阅读说明：本技术 医用压敏胶组合物及其制备方法和胶粘材料 (Medical pressure-sensitive adhesive composition, preparation method thereof and adhesive material ) 是由 姜伟 李娜 王茜 骆小红 马慧君 宋书锋 于 2020-07-21 设计创作，主要内容包括：本发明提出了压敏胶组合物,所述压敏胶组合物包括：丙烯酸酯树脂、第一溶剂、增粘树脂和纤维素树脂。本发明的压敏胶组合物固化形成的胶层粘接性好,可持久贴合于基材和皮肤上,不易从皮肤或基材上脱落,并且,胶层中间和底部的溶剂分子和单体残留少,不易对皮肤造成损伤,提高了压敏胶的使用效果,应用前景为好。(The present invention provides a pressure-sensitive adhesive composition comprising: acrylate resin, a first solvent, tackifying resin and cellulose resin. The adhesive layer formed by curing the pressure-sensitive adhesive composition disclosed by the invention is good in adhesiveness, can be attached to a substrate and skin for a long time, is not easy to fall off from the skin or the substrate, has less solvent molecules and monomer residues in the middle and at the bottom of the adhesive layer, is not easy to damage the skin, improves the using effect of the pressure-sensitive adhesive, and has a good application prospect.)

1. A medical pressure-sensitive adhesive composition, comprising: acrylate resin, a first solvent, tackifying resin and cellulose resin.

2. The pressure-sensitive adhesive composition according to claim 1, wherein the medical pressure-sensitive adhesive composition comprises:

30-60 parts by weight of an acrylate resin;

30-60 parts by weight of a first solvent;

1-5 parts by weight of tackifying resin;

0.1 to 5 parts by weight of a cellulose resin.

3. The pressure-sensitive adhesive composition according to claim 1, wherein the acrylate resin comprises a structural unit of the following monomers: soft monomer, hard monomer, functional monomer and second solvent,

wherein the soft monomer is selected from the group consisting of C_4～10Alkyl acrylates;

the hard monomer is selected from at least one of methyl methacrylate, acrylic acid, N-vinyl pyrrolidone and vinyl acetate;

the functional monomer is selected from at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, glycidyl methacrylate and allyl glycidyl ether;

the second solvent is selected from at least one of ethyl acetate, butyl acetate and isopropanol;

the molecular weight of the acrylate resin is 400000-800000.

4. The pressure-sensitive adhesive composition according to claim 1, wherein the acrylate resin comprises a structural unit of the following monomers:

40 to 50 parts by weight of a soft monomer;

1 to 10 parts by weight of a hard monomer;

1-5 parts by weight of a functional monomer;

the mass ratio of the total mass of the soft monomer, the hard monomer and the functional monomer to the second solvent is 1: (1-1.5).

5. The pressure-sensitive adhesive composition according to claim 1, wherein the first solvent is at least one selected from the group consisting of ethyl acetate, butyl acetate, isopropyl alcohol and toluene.

6. The pressure-sensitive adhesive composition according to claim 1, wherein the tackifier resin is at least one selected from the group consisting of rosin, petroleum resin, terpene resin, pinene resin, and coumarone resin.

7. The pressure-sensitive adhesive composition according to claim 1, wherein the cellulose resin is at least one selected from the group consisting of hydroxyethyl cellulose, hydroxymethyl cellulose, cellulose nitrate and cellulose acetate butyrate.

8. A method for preparing the medical pressure-sensitive adhesive composition as defined in any one of claims 1 to 7, comprising:

mixing the acrylate resin, the first solvent, the tackifying resin and the cellulose resin.

9. The method according to claim 8, characterized in that the acrylate resin is obtained by:

mixing part of the soft monomer, part or all of the hard monomer, part or all of the functional monomer and part or all of the initiator to obtain a first mixed solution;

mixing the rest of the soft monomer, the rest of the hard monomer, the rest of the functional monomer, the rest of the initiator and the second solvent to obtain a second mixed solution;

dropwise adding the first mixed solution into the second mixed solution, stirring the second mixed solution while dropwise adding, and then carrying out heat preservation so as to obtain the acrylate resin;

optionally, the dropping time of the first mixed solution is 2-5 hours, and the temperature of the first mixed solution is 70-85 ℃ during dropping; the temperature for heat preservation is 70-85 ℃, and the time is 3-8 hours.

10. An adhesive material, comprising: a base material, a pressure sensitive adhesive layer and a release layer which are sequentially stacked,

wherein the pressure-sensitive adhesive layer is formed of the medical pressure-sensitive adhesive composition according to any one of claims 1 to 7.

Technical Field

The invention relates to the field of materials. In particular, the invention relates to a medical pressure-sensitive adhesive composition, a preparation method thereof and an adhesive material.

Background

The pressure-sensitive adhesive can be adhered to an adherend only by applying external force, is convenient to use, has wide application in the aspects of medical health and stability, and the application range of the current medical pressure-sensitive adhesive comprises wound treatment, adhesion of biomedical devices, transdermal drug release patches, medical labels, medical tapes and the like.

Among the various types of medical pressure-sensitive adhesives, acrylic pressure-sensitive adhesives have two major advantages: firstly, the acrylate pressure-sensitive adhesive does not need to be added with other additives, is a single-component adhesive, avoids potential safety problems caused by the additives, is polymerized by emulsion or solution, can be directly used as an adhesive for use as a polymerization product, has great advantages in the production process due to convenient operation, and can be used for preparing the acrylate pressure-sensitive adhesive meeting different use requirements by adjusting the content and the components of the comonomer, thereby having great advantages in use convenience.

With the increasing and wider requirements for the performance of medical pressure-sensitive adhesives, the medical pressure-sensitive adhesives need to satisfy the adhesive performance (initial adhesion, peeling force, permanent adhesion and the like) and have different additional characteristics according to different applications, for example, the pressure-sensitive adhesive adhered to the skin must be non-irritating to the skin and non-toxic.

However, most of the existing acrylate pressure-sensitive adhesives are synthesized, and in the process of curing and drying, residual small-molecule acrylic monomers are in the process of being bonded on the skin for a long time, solvent molecules remained in an adhesive layer can migrate to the surface of the adhesive layer to be contacted with the skin, and irritation can be generated on the skin, so that the allergy phenomenon occurs, and sweat and lactic acid formed by skin sweating can not be timely discharged due to long-time bonding of some adhesives, so that the skin redness phenomenon occurs.

Compared with the acrylate compounds in CN201010557593.3 and CN201010557610.3, the amide monomers are used in the acrylate compounds, and most of the amide monomers are easy to cause skin irritation; in CN96199252.2, styrene monomer is used in acrylate compound, styrene is national second grade carcinogen, and acrylate compound containing styrene is not suitable for skin contact substance.

Therefore, safe and reliable skin contact pressure sensitive adhesives are still under study.

Disclosure of Invention

The present invention aims to solve at least to some extent at least one of the technical problems of the prior art. Therefore, the medical pressure-sensitive adhesive with low irritation, the preparation method thereof and the adhesive material are provided by the invention, the adhesive layer formed by curing the medical pressure-sensitive adhesive composition has good adhesiveness, can be permanently attached to a substrate and skin, is not easy to fall off from the skin or the substrate, has less solvent molecules and monomers in the middle and at the bottom of the adhesive layer, is not easy to damage the skin, improves the use effect of the pressure-sensitive adhesive, and has good application prospect.

In one aspect of the present invention, a pressure sensitive adhesive composition is provided. According to an embodiment of the present invention, the pressure-sensitive adhesive composition includes: acrylate resin, a first solvent, tackifying resin and cellulose resin.

The acrylate resin is main resin, and forms a cross-linked network after being cured, so that the mechanical property of the pressure-sensitive adhesive is improved; the tackifying resin improves the permanent adhesion of the adhesive and is beneficial to firmly adhering an adhesive on the skin for a long time; the cellulose resin and the acrylate resin can form a microphase compatible structure, the loose structure is more favorable for releasing solvent molecules and residual monomers in the middle and at the bottom of the adhesive layer during curing, so that the residual monomer content and the residual solvent molecules of the adhesive layer which is directly contacted with the skin of a human body are greatly reduced, the cellulose resin has hydrophilicity, the absorption, the maintenance and the conduction of skin moisture are facilitated, the use effect of the pressure-sensitive adhesive is improved, and the application prospect is good.

According to an embodiment of the present invention, the above medical pressure-sensitive adhesive composition may further have the following additional technical features:

according to an embodiment of the present invention, the medical pressure-sensitive adhesive composition includes: 30-60 parts by weight of an acrylate resin; 30-60 parts by weight of a first solvent; 1-5 parts by weight of tackifying resin; 0.1 to 5 parts by weight of a cellulose resin.

According to an embodiment of the present invention, the acrylate resin comprises structural units of the following monomers: a soft monomer, a hard monomer, a functional monomer and a second solvent, wherein the soft monomer is selected from C_4～10Alkyl acrylates; the hard monomer is selected from at least one of methyl methacrylate, acrylic acid, N-vinyl pyrrolidone and vinyl acetate; the functional monomer is selected from at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, glycidyl methacrylate and allyl glycidyl ether; the second solvent is selected from at least one of ethyl acetate, butyl acetate and isopropanol; the molecular weight of the acrylate resin is 400000-800000.

According to an embodiment of the present invention, the acrylate resin comprises structural units of the following monomers: 40 to 50 parts by weight of a soft monomer; 1 to 10 parts by weight of a hard monomer; 1-5 parts by weight of a functional monomer; the mass ratio of the total mass of the soft monomer, the hard monomer and the functional monomer to the second solvent is 1: (1-1.5).

According to an embodiment of the present invention, the first solvent is selected from at least one of ethyl acetate, butyl acetate, isopropanol and toluene.

According to an embodiment of the present invention, the tackifying resin is selected from at least one of rosin, petroleum resin, terpene resin, pinene resin and coumarone resin.

According to an embodiment of the invention, the cellulose resin is selected from at least one of hydroxyethyl cellulose, hydroxymethyl cellulose, cellulose nitrate and cellulose acetate butyrate.

In still another aspect of the present invention, the present invention provides a method for preparing the aforementioned medical pressure-sensitive adhesive composition. According to an embodiment of the invention, the method comprises: mixing the acrylate resin, the first solvent, the tackifying resin and the cellulose resin. Therefore, the adhesive layer formed by curing the pressure-sensitive adhesive composition obtained by the method provided by the embodiment of the invention has good adhesiveness, can be attached to a substrate and skin, is not easy to fall off from the skin or the substrate, has less solvent molecules and monomer residues in the middle and at the bottom of the adhesive layer, is not easy to damage the skin, improves the using effect of the pressure-sensitive adhesive, and has a good application prospect.

According to an embodiment of the invention, the acrylate resin is obtained by: mixing part of the soft monomer, part or all of the hard monomer, part or all of the functional monomer and part or all of the initiator to obtain a first mixed solution; mixing the rest of the soft monomer, the rest of the hard monomer, the rest of the functional monomer, the rest of the initiator and the second solvent to obtain a second mixed solution; and dropwise adding the first mixed solution into the second mixed solution, stirring the second mixed solution while dropwise adding, and then carrying out heat preservation so as to obtain the acrylate resin.

According to the embodiment of the invention, the dropping time of the first mixed solution is 2-5 hours, and the temperature of the first mixed solution is 70-85 ℃ during dropping; the temperature for heat preservation is 70-85 ℃, and the time is 3-8 hours.

In yet another aspect of the present invention, an adhesive material is provided. According to an embodiment of the invention, the adhesive material comprises: the medical pressure-sensitive adhesive comprises a base material, a pressure-sensitive adhesive layer and a release layer which are sequentially stacked, wherein the pressure-sensitive adhesive layer is formed by the medical pressure-sensitive adhesive composition. Therefore, the adhesive material disclosed by the embodiment of the invention has good adhesion, can be attached to a substrate and skin for a long time, is not easy to fall off from the skin or the substrate, has few solvent molecules and monomers in the middle and at the bottom of an adhesive layer, is not easy to damage the skin, improves the using effect, and has a good application prospect.

Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.

Detailed Description

The following describes embodiments of the present invention in detail. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.

The present invention provides a medical pressure-sensitive adhesive composition, a method for preparing the same, and an adhesive material, which will be described in detail below.

Medical pressure-sensitive adhesive composition

In one aspect of the present invention, a medical pressure sensitive adhesive composition is provided. According to an embodiment of the present invention, a medical pressure-sensitive adhesive composition includes: acrylate resin, a first solvent, tackifying resin and cellulose resin.

The acrylate resin is main resin, and forms a cross-linked network after being cured, so that the mechanical property of the pressure-sensitive adhesive is improved; the tackifying resin improves the permanent adhesion of the adhesive and is beneficial to firmly adhering an adhesive on the skin for a long time; the cellulose resin and the acrylate resin can form a microphase compatible structure, the loose structure is more favorable for releasing solvent molecules and residual monomers in the middle and at the bottom of the adhesive layer during curing, so that the residual monomer content and the residual solvent molecules of the adhesive layer which is directly contacted with the skin of a human body are greatly reduced, the cellulose resin has hydrophilicity, the absorption, the maintenance and the conduction of skin moisture are facilitated, the use effect of the pressure-sensitive adhesive is improved, and the application prospect is good.

According to an embodiment of the present invention, a pressure-sensitive adhesive composition includes: 30-60 parts by weight of an acrylate resin; 30-60 parts by weight of a first solvent; 1-5 parts by weight of tackifying resin; 0.1 to 5 parts by weight of a cellulose resin. The inventor obtains the better proportion through a large number of experiments, thereby endowing the pressure-sensitive adhesive with better bonding effect, having less residual monomer and solvent molecule residues on the adhesive layer, and improving the use effect of the pressure-sensitive adhesive. If the content of the acrylate resin and the tackifying resin is too high, the structure formed by curing is too compact, the adhesion with a base material is poor, and solvent and monomer residues are easy to cause; if the content of the cellulose resin is too high, the structure formed by curing is easy to loosen, the cellulose resin is easy to adhere to the skin, and residues are left after tearing.

According to an embodiment of the present invention, the acrylate resin comprises structural units of the following monomers: soft monomer, hard monomer, functional monomer and second solvent, wherein the soft monomer is selected from C_4～10Alkyl acrylates. The soft monomer imparts basic properties to the pressure sensitive adhesive, such as low glass transition temperature, low peel force, high tack. The acrylic ester with the C4-10 alkyl is used as a soft monomer, so that the stripping force of the pressure-sensitive adhesive is easy to control to be very low, the re-stripping property is excellent, and the pressure-sensitive adhesive can be repeatedly used. The soft monomer is of a weak-polarity structure, the cellulose resin is of a medium-polarity structure, and the soft monomer and the cellulose resin can form a microphase compatible structure by mixing to increase the viscoelasticity of the material; in addition, the cellulose is a hydrophilic material, so that the diffusion of moisture on the surface of the skin into the adhesive and the retention and conduction of moisture in the adhesive are facilitated.

According to an embodiment of the invention, having C_4～10Alkyl (meth) acrylate monomers include, but are not limited to: hexyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, and the like. Among them, isooctyl acrylate and butyl acrylate have better effect.

According to an embodiment of the invention, the hard monomer is selected from at least one of methyl methacrylate, acrylic acid, N-vinyl pyrrolidone and vinyl acetate. The inventor obtains the better hard monomer through a large number of experiments, so that the permanent adhesion of the pressure-sensitive adhesive can be improved, the adhesion time is long, and the phenomenon of peripheral tilting is not easy to occur even if the pressure-sensitive adhesive is attached to the skin for a long time. The hard monomer plays a role of a physical crosslinking point in a polymer system, so that the resilience of the adhesive is enhanced; when acrylic acid and N-vinyl pyrrolidone are selected as hard monomers, the water absorption of the adhesive can be increased, so that the adhesive still keeps high viscosity after absorbing water. Among them, at least one of methyl methacrylate and vinyl acetate is preferable.

According to an embodiment of the present invention, the functional monomer is selected from at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, glycidyl methacrylate and allyl glycidyl ether. The pendant hydroxyl and/or epoxy groups react with the crosslinking agent and the polymer forms a crosslinked system, preferably at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate.

According to an embodiment of the present invention, the second solvent is selected from at least one of ethyl acetate, butyl acetate and isopropanol, preferably at least one of ethyl acetate and isopropanol.

According to the embodiment of the invention, the molecular weight of the acrylate resin is 400000-800000. If the molecular weight is less than 400000, the polymer has high molecular content, and the adhesive has the risk of residue; if the molecular weight is more than 800000, the viscosity of the adhesive is relatively high, and the processability is not ideal.

According to an embodiment of the present invention, the acrylate resin comprises structural units of the following monomers: 40 to 50 parts by weight of a soft monomer; 1 to 10 parts by weight of a hard monomer; 1-5 parts by weight of a functional monomer. The inventor obtains the above-mentioned better proportion through a large amount of experiments, and the glue line structure compactness that the pressure sensitive adhesive formed is moderate, both had better adhesion with skin and substrate to difficult residue after tearing off from the skin, also difficult solvent and monomer remain, improve the result of use.

According to the embodiment of the present invention, the mass ratio of the total mass of the soft monomer, the hard monomer and the functional monomer to the second solvent is 1: (1-1.5). If the ratio is less than 1: (1-1.5), the monomer concentration is low, the improvement of the conversion rate of each monomer is not facilitated, and the monomer residual rate is high; if the ratio is higher than 1: (1-1.5), the monomer concentration is relatively high, the reaction heat release is obvious, and an automatic acceleration effect can be generated.

According to an embodiment of the present invention, the second solvent is selected from ethyl acetate and isopropanol, wherein the volume ratio of ethyl acetate to isopropanol is 1: (0.1 to 1). During the storage of the pressure-sensitive adhesive composition, some components may react, such as the acrylate polymer and the crosslinking agent, and the time for the composition to be stored stably can be significantly increased after the isopropanol is added. If the content of the isopropanol is relatively small, the content is less than 1: (0.1-1), the composition has short storage time; if the content of the isopropanol is relatively high, the ratio is higher than 1: (0.1 to 1), the composition may be insufficiently crosslinked during the crosslinking process.

According to an embodiment of the present invention, the first solvent is selected from at least one of ethyl acetate, butyl acetate, isopropanol and toluene. Thereby facilitating dissolution of the acrylate resin, tackifying resin, and cellulosic resin.

According to an embodiment of the present invention, the tackifying resin is selected from at least one of rosin, petroleum resin, terpene resin, pinene resin and coumarone resin. Therefore, the permanent adhesion force is further increased, and the pressure-sensitive adhesive is convenient to adhere to the skin for a long time.

According to an embodiment of the invention, the cellulose resin is selected from at least one of hydroxyethyl cellulose, hydroxymethyl cellulose, cellulose nitrate and cellulose acetate butyrate, preferably cellulose acetate butyrate. The cellulose resin is derived from natural materials, has hydrophilicity, can reduce skin irritation, is beneficial to skin moisture dispersion, and improves the use effect of the pressure-sensitive adhesive.

According to an embodiment of the present invention, the medical pressure-sensitive adhesive composition of the present invention may further include a crosslinking agent, a leveling agent, a stabilizer, a defoaming agent, a filler, a compatibilization aid, a catalyst accelerator, a surfactant, a diluent, a plasticizer, a filler, a crosslinking inhibitor, an antioxidant, an anti-aging agent, a processing aid, and the like. Wherein the cross-linking agent can be at least one of blocked isocyanate compound or metal chelate, and the dosage of the cross-linking agent is 0.05-5 parts by weight. The catalyst can be one or more of tin catalyst, iron catalyst, copper catalyst, phosphorus catalyst, amine catalyst, etc.

Method for preparing pressure-sensitive adhesive composition

In still another aspect of the present invention, the present invention provides a method for preparing the aforementioned medical pressure-sensitive adhesive composition. According to an embodiment of the invention, the method comprises: the acrylate resin, the first solvent, the tackifying resin and the cellulose resin are mixed. Therefore, the adhesive layer formed by curing the pressure-sensitive adhesive composition obtained by the method provided by the embodiment of the invention has good adhesiveness, can be attached to a substrate and skin, is not easy to fall off from the skin or the substrate, has less solvent molecules and monomer residues in the middle and at the bottom of the adhesive layer, is not easy to damage the skin, improves the using effect of the pressure-sensitive adhesive, and has a good application prospect.

The polymerization method of the acrylate resin in the present invention includes, but is not limited to, bulk polymerization, solution polymerization, emulsion polymerization and suspension polymerization, and solution polymerization is preferred. In the free radical copolymerization process, a large amount of heat is generated, and the invention prefers to add a monomer to make the reaction smoothly, namely, adding a part of monomer, initiator and solvent as substrates, and then slowly adding a mixed solution of other monomers and initiator. According to an embodiment of the present invention, the acrylate resin is obtained by: mixing part of soft monomers, part or all of hard monomers, part or all of functional monomers and an initiator to obtain a first mixed solution; mixing the rest of soft monomers, the rest of hard monomers, the rest of functional monomers, the rest of initiators and a second solvent to obtain a second mixed solution; and dropwise adding the first mixed solution into the second mixed solution while stirring, and then carrying out heat preservation to obtain the acrylate resin. Thereby, the polymerization reaction is sufficiently performed, and a large amount of heat generation is avoided.

According to the embodiment of the invention, the dropping time of the first mixed solution is 2-5 hours, and the temperature of the first mixed solution is 70-85 ℃ during dropping; the temperature for heat preservation is 70-85 ℃, and the time is 3-8 hours. Thereby, the polymerization reaction is sufficiently performed, and a large amount of heat generation is avoided.

It will be understood by those skilled in the art that the features and advantages previously described for the pressure sensitive adhesive composition apply equally to the method of preparing the pressure sensitive adhesive composition and will not be described in detail here.

Adhesive material

In yet another aspect of the present invention, an adhesive material is provided. According to an embodiment of the invention, the adhesive material comprises: the medical pressure-sensitive adhesive comprises a base material, a pressure-sensitive adhesive layer and a release layer which are sequentially stacked, wherein the pressure-sensitive adhesive layer is formed by the medical pressure-sensitive adhesive composition. Therefore, the adhesive material disclosed by the embodiment of the invention has good adhesiveness, can be attached to a base material and skin for a long time, is not easy to fall off from the skin or the base material, has few solvent molecules and monomers in the middle and at the bottom of an adhesive layer, is not easy to damage the skin, improves the using effect, and has a good application prospect.

The material of the substrate in the present invention is not particularly limited, and examples thereof include materials excellent in transparency, mechanical strength, thermal stability, water resistance, isotropy, flexibility, dimensional stability, and other properties, such as polyesters such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate, cellulose polymers such as diacetyl cellulose and triacetyl cellulose, and polycarbonate polymers.

It will be appreciated by those skilled in the art that the features and advantages described above for the medical pressure sensitive adhesive composition apply equally to the adhesive material and will not be described in further detail herein.

The scheme of the invention will be explained with reference to the examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.