the thermoplastic resin, and thus may form a crosslinked structure together with the fluorine compound.

In the liquid-repellent structure according to the third aspect and the fourth aspect described later, the average particle diameter of the filler is, for example, 5nm to 30 μm. The filler may include at least one filler selected from the group consisting of a scale-like filler having an average particle diameter of 0.1 to 6 μm, a 2 nd filler having an average particle diameter of 5 to 1000nm, and a 3 rd filler having an average particle diameter of 10 to 100 μm, from the viewpoint of forming irregularities on the surface of the liquid-repellent layer, which are more likely to improve liquid repellency. When the filler comprises a scale-like filler, the liquid repellent layer may comprise an aggregate of the scale-like filler. Preferred examples of the combination of fillers include the following combinations: the scale-like filler and the 2 nd filler, the scale-like filler and the 3 rd filler, and the scale-like filler and the 2 nd filler and the 3 rd filler.

Mass W of filler contained in the liquid repellent layer-forming composition_SMass W of the fluorine compound contained in the liquid repellent layer-forming composition_FCAnd mass W of crosslinking agent_CTotal (W) of_FC+W_C) Ratio W of_S/(W_FC+W_C) Or the mass W of the filler contained in the liquid repellent layer-forming composition_SMass W of the thermoplastic resin contained in the liquid repellent layer-forming composition_PAnd mass W of fluorine compound_FCAnd mass W of crosslinking agent_CTotal (W) of_P+W_FC+W_C) Ratio W of_S/(W_P+W_FC+W_C) Can be 0.3 to 10. If the ratio W_S/(W_FC+W_C) Or W_S/(W_P+W_FC+W_C) Within the above range, irregularities contributing to improvement of liquid repellency are easily formed on the surface of the liquid-repellent layer, and even in a state where the liquid substance contacts the liquid-repellent layer, the contact area with the liquid substance can be reduced, and thus high liquid repellency is easily exhibited.

According to the bookA liquid-repellent structure according to a fourth aspect of the disclosure includes: a surface to be treated, and a liquid-repellent layer formed on the surface to be treated, wherein the liquid-repellent layer contains a binder resin containing a fluorine-containing resin and a filler dispersed in the binder resin, and the mass W of fluorine contained in the fluorine-containing resin_FMass W relative to the above filler_SRatio W of_F/W_S0.06 to 0.90.

The liquid-repellent layer has excellent liquid repellency to water, and also has excellent liquid repellency to oil or liquid substances containing oil (e.g., curry, fresh cream), and the like. The present inventors consider the following reasons for obtaining the above-described effects. In the liquid-repellent layer, the fluorine content W in the fluorine-containing resin is determined by the mass W of fluorine contained in the fluorine-containing resin_FMass W relative to the filler_SRatio W of_F/W_S0.06 to 0.90, so that fluorine can be efficiently disposed on the surface of the filler. Thereby, the surface free energy of the liquid repellent layer can be effectively reduced, and excellent liquid repellency can be obtained for the liquid repellent layer. In addition, due to the above ratio W_F/W_SThe surface roughness of the liquid repellent layer is 0.06 to 0.90, and therefore, even in a state where a liquid material (water, oil, a liquid material containing oil, or the like) is in contact with the liquid repellent layer, the contact area with the liquid material can be reduced, and excellent liquid repellency can be obtained. Since the fluorine-containing resin forms the liquid repellent layer together with the filler, the unevenness can be suppressed from being buried in the fluorine-containing resin and excellent liquid repellency can be easily exhibited, as compared with the case where the unevenness is formed by the filler and then the layer of the fluorine-containing resin is laminated thereon.

In the above liquid-repellent structure, the fluorine-containing resin may contain a fluorine-acrylic copolymer. Since the liquid repellent layer contains the fluorine-acrylic acid copolymer, the liquid repellent layer easily exhibits more excellent liquid repellency to water, oil, or a liquid substance containing oil.

In the liquid-repellent structure described above, the liquid-repellent layer may further contain a thermoplastic resin. This can more sufficiently suppress the filler from falling off from the liquid-repellent layer, and can further improve the liquid repellency and durability of the liquid-repellent layer.

In the above liquid-repellent structure, the liquid-repellent layer may further contain a crosslinking agent. Since the liquid-repellent layer contains the crosslinking agent, for example, the fluorine-containing resin reacts with the crosslinking agent to form a crosslinked structure in the liquid-repellent layer, and the filler can be further prevented from falling off from the liquid-repellent layer. When the liquid repellent layer contains a thermoplastic resin, the crosslinking agent also reacts with the thermoplastic resin, and the crosslinking structure can be formed together with the fluorine-containing resin. Further, since the crosslinking agent reacts with the fluorine-containing resin, the reaction points (functional groups such as hydroxyl groups) of the fluorine-containing resin can be reduced, and the affinity between the liquid repellent layer and the liquid substance (water, oil, or a liquid substance including oil) due to the reaction points can be reduced. Further, it is considered that the fluorine-containing resin and the crosslinking agent form a crosslinked structure, whereby the orientation of the fluorine-containing group such as a perfluoroalkyl group (Rf group) of the fluorine-containing resin can be made rigid, and the reduction of the liquid repellency due to the disturbance of the orientation of the fluorine-containing group when the liquid repellent layer is brought into contact with the liquid substance for a long time can be suppressed. By these actions caused by the addition of the crosslinking agent, the liquid repellent layer of the liquid repellent structure can maintain excellent liquid repellency even when it is in contact with a liquid substance for a long time.

The crosslinking agent may have at least one group selected from the group consisting of an aziridine group, an isocyanate group and a carbodiimide group as the functional group, from the viewpoint of more sufficiently obtaining the effects of the addition of the crosslinking agent. These groups are excellent in reactivity with the fluorine-containing resin and the thermoplastic resin.

The liquid-repellent structure of the present disclosure may further include a base layer that is disposed between the treated surface and the liquid-repellent layer and that includes a thermoplastic resin. The base layer may further include a 5 th filler having an average primary particle diameter of 10 to 100 μm. By providing such a foundation layer, the adhesion between the surface to be treated and the liquid-repellent layer can be improved, and the liquid repellency to liquid substances (for example, hand soaps, shower creams, shampoos, moisturizing creams, and cosmetics) containing surfactants and the like and having high viscosity can be further improved. The reason why the liquid repellency against a liquid substance having a high viscosity and containing a surfactant or the like is improved is that the liquid repellent layer can be prevented from falling off when the liquid substance having a high viscosity is peeled off by improving the adhesion between the surface to be treated and the liquid repellent layer. In other words, since the liquid repellent layer can be prevented from dropping off due to the liquid substance having a high viscosity, the liquid repellent property against the liquid substance having a high viscosity and containing a surfactant or the like is improved. In addition, when the 5 th filler is contained in the base layer, it is possible to form a coarser unevenness on the surface of the base layer than the unevenness generated by the aggregate composed of the scale-like fillers in the liquid-repellent layer, and to provide the liquid-repellent layer thereon, so that it is possible to form a coarser and complicated unevenness on the surface of the liquid-repellent layer. As a result, the liquid repellency to a liquid substance having high viscosity and containing a surfactant or the like can be further improved. From the viewpoint of obtaining excellent liquid repellency, the 5 th filler may have an average primary particle diameter of 5 to 30 μm or 10 to 20 μm.

The present disclosure provides a packaging material and a release sheet having the above-described liquid-repellent structure on the side in contact with an article. As described above, the liquid repellent layer provided in the liquid repellent structure has excellent liquid repellency to water and also excellent liquid repellency to oil or a liquid substance containing oil. Therefore, the packaging material and the peeling sheet can be suitably used for articles containing water (e.g., water, drinks, yogurt) and articles containing oil (e.g., curry and whipped cream). The packaging material and the release sheet may also be applied to one selected from the group consisting of hand soaps, shower gels, shampoos, moisturizers, creams, and cosmetics.

The present disclosure provides a method for manufacturing the above liquid-repellent structure. The method for manufacturing a liquid-repellent structure includes: a step of preparing a coating liquid for forming a liquid repellent layer; a step of forming a coating film of a coating liquid on a surface to be imparted with liquid repellency; and a step of drying the coating film. A method for manufacturing a liquid-repellent structure having a foundation layer, comprising: a step of forming a base layer on a surface to be imparted with liquid repellency; a step of preparing a coating liquid for forming a liquid repellent layer; a step of forming a coating film of a coating liquid on the base layer; and a step of drying the coating film.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present disclosure, a liquid-repellent structure having excellent liquid repellency to water and also excellent liquid repellency to oil or a liquid substance containing oil, and a method for producing the same can be provided. Further, according to the present disclosure, a packaging material and a release sheet having the liquid-repellent structure described above on the side in contact with an article can be provided.

Brief description of the drawings

Fig. 1 is a sectional view schematically showing one embodiment of a liquid-repellent structure according to the present disclosure.

FIG. 2 is an SEM image of a commercially available scaly silica filler (Sunlevely manufactured by AGC Si-Tech Co., Ltd.) in FIG. 2(a), and an SEM image taken at a higher magnification than that in FIG. 2(a) in FIG. 2 (b).

[ FIG. 3]]FIG. 3(a) is a schematic view showing the ratio W_S1/(W_P+W_FC) A cross-sectional view of the liquid-repellent layer having a ratio W of less than 1 and relatively insufficient scaly filler, and FIG. 3(b) is a schematic view showing the ratio W_S1/(W_P+W_FC) A cross-sectional view of a liquid repellent layer exceeding 10 and relatively insufficient binder resin.

Fig. 4(a) is an SEM image of the surface of the liquid repellent layer, and fig. 4(b) is an SEM image taken at a higher magnification than fig. 4 (a).

Fig. 5(a) is an SEM image of the surface of the liquid repellent layer, and fig. 5(b) is an SEM image taken at a higher magnification than fig. 5 (a).

Fig. 6 is a cross-sectional view schematically showing a modification of the liquid-repellent structure according to the present disclosure.

Fig. 7 is a cross-sectional view schematically showing a modification of the liquid-repellent structure according to the present disclosure.

Fig. 8 is a cross-sectional view schematically showing a modification of the liquid-repellent structure according to the present disclosure.

Fig. 9 is a cross-sectional view schematically showing a modification of the liquid-repellent structure according to the present disclosure.

Fig. 10 is a cross-sectional view schematically showing a liquid-repellent structure according to a second embodiment.

Fig. 11 is a cross-sectional view schematically showing a liquid-repellent structure according to a second embodiment.

[ FIG. 12] A]FIG. 12(a) is a schematic view showing the ratio (W)_S1+W_S3)/(W_P+W_FC) Less than 1, and the scale-like filler is relatively insufficient in the liquid-repellent layer, and FIG. 12(b) is a schematic representation of the ratio (W)_S1+W_S3)/(W_P+W_FC) A cross-sectional view of a liquid repellent layer exceeding 10 and relatively insufficient binder resin.

Fig. 13 is a cross-sectional view schematically showing a modification of the liquid-repellent structure according to the fourth embodiment.

Fig. 14(a) is an SEM image of an undercoat layer containing a scaly filler, and fig. 14(b) is an SEM image of an undercoat layer containing a scaly filler and an overcoat layer covering the undercoat layer.

Fig. 15 is a table showing SEM images of the surfaces of the liquid-repellent layers produced in examples 1c to 3c, taken at different magnifications.

Fig. 16 is a table showing SEM images of the surfaces of the liquid-repellent layers produced in examples 1c to 3c, which were photographed with varying magnifications.

Detailed Description

Hereinafter, a plurality of embodiments of the present disclosure will be described in detail with reference to the drawings. The present invention is not limited to the embodiments described below. In the following description, the same elements or elements having the same function are denoted by the same reference numerals, and redundant description thereof is omitted. In the numerical ranges recited in the present specification, the upper limit or the lower limit of the numerical range in one stage may be replaced with the upper limit or the lower limit of the numerical range in another stage. In the numerical ranges described in the present specification, the upper limit or the lower limit of the numerical range may be replaced with the values shown in the examples. The configuration of one embodiment can be applied to other embodiments.

[ first embodiment ]

< liquid-repellent Structure >

Fig. 1 is a schematic sectional view of a liquid-repellent structure according to the present embodiment. As shown in fig. 1, the liquid-repellent structure 10 includes: a substrate 1 having a surface to be treated 1a (surface to be liquid-repellent) and a liquid-repellent layer 3 formed on the surface to be treated 1 a.

(substrate)

The substrate 1 is not particularly limited as long as it has a surface to be liquid repellent and serves as a support, and may be, for example, a film shape (thickness: about 10 to 200 μm) or a plate shape (thickness: about 1 to 10 mm). Examples of the film-like substrate include paper, resin film, and metal foil. The inner surface of the film packaging material made of these materials is set as the treated surface 1a, and the liquid repellent layer 3 is formed thereon, whereby a packaging bag in which the content is hard to adhere can be obtained. Examples of the plate-like substrate include paper, resin, metal, and glass. The inner surface of the container obtained by molding these materials is the surface to be treated 1a, and the liquid repellent layer 3 is formed thereon, whereby a container in which the content is less likely to adhere can be obtained.

Examples of the paper include fine paper, special fine paper, coated paper, cast paper, molded paper, and kraft paper. Examples of the resin include polyolefin, acid-modified polyolefin, polyester (for example, polyethylene terephthalate (PET)), Polyethylene (PE), polypropylene (PP), Polyamide (PA), polyvinyl chloride (PVC), cellulose acetate, cellophane resin, and the like. Examples of the metal include aluminum and nickel.

When the substrate 1 is in the form of a film, it preferably has thermal adhesiveness to a thermoplastic resin that is a constituent of the liquid repellent layer 3. The melting point of the substrate 1 is preferably 170 ℃ or lower. Thereby, when the packaging bag is formed by heat sealing, the adhesion between the base material 1 and the liquid-repellent layer 3 becomes stronger, so that the heat sealability is further improved. From this viewpoint, the melting point of the base material 1 is more preferably 150 ℃. The melting point of the substrate 1 can be determined by differential scanning calorimetry.

(liquid repellent)

The liquid repellent layer 3 is a layer having liquid repellency and is formed so as to cover a part or the whole of the surface of the base material 1. The liquid repellency is a concept including both water repellency and oil repellency, and specifically, is a property of repelling a liquid, semisolid, or gel-like aqueous or oil material. Examples of the water-based or oil-based material include foods such as water, oil, yogurt, curry, fresh cream, jelly, pudding, syrup, porridge, soup, etc.; lotions such as hand soaps and shampoos; a pharmaceutical; a cosmetic; chemicals, etc. In the liquid-repellent structure 10, the liquid-repellent layer 3 becomes the innermost layer or the outermost layer to be in direct contact with these.

As shown in fig. 1, the liquid repellent layer 3 has aggregates 5 formed of a large amount of scale-like fillers 5 f. The aggregate 5 allows irregularities to be formed on the surface of the liquid repellent layer 3. The aggregate 5 is composed of a flaky filler 5f having an average particle diameter of 0.1 to 6 μm and a binder resin 5b covering the flaky filler. The aggregate 5 forms irregularities on the surface of the liquid repellent layer 3. The size of the irregularities is, for example, in the order of nm.

The flaky filler 5f may be present in the form of primary particles, secondary aggregates or tertiary aggregates thereof. The secondary aggregate is formed by orienting the primary particles of the scale-like filler 5f in parallel so as to overlap a plurality of pieces. The tertiary aggregates of the scaly filler 5f are obtained by irregularly overlapping primary particles or secondary aggregates to perform crystal growth in each direction.

As described above, the average particle diameter of the flaky filler 5f (hereinafter, referred to as "average primary particle diameter" in some cases, the same applies to other types of fillers) is 0.1 to 6 μm, and may be 0.1 to 4 μm or 4 to 6 μm. Since the average particle diameter of the scale-like filler 5f is 0.1 μm or more, the aggregates 5 are easily formed, and on the other hand, since it is 6 μm or less, the liquid repellency derived from the complicated and fine shape of the scale-like filler 5f can be sufficiently exhibited. The average particle diameter of the flaky filler is an average value of values obtained by measuring the lengths of the major axis and the minor axis of an arbitrary total of 10 flaky fillers in the SEM field and dividing the sum of the measured lengths by 2.

Examples of the material constituting the flaky filler 5f include silica, talc, mica, titanium oxide, calcium carbonate, barium sulfate, zinc oxide, bentonite, zeolite, and alumina. Examples of commercially available scaly silica include Sunlovely manufactured by AGC Si-Tech Co. Examples of commercially available scaly Mica include, for example, Renco Mica manufactured by Renco corporation. Examples of commercially available scaly alumina include Ceracur manufactured by Hey lime industries, Ltd. Fig. 2(a) is an SEM image of a commercially available scaly silica filler (Sunlovely manufactured by AGC Si-Tech gmbh), and fig. 2(b) is an SEM image taken at a higher magnification than fig. 2 (a). The scaly filler 5f may not be subjected to the hydrophobic treatment or the liquid repellent treatment.

The binder resin 5b contains a thermoplastic resin and a fluorine compound having liquid repellency. As described above, the binder resin 5b and the scale-like filler 5f together constitute the aggregate 5. The content of the thermoplastic resin in the binder resin 5b (based on the mass of the binder resin 5 b) is, for example, 50 to 95 mass%, and may be 60 to 95 mass% or 70 to 90 mass%. Since the content of the thermoplastic resin in the binder resin 5b is 50 mass% or more, the scale-like filler 5f can be sufficiently suppressed from falling off from the liquid-repellent layer 3, while since the content is 95 mass% or less, the content of the fluorine compound can be sufficiently secured, and the liquid-repellent layer 3 easily exhibits excellent liquid repellency. The content of the fluorine compound in the binder resin 5b (based on the mass of the binder resin 5 b) may be, for example, 5 to 50 mass%, or 5 to 40 mass%, or 10 to 30 mass%. Since the content of the fluorine compound in the binder resin 5b is 5% by mass or more, the liquid-repellent layer 3 easily exhibits excellent liquid repellency, while since the content is 50% by mass or less, the content of the thermoplastic resin can be sufficiently secured, and the scale-like filler 5f can be sufficiently suppressed from falling off from the liquid-repellent layer 3.

The thermoplastic resin is not particularly limited, and examples thereof include low-density polyethylene, medium-density polyethylene, high-density polyethylene, and ethylene- α -olefin copolymer; homo, block or random polypropylene; propylene-alpha olefin copolymers, ethylene-vinyl acetate copolymers, and the like. For example, in the case of an ethylene- α -olefin copolymer, it may be a block copolymer, a random copolymer or the like of propylene and α -olefin. Examples of the α -olefin component include ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and 4-methyl-1-pentene.

The melting point of the thermoplastic resin is, for example, 50 to 135 ℃. When the melting point is 135 ℃ or lower, the fluorine compound can easily bleed out to the surface of the liquid repellent layer 3. Since the fluorine compound bleeds out to the surface, the surface free energy can be lowered, whereby excellent liquid repellency can be exhibited at the surface of the liquid repellent layer 3. Although there is a method of drying the fluorine compound at a high temperature in order to promote the bleeding of the fluorine compound, when the melting point of the thermoplastic resin is too high, a corresponding high temperature is necessary, and thus the substrate 1 may be deformed or otherwise damaged. On the other hand, since the melting point is 50 ℃ or higher, the occurrence of blocking due to softening for ensuring a certain degree of crystallinity can be suppressed. From this viewpoint, the melting point of the thermoplastic resin is more preferably 60 to 120 ℃.

The thermoplastic resin may be a modified polyolefin modified with a predetermined acid. The modified polyolefin can be obtained by, for example, graft-modifying a polyolefin with an unsaturated carboxylic acid derivative component derived from an unsaturated carboxylic acid, an anhydride of an unsaturated carboxylic acid, an ester of an unsaturated carboxylic acid, or the like. Further, as the polyolefin, a modified polyolefin such as a hydroxyl-modified polyolefin or an acrylic-modified polyolefin may be used. Examples of the modified polyolefin resin include Auroren manufactured by japan paper-making ltd, Zaikthene manufactured by sumitomo chemical ltd, Unistole manufactured by mitsui chemical ltd, and Arrowbase manufactured by Unitika ltd.

The fluorine compound is not particularly limited, and a compound having a structure such as a perfluoroalkyl group, a perfluoroalkenyl group, or a perfluoropolyether can be suitably used. As the fluorine compound, a commercially available fluorine-based coating material can be used. Examples of commercially available fluorine-based coating materials include Asahiguard manufactured by Asahi glass Co., Ltd, SFcoat manufactured by AGC Seimi chemical Co., Ltd, Ftergent manufactured by Neos Co., Ltd, Fluorolink manufactured by Solvay Co., Ltd, and Unidyne manufactured by Daikin Industrial Co., Ltd.

From the viewpoint of further improving the liquid repellency against liquid substances (for example, hand soaps, shower gels, shampoos, moisturizing creams, and cosmetics) containing surfactants and the like and having high viscosity, the fluorine compound may be a compound containing no structural unit derived from pyrrolidone or its derivative (pyrrolidone). Examples of the pyrrolidones include N-vinyl-2-pyrrolidone, N-vinyl-3-methyl-2-pyrrolidone, N-vinyl-5-methyl-2-pyrrolidone, and N-vinyl-3, 3-dimethyl-2-pyrrolidone. Examples of the fluorine compound not containing a structural unit derived from a pyrrolidone include Asahiguard AG-E060, AG-E070, AG-E090, manufactured by Asahi glass Co., Ltd; unidyne TG-8111 manufactured by Daikin industries, Ltd.

Mass W of scale-like filler 5f contained in liquid-repellent layer 3_S1Mass W relative to the thermoplastic resin contained in the liquid-repellent layer 3_PAnd mass W of fluorine compound_FCTotal (W) of_P+W_FC) Ratio W of_S1/(W_P+W_FC) 0.1 to 10, or 0.5 to 10 or 1 to 5. Since the value is within this range, the scale-like filler 5f is fully covered with the binder resin 5b as a whole, but the complex and fine shape of the scale-like filler 5f appears on the surface of the liquid repellent layer 3. This can suppress the scale-like filler 5f from falling off from the liquid-repellent layer 3, and at the same time, can realize both the liquid repellency by the scale-like filler 5f and the liquid repellency by the fluorine compound contained in the binder resin 5 b. Since the mass of the inorganic scale-like filler 5f does not substantially change even when the liquid-repellent layer 3 is burned, the mass change of the liquid-repellent layer 3 due to the burning can be measured, and W can be calculated from the measured values_S1/(W_P+W_FC) The value of (c).

FIG. 3(a) is a schematic view showing the ratio W_S1/(W_P+W_FC) A cross-sectional view of the liquid repellent layer of less than 0.1 and relatively insufficient scaly filler 5 f. Since the amount of the scaly filler 5f is relatively small (the binder resin 5b is excessive), the complex and fine shape of the scaly filler 5f is covered with the binder resin 5b, and the exhibition of liquid repellency by the shape of the scaly filler 5f becomes insufficient. On the other hand, FIG. 3(b) schematically shows the ratio W_S1/(W_P+W_FC) A cross-sectional view of the liquid repellent layer exceeding 10 and relatively insufficient binder resin 5 b. Since the amount of the scale-like filler 5f is relatively large (the binder resin 5b is insufficient), the scale-like filler 5f or aggregates thereof easily fall off from the liquid repellent layer. In addition, the scale-like filler 5f is easily deposited in the coating liquid for forming the liquid-repellent layer 3, and it tends to be difficult to stably form the liquid-repellent layer 3 by coating.

The aggregate 5 is obtained by integrating a large amount of the scaly filler 5f with the binder resin 5b (thermoplastic resin and fluorine compound). The aggregate 5 forms irregularities on the surface of the liquid repellent layer 3. Fig. 4(a) is an SEM image of the surface of the liquid repellent layer 3, and fig. 4(b) is an SEM image taken at a higher magnification than fig. 4 (a). According to the study of the present inventors, if the size ((long diameter + short diameter)/2) of one aggregate 5 is 4 μm or more, the aggregate 5 contributes to improvement of the liquid repellency of the liquid repellent layer 3.

The liquid repellent layer shown in the SEM image of fig. 5 is formed by using the same coating liquid as the liquid repellent layer shown in the SEM image of fig. 4, but is formed by further increasing the coating amount of the coating liquid by about 5 times than the liquid repellent layer of fig. 4. The aggregate shown in fig. 5(a) is formed as a layer on the substrate 1, although it has a gap in a part thereof. The coating amount of the coating liquid can be adjusted by the concentration of the coating liquid or the number of the wire rods used for coating.

As shown in fig. 4(a), a plurality of aggregates 5 may be disposed at intervals in the liquid repellent layer 3. That is, the plurality of aggregates 5 may be arranged in an island shape. Alternatively, as shown in fig. 5(a), a large number of aggregates 5 may be continuously formed, and a porous layer composed of the aggregates 5 may be formed in the liquid-repellent layer 3. As shown in fig. 4(b) and 5(b), the aggregate 5 has a complex shape resulting from the complex and fine shape of the scale-like filler 5 f. That is, the aggregate 5 has a wrinkled surface and voids formed by wrinkles by aggregating primary particles (average particle diameter of 0.1 to 6 μm) of the plurality of scale-like fillers 5f in a state of being randomly arranged.

The thickness of the binder resin 5b in the liquid-repellent layer 3 (thickness T in FIG. 1) is, for example, 0.05 to 10 μm, and may be 0.5 to 10 μm or 1 to 5 μm. Since the thickness of the binder resin 5b is 0.05 μm or more, the scale-like filler 5f can be sufficiently suppressed from falling off from the liquid-repellent layer 3, and excellent liquid repellency by the fluorine compound can be achieved. On the other hand, since the thickness of the binder resin 5b is 10 μm or less, a complicated and fine shape of the scaly filler 5f is likely to appear on the surface of the liquid-repellent layer 3, and excellent liquid repellency by the scaly filler 5f can be achieved.

The liquid-repellent layer 3 may contain other additives as necessary within a range not impairing the liquid-repellent function. Examples of the other additives include flame retardants, lubricants, antiblocking agents, antioxidants, light stabilizers, and tackifiers.

From the viewpoint of further improving the liquid repellency against a liquid substance having high viscosity and containing a surfactant or the like, the liquid repellent layer 3 may not contain a structural unit derived from a pyrrolidone. That is, the structural unit derived from the pyrrolidone compound may not be contained in the fluorine compound, and may not be contained in any of the components constituting the liquid repellent layer 3 other than the fluorine compound. The presence of a structural unit derived from a passive pyrrolidone in the liquid-repellent layer 3 can be determined by infrared spectroscopy, nuclear magnetic resonance spectroscopy, thermal decomposition GC-MS, or the like.

< method for producing liquid-repellent Structure >

A method for producing the liquid-repellent structure 10 will be described. The manufacturing method according to the present embodiment includes: preparing a coating liquid containing a scaly filler having an average particle diameter of 0.1 to 6 μm, a thermoplastic resin, a fluorine compound, and a solvent; a step of forming a coating film of the coating liquid on the surface 1a to be treated of the substrate 1; and a step of forming a liquid-repellent layer having an aggregate of a flaky filler by drying the coating film. By adjusting the composition of the coating liquid, W satisfying the condition of 0.1-W_S1/(W_P+W_FC) A liquid repellent layer 3 with the liquid repellency of less than or equal to 10. Hereinafter, each step will be described.

First, a coating liquid containing the scaly filler 5f, the thermoplastic resin, the fluorine compound, and the solvent is prepared. Examples of the solvent include water, alcohol, and organic solvents. The blending amount (solid content) of each component in the coating liquid may be appropriately adjusted so that the content of each component in the liquid repellent layer 3 is as described above. The thermoplastic resin may be in the form of an emulsion dispersed in water, alcohol, or the like. Such a polyolefin emulsion can be prepared by a method of emulsifying a polymer produced by polymerization reaction of a corresponding monomer or the like, or can be prepared by emulsion polymerization of a corresponding monomer.

The resulting coating liquid was applied to the substrate 1. As the coating method, a known method can be used without particular limitation, and a dipping method (dipping method); a method using a sprayer, a coater, a printer, a brush, or the like. Examples of the type of the coating machine and the printing machine used in these methods and the coating method thereof include gravure coating machines such as a direct gravure method, a reverse gravure method, a kiss reverse gravure method, and a lithographic gravure method, reverse roll coating machines, micro-gravure coating machines, chamber (chamber) blade combination coating machines, air knife coating machines, dip coating machines, bar coating machines, comma roll coating machines, and die coating machines. The coating amount of the coating liquid can be appropriately adjusted to obtain the liquid repellent layer 3 of the above thickness.

The coating film formed on the substrate 1 is dried by heating. This makes it possible to obtain a liquid-repellent structure 10 including a substrate 1 and a liquid-repellent layer 3 provided on the substrate 1. The heating condition is not limited as long as the solvent can be volatilized, and may be, for example, 60 to 100 ℃ for 0.5 to 5 minutes.

< packaging Material >

The packaging material according to the present embodiment has the liquid-repellent structure 10 on the side that contacts the article. The packaging material according to the present embodiment is applicable to articles containing water (e.g., water, beverages, yogurt) and oil (e.g., curry and fresh cream), and also applicable to articles selected from the group consisting of hand soaps, shower milks, shampoos, moisturizing creams, and cosmetics. Specific examples of the packaging material include a tetra pack for curry or pasta sauce, a container and lid material for yogurt or pudding, a hygienic container such as soap for hand, shampoo or moisturizing cream, a bag for supplementing them, a tube for toothpaste or medicine, and the like.

< Release sheet >

The release sheet according to the present embodiment has the liquid-repellent structure 10 on the side that contacts the article. The release sheet according to the present embodiment can be applied to an article containing water and an article containing oil, and can also be applied to one selected from the group consisting of a hand soap, a bath lotion, a shampoo, a moisturizer, a cream, and a cosmetic. More specifically, the use of a release sheet is a sheet material disposed between a lid of a lunch box and an edible material, and is used for preventing a viscous substance (e.g., mayonnaise, tagatose, or ketchup) from adhering to the lid of the lunch box. The release sheet is, for example, a sheet disposed at the inner surface of the lid of a container containing creams or cosmetics, and is also used for the purpose of preventing adhesion of viscous substances (for example, hair wax, moisturizing cream, or skin cream) to the container lid.

Although the first embodiment of the present disclosure has been described in detail above, the present invention is not limited to the above embodiment. For example, in the above embodiment, the liquid repellent layer 3 containing the scaly filler 5f alone as the filler is exemplified, but the liquid repellent layer 3 may further contain at least one of a filler (2 nd filler) having a smaller size than the scaly filler 5f and a filler (3 rd filler) having a larger size than the scaly filler 5 f.

The liquid-repellent structure 10A shown in fig. 6 includes a liquid-repellent layer 3A further containing a filler 6f (2 nd filler) having a smaller size than the scale-like filler 5 f. The filler 6f is, for example, spherical and has an average particle diameter of 5 to 1000 nm. By adding an appropriate amount of the filler 6f to the coating liquid for forming the liquid repellent layer, the filler 6f can be interposed between the primary particles of the scale-like filler 5f (see fig. 6). This can suppress formation of excessively large aggregates caused by excessive stacking (aggregation) of the primary particles of the scale-like filler 5 f.

Mass W of scale-like filler contained in liquid-repellent layer 3A_S1And the mass W of the 2 nd filler (filler 6f)_S2Of (2)Meter (W)_S1+W_S2) Mass W with respect to the thermoplastic resin contained in the liquid-repellent layer 3A_PAnd mass W of fluorine compound_FCTotal (W) of_P+W_FC) Ratio (W) of_S1+W_S2)/(W_P+W_FC) For example, 0.1 to 10, or 0.5 to 10 or 1 to 5. Due to the above ratio (W)_S1+W_S2)/(W_P+W_FC) Within the above range, the scaly filler 5f and the 2 nd filler (filler 6f) are entirely covered with the binder resin 5b sufficiently, but the shape of aggregates containing the scaly filler 5f and the 2 nd filler (filler 6f) can be easily made to appear on the surface of the liquid-repellent layer 3. This can suppress the scale-like filler 5f and the 2 nd filler (filler 6f) from falling off from the liquid-repellent layer 3, and can realize both the liquid repellency by the scale-like filler 5f and the 2 nd filler (filler 6f) and the liquid repellency by the fluorine compound contained in the binder resin 5 b.

The content of the 2 nd filler (filler 6f) in the liquid-repellent layer 3A is, for example, 5 to 300 parts by mass, or may be 10 to 250 parts by mass or 20 to 200 parts by mass, relative to 100 parts by mass of the scaly filler 5 f. When the content of the 2 nd filler (filler 6f) is within the above range, formation of excessively large aggregates due to excessive stacking (aggregation) of the primary particles of the scaly filler 5f can be more sufficiently suppressed, and excellent liquid repellency by the scaly filler 5f and the 2 nd filler (filler 6f) can be easily obtained.

Examples of the material constituting the filler 6f include silica, talc, mica, titanium oxide, calcium carbonate, barium sulfate, zinc oxide, montmorillonite, zeolite, and alumina. As the filler 6f, for example, the following commercially available products can be used. Examples of commercially available silica fillers include Aerosil manufactured by Aerosil of japan, Seahostar manufactured by catalyst limited of japan, spherical silica fine particles QSG manufactured by silseofish silicone, and QCB. As a commercially available titanium oxide filler, for example, AEROXIDE TiO available from Evonik Degussa₂. Examples of commercially available alumina fillers include AEROXIDE Alu manufactured by Evonik Degussa, Inc.

The liquid-repellent structure 10B shown in fig. 7 includes a liquid-repellent layer 3B further containing a filler 7f having a larger size than the scale-like filler 5 f. The filler 7f is, for example, spherical and has an average particle diameter of 10 to 100 μm. On the surface of the liquid repellent layer 3B containing the filler 7f having such a size, irregularities are formed which are coarser than the irregularities generated by the aggregates 5 composed of the scale-like filler 5 f. Thus, the liquid repellent layer 3B has particularly excellent liquid repellency even for liquid substances (for example, hand soaps, shower gels, shampoos, moisturizers, creams, and cosmetics) containing surfactants and the like and having high viscosity. The filler 7f may also have liquid repellency.

Mass W of scale-like filler contained in liquid-repellent layer 3B_S1And the mass W of the No. 3 filler (filler 7f)_S3Total (W) of_S1+W_S3) Mass W relative to the thermoplastic resin contained in the liquid-repellent layer 3B_PAnd mass W of fluorine compound_FCTotal (W) of_P+W_FC) Ratio (W) of_S1+W_S3)/(W_P+W_FC) For example, 0.1 to 10, or 0.5 to 10 or 1 to 5. Due to the above ratio (W)_S1+W_S3)/(W_P+W_FC) Within the above range, the scaly filler 5f and the 3 rd filler (filler 7f) are entirely covered with the binder resin 5b sufficiently, but the aggregate including the scaly filler 5f and the shape of the 3 rd filler (filler 7f) can be easily formed on the surface of the liquid-repellent layer 3. This can suppress the scale-like filler 5f and the 3 rd filler (filler 7f) from falling off from the liquid-repellent layer 3, and at the same time, can realize both the liquid repellency by the scale-like filler 5f and the 3 rd filler (filler 7f) and the liquid repellency by the fluorine compound contained in the binder resin 5 b.

The content of the 3 rd filler (filler 7f) in the liquid-repellent layer 3B may be, for example, 50 to 5000 parts by mass, 100 to 2000 parts by mass, 80 to 1000 parts by mass, or 100 to 400 parts by mass with respect to 100 parts by mass of the scale-like filler 5 f. When the content of the 3 rd filler (filler 7f) is within the above range, the 3 rd filler (filler 7f) appropriately forms an uneven portion coarser than the uneven portion generated by the aggregate 5 composed of the scale-like filler 5 f. Thus, the liquid repellent layer 3B can easily obtain more excellent liquid repellency even for a liquid substance having high viscosity and containing a surfactant or the like.

The average particle size of these fillers means: the average value of the values obtained by measuring the lengths of the major axis and the minor axis of a total of 10 fillers in the SEM field and dividing the sum by 2.

Examples of the material constituting the filler 7f include silica, talc, mica, titanium oxide, calcium carbonate, barium sulfate, zinc oxide, montmorillonite, zeolite, alumina, silicone resin, acrylic resin, urethane resin, and the like. As the filler 7f, for example, the following commercially available products can be used. Examples of commercially available silica fillers include Sunsphere manufactured by AGC Si-Tech Co., Ltd. As a commercially available product of the silicone resin filler, silicone resin powder KMP made of silicone resin is cited. As a commercially available product of the acrylic resin filler, Ganz Pearl manufactured by AICA Industrial Co., Ltd and Art Pearl (crosslinked acrylic beads) manufactured by Yokoku Industrial Co., Ltd are listed. As a commercially available product of the urethane resin filler, there is exemplified Art Pearl (crosslinked urethane beads) manufactured by Industrial Co., Ltd.

The liquid-repellent layer may further contain both the 2 nd filler (filler 6f) and the 3 rd filler (filler 7f) described above in addition to the scale-like filler 5 f. The liquid-repellent structure 10C shown in fig. 8 includes a liquid-repellent layer 3C containing scale-like fillers 5f, fillers 6f, and fillers 7 f. On the surface of the liquid repellent layer 3C, irregularities due to the aggregate 5 composed of the binder resin 5b, the scaly filler 5f, and the filler 6f, and coarse irregularities due to the filler 7f are formed. Thus, the liquid repellent layer 3C has particularly excellent liquid repellency even for liquid substances (for example, hand soaps, shower gels, shampoos, moisturizers, creams, and cosmetics) containing surfactants and the like and having high viscosity.

Mass W of scale-like filler contained in liquid-repellent layer 3C_S1Mass W of No. 2 Filler (Filler 6f)_S2And the mass W of the No. 3 filler (filler 7f)_S3Total (W) of_S1+W_S2+W_S3) Mass W relative to thermoplastic resin contained in liquid repellent layer_PAnd mass W of fluorine compound_FCTotal (W) of_P+W_FC) Ratio (W) of_S1+W_S2+W_S3)/(W_P+W_FC) For example, 0.1 to 10, or 0.3 to 10, 0.5 to 10, or 1 to 5. The content of the 2 nd filler (filler 6f) in the liquid-repellent layer 3C is, for example, 5 to 300 parts by mass, or may be 10 to 250 parts by mass or 20 to 200 parts by mass, relative to 100 parts by mass of the scaly filler 5 f. The content of the 3 rd filler (filler 7f) in the liquid-repellent layer 3C may be, for example, 50 to 5000 parts by mass, 100 to 2000 parts by mass, 80 to 1000 parts by mass, or 100 to 400 parts by mass with respect to 100 parts by mass of the scale-like filler 5 f.

The binder resin 5b contains a thermoplastic resin and a fluorine compound having liquid repellency. The binder resin 5b constitutes the aggregate 5 together with the scale-like filler 5 f. The binder resin 5b binds the filler 7f together. The content of the thermoplastic resin in the binder resin 5b (based on the mass of the binder resin 5 b) is, for example, 50 to 95 mass%, and may be 60 to 95 mass% or 70 to 90 mass%. Since the content of the thermoplastic resin in the binder resin 51b is 50 mass% or more, the scale-like filler 5f or the filler 7f can be sufficiently suppressed from falling off from the liquid-repellent layer 3, while since the content is 95 mass% or less, the content of the fluorine compound can be sufficiently secured, and the liquid-repellent layer 3 easily exhibits excellent liquid repellency.

In the above embodiment, the liquid repellent layer 3 is formed in direct contact with the surface 1a to be treated of the substrate 1, but a foundation layer may be formed on the surface 1a to be treated of the substrate 1 and the liquid repellent layer 3 may be formed on the foundation layer. The underlayer will be described below.

(base layer)

The base layer is a layer disposed between the substrate 1 and the liquid repellent layer 3, and is formed so as to cover a part or all of the surface (surface to be treated 1a) of the substrate 1. Since the foundation layer is interposed between the substrate 1 and the liquid-repellent layer 3, the adhesion between the substrate 1 and the liquid-repellent layer 3 can be improved. In addition, since the foundation layer is provided, the liquid repellency of the liquid-repellent structure can be further improved. When the base layer is interposed between the base material 1 and the liquid-repellent layer 3, the base material 1 preferably has thermal adhesiveness to the base layer.

The base layer contains at least a thermoplastic resin and may contain a filler. As the thermoplastic resin, the same material as the thermoplastic resin used in the liquid repellent layer 3 can be used. The filler used may be the same as the filler 7f (having an average particle diameter of 10 to 100 μm) used in the liquid-repellent layer 3. The filler contained in the foundation layer may have an average primary particle diameter of 5 to 30 μm or 10 to 20 μm from the viewpoint of excellent liquid repellency.

The base layer may contain the scale-like filler 5f used in the liquid-repellent layer 3, but may not contain the filler from the viewpoint of effectively forming the uneven structure. The base layer may contain the 2 nd filler (filler 6f) used in the liquid-repellent layer 3, but may not contain the filler from the viewpoint of efficiently forming the uneven structure.

When the base layer contains a filler, the mass W of the filler (5 th filler) contained in the base layer_S5Mass W of thermoplastic resin contained in base layer_PRatio W of_S5/W_PCan be 0.5 to 10, can be 1 to 7.5, or 3 to 5. Since the value is within the above range, the concavo-convex structure tends to be effectively formed in the liquid-repellent structure.

The thickness of the base layer is, for example, 0.1 to 10 μm, 0.5 to 5 μm, or 1 to 3 μm. Since the thickness of the underlayer is 0.1 μm or more, the adhesion to the liquid repellent layer tends to be improved. On the other hand, since the thickness of the underlayer is 10 μm or less, when the underlayer contains a filler, unevenness tends to be formed efficiently. When the base layer contains a filler, the thickness of the base layer refers to the thickness of the thermoplastic resin (the thickness of a portion without the filler), as in the thickness of the binder resin 5b in the liquid-repellent layer 3 (the thickness T in fig. 1).

The base layer has a mass per unit area of, for example, 1.0 to 30.0g/cm²And may be 3 to 10g/cm²Or 4 to 8g/cm². Since the mass per unit area of the base layer was 1.0g/cm²Above, therefore, the adhesiveness to the liquid-repellent layer tends to be improvedHigh. On the other hand, since the mass per unit area of the base layer was 30.0g/cm²Hereinafter, when the base layer contains a filler, adhesion between the uneven structure and the liquid-repellent layer can be effectively obtained.

The base layer may also contain other additives as desired. Examples of the other additives include flame retardants, lubricants, antiblocking agents, antioxidants, light stabilizers, and tackifiers.

The method of forming the base layer is the same as the method of forming the liquid repellent layer 3. That is, a primer layer can be formed by preparing a coating liquid containing a thermoplastic resin, a filler and other additives added as needed, and a solvent, applying the coating liquid onto the substrate 1 to form a coating film, and drying the coating film. The solvent used for the coating liquid, the coating method of the coating liquid, and the drying method of the coating film are the same as in the case of forming the liquid repellent layer 3.

Fig. 9 is a schematic cross-sectional view showing an example of a liquid-repellent structure having a foundation layer. The liquid-repellent structure 10D shown in fig. 9 includes: a base layer 8 formed on the surface 1a to be treated of the substrate 1, and a liquid repellent layer 3A formed on the base layer 8. In the liquid-repellent structure 10D, the foundation layer 8 is composed of the thermoplastic resin 8b and the filler 8 f. As described above, the thickness T' of the base layer refers to the thickness of the thermoplastic resin 8b (the thickness of the portion without the filler 8 f). In the liquid-repellent structure 10D, the liquid-repellent layer 3A has the same configuration as the liquid-repellent layer 3A in the liquid-repellent structure 10A shown in fig. 6. However, the configuration of the liquid repellent layer formed on the base layer 8 is not limited to this. As shown in fig. 9, since the foundation layer 8 is interposed between the substrate 1 and the liquid-repellent layer 3A, the adhesion between the substrate 1 and the liquid-repellent layer 3A can be further improved. Further, since the liquid repellent layer 3A is provided on the base layer 8 containing the filler 8f, coarse and complicated irregularities can be formed on the surface of the liquid repellent layer 3A, and the liquid repellency of the liquid repellent structure can be further improved.

[ second embodiment ]

The liquid-repellent structure 20 according to the second embodiment includes a treated surface 1a and a liquid-repellent layer 3D formed on the treated surface 1a, the liquid-repellent layer 3D includes a scaly filler 5f having an average particle diameter of 0.1 to 6 μm, a filler 7f (coarse filler) having an average particle diameter of 10 to 100 μm, a thermoplastic resin, and a fluorine compound, and includes aggregates 5 including the scaly filler 5f, and a ratio of an area occupied by the filler 7f to an area of the liquid-repellent layer is 0.25 to 0.95 when the liquid-repellent layer 3D is viewed from a normal direction.

The components contained in the liquid repellent layer 3D, the content ratio thereof, and the like may be the same as those of the first embodiment and the modification thereof. Hereinafter, the second embodiment will be described mainly about matters different from the above-described embodiment.

The liquid repellent layer 3D contains a scale-like filler 5f and a filler 7f having a larger size than that. The filler 7f is, for example, spherical and has an average particle diameter of 10 to 100 μm. Since the filler 7f having such a size is contained, irregularities of a μm level coarser than those of the surface of the aggregate 5 composed of the scale-like filler 5f are formed on the surface of the liquid repellent layer 3D, and the recessed portions become the voids 9. Thus, the liquid repellent layer 3 has particularly excellent liquid repellency even for liquid substances (for example, hand soaps, shower gels, shampoos, moisturizers, creams, and cosmetics) containing surfactants and the like and having high viscosity. The filler 7f may also have liquid repellency.

Mass W of scale-like filler 5f contained in liquid-repellent layer 3_S1And mass W of filler 7f_S3Total (W) of_S1+W_S3) Mass W relative to the thermoplastic resin contained in the liquid-repellent layer 3_PAnd mass W of fluorine compound_FCTotal (W) of_P+W_FC) Ratio (W) of_S1+W_S3)/(W_P+W_FC) For example, 0.1 to 10, or 0.5 to 10 or 1 to 5. Mass W of filler 7f in liquid repellent layer 3_S3Mass W of flaky filler 5f_S1Ratio W of_S3/W_S1For example, 1.0 to 20.0.

Fig. 11 is a view of the liquid repellent layer 3D as viewed from the normal direction, and the liquid repellent layer 3D is partially occupied by the filler 7 f. In the portion not occupied by the filler 7f, an aggregate 5 of a scale-like filler (not shown in fig. 11) as shown in fig. 10 is formed. An area A occupied by the filler 7f when the liquid repellent layer 3D is viewed from the normal direction₃Ratio a of area a of (portion shown by circle) with respect to the entire liquid-repellent layer 3D₃the/A is 0.25 to 10. Since the ratio is 0.25 or more, coarse irregularities of the order of μm can be sufficiently formed, droplets of a liquid substance can be held on the filler 7f, and excellent liquid repellency is obtained. Since the ratio is 0.95 or less, smoothing due to filling of the liquid repellent layer 3D with the filler 7f can be suppressed, sufficient voids can be formed to keep the liquid droplets spaced apart from the liquid repellent layer 3D, and excellent liquid repellency is obtained.

Mass W of scale-like filler 5f contained in liquid-repellent layer 3D_S1And mass W of filler 7f_S3Total (W) of_S1+W_S3) Mass W relative to thermoplastic resin contained in liquid-repellent layer 3D_PAnd mass W of fluorine compound_FCTotal (W) of_P+W_FC) Ratio (W) of_S1+W_S3)/(W_P+W_FC) 0.1 to 10, or 0.5 to 10 or 1 to 5. Since this value is within the above range, the scaly filler 5f and the filler 7f are entirely covered with the binder resin 5b sufficiently, but the complex and fine shape of the scaly filler 5f can be made to appear on the surface of the liquid repellent layer 3D. This can suppress the scale-like filler 5f or the filler 7f from falling off from the liquid-repellent layer 3D, and can realize both liquid repellency by the scale-like filler 5f and the filler 7f and liquid repellency by the fluorine compound contained in the binder resin 5 b. Note that, even when the liquid-repellent layer 3D is burned, the mass of the inorganic scaly filler 5f and filler 7f does not substantially change, and therefore, the mass change of the liquid-repellent layer 3D due to the burning is measured and calculated from the measured values (W)_S1+W_S3)/(W_P+W_FC) The value of (c).

FIG. 12(a) is a schematic view showing the ratio (W)_S1+W_S3)/(W_P+W_FC) A cross-sectional view of the liquid repellent layer in which the binder resin 5b is relatively excessive and is less than 0.1. The amount of the scaly filler 5f is relatively small, so that the complicated and fine shape of the scaly filler 5f is covered with the binder resin 5b, and the exhibition of liquid repellency by the shape of the scaly filler 5f may become insufficient. On the other hand, FIG. 12(b) is a schematic viewCharacteristically, the ratio (W)_S1+W_S3)/(W_P+W_FC) A cross-sectional view of the liquid repellent layer exceeding 10 and relatively insufficient binder resin 5 b. The amount of the scale-like filler 5f and the filler 7f is relatively large, so that the scale-like filler 5f, the aggregate thereof, or the filler 7f is easily dropped from the liquid repellent layer. In addition, the scale-like filler 5f is easily precipitated in the coating liquid for forming the liquid repellent layer, and it tends to be difficult to stably form the liquid repellent layer by coating.

The aggregate 5 is obtained by integrating a large amount of the flaky filler 5f and the binder resin 5b (thermoplastic resin and fluorine compound). The aggregates 5 form a surface of the liquid repellent layer 3D with a surface roughness of nm order. According to the study of the present inventors, if the size ((long diameter + short diameter)/2) of one aggregate 5 is 4 μm or more, the aggregate 5 contributes to the improvement of the liquid repellency of the liquid repellent layer. The filler 7f is fixed in the liquid repellent layer by the binder resin 5 b. The filler 7f forms a μm-level unevenness, and a void 9 is formed in the aggregate 5, so that liquid droplets of the liquid substance can be separated and held, which contributes to improvement of liquid repellency.

The thickness of the binder resin 5b in the liquid-repellent layer 3D (thickness T in FIG. 10) is, for example, 0.05 to 10 μm, and may be 0.5 to 10 μm or 1 to 5 μm. Since the thickness of the binder resin 5b is 0.05 μm or more, the scale-like filler 5f or the filler 7f can be sufficiently suppressed from falling off from the liquid-repellent layer 3, and excellent liquid repellency by the fluorine compound can be achieved. On the other hand, since the thickness of the binder resin 5b is 10 μm or less, a complicated and fine shape of the scaly filler 5f is likely to appear on the surface of the liquid-repellent layer 3, and excellent liquid repellency by the scaly filler 5f can be achieved.

A method of manufacturing a liquid-repellent structure according to a second embodiment includes: preparing a coating solution containing a scaly filler 5f having an average particle diameter of 0.1 to 6 μm, a filler 7f having an average particle diameter of 10 to 100 μm, a thermoplastic resin, a fluorine compound, and a solvent; a step of forming a coating film of the coating liquid on the surface 1a to be processed; and a step of forming a liquid-repellent layer 3D having aggregates 5 of the scale-like filler 5f and the filler 7f by drying the coating film. This makes it possible to form both the nm-order unevenness and the μm-order unevenness. By forming the water repellent layer collectively, the water repellent layer can be formed efficiently without burying the unevenness of the nm level as in the case of separately applying the water repellent.

The second embodiment of the present disclosure has been described above in detail, but the present invention is not limited to the above embodiment. For example, although the liquid repellent layer 3D including the scale-like filler 5f and the filler 7f as fillers is exemplified in the above embodiment, the liquid repellent layer 3D may further include a filler 6f having a smaller size, as in the liquid repellent layer 3 shown in fig. 8. Further, a base layer 8 (see fig. 9) may be provided between the surface to be treated 1a and the liquid repellent layer 3D.

[ third embodiment ]

The liquid-repellent structure according to the third embodiment includes a treated surface 1a, and a liquid-repellent layer formed on the treated surface 1a, the liquid-repellent layer including a cured product of a liquid-repellent layer-forming composition containing a filler, a fluorine compound, and a crosslinking agent having a functional group that reacts with the fluorine compound. The components contained in the liquid-repellent layer according to the third embodiment, the content ratio thereof, and the like may be the same as those of the first embodiment and the modifications thereof, and the second embodiment. Hereinafter, the third embodiment will be described mainly about matters different from the above-described embodiments and the like.

The average primary particle diameter of the filler contained in the liquid-repellent layer may be, for example, 5nm to 30 μm. The filler may contain a flaky filler 5f having an average primary particle diameter of 0.1 to 6 μm, a filler 6f having an average primary particle diameter of 5 to 1000nm, and a No. 4 filler having an average primary particle diameter of 5 to 30 μm. That is, the filler may contain at least one filler selected from the group consisting of a scaly filler 5f having an average primary particle diameter of 0.1 to 6 μm, a filler 6f having an average primary particle diameter of 5 to 1000nm, and a4 th filler having an average primary particle diameter of 5 to 30 μm. When the filler comprises the scale-like filler 5f, the liquid repellent layer may comprise the aggregates 5 of the scale-like filler 5 f. By including these fillers, the liquid repellent layer is more effectively formed with irregularities on the surface thereof, and more excellent liquid repellency is easily exhibited with respect to water, oil, a liquid substance including oil, or the like.

When the filler contains 2 or more kinds of fillers, preferable examples of the combination of the fillers include a combination of a scaly filler and a 2 nd filler, a combination of a scaly filler and a4 th filler, and a combination of a scaly filler and a 2 nd filler and a4 th filler. By using 2 or more fillers having different particle diameters or shapes in combination, a complicated uneven structure which cannot be formed by a single filler can be formed on the surface of the liquid-repellent layer, and the liquid repellency can be further improved. In this case, since at least a scale-like (plate-like) filler is used, a complicated uneven structure can be formed more efficiently, and the liquid repellency can be easily further improved.

The binder resin 5b is a cured product of a composition (hereinafter, sometimes referred to as "binder composition") composed of components other than the filler among the liquid-repellent layer-forming composition containing the filler, the fluorine compound having liquid repellency, the crosslinking agent having a functional group that reacts with the fluorine compound, and the components (for example, thermoplastic resin) used as needed. The binder resin 5b constitutes the aggregate 5 together with the scale-like filler 5 f. The aggregate 5 is obtained by integrating a large amount of the flaky filler 5f with the binder resin 5 b. The aggregate 5 forms irregularities on the surface of the liquid repellent layer (see fig. 1).

The content of the fluorine compound in the binder composition (based on the mass of the solid content of the binder composition) may be, for example, 5 to 99 mass%, or 15 to 75 mass%, or 20 to 50 mass%. Since the content of the fluorine compound in the binder composition is 5% by mass or more, the liquid repellent layer easily exhibits excellent liquid repellency, while since the content is 99% by mass or less, the content of the crosslinking agent or the thermoplastic resin used as needed can be sufficiently ensured, the scale-like filler 5f can be sufficiently suppressed from falling off from the liquid repellent layer, and the durability of the liquid repellent layer can be sufficiently improved.

The content of the thermoplastic resin in the adhesive composition (based on the mass of the solid content of the adhesive composition) may be, for example, 5 to 90 mass%, or 10 to 50 mass%, or 20 to 30 mass%. Since the content of the thermoplastic resin in the adhesive composition is 5 mass% or more, the scale-like filler 5f can be sufficiently suppressed from falling off from the liquid-repellent layer, while since the content is 90 mass% or less, the content of the fluorine compound and the crosslinking agent can be sufficiently secured, and the liquid-repellent layer easily exhibits excellent liquid repellency and durability.

Mass W of crosslinking agent contained in adhesive composition_CWith respect to the mass W of the fluorine compound contained in the binder composition_FCRatio W of_C/W_FCFor example, 0.01 to 0.5, or 0.05 to 0.3, or 0.1 to 0.2. If the above ratio W is_C/W_FCWhen the amount is 0.01 or more, the scale-like filler 5f can be sufficiently suppressed from falling off from the liquid-repellent layer, and the durability of the liquid-repellent layer can be sufficiently improved. On the other hand, if the above ratio W is_C/W_FCWhen the content is 0.5 or less, the content of the fluorine compound can be sufficiently secured, and the fluorine compound can be easily and sufficiently oozed out to the surface of the liquid-repellent layer, and thus good liquid repellency can be exhibited.

When the adhesive composition contains a thermoplastic resin, the mass W of the crosslinking agent contained in the adhesive composition_CMass W of the thermoplastic resin contained in the adhesive composition_PAnd mass W of fluorine compound_FCTotal (W) of_P+W_FC) Ratio W of_C/(W_P+W_FC) For example, 0.01 to 0.5, or 0.05 to 0.3, or 0.1 to 0.2. If the above ratio W is_C/(W_P+W_FC) When the amount is 0.01 or more, the scale-like filler 5f can be sufficiently suppressed from falling off from the liquid-repellent layer, and the durability of the liquid-repellent layer can be sufficiently improved. On the other hand, if the above ratio W is_C/(W_P+W_FC) When the content is 0.5 or less, the content of the fluorine compound and the thermoplastic resin can be sufficiently secured, the fluorine compound can be easily and sufficiently oozed out to the surface of the liquid-repellent layer, and thus good liquid repellency can be exhibited, and the effect of suppressing the falling-off of the scale-like filler 5f from the liquid-repellent layer 3 by the thermoplastic resin can be sufficiently obtained.

The fluorine compound is generally used in the form of an aqueous dispersion dispersed in water. Therefore, in order to improve the affinity with water, many fluorine compounds have a hydrophilic group such as a hydroxyl group or an amino group. These functional groups of the fluorine compound react with the functional groups of the crosslinking agent to form a crosslinked structure in the liquid-repellent layer 3. In addition, since these functional groups of the fluorine compound are reduced by the reaction with the crosslinking agent, the functional groups remaining in the liquid repellent layer are reduced. Therefore, even when the liquid repellent layer is in contact with the liquid substance for a long time, the decrease in liquid repellency is suppressed, and excellent liquid repellency can be maintained for a long time. When the fluorine compound is used in the form of a dispersion obtained by dispersing the fluorine compound in a solvent other than water, the fluorine compound may have a structure (for example, a hydrocarbon chain) for improving affinity with the solvent used.

The crosslinking agent is not particularly limited as long as it has a functional group that reacts with the fluorine compound, and for example, a crosslinking agent having a functional group such as an aziridine group, an isocyanate group, a carbodiimide group, or an amino group can be used. Examples of commercially available crosslinking agents include Chemite manufactured by Nippon catalyst Co., Ltd., Takenate manufactured by Mitsui chemical Co., Ltd., Carbodilite manufactured by Nisshinbo chemical Co., Ltd., Meikanate manufactured by Ming Dynasty chemical Industries Co., Ltd., and Cymel manufactured by Cytec Industries, Ltd.

When the adhesive composition contains a thermoplastic resin, the thermoplastic resin may also be a modified polyolefin modified with a predetermined acid. Since a functional group is introduced, the modified polyolefin is preferable from the viewpoint of easily reacting with a crosslinking agent to form a crosslinked structure. Examples of the functional group include a carboxyl group, a hydroxyl group, (meth) acryloyl group, and an amino group. By using the modified polyolefin having these functional groups, a crosslinked structure composed of a thermoplastic resin, a fluorine compound, and a crosslinking agent can be formed in the liquid-repellent layer, and more excellent durability can be imparted to the liquid-repellent layer.

Mass W of scaly filler 5f contained in liquid repellent layer-forming composition_S1Mass W of fluorine compound contained in composition for forming liquid repellent layer_FCAnd mass W of crosslinking agent_CTotal (W) of_FC+W_C) Ratio W of_S1/(W_FC+W_C) Or the mass W_S1Mass W of thermoplastic resin contained in composition for forming liquid repellent layer_PAnd mass W of fluorine compound_FCAnd mass W of crosslinking agent_CTotal (W) of_P+W_FC+W_C) Ratio W of_S1/(W_P+W_FC+W_C) Can be 0.3 to 10, can also be 0.5 to 10 or 1 to 5. Since this value is within the above range, the scale-like filler 5f can be covered with the binder resin 5b sufficiently as a whole, but the complex and fine shape of the scale-like filler 5f can be easily formed on the surface of the liquid repellent layer. This can suppress the scale-like filler 5f from falling off from the liquid-repellent layer, and can realize both the liquid repellency by the scale-like filler 5f and the liquid repellency by the fluorine compound contained in the binder resin 5 b.

The mass ratio of the scaly filler 5f, the fluorine compound, the thermoplastic resin and the crosslinking agent contained in the liquid repellent layer-forming composition was substantially the same as the mass ratio of the above-mentioned components contained in the liquid repellent layer, and even if the liquid repellent layer was burned, the mass of the scaly filler 5f as an inorganic substance was not substantially changed, and therefore, the mass change of the liquid repellent layer due to the burning was measured, and the ratio W was calculated from these measured values_S1/(W_FC+W_C) Or a ratio W_S1/(W_P+W_FC+W_C) The value of (c).

A method of manufacturing a liquid-repellent structure according to a third embodiment includes: preparing a coating liquid containing a filler, a fluorine compound, a crosslinking agent having a functional group that reacts with the fluorine compound, and a solvent; forming a coating film of the coating liquid on a surface to be treated; and a step of forming a liquid-repellent layer by drying and curing the coating film. By the above method, a liquid-repellent structure capable of achieving the above effects can be manufactured.

The third embodiment of the present disclosure has been described above in detail, but the present invention is not limited to the above embodiment. For example, the base layer 8 may be provided between the surface to be treated 1a and the liquid repellent layer (see fig. 9).

[ fourth embodiment ]

A liquid-repellent structure according to a fourth embodiment includes a surface to be treated 1a and a liquid-repellent layer formed on the surface to be treated 1a, the liquid-repellent layer containing a binder resin containing a fluorine-containing resin and a filler dispersed in the binder resin, and the fluorine content W of the fluorine-containing resin_FMass W relative to the above filler_SRatio W of_F/W_S0.06 to 0.90. The components contained in the liquid-repellent layer according to the fourth embodiment, the content ratio thereof, and the like may be the same as those of the first embodiment and the modifications thereof, and the second embodiment and the third embodiment. Hereinafter, the fourth embodiment will be described mainly about matters different from the above-described embodiments and the like.

The binder resin contains at least a fluorine-containing resin. The fluorine-containing resin is not particularly limited, and resins having a structure such as perfluoroalkyl group, perfluoroalkenyl group, perfluoropolyether, and the like can be suitably used. From the viewpoint of further improving the liquid repellency of the liquid repellent layer 3, the fluorine-containing resin preferably contains a fluorine-acrylic acid copolymer. The fluorine-acrylic acid copolymer is a copolymer of a fluorine-containing monomer and an acrylic monomer. The fluorine-acrylic acid copolymer may be a block copolymer or a random copolymer. By using the fluorine-acrylic acid copolymer, weather resistance, water resistance, chemical resistance, and film forming property of the liquid-repellent layer 3 can also be improved.

The fluorine content in the fluorine-containing resin may be, for example, 30 to 60 mass%, or 40 to 50 mass%. The fluorine content is a ratio of the mass of fluorine atoms to the total mass of atoms constituting the fluorine-containing resin.

As the fluorine-containing resin, a commercially available fluorine-based coating material can be used. Examples of commercially available fluorine-based coating materials include Asahiguard manufactured by Asahi glass Co., Ltd, SFcoat manufactured by AGC Seimi Chemical Co., Ltd, Ftergent manufactured by Neos Co., Ltd, Fluorolink manufactured by Solvay Co., Ltd, Unidyne manufactured by Daikin Industrial Co., Ltd, H-3539 series manufactured by first Industrial pharmaceutical Co., Ltd, Modiper F series manufactured by Nichio oil Co., Ltd, and the like.

As described above, in the case ofMass W of fluorine contained in the fluorine-containing resin in the liquid layer_FMass W relative to the filler_SRatio W of_F/W_S0.06 to 0.90. Here, when 2 or more kinds of fillers are used, the mass W of the filler_SRefers to their total amount. For example, in the liquid repellent layer 3 shown in fig. 1, the mass W of the scale-like filler 5f_S1Mass W corresponding to the filler_S. If the above ratio W is_F/W_SWhen the amount is 0.06 or more, a sufficient amount of fluorine can be effectively disposed on the filler surface, and the surface free energy of the liquid-repellent layer can be effectively reduced, so that excellent liquid repellency can be obtained in the liquid-repellent layer. From the viewpoint of more sufficiently obtaining this effect, the ratio W_F/W_SMay be 0.10 or more, may be 0.15 or more, and may be 0.21 or more. In particular, if the ratio W_F/W_SIf the amount is 0.21 or more, the amount of fluorine present on the surface of the liquid repellent layer increases, and the liquid repellency is further improved. In addition, when a fluorine-acrylic acid copolymer is used as the fluorine-containing resin, the ratio W_F/W_SWhen the amount is 0.21 or more, the amount of the acrylic component is also increased, so that the strength of the coating film is improved and the falling-off of the filler can be suppressed. On the other hand, if the above ratio W is_F/W_SWhen the amount is 0.90 or less, the filler is not buried in the fluorine-containing resin, unevenness can be effectively formed on the surface of the liquid-repellent layer, and excellent liquid repellency can be obtained in the liquid-repellent layer. From the viewpoint of more sufficiently obtaining this effect, the ratio W_F/W_SMay be 0.80 or less, may be 0.70 or less, may be 0.60 or less, and may be 0.50 or less. The above ratio W_F/W_SFor example, the measurement can be carried out by thermal decomposition GC-MS, combustion IC method, or the like. When the blending amount of each component constituting the liquid repellent layer is known, the above ratio W is_F/W_SThe amount of the additive may be calculated from the above-mentioned amount. The mass W is_FWith mass W_SThe units of (a) are the same.

The content of the fluorine-containing resin in the binder resin 5b (based on the mass of the binder resin 5 b) may be, for example, 5 mass% or more, or 15 mass% or more, or 50 mass% or more. The content of the fluorine-containing resin in the binder resin 5b may be 100% by mass, but when the binder resin 5b contains a thermoplastic resin or a crosslinking agent, the content of the fluorine-containing resin may be 99% by mass or less, or may be 75% by mass or less. When the content of the fluorine-containing resin in the binder resin 5b is 5% by mass or more, the liquid repellent layer easily exhibits excellent liquid repellency, while when the content is 99% by mass or less, the content of the thermoplastic resin or the crosslinking agent can be sufficiently secured, the filler can be sufficiently suppressed from falling off from the liquid repellent layer, and the durability of the liquid repellent layer can be sufficiently improved.

The content of the thermoplastic resin in the binder resin 5b (based on the mass of the binder resin 5 b) is, for example, 5 to 90 mass%, and may be 10 to 50 mass% or 20 to 30 mass%. When the content of the thermoplastic resin in the binder resin 5b is 5% by mass or more, the falling of the filler from the liquid-repellent layer can be sufficiently suppressed, and when the content is 90% by mass or less, the content of the fluorine-containing resin or the crosslinking agent can be sufficiently secured, and the liquid-repellent layer easily exhibits excellent liquid repellency and durability.

Mass W of the crosslinking agent contained in the binder resin 5b_CMass W of the fluorine-containing resin contained in the binder resin 5b_JRatio W of_C/W_JFor example, 0.01 to 0.5, or 0.05 to 0.3, or 0.1 to 0.2. If the above ratio W is_C/W_JWhen the amount is 0.01 or more, the filler can be sufficiently prevented from falling off from the liquid-repellent layer, and the durability of the liquid-repellent layer can be sufficiently improved. On the other hand, if the above ratio W is_C/W_JWhen the content is 0.5 or less, the content of the fluorine-containing resin can be sufficiently secured, and the fluorine-containing resin can be sufficiently exuded to the surface of the liquid-repellent layer, and thus, excellent liquid repellency can be exhibited.

When the binder resin 5b contains a thermoplastic resin and a crosslinking agent, the mass W of the crosslinking agent contained in the binder resin 5b_CMass W of the thermoplastic resin contained in the binder resin 5b_PAnd mass W of fluorine-containing resin_JTotal (W) of_P+W_J) Ratio W of_C/(W_P+W_J) For example, 0.01 to 0.5, or 0.05 to 0.3, or 0.07 to 0.2. If the above ratio W is_C/(W_P+W_J) When the amount is 0.01 or more, the filler can be sufficiently prevented from falling off from the liquid-repellent layer, and the durability of the liquid-repellent layer can be sufficiently improved. On the other hand, if the above ratio W is_C/(W_P+W_J) When the content is 0.5 or less, the content of the fluorine-containing resin and the content of the thermoplastic resin can be sufficiently secured, the fluorine-containing resin can be sufficiently exuded to the surface of the liquid-repellent layer, and therefore, the excellent liquid repellency can be exhibited, and at the same time, the effect of suppressing the filler from falling off from the liquid-repellent layer by the thermoplastic resin can be sufficiently obtained.

Mass W of binder resin 5b contained in liquid repellent layer_BMass W relative to the filler_SRatio W of_B/W_SCan be 0.1 to 5, can also be 0.2 to 2, or 0.3 to 1. Here, the mass W of the binder resin 5b_BMass W corresponding to the fluorine-containing resin_JMass W of thermoplastic resin_PAnd mass W of crosslinking agent_CThe total mass of (2). Due to the above ratio W_B/W_SWithin the above range, the entire filler is sufficiently covered with the binder resin 5b, but the uneven structure caused by the filler is easily formed at the surface of the liquid repellent layer. This can suppress the filler from falling off from the liquid-repellent layer, and can achieve both liquid repellency by the filler and liquid repellency by the fluorine-containing resin contained in the binder resin 5 b. Note that, even if the liquid repellent layer 3 is burned, the mass W of the filler_SSince there is substantially no change, the mass change of the liquid repellent layer due to combustion can be measured, and the ratio W can be calculated from the measured value_B/W_SThe value of (c).

The aggregate 5 is obtained by integrating a large amount of the flaky filler 5f and the binder resin 5b (a cured product of a fluorine-containing resin, a thermoplastic resin, a crosslinking agent, and the like). The aggregate 5 forms irregularities on the surface of the liquid repellent layer 3 (see fig. 1). According to the study of the present inventors, if the size ((long diameter + short diameter)/2) of one aggregate 5 is 4 μm or more, the aggregate 5 greatly contributes to the improvement of the liquid repellency of the liquid repellent layer 3.

The plurality of aggregates 5 may be disposed so as to be separated from each other in the liquid-repellent layer 3. That is, the plurality of aggregates 5 may be arranged in an island shape. Alternatively, a large number of aggregates 5 may be continuously formed, and a porous layer composed of the aggregates 5 may be formed in the liquid-repellent layer 3. The aggregate 5 has a complex shape derived from the complex and fine shape of the scale-like filler 5 f. That is, the aggregate 5 has a wrinkled surface and voids formed by wrinkles by aggregating a plurality of primary particles (for example, particles having an average particle diameter of 0.1 to 6 μm) of the scale-like filler 5f in a state of being randomly arranged.

The mass per unit area of the liquid repellent layer 3 is, for example, 0.3 to 10.0g/m²And may be 1.0 to 3.0g/m²Or 1.5 to 2.5g/m². Since the mass per unit area of the liquid repellent layer 3 was 0.3g/m²As described above, the fluorine-containing resin can exhibit excellent liquid repellency. On the other hand, since the mass per unit area of the liquid-repellent layer 3 was 10.0g/m²Hereinafter, the uneven structure and the liquid repellent effect of the fluorine-containing resin can be effectively obtained.

The fluorine-containing resin may not contain a structural unit derived from pyrrolidone or a derivative thereof (pyrrolidone) from the viewpoint of further improving liquid repellency against a liquid substance having high viscosity and containing a surfactant or the like (for example, hand soap, bath cream, shampoo, moisturizing cream, and cosmetics). Examples of the pyrrolidones include N-vinyl-2-pyrrolidone, N-vinyl-3-methyl-2-pyrrolidone, N-vinyl-5-methyl-2-pyrrolidone, and N-vinyl-3, 3-dimethyl-2-pyrrolidone. Examples of the fluorine compound not containing a structural unit derived from a pyrrolidone include Asahiguard AG-E060, AG-E070, AG-E090, manufactured by Asahi glass Co., Ltd; unidyne TG-8111 manufactured by Daikin industries, Ltd.

The binder resin may further comprise one or both of a thermoplastic resin and a crosslinking agent. Since the binder resin contains a thermoplastic resin, the falling-off of the filler from the liquid-repellent layer can be more sufficiently suppressed, and the liquid repellency and durability of the liquid-repellent layer can be further improved. The thermoplastic resin may be selected from the resins listed in the first embodiment. When the binder resin contains a crosslinking agent, a crosslinked structure obtained by crosslinking the fluorine-containing resin or the thermoplastic resin in the binder resin via the crosslinking agent may be present in the liquid repellent layer. Since the liquid-repellent layer further contains a crosslinking agent, for example, the fluorine-containing resin reacts with the crosslinking agent to form a crosslinked structure in the liquid-repellent layer, and the filler can be further prevented from falling off from the liquid-repellent layer. Further, by reacting the crosslinking agent with the fluorine-containing resin, the reaction points (functional groups such as hydroxyl groups) of the fluorine-containing resin can be reduced, and the affinity between the liquid repellent layer generated at the reaction points and the liquid substance (water, oil, or a liquid substance containing oil, etc.) can be reduced. Further, it is considered that the fluorine-containing resin and the crosslinking agent form a crosslinked structure, whereby the orientation of the fluorine-containing group such as a perfluoroalkyl group (Rf group) of the fluorine-containing resin can be made rigid, and the reduction of the liquid repellency due to the disturbance of the orientation of the fluorine-containing group when the liquid repellent layer is brought into contact with the liquid substance for a long time can be suppressed. By these actions caused by the addition of the crosslinking agent, the liquid repellent layer can maintain excellent liquid repellency even when it is in contact with a liquid substance for a long time. The crosslinking agent may be selected from the crosslinking agents listed in the third embodiment.

A method of manufacturing a liquid-repellent structure according to a fourth embodiment includes: a step of preparing a coating liquid containing a binder resin containing a fluorine-containing resin and a filler; a step of forming a coating film of the coating liquid on a surface to be imparted with liquid repellency; and a step of forming a liquid-repellent layer by drying and curing the coating film. Mass W of fluorine contained in fluorine-containing resin in coating liquid_FMass W relative to the filler_SRatio W of_F/W_S0.06 to 0.90. The coating liquid contains, for example, the scaly filler 5f, the fluorine-containing resin, the solvent, and, if necessary, at least one of the thermoplastic resin and the crosslinking agent. When the coating liquid contains a crosslinking agent, a crosslinked structure composed of a fluorine-containing resin, a thermoplastic resin used as needed, and a crosslinking agent is formed in the liquid repellent layer 3. The heating condition is not limited as long as the solvent can be volatilized and the crosslinking reaction can be caused, and may be, for example, 0.5 to 5 minutes at 60 to 100 ℃. By the above method, the liquid-repellent structure of the present disclosure that achieves the above effects can be manufactured.

The liquid repellent layer 3 may be a layer containing the 2 nd filler alone instead of the scale-like filler 5f, or may be a layer containing the 3 rd filler alone instead of the scale-like filler 5 f. The liquid-repellent structure 40A shown in fig. 13 includes a liquid-repellent layer 3E containing, as a filler, a 2 nd filler (filler 6f) smaller in size than the scaly filler 5f alone. The filler 6f is, for example, spherical and has an average primary particle diameter of 5 to 1000 nm. In the liquid repellent layer 32E, the above ratio W is also set_F/W_SThe liquid-repellent layer 3E has an excellent liquid-repellent property because the liquid-repellent layer is set to 0.06 to 0.90. In the liquid repellent layer 3E shown in fig. 13, the mass W of the filler 6f_S2Mass W corresponding to the filler_S. In this modification, the ratio W_F/W_SThe preferred ranges and effects thereof are the same as those described above in the present embodiment.

As in the liquid repellent layer 3A shown in fig. 6, the liquid repellent layer in the present embodiment may be an embodiment containing, as fillers, scaly fillers 5f and fillers 6f having a smaller size than the scaly fillers 5 f. By adding an appropriate amount of the filler 6f to the coating liquid for forming the liquid repellent layer, the filler 6f can be interposed between the primary particles of the scale-like filler 5f (see fig. 6). This can suppress the formation of excessively large aggregates caused by excessive stacking (aggregation) of the primary particles of the scale-like filler 5 f. In this embodiment, too, the above-mentioned ratio W is set_F/W_SThe liquid-repellent layer has a liquid-repellent property of 0.06 to 0.90. In this embodiment, the mass W of the scale-like filler 5f_S1Mass W of filler 6f_S2The sum of (a) and (b) corresponds to the mass Ws of the filler. The aggregate according to this embodiment is composed of a scaly filler 5f, a filler 6f, and a binder resin 5b covering them. In this mode, the ratio W_F/W_SThe preferable range of (b) and the effects thereof are the same as those described in the liquid-repellent structure 10. The configuration other than the difference in the filler contained in the liquid repellent layer is the same as that described above in the present embodiment. The liquid-repellent structure 10 is similar to the liquid-repellent structure described above except that the filler contained in the liquid-repellent layer is differentThe above is the same.

The content of the filler 6f may be, for example, 5 to 300 parts by mass, 10 to 250 parts by mass, or 20 to 200 parts by mass with respect to 100 parts by mass of the flaky filler 5 f. When the content of the filler 6f is within the above range, formation of excessively large aggregates due to excessive stacking (aggregation) of the primary particles of the scaly filler 5f can be more sufficiently suppressed, and at the same time, excellent liquid repellency due to the scaly filler 5f and the filler 6f can be easily obtained.

As in the liquid repellent layer 3B shown in fig. 7, the liquid repellent layer in the present embodiment may further include, as fillers, scaly fillers 5f and fillers 7f having a size larger than that of the scaly fillers 5 f. The filler 7f is, for example, spherical and has an average primary particle diameter of 5 to 30 μm. On the surface of the liquid repellent layer containing the filler 7f having such a size, irregularities are formed which are coarser than those formed by the aggregates composed of the scale-like filler 5 f. Thus, the liquid repellent layer according to this embodiment has particularly excellent liquid repellency even for liquid substances (for example, hand soaps, shower gels, shampoos, moisturizers, creams, and cosmetics) containing surfactants and the like and having high viscosity. The filler 7f may also have liquid repellency.

In the liquid repellent layer according to this mode, by setting the above ratio W_F/W_SThe liquid-repellent layer is set to 0.06 to 0.90, and excellent liquid repellency can be obtained. In the liquid-repellent layer according to this embodiment, the mass W of the scale-like filler 5f_S1Mass W of filler 7f_S3Is equivalent to the mass W of the filler_S. In this mode, the ratio W_F/W_SThe preferred ranges and effects thereof are the same as those described above in the present embodiment. The liquid-repellent structure 10 is similar to the liquid-repellent structure described above except that the filler contained in the liquid-repellent layer is different.

The liquid-repellent layer may further contain both the filler 6f and the filler 7f, together with the scale-like filler 5 f. The liquid-repellent structure 10D shown in fig. 6 includes a liquid-repellent layer 3D containing scale-like fillers 5f, fillers 6f, and fillers 7 f. Irregularities due to aggregates 5 composed of the binder resin 5b, the scale-like filler 5f, and the filler 6f, and rough irregularities due to the filler 7f are formed on the surface of the liquid repellent layer 3D. Thus, the liquid repellent layer 3D has particularly excellent liquid repellency even for liquid substances (for example, hand soaps, shower gels, shampoos, moisturizers, creams, and cosmetics) containing surfactants and the like and having high viscosity.

In the liquid repellent layer 3D, by setting the above ratio W_F/W_SThe liquid-repellent layer 3D has an excellent liquid-repellent property when set to 0.06 to 0.90. In the liquid repellent layer 3D shown in fig. 6, the mass W of the scale-like filler 5f_S1Mass W of filler 6f_S2And mass W of filler 7f_S3Is equivalent to the mass W of the filler_S. In the present embodiment, the ratio W_F/W_SThe preferable range of (b) and the effects thereof are the same as those described above in the liquid-repellent structure 10. The liquid-repellent structure 10 is similar to the liquid-repellent structure described above except that the filler contained in the liquid-repellent layer is different.

The filler for the liquid repellent layer may be appropriately selected without being limited to the above-described embodiments. For example, the filler contained in the liquid repellent layer may contain a filler other than the scale-like filler 5f, the filler 6f, and the filler 7 f. From the viewpoint of imparting more excellent liquid repellency to the liquid repellent layer, the liquid repellent layer preferably contains at least one selected from the group consisting of the scaly fillers 5f, the fillers 6f, and the fillers 7f, more preferably contains at least the scaly fillers 5f, still more preferably contains at least one of the fillers 6f and the fillers 7f and the scaly fillers 5f, and particularly preferably contains three kinds of the fillers, namely the scaly fillers 5f, the fillers 6f, and the fillers 7 f.

Although the fourth embodiment of the present disclosure has been described in detail, the present invention is not limited to the above embodiment. For example, a base layer may be provided between the surface to be treated 1a and the liquid repellent layer (see fig. 9).

Examples

The present disclosure is described in more detail by the following examples, but the present invention is not limited to these examples.

In order to produce the liquid-repellent structure according to the first embodiment and the liquid-repellent structure according to the comparative example, the following materials were prepared.

(substrate)

Polyethylene terephthalate (PET) film

(thermoplastic resin)

Modified polyolefin: auroren AE-301 (trade name, manufactured by Nippon paper-making Co., Ltd., melting point 60-70 ℃ C.)

(fluorine Compound)

Fluorine-based coating material a: asahiguard AG-E060 (trade name, a compound having no structural unit derived from pyrrolidones, manufactured by Asahi glass Co., Ltd., cationic aqueous material)

Fluorine-based coating b: asahiguard AG-E070 (trade name, manufactured by Asahi glass Co., Ltd., a compound having no structural unit derived from pyrrolidones, cationic aqueous material)

Fluorine-based coating c: asahiguard AG-E090 (trade name, manufactured by Asahi glass Co., Ltd., a compound having no structural unit derived from pyrrolidones, anionic water-based material)

Fluorine-based coating material d: unidyne TG-8111 (product name, manufactured by Daikin industries, Ltd., compound having no structural unit derived from pyrrolidones, anionic water-based material)

Fluorine-based coating material e: unidyne TG-8811 (trade name, manufactured by Daikin industries, Ltd., compound having structural units derived from pyrrolidones, cationic aqueous material)

(Scale-like Filler)

Flaky silica a: sunlevely (trade name, product name, AGC Si-Tech Co., Ltd., average particle size 4 to 6 μm)

Flaky silica b: sunlevely (trade name, manufactured by AGC Si-Tech Co., Ltd., average particle diameter of 0.1 μm)

Scaly mica: renco Mica (trade name, manufactured by Renco Ltd., average particle diameter: 4 μm)

(2 nd Filler)

Silica particles a: AEROSIL (trade name, manufactured by Nippon AEROSIL Co., Ltd., average particle diameter 7nm)

Silica particles b: AEROSIL (trade name, manufactured by Nippon AEROSIL Co., Ltd., average particle diameter 30nm)

Silica particles c: seahostat (trade name, manufactured by Nippon catalyst Co., Ltd., average particle diameter 500nm)

Silica particles d: seahostat (trade name, manufactured by Nippon catalyst Co., Ltd., average particle diameter 1000nm)

(3 rd Filler and 5 th Filler)

Silica particles e: sunsphere (trade name, manufactured by AGC Si-Tech Co., Ltd., average particle diameter 10 μm)

Silica particles f: sunsphere (trade name, manufactured by AGC Si-Tech Co., Ltd., average particle diameter 20 μm)

Acrylic bead a: art Pearl (trade name, manufactured by Kogyo Co., Ltd., average particle diameter 90 μm)

Acryl beads b: art Pearl (trade name, product of Geng Industrial Co., Ltd., average particle diameter 10 μm)

Silica particle g: HS-304 (trade name, manufactured by Nippon iron chemical & materials Co., Ltd., average particle diameter 28 μm)

Silica particles h: sunsphere (trade name, manufactured by AGC Si-Tech Co., Ltd., average particle diameter 5 μm)

Silica particles i: sunsphere (trade name, manufactured by AGC Si-Tech Co., Ltd., average particle diameter 12 μm)

Polyethylene particles: Flo-Beads (trade name, product of Sumitomo Seiko Ltd., average particle diameter 11 μm)

(solvent)

Alcohol solvent (2-propanol)

< preparation of liquid-repellent Structure >

Examples 1a to 12a)

The components used in the thermoplastic resin, the fluorine-based coating material (fluorine compound), the scaly filler, the 2 nd filler and the 3 rd filler were added to the solvent so that the mass ratios (solid contents) of the components in the liquid-repellent layer were as shown in examples 1a to 12a of tables 1 to 3, respectively. This was sufficiently stirred to prepare a coating liquid for liquid-repellent layer formation, which was coated on a PET film as a substrate using a bar coater. Then, the applied coating liquid was dried by heating at 80 ℃ for 1 minute, thereby forming a liquid repellent layer on the substrate. The coating amount was adjusted so that the thickness of the adhesive layer in the liquid repellent layer (thickness T in fig. 1) became 0.5 μm.

(examples 13a, 22a to 25a and 28a)

The components used in the thermoplastic resin, the fluorine-based coating material (fluorine compound), the scaly filler, the 2 nd filler and the 3 rd filler were added to the solvent so that the mass ratios (solid contents) of the components in the liquid-repellent layer were as shown in examples 13a, 22a to 25a and 28a of tables 4 to 5, respectively. This was sufficiently stirred to prepare a coating liquid for liquid-repellent layer formation, which was coated on a PET film as a substrate using a bar coater. Then, the applied coating liquid was dried by heating at 80 ℃ for 1 minute, thereby forming a liquid repellent layer on the substrate. The coating amount was adjusted so that the thickness of the adhesive layer in the liquid repellent layer (thickness T in fig. 1) became 0.5 μm.

Examples 14a to 21a and 26a to 27a

Thermoplastic resin and, if necessary, 5 th filler were added to the solvent so that the mass ratios (solid contents) of the respective components in the base layer were as shown in examples 14a to 21a and 26A to 27A of tables 4 to 5, respectively. This was sufficiently stirred to prepare a coating liquid for forming a base layer, which was coated on a PET film as a substrate using a bar coater. Then, the applied coating liquid was dried by heating at 80 ℃ for 1 minute, thereby forming a base layer on the substrate. The coating amount was adjusted so that the thickness of the thermoplastic resin layer in the base layer (thickness T' in fig. 9) became 0.5 μm.

Next, the components used in the thermoplastic resin, the fluorine-based coating material (fluorine compound), the scaly filler, the 2 nd filler and the 3 rd filler were added to the solvent so that the mass ratios (solid contents) of the components in the liquid-repellent layer were as shown in examples 14a to 21a and 26a to 27a of tables 4 to 5, respectively. This was sufficiently stirred to prepare a coating liquid for liquid-repellent layer formation, which was coated on the base layer using a bar coater. Then, the applied coating liquid was dried by heating at 80 ℃ for 1 minute, thereby forming a liquid repellent layer on the base layer. The coating amount was adjusted so that the thickness of the adhesive layer in the liquid repellent layer (thickness T in fig. 1) became 0.5 μm.

Examples 29a to 37a

Thermoplastic resin and 5 th filler were added to a solvent so that the mass ratios (solid contents) of the respective components in the underlayer became as shown in examples 29a to 37a of tables 6 to 7, respectively. This was sufficiently stirred to prepare a coating liquid for forming a base layer, which was coated on a PET film as a substrate using a bar coater. Then, the applied coating liquid was dried by heating at 80 ℃ for 1 minute, thereby forming a base layer on the substrate. The coating amount was adjusted so that the thickness of the thermoplastic resin layer in the base layer (thickness T' in fig. 9) became 0.5 μm.

Next, the components used for the thermoplastic resin, the fluorine-based coating material (fluorine compound), the flaky filler, the 2 nd filler and the 3 rd filler were added to the solvent so that the mass ratios (solid contents) of the components in the liquid-repellent layer were as shown in examples 29a to 37a of table 6, respectively. This was sufficiently stirred to prepare a coating liquid for liquid-repellent layer formation, which was coated on the base layer using a bar coater. Then, the applied coating liquid was dried by heating at 80 ℃ for 1 minute, thereby forming a liquid repellent layer on the base layer. The coating amount was adjusted so that the thickness of the adhesive layer in the liquid repellent layer (thickness T in fig. 1) became 0.5 μm.

[ Table 1]

[ Table 2]

[ Table 3]

[ Table 4]

[ Table 5]

[ Table 6]

In order to produce the liquid-repellent structure according to the comparative example, the following materials were prepared.

(substrate)

Polyethylene terephthalate (PET) film

(thermoplastic resin)

Modified polyolefin: auroren AE-301 (trade name, manufactured by Nippon paper-making Co., Ltd., melting point 60-70 ℃ C.)

(fluorine Compound)

Fluorine-based coating material a: asahiguard AG-E060 (trade name, a compound having no structural unit derived from pyrrolidones, manufactured by Asahi glass Co., Ltd.)

(Scale-like Filler)

Flaky silica a: sunlevely (trade name, product name, AGC Si-Tech Co., Ltd., average particle size 4 to 6 μm)

(spherical Filler)

Spherical silica: sunsphere (trade name, manufactured by AGC Si-Tech Co., Ltd., average particle diameter: 4 μm)

< preparation of liquid-repellent Structure >

Comparative example 1a

As shown in comparative example 1a of table 7, first, a layer (hereinafter referred to as "undercoat layer") containing a scaly filler and a thermoplastic resin was formed on a base material in the same manner as in example 1a, except that a coating liquid containing a fluorine-free coating material was used. Then, the fluorine-based paint used in example 1a was applied on the surface of the base layer using a bar coater. The applied fluorine-based paint was dried by heating at 80 ℃ for 1 minute, thereby forming an overcoat layer on the surface of the base layer.

Although the structure according to comparative example 1a was not photographed in fig. 14(a) and 14(b), fig. 14(a) is an SEM image of the undercoat layer containing the flaky filler, and fig. 14(b) is an SEM image of the undercoat layer containing the flaky filler and the overcoat layer covering the undercoat layer. From these images, the morphology in which the fine irregularities of the scaly filler are buried in the overcoat layer can be seen.

Comparative example 2a

As shown in comparative example 2a of table 7, a liquid repellent layer comprising a thermoplastic resin and a fluorine-based coating material was formed on a substrate in the same manner as in example 1a, except that a coating liquid containing no scaly filler was used.

Comparative example 3a

As shown in comparative example 3a of table 7, a liquid repellent layer was formed on a base material in the same manner as in example 1a, except that a coating liquid containing a spherical filler was used instead of the scaly filler. The ratio W was calculated by taking the mass of the spherical silica as a_S1/(W_P+W_FC)。

Comparative examples 4a and 5a

A liquid repellent layer was formed on the substrate in the same manner as in example 1a, except that the mass ratios (solid contents) of the components in the liquid repellent layer were set as shown in comparative examples 4a and 5a in table 7, respectively.

[ Table 7]

< evaluation of liquid-repellent Structure >

The liquid-repellent structure was evaluated from the following points. The evaluation results are shown in tables 8 to 17.

(evaluation of liquid repellency)

The liquid-repellent structure was laid flat so that the surface on the liquid-repellent layer side was upward, and 2 μ L of the following liquid (not including fresh cream) was dropped onto the liquid-repellent layer by a dropper. Then, the liquid-repellent structure was stood upright for 30 seconds, and the state of the dropped liquid was visually observed. The fresh cream can not be collected by a dropper, so a small amount of block mass is taken by the medicine spoon and falls on the liquid repellent layer. Then, the liquid-repellent structure was stood vertically for 30 seconds, and the state of fresh cream was visually observed.

[ liquids used ]

Pure water

Curry: bon curry Gold middle hot (Otsuka food)

Fresh cream: raspberry cream cake (Family Mart)

And (3) yogurt: mingzhi bulgaria yoghourt L81 low sugar (Mingzhi)

Salad oil: ralsh salad oil (Ralsh OilliO)

Hand soap: Kurashi-More medicinal soap (Japanese soap)

Shampoo 1: botanical shampoo (SEVEN-ELEVAN JAPAN) mild to the hair

Shampoo 2: skin-penetrating comfortable cleansing shampoo (SEVEN-ELEVAEN JAPAN)

Shampoo 3: tsubaki Shining shampoo (senegal)

Shampoo 4: je l' aime Moist Repiair shampoo (Kose)

Shampoo 5: je l' air Relay shampoo Soft & Moist (Kose)

[ evaluation standards ]

A: the liquid drops roll off from the liquid repellent layer in a circle; or spalling.

B: and the liquid was dropped from the liquid repellent layer, and no flow mark remained.

C: the liquid was allowed to flow down from the liquid repellent layer, but a dot-like flow mark remained.

D: the liquid was allowed to flow down from the liquid repellent layer, but a linear flow mark remained.

E: staying on the liquid repellent layer; or penetrate into the liquid repellent layer.

(evaluation of adhesion)

The following method was used to evaluate the adhesion of a viscous material. The polypropylene (PP) film was laid flat and 2g of the following dope was collected with a spatula and allowed to fall onto the PP film. A liquid-repellent structure is disposed so that the surface of the liquid-repellent layer side faces the PP film, and the thickness of the liquid-repellent structure is 50g/25cm²The load of (2) pushes it to a viscous substance, and the viscous substance is left standing for 10 seconds in this manner. Then, the liquid-repellent structure was peeled off, and the adhesion state of the viscous material to the contact surface of the liquid-repellent layer with the viscous material was visually observed. From the observation results, the adhesion was evaluated based on the following evaluation criteria. If the evaluation results are a to D, it is considered that there is no problem in practical use. The evaluation results are desirably A to C.

[ dope used ]

Dope 1: kewpie mayonnaise (Kewpie)

Dope 2: uno Hybrid Hard (Zingsheng hall)

Dope 3: free Plus moisturizing lotion (Kanebo cosmetics)

Dope 4: eaude Muge medicinal moisturizer (Xiaolin pharmacy)

[ evaluation standards ]

A: no sticky matter was observed to adhere to the contact surface.

B: the dope was observed to adhere to less than 10% of the area of the contact surface.

C: the dope was observed to adhere to more than 10% but less than 30% of the area of the contact surface.

D: the dope was observed to adhere to more than 30% but less than 70% of the area of the contact surface.

E: the dope was observed to adhere to 70% or more of the area of the contact surface.

[ Table 8]

[ Table 9]

[ Table 10]

[ Table 11]

[ Table 12]

[ Table 13]

[ Table 14]

[ Table 15]

[ Table 16]

[ Table 17]

In the liquid repellent layer according to comparative example 5a, the filler fell off, and therefore, the liquid repellency and adhesion could not be evaluated.

In order to produce the liquid-repellent structure according to the second embodiment and the liquid-repellent structure according to the comparative example, the following materials were prepared.

(substrate)

Polyethylene terephthalate (PET) film

(thermoplastic resin)

Modified polyolefin: auroren (trade name, made of Japanese paper, melting point 60-70 ℃ C.)

(fluorine Compound)

Fluorine-based coating: asahiguard (trade name, manufactured by Asahi glass)

(Scale-like Filler)

Flaky silica a: sunlevely (trade name, manufactured by AGC Si-Tech, average particle size 4 to 6 μm)

Flaky silica b: sunlevely (trade name, manufactured by AGC Si-Tech, average particle size 0.1 μm)

Scaly mica: renco Mica (trade name, manufactured by Renco, average particle size 4 μm)

(coarse filler)

Silica particles a: sunsphere (trade name, manufactured by AGC Si-Tech, average particle size 10 μm)

Silica particles b: sunsphere (trade name, manufactured by AGC Si-Tech, average particle size 20 μm)

Acryl beads: art Pearl (trade name, commercially available from Okinawa Co., Ltd., average particle size: 90 μm)

(2 nd Filler)

Silica particles c: AEROSIL (trade name, manufactured by Japan AEROSIL, average particle diameter 7nm)

Silica particles d: AEROSIL (trade name, manufactured by Japan AEROSIL, average particle diameter 13nm)

Silica particles e: AEROSIL (trade name, manufactured by Japan AEROSIL, average particle diameter 30nm)

Silica particles f: seahostat (trade name, manufactured by Nippon catalyst, average particle diameter 500nm)

Silica particle g: seahostat (trade name, manufactured by Nippon catalyst, average particle diameter: 1000nm)

(outer coating)

Fluorine-based coating: asahiguard (trade name, manufactured by Asahi glass)

< preparation of liquid-repellent Structure >

Examples 1b to 14b

Thermoplastic resin, fluorine compound, scaly filler and coarse filler were added to the solvent so that the mass ratio (solid content) of each component in the liquid-repellent layer was as shown in examples 1b to 14b of table 18, respectively. This was sufficiently stirred to prepare a coating liquid for liquid-repellent layer formation, which was coated on a PET film as a substrate using a bar coater. Then, the applied coating liquid was dried by heating at 80 ℃ for 1 minute, thereby forming a liquid repellent layer on the substrate. The coating amount was adjusted so that the thickness of the adhesive layer in the liquid repellent layer (thickness T in fig. 1) became 0.5 μm.

[ Table 18]

Examples 15b to 19b

Thermoplastic resin, fluorine compound, scaly filler, coarse filler and 2 nd filler were added to the solvent so that the mass ratios (solid contents) of the components in the liquid-repellent layer were as shown in examples 15b to 19b of table 19, respectively. This was sufficiently stirred to prepare a coating liquid for liquid-repellent layer formation, which was coated on a PET film as a substrate using a bar coater. Then, the applied coating liquid was dried by heating at 80 ℃ for 1 minute, thereby forming a liquid repellent layer on the substrate. The coating amount was adjusted so that the thickness of the adhesive layer in the liquid repellent layer (thickness T in fig. 1) became 0.5 μm.

[ Table 19]

Comparative example 1b

The scaly filler and the thermoplastic resin were added to the solvent so that the mass ratio (solid content) of each component in the liquid-repellent layer was as shown in comparative example 1b of table 20. This was sufficiently stirred to prepare a coating liquid for forming a base layer, which was coated on a PET film as a substrate using a bar coater. Then, the applied coating liquid was dried by heating at 80 ℃ for 1 minute, thereby forming a base layer on the substrate. The coating amount was adjusted so that the thickness of the base layer became 0.5 μm. Next, a coating liquid obtained by adding a fluorine compound to a solvent was applied to the surface of the base layer by a bar coater. Then, the applied coating liquid was dried by heating at 80 ℃ for 1 minute, thereby forming an overcoat layer on the base layer.

Comparative example 2b

A liquid repellent layer comprising a thermoplastic resin and a fluorine-based coating material was formed on a substrate in the same manner as in example 1b, except that a coating liquid comprising a thermoplastic resin and a fluorine compound but not containing a scaly filler and a coarse filler was used as shown in comparative example 2b of table 20.

Comparative examples 3b and 4b

A liquid repellent layer containing a thermoplastic resin, a fluorine-based coating material, a scaly filler and a coarse filler was formed on a substrate in the same manner as in example 1b, except that the mass ratio was set as shown in comparative examples 3b and 4b in table 20.

Comparative examples 5b and 6b

A liquid repellent layer comprising a thermoplastic resin and a fluorine-based coating material was formed on a substrate in the same manner as in example 1b, except that the scale-like filler and the coarse filler were not contained in the liquid repellent layer, and the 3 rd filler was used in the coating liquid as shown in each of comparative examples 5b and 6b in table 20.

[ Table 20]

< evaluation of liquid-repellent Structure >

The liquid-repellent structure was evaluated from the following points. The evaluation results are shown in tables 21 to 23.

(measurement of area ratio)

The visual field range (82,872 μm) which could be observed with a 1000-fold lens under a microscope (VHX-1000 manufactured by Keyence)²) The area A of the liquid-repellent layer was determined, and the area A occupied by the detectable coarse filler was determined₃Calculating the area ratio A₃/A。

(evaluation of liquid repellency)

The liquid-repellent structure was laid flat so that the surface on the liquid-repellent layer side was upward, and 2 μ L of the following liquid (not including fresh cream) was dropped onto the liquid-repellent layer by a dropper. Then, the liquid-repellent structure was stood upright for 30 seconds, and the state of the dropped liquid was visually observed. The fresh cream can not be collected by a dropper, so a small amount of lumps are collected by a medicine spoon and fall onto the liquid repellent layer. Then, the liquid-repellent structure was stood vertically for 30 seconds, and the state of fresh cream was visually observed.

[ liquids used ]

Pure water

Curry: bon curry Gold middle hot (Otsuka food)

Fresh cream: raspberry cream cake (Family Mart)

And (3) yogurt: mingzhi bulgaria yoghourt L81 low sugar (Mingzhi)

Salad oil: ralsh salad oil (Ralsh OilliO)

Hand soap: Kurashi-More medicinal soap (Japanese soap)

Shampoo: shampoo with plant mild to hair (SEVEN-ELEVAEN JAPAN)

[ evaluation standards ]

1: staying on the liquid repellent layer; or penetrate into the liquid repellent layer.

2: the liquid was allowed to flow down from the liquid repellent layer, but a linear flow mark remained.

3: the liquid was allowed to flow down from the liquid repellent layer, but a dot-like flow mark remained.

4: and the liquid was dropped from the liquid repellent layer, and no flow mark remained.

5: the liquid drops roll off from the liquid repellent layer in a round shape; or spalling.

(5 is the best, 1 is the worst)

If the evaluation value is 2 or more, there is no problem in practical use, but it is more preferable that the evaluation value is 3 or more. As is clear from tables 21 to 23, in the liquid-repellent structure according to the second embodiment, a liquid-repellent property that does not cause a problem in actual use was obtained for any liquid. On the other hand, sufficient liquid repellency was not obtained in the comparative examples.

[ Table 21]

[ Table 22]

[ Table 23]

In order to produce the liquid-repellent structure according to the third embodiment and the liquid-repellent structure according to the comparative example, the following materials were prepared.

(substrate)

Polyethylene terephthalate (PET) film

(thermoplastic resin)

Modified polyolefin: auroren AE-301 (trade name, manufactured by Nippon paper-making Co., Ltd., melting point 60-70 ℃ C.)

(fluorine Compound)

Fluorine-based coating: asahiguard (trade name, manufactured by Asahi glass Co., Ltd.)

( flake Filler)

Flaky silica a: sunlevely (trade name, product name, AGC Si-Tech Co., Ltd., average particle size 4 to 6 μm)

Flaky silica b: sunlevely (trade name, manufactured by AGC Si-Tech Co., Ltd., average particle diameter of 0.1 μm)

Scaly mica: renco Mica (trade name, manufactured by Renco Ltd., average particle diameter: 4 μm)

(2 nd Filler)

Silica particles a: AEROSIL (trade name, manufactured by Nippon AEROSIL Co., Ltd., average particle diameter 7nm)

Silica particles b: AEROSIL (trade name, manufactured by Japan AEROSIL, average particle diameter 30nm)

Silica particles c: seahostat (trade name, manufactured by Nippon catalyst Co., Ltd., average particle diameter 500nm)

Silica particles d: seahostat (trade name, manufactured by Nippon catalyst Co., Ltd., average particle diameter 1000nm)

(3 rd Filler and 5 th Filler)

Silica particles e: sunsphere (trade name, manufactured by AGC Si-Tech Co., Ltd., average particle diameter 10 μm)

Silica particles f: sunsphere (trade name, manufactured by AGC Si-Tech Co., Ltd., average particle diameter 20 μm)

Acryl beads: art Pearl (trade name, manufactured by Kogyo Co., Ltd., average particle diameter 90 μm)

(crosslinking agent)

Crosslinker a: takenate WD-725 (trade name, available from Mitsui Chemicals Co., Ltd., isocyanate group-containing crosslinking agent)

Crosslinker b: chemite PZ-33 (trade name, manufactured by Nippon catalyst Co., Ltd., aziridinyl group-containing crosslinking agent)

Crosslinker c: carbodilite V-02 (trade name, manufactured by Nisshinbo Chemicals Co., Ltd., carbodiimide group-containing crosslinking agent)

Crosslinking agent d: meikanate CX (trade name, Ming chemical industries, Ltd., crosslinking agent containing blocked isocyanate group)

Crosslinker e: cymel 303 (trade name, Cytec Industries Japan, product of the Cross-linking agent containing Melamine skeleton)

(solvent)

Alcohol solvent (2-propanol)

< preparation of liquid-repellent Structure >

Examples 1c to 19c

The components used in the thermoplastic resin, the fluorine-based coating material (fluorine compound), the scaly filler, the 2 nd filler, the 3 rd filler, and the crosslinking agent were added to the solvent so that the mass ratios (solid contents) of the components in the liquid-repellent layer were as shown in examples 1c to 19c of tables 24 to 26, respectively. This was sufficiently stirred to prepare a coating liquid for liquid-repellent layer formation, which was coated on a PET film as a substrate using a bar coater. Then, the applied coating liquid was dried by heating at 80 ℃ for 1 minute to be cured, thereby forming a liquid repellent layer on the substrate. The coating amount was adjusted so that the thickness of the adhesive layer in the liquid repellent layer (thickness T in fig. 1) became 0.5 μm.

Fig. 15 and 16 are tables showing SEM images obtained by scanning the surfaces of the liquid repellent layers produced in examples 1c to 3c with a magnification changed. The shooting magnification is shown in the table. As is clear from the SEM images shown in fig. 15 and 16, irregularities due to aggregates of the scale-like filler are formed on the surface of the liquid repellent layer.

Examples 20c to 22c

Thermoplastic resins and, if necessary, 5 th fillers were added to the solvent so that the mass ratios (solid contents) of the respective components in the underlayer became as shown in examples 20c to 22c in table 26, respectively. This was sufficiently stirred to prepare a coating liquid for forming a base layer, which was coated on a PET film as a substrate using a bar coater. Then, the applied coating liquid was dried by heating at 80 ℃ for 1 minute, thereby forming a base layer on the substrate. The coating amount was adjusted so that the thickness of the thermoplastic resin layer in the base layer (thickness T' in fig. 9) became 0.5 μm.

Next, the components used in the thermoplastic resin, the fluorine-based coating material (fluorine compound), the scaly filler, the 2 nd filler, the 3 rd filler, and the crosslinking agent were added to the solvent so that the mass ratios (solid contents) of the components in the liquid repellent layer were as shown in examples 20c to 22c of table 26, respectively. This was sufficiently stirred to prepare a coating liquid for liquid-repellent layer formation, which was coated on the base layer using a bar coater. Then, the applied coating liquid was dried by heating at 80 ℃ for 1 minute to be cured, thereby forming a liquid repellent layer on the base layer. The coating amount was adjusted so that the thickness of the adhesive layer in the liquid repellent layer (thickness T in fig. 1) became 0.5 μm.

Comparative example 1c

As shown in comparative example 1c of Table 27, first, a layer containing a scaly filler and a thermoplastic resin was formed on a base material as an undercoat layer (thickness T' of the layer of the thermoplastic resin: 0.5. mu.m). Then, the fluorine-based paint used in example 1c was applied on the surface of the base layer using a bar coater. The applied fluorine-based paint was dried by heating at 80 ℃ for 1 minute, thereby forming an overcoat layer on the surface of the base layer.

Comparative example 2c

The procedure was carried out in the same manner as in comparative example 1c except that a coating liquid obtained by adding a crosslinking agent to a fluorine-based coating material was used to form a topcoat layer on the surface of the primer layer as shown in comparative example 2c of table 27.

Comparative example 3c

A liquid-repellent layer containing a fluorine-based coating material and a scaly filler (thickness of adhesive layer: 0.5 μm) was formed on a substrate in the same manner as in example 2c, except that a coating liquid containing no crosslinking agent was used as shown in comparative example 3c of Table 27.

[ Table 24]

[ Table 25]

[ Table 26]

[ Table 27]

< evaluation of liquid-repellent Structure >

The liquid-repellent structure was evaluated from the following points. The evaluation results are shown in tables 28 to 29.

(evaluation of liquid repellency)

The liquid-repellent structure was laid flat so that the surface on the liquid-repellent layer side was upward, and 2 μ L of the following liquid (not including fresh cream) was dropped onto the liquid-repellent layer by a dropper. Then, the liquid-repellent structure was stood upright for 30 seconds, and the state of the dropped liquid was visually observed. The fresh cream can not be collected by a dropper, so a small amount of lumps are collected by a medicine spoon and fall onto the liquid repellent layer. Then, the liquid-repellent structure was stood vertically for 30 seconds, and the state of fresh cream was visually observed.

[ liquids used ]

Pure water

Curry: bon curry Gold middle hot (Otsuka food)

Fresh cream: raspberry cream cake (Family Mart)

And (3) yogurt: mingzhi bulgaria yoghourt L81 low sugar (Mingzhi)

Salad oil: ralsh salad oil (Ralsh OilliO)

Hand soap: Kurashi-More medicinal soap (Japanese soap)

Shampoo: skin-penetrating comfortable cleansing shampoo (SEVEN-ELEVAEN JAPAN)

[ evaluation standards ]

A: the liquid drops roll off from the liquid repellent layer in a round shape; or spalling.

B: and the liquid was dropped from the liquid repellent layer, and no flow mark remained.

C: the liquid was allowed to flow down from the liquid repellent layer, but a dot-like flow mark remained.

D: the liquid was allowed to flow down from the liquid repellent layer, but a linear flow mark remained.

E: staying on the liquid repellent layer; or penetrate into the liquid repellent layer.

(evaluation of durability)

A dimension having a width of 50mm and a length of 100mm was cut out from the liquid-repellent structure as a test piece. 150ml of each of the liquids (excluding whipped cream) used for the liquid repellency evaluation was poured into a 200ml beaker, and the test piece was immersed in the liquid until half of the length thereof was reached and left at room temperature (25 ℃ C.) for 30 days. After the standing, the test piece was pulled up from the liquid, and the adhesion state of each liquid on the surface of the liquid-repellent structure-impregnated portion on the side where the liquid-repellent layer was formed was visually observed, and the durability (liquid repellency after long-term contact with each liquid) was evaluated based on the following evaluation criteria.

[ evaluation standards ]

A: no liquid was observed to adhere to the impregnated portion.

B: the liquid was observed to adhere to less than 10% of the area of the impregnated portion.

C: the liquid was observed to adhere to 10% or more but less than 30% of the area of the impregnated portion.

D: the liquid was observed to adhere to 30% or more but less than 70% of the area of the impregnated portion.

E: the liquid was observed to adhere to 70% or more of the area of the impregnated portion.

[ Table 28]

[ Table 29]

In order to produce the liquid-repellent structure according to the fourth embodiment and the liquid-repellent structure according to the comparative example, the following materials were prepared.

(substrate)

Polyethylene terephthalate (PET) film

(fluorine-containing resin)

Fluorine-based coating material a: asahiguard AG-E060 (trade name, manufactured by Asahi glass Co., Ltd., fluorine-acrylic acid copolymer having no structural unit derived from pyrrolidones, cationic aqueous material, fluorine content: 45% by mass)

Fluorine-based coating b: unidyne TG-8811 (trade name, manufactured by Daikin industries, Ltd., fluorine-acrylic acid copolymer having structural units derived from pyrrolidones, cationic aqueous material, fluorine content 44 mass%)

(Scale-like Filler)

Flaky silica a: sunlevely (trade name, product name, AGC Si-Tech Co., Ltd., average primary particle diameter of 4 to 6 μm)

Flaky silica b: sunlevely (trade name, manufactured by AGC Si-Tech Co., Ltd., average primary particle diameter of 0.1 μm)

(2 nd Filler)

Silica particles a: AEROSIL 200 (product name, manufactured by Nippon AEROSIL Co., Ltd., average primary particle diameter of 12nm)

Silica particles b: AEROSIL 300 (product name, manufactured by Japan Aerosil Co., Ltd., average primary particle diameter of 7nm)

Silica particles c: AEROSIL 50 (product name, manufactured by Nippon AEROSIL Co., Ltd., average primary particle diameter of 30nm)

(3 rd Filler)

Silica particles d: HS-304 (trade name, manufactured by Nippon iron chemical & materials Co., Ltd., average primary particle diameter of 28 μm)

(3 rd and 5 th fillers)

Silica particles e: sunsphere NP-100 (trade name, manufactured by AGC Si-Tech Co., Ltd., average primary particle diameter of 10 μm)

(thermoplastic resin)

Resin a: sepolsion VA407 (trade name, manufactured by Sumitomo Seiko Ltd., ethylene-vinyl acetate copolymer, melting Point 70-80 ℃ C.)

Resin b: auroren AE-301 (trade name, modified polyolefin, manufactured by Nippon paper-making Co., Ltd., melting point 60-70 ℃ C.)

(crosslinking agent)

Crosslinking agent: takenate WD-725 (trade name, available from Mitsui Chemicals Co., Ltd., isocyanate group-containing crosslinking agent)

(solvent)

Alcohol solvent (2-propanol)

< preparation of liquid-repellent Structure >

(examples 1d to 18d and comparative examples 1d to 2d)

The components used in the fluorine-based coating material (fluorine-containing resin), the scaly filler, the 2 nd filler and the 3 rd filler were added to the solvent so that the mass ratios (solid contents) of the components in the liquid-repellent layer were as shown in examples 1d to 18d and comparative examples 1d to 2d of tables 30 to 31, respectively. This was sufficiently stirred to prepare a coating liquid for liquid-repellent layer formation, which was coated on a PET film as a substrate using a bar coater. Then, the applied coating liquid was dried by heating at 80 ℃ for 1 minute to be cured, thereby forming a liquid repellent layer on the substrate. The coating amount was adjusted so that the mass per unit area of the liquid-repellent layer became 2.0g/m²。

(examples 19d to 29d)

Thermoplastic resin and, if necessary, 5 th filler were added to the solvent so that the mass ratio (solid content) of each component in the underlayer was as shown in examples 19d to 29d in table 32. This was sufficiently stirred to prepare a coating liquid for forming a base layer, which was coated on a PET film as a substrate using a bar coater. Then, the applied coating liquid was dried by heating at 80 ℃ for 1 minute, thereby forming a base layer on the substrate. The coating amount was adjusted so that the mass per unit area of the base layer became 5.0g/m²。

Next, the mass ratios (solid contents) of the respective components in the liquid-repellent layer are shown in Table 32In examples 19d to 29d, the respective components used in the fluorine-based coating material (fluorine-containing resin), the scaly filler, the 2 nd filler, the 3 rd filler, the thermoplastic resin, and the crosslinking agent were added to the solvent. This was sufficiently stirred to prepare a coating liquid for liquid-repellent layer formation, which was coated on the base layer using a bar coater. Then, the applied coating liquid was dried by heating at 80 ℃ for 1 minute to be cured, thereby forming a liquid repellent layer on the base layer. The coating amount was adjusted so that the mass per unit area of the liquid-repellent layer became 2.0g/m²。

[ Table 30]

[ Table 31]

[ Table 32]

< evaluation of liquid-repellent Structure >

The liquid-repellent structure was evaluated from the following points. The evaluation results are shown in tables 33 to 34.

(evaluation of liquid repellency)

The liquid-repellent structure was laid flat so that the surface on the liquid-repellent layer side was upward, and 2 μ L of the following liquid was dropped on the liquid-repellent layer by a dropper. Then, the liquid-repellent structure was stood upright for 30 seconds, and the state of the dropped liquid was visually observed. The liquid repellency was evaluated according to the observation results and based on the following evaluation criteria. When the evaluation results are a to D, it is considered that there is no problem in practical use. The evaluation results are expected to be A to C.

[ liquids used ]

Pure water

And (3) yogurt: mingzhi bulgaria yoghourt L81 low sugar (Mingzhi)

Curry (normal temperature): bon curry Gold middle hot (Otsuka food)

Salad oil: ralsh salad oil (Ralsh OilliO)

Hand soap: Kurashi-More medicinal soap (Japanese soap)

Shampoo: skin-penetrating comfortable cleansing shampoo (SEVEN-ELEVAEN JAPAN)

[ evaluation standards ]

A: the liquid drops roll off from the liquid repellent layer in a round shape; or spalling.

B: and the liquid was dropped from the liquid repellent layer, and no flow mark remained.

C: the liquid was allowed to flow down from the liquid repellent layer, but a dot-like flow mark remained.

D: the liquid was allowed to flow down from the liquid repellent layer, but a linear flow mark remained.

E: staying on the liquid repellent layer; or penetrate into the liquid repellent layer.

(evaluation of adhesion)

The following method was used to evaluate the adhesiveness of a viscous food. The polypropylene (PP) film was laid flat and 2g of the following viscous food was collected with a spatula and allowed to fall onto the PP film. The liquid-repellent structure was disposed so that the surface on the liquid-repellent layer side was opposed to the PP film, and the thickness was 50g/25cm²The load of (2) pushes it to the viscous food, and thus it is left standing for 10 seconds. Then, the liquid-repellent structure was peeled off, and the adhesion state of the viscous food on the contact surface of the liquid-repellent layer with the viscous food was visually observed. From the observation results, the adhesion was evaluated based on the following evaluation criteria. If the evaluation results are a to D, it is considered that there is no problem in practical use. The evaluation results are desirably A to C.

[ viscous food used ]

Fresh cream: raspberry cream cake (Family Mart)

Mayonnaise: kewpie mayonnaise (Kewpie GmbH)

[ evaluation standards ]

A: no sticky food was observed to adhere to the contact surface.

B: the viscous food product was observed to adhere to less than 10% of the area of the contact surface.

C: the viscous food product was observed to adhere to more than 10% but less than 30% of the area of the contact surface.

D: the viscous food product was observed to adhere to more than 30% but less than 70% of the area of the contact surface.

E: the viscous food was observed to adhere to more than 70% of the area of the contact surface.

(evaluation of durability)

A dimension having a width of 50mm and a length of 100mm was cut out from the liquid-repellent structure as a test piece. Among the liquids used for the evaluation of liquid repellency, 150ml of pure water, salad oil, soap, and shampoo were poured into 200ml beakers, and the test pieces were immersed in the liquids until half of the length thereof was reached, and left at room temperature (25 ℃) for 30 days. After the standing, the test piece was pulled up from the liquid, and the adhesion state of each liquid on the surface of the liquid-repellent structure-impregnated portion on the side where the liquid-repellent layer was formed was visually observed, and the durability (liquid repellency after long-term contact with each liquid) was evaluated based on the following evaluation criteria. If the evaluation results are a to D, it is considered that there is no problem in practical use. The evaluation results are desirably A to C.

[ evaluation standards ]

A: no liquid was observed to adhere to the impregnated portion.

B: the liquid was observed to adhere to less than 10% of the area of the impregnated portion.

C: the liquid was observed to adhere to 10% or more but less than 30% of the area of the impregnated portion.

D: the liquid was observed to adhere to 30% or more but less than 70% of the area of the impregnated portion.

E: the liquid was observed to adhere to 70% or more of the area of the impregnated portion.

[ Table 33]

[ Table 34]

Industrial applicability

The present disclosure provides a liquid-repellent structure having excellent liquid repellency to water and excellent liquid repellency to oil or a liquid substance containing oil, and a method for producing the same. Further, according to the present disclosure, there are provided a packaging material and a release sheet having the above-described liquid-repellent structure on the side in contact with an article.

Description of the symbols

1. substrate; 1a · to-be-treated surface (surface to be imparted with liquid repellency); 3. 3A, 3B, 3C, 3D, 3 E.cndot.liquid repellent layer; 5. coacervate; 5b · binder resin; 5f · platy filler; 6 f. filler (filler 2); 7 f. filler (filler No. 3); 8. base layer; 8b · thermoplastic resin; 8 f. filler (5 th filler); 9. void; 10. 10A, 10B, 10C, 10D, 20, 40A. liquid repellent structure.