阅读说明：本技术 一种硬化层涂布液及一种硬化膜 (Hardened layer coating liquid and hardened film ) 是由 张克然 丁晓超 于 2020-04-30 设计创作，主要内容包括：本发明属于功能性薄膜技术领域,尤其涉及一种硬化层涂布液及一种硬化膜。为了解决现有硬化膜不能兼具高耐磨性、良好的闪点性能和书写性能的问题,本发明提供一种硬化层涂布液及一种硬化膜。所述的硬化层涂布液包含六官能团聚氨酯丙烯酸树脂齐聚物,四官能团聚氨酯丙烯酸树脂齐聚物,丙烯酸酯单体,二氧化硅粒子,助剂,光引发剂,丙二醇甲醚；所述二氧化硅粒子包括二氧化硅无机大粒子和二氧化硅无机小粒子,所述二氧化硅无机大粒子的粒径为4～8μm,所述二氧化硅无机小粒子的粒径为0.5～1.0μm；所述百分含量为重量百分含量。该硬化层涂布液固化后形成硬化膜的硬化层,同时具有高耐磨性、良好甚至优秀的闪点性能和书写性能。(The invention belongs to the technical field of functional films, and particularly relates to a hardened layer coating liquid and a hardened film. The invention provides a hardened layer coating liquid and a hardened film, aiming at solving the problem that the existing hardened film cannot have high wear resistance, good flash point performance and writing performance. The hardened layer coating liquid contains a hexafunctional group polyurethane acrylic resin oligomer, a tetrafunctional group polyurethane acrylic resin oligomer, an acrylate monomer, silicon dioxide particles, an auxiliary agent, a photoinitiator and propylene glycol methyl ether; the silica particles comprise silica inorganic macro particles and silica inorganic micro particles, the particle size of the silica inorganic macro particles is 4-8 mu m, and the particle size of the silica inorganic micro particles is 0.5-1.0 mu m; the percentage is weight percentage. The hardened layer coating liquid forms a hardened layer of a hardened film after being cured, and simultaneously has high wear resistance, good flash point performance and excellent writing performance.)

1. The coating liquid for the hardened layer is characterized by comprising a polyfunctional group polyurethane acrylic resin oligomer, an acrylate monomer and 2.2-7% of silicon dioxide particles; the 2.2-7% of silica particles comprise 1-4% of silica inorganic macro particles and 1-3% of silica inorganic micro particles, the particle size of the silica inorganic macro particles is 4-8 mu m, and the particle size of the silica inorganic micro particles is 0.5-1.0 mu m; the percentage is weight percentage.

2. The hardened layer coating liquid as claimed in claim 1, wherein the hardened layer coating liquid comprises 10 to 30% of a hexafunctional urethane acrylate oligomer, 20 to 30% of a tetrafunctional urethane acrylate oligomer, 10 to 18% of an acrylate monomer, 2.2 to 7% of silica particles, 0.2 to 0.3% of an auxiliary agent, 1 to 2% of a photoinitiator, 12.7 to 56.6% of propylene glycol methyl ether; the 2.2-7% of silica particles comprise 1-4% of silica inorganic macro particles and 1-3% of silica inorganic micro particles, the particle size of the silica inorganic macro particles is 4-8 mu m, and the particle size of the silica inorganic micro particles is 0.5-1.0 mu m; the percentage is weight percentage.

3. The hardened layer coating liquid as claimed in claim 2, wherein the auxiliary agent is a leveling agent.

4. The hardened layer coating liquid as claimed in claim 1, wherein the hardened layer coating liquid has a solid content of 22 to 56% by weight.

5. The hardened layer coating liquid as claimed in claim 2, wherein the hardened layer coating liquid comprises 30% of a hexafunctional urethane acrylate oligomer, 20% to 30% of a tetrafunctional urethane acrylate oligomer, 12% to 18% of an acrylate monomer, 5% to 7% of silica particles, 0.2% to 0.3% of an auxiliary agent, 1.3% to 2% of a photoinitiator, 12.7% to 31.5% of propylene glycol methyl ether; the 5-7% of silica particles comprise 2-4% of silica inorganic macro particles and 2-3% of silica inorganic micro particles, the particle size of the silica inorganic macro particles is 4-8 mu m, and the particle size of the silica inorganic micro particles is 0.5-1.0 mu m; the percentage is weight percentage.

6. The hardened layer coating liquid as claimed in claim 5, wherein the hardened layer coating liquid has a solid content of 35 to 56% by weight.

7. The hardened layer coating liquid as claimed in claim 6, wherein the leveling agent is a siloxane leveling agent.

8. A cured film comprising a substrate and a cured layer, wherein the cured layer is formed by curing the cured layer coating liquid according to any one of claims 1 to 7.

9. The cured film according to claim 8, wherein a primer layer is provided on the substrate, and the cured layer is applied to the primer layer.

10. The cured film according to claim 7, wherein the substrate has a thickness of 100 μm to 250 μm, and the cured layer has a thickness of 3 μm to 10 μm; the substrate is a PET substrate.

Technical Field

The invention belongs to the technical field of functional films, and particularly relates to a hardened layer coating liquid and a hardened film.

Background

The anti-glare hardened film for commercial display is also required to have high abrasion resistance, good flash point and good writing effect on the basis of the existing anti-glare hardened film. The anti-glare is mainly due to the fact that a light source with extremely high brightness in the environment forms strong brightness contrast through reflection, and the overall effect is that human eyes generate glare. At present, the proportion of glare generated by liquid crystal display equipment is very large, the glare of the liquid crystal display equipment generally acts on human eyes by mutually overlapping light emitted by the liquid crystal display equipment and light reflected by a light source in an environment on a display screen, long-term glare can not only cause uncomfortable feeling in vision, but also strong glare can damage vision and even cause blindness. Therefore, the surfaces of various liquid crystal display devices in the market are all adhered with the hard films with the anti-dazzle effect, the hard films also have high wear resistance, and the anti-dazzle hard films for electronic blackboards have good flash points and writing effects.

The existing hardening film can not have high wear resistance, good flash point and writing hand feeling.

Disclosure of Invention

The invention provides a hardened layer coating liquid and a hardened film, aiming at solving the problem that the existing hardened film cannot have high wear resistance, good flash point performance and writing performance. The hardened layer coating liquid forms a hardened layer of a hardened film after being cured, has high wear resistance, good flash point performance and excellent writing performance, and solves the problem that the existing hardened film cannot have high wear resistance, good flash point performance and writing performance at the same time.

In order to solve the technical problem, the invention provides a technical scheme.

The invention provides a coating liquid for a hardened layer, which comprises a polyfunctional group polyurethane acrylic resin oligomer, an acrylate monomer and 2.2-7% of silicon dioxide particles; the 2.2-7% of silica particles comprise 1-4% of silica inorganic macro particles and 1-3% of silica inorganic micro particles, the particle size of the silica inorganic macro particles is 4-8 mu m, and the particle size of the silica inorganic micro particles is 0.5-1.0 mu m; the percentage is weight percentage.

Further, the multifunctional polyurethane acrylic resin oligomer is selected from one or a combination of at least two of four functional group polyurethane acrylic resin oligomers, five functional group polyurethane acrylic resin oligomers, six functional group polyurethane acrylic resin oligomers, seven functional group polyurethane acrylic resin oligomers or nine functional group polyurethane acrylic resin oligomers.

Further, the polyfunctional group polyurethane acrylic resin oligomer is selected from the combination of a tetrafunctional group polyurethane acrylic resin oligomer and a hexafunctional group polyurethane acrylic resin oligomer.

Further, the invention provides a hardened layer coating liquid, which comprises a hexafunctional group polyurethane acrylic resin oligomer, a tetrafunctional group polyurethane acrylic resin oligomer, an acrylate monomer, 2.2-7% of silica particles and a photoinitiator; the 2.2-7% of silica particles comprise 1-4% of silica inorganic macro particles and 1-3% of silica inorganic micro particles, the particle size of the silica inorganic macro particles is 4-8 mu m, and the particle size of the silica inorganic micro particles is 0.5-1.0 mu m; the percentage is weight percentage.

Further, the hardened layer coating liquid further includes propylene glycol methyl ether.

Further, the hardened layer coating liquid further comprises an auxiliary agent.

Further, the invention provides a hardened layer coating liquid, which comprises a hexafunctional group polyurethane acrylic resin oligomer (also called oligomer), a tetrafunctional group polyurethane acrylic resin oligomer, an acrylate monomer, 2.2-7% of silicon dioxide particles, an auxiliary agent, a photoinitiator and propylene glycol methyl ether; the 2.2-7% of silica particles comprise 1-4% of silica inorganic macro particles and 1-3% of silica inorganic micro particles, the particle size of the silica inorganic macro particles is 4-8 mu m, and the particle size of the silica inorganic micro particles is 0.5-1.0 mu m; the percentage is weight percentage.

The invention provides a hardened layer coating liquid (called as hard coating liquid for short), which comprises 10-30% of hexafunctional group polyurethane acrylic resin oligomer (also called oligomer), 20-30% of tetrafunctional group polyurethane acrylic resin oligomer, 10-18% of acrylate monomer, 2.2-7% of silicon dioxide particles, 0.2-0.3% of auxiliary agent, 1-2% of photoinitiator and 12.7-56.6% of propylene glycol methyl ether; the 2.2-7% of silica particles comprise 1-4% of silica inorganic macro particles and 1-3% of silica inorganic micro particles, the particle size of the silica inorganic macro particles is 4-8 mu m, and the particle size of the silica inorganic micro particles is 0.5-1.0 mu m; the percentage is weight percentage.

Further, the auxiliary agent is a leveling agent.

Further, the solid content of the hardened layer coating liquid is 22-56%, and the percentage is weight percentage.

The hardened layer coating liquid comprises 30% of hexa-functional group polyurethane acrylic resin oligomer, 20% to 30% of tetrafunctional group polyurethane acrylic resin oligomer, 12% to 18% of acrylate monomer, 5% to 7% of silicon dioxide particles, 0.2% to 0.3% of auxiliary agent, 1.3% to 2% of photoinitiator and 12.7% to 31.5% of propylene glycol methyl ether; the 5-7% of silica particles comprise 2-4% of silica inorganic macro particles and 2-3% of silica inorganic micro particles, the particle size of the silica inorganic macro particles is 4-8 mu m, and the particle size of the silica inorganic micro particles is 0.5-1.0 mu m; the percentage is weight percentage. Further, the solid content of the hardened layer coating liquid is 35-56%, and the percentage is weight percentage. The foregoing technical solutions include examples 4 to 6.

The hardened layer coating liquid provided by the invention forms a hardened layer after UV photocuring, and the hardened layer can effectively achieve the effects of high wear resistance, low flash point and good writing hand feeling.

Further, the composition of the hardened layer coating liquid is as follows:

1. 10-30% of hexafunctional group polyurethane acrylic resin, 20-30% of tetrafunctional group polyurethane acrylic resin and 10-18% of acrylate monomer. Wherein the oligomer is polyurethane acrylic resin oligomer with hydroxyl or carboxyl functional groups.

2. 1 to 4 percent of silica particle inorganic macroparticles with the diameter of 4 to 8 mu m; 1 to 3 percent of silica inorganic small particles with the diameter of 0.5 to 1 mu m;

3. 0.2 to 0.3 percent of siloxane flatting agent;

4. 1% -2% of photoinitiator;

5. 12.7 to 56.6 percent of propylene glycol methyl ether;

the components are in a specified proportion, and under the irradiation of ultraviolet light, the acrylic resin oligomer with multiple functional groups and the acrylic ester monomer can be rapidly polymerized to enable particles to protrude out of the surface of the matrix resin and to be suspended in the matrix resin, so that high wear resistance and anti-dazzle performance can be achieved, and the proportion of the large particles and the small particles has influence on the writing performance and the flash point performance of the coating.

The mechanism of the technical scheme of the application is as follows:

1. the wear-resistant coating is prepared by adopting an inorganic large particle mixing technology, wherein small particles with the particle size of 0.5-1.0 mu m are prepared by special equipment and are well dispersed in resin after being mixed with large particles with the particle size of 4-8 mu m, the wear resistance of a hardened layer can be improved by the large particles, and the flash point performance can be improved by the small particles. The special equipment is equipment capable of preparing particles with larger particle size into small particles with the particle size of 0.5-1.0 mu m.

2. The control of the content of the polyurethane acrylic resin oligomer and the acrylate monomer has certain influence on the wear resistance of the surface of the hardened layer, and the polyurethane acrylic resin oligomer and the acrylate monomer with hydroxyl and carboxyl functional groups have ultrahigh hardness characteristics, such as the polyurethane acrylic resin oligomer with six functional groups, the polyurethane acrylic resin oligomer with four functional groups and the acrylate monomer are mixed and then undergo a crosslinking reaction after photocuring to form the hardened layer with ultrahigh hardness, so that the wear resistance of the hardened film is improved.

3. Mixing inorganic particles with the resin, adding NH₄The Cl inorganic electrolyte is used as a dispersant, and the large particles can improve the wear resistance of a hardened layer and can increase the hardeningThe writing performance of the surface of the layer, the flash point performance of small particles can be improved, the haze and the anti-glare effect can be influenced by the content of the silicon dioxide particles with different particle sizes, and the writing performance and the flash point performance can be influenced by the different proportions of the large particles and the small particles.

By adopting the nano inorganic particle dispersion technology, due to the miniaturization of the silicon dioxide particles, the surface atoms are subjected to asymmetric force, namely asymmetric valence bond force of internal atoms adjacent to the surface atoms and van der Waals force of other atoms, the valence bonds of the surface atoms are unsaturated, and the particles are saturated in order to reach the valence bonds of the surface particles, so that the total energy of a system is reduced and a coagulation phenomenon is generated. Silica particles can be positively, negatively and neutrally charged depending on their PH in solution. When the pH is low, Si-OH2(OH2 represents 1O and 2H) bonds are formed on the surface, which leads to the particles being positively charged, when the pH is high, Si-O bonds are formed on the surface of the particles, which leads to the particles being negatively charged, and when the pH is at an intermediate value, Si-OH bonds are formed on the surface of the particles, which leads to the particles being neutral.

When the surface charge is positive, the effective counter ions for balancing the surface charge of the particles are Cl-NO₃Plasma anion, Na if the surface charge is negative⁺、NH₄ ⁺The isocationic ions are effective counter ions to balance the surface charge of the particles. Therefore, NH with the above-mentioned effective counter ion is added according to the type of surface charge of the particle₄Cl inorganic electrolyte is used as a dispersing agent, so that the surface of the particles attracts heterocharge ions to form an electric double layer, and the attractive force generated by agglomeration among the particles is greatly reduced through the coulomb repulsion action among the electric double layers, thereby realizing the purpose of dispersing the inorganic particles. Therefore, NH with the above-mentioned effective counter ion is added according to the type of surface charge of the particle₄The Cl inorganic electrolyte is used as a dispersing agent, so that the surface of the particles attracts heterocharge ions to form an electric double layer, and the attractive force generated by agglomeration among the particles is greatly reduced through the coulomb repulsion action among the electric double layers, so that the aim of dispersing the inorganic particles is fulfilled, and the particles can be uniformly and stably dispersed in a resin system.

The rougher the film surface of the hardened film is, the better the powder hanging effect of the chalk on the hardened film is, and the better the writing performance is.

The surface of the hardened film is required to have the wear resistance of more than 1Kg/1500 times, and simultaneously has excellent writing performance and flash point performance.

The invention also provides a hardened film which comprises a substrate and a hardened layer, wherein the hardened layer is formed by curing the hardened layer coating liquid provided by the invention.

Further, the hardened layer is attached to a substrate.

Furthermore, the base material is an optical grade PET base material layer, and a hardening layer with particles is arranged on the base material.

Further, in order to improve the adhesion of the hardened layer to the substrate, a primer layer is provided on the substrate, and the hardened layer is applied on the primer layer. Further, the substrate is a PET substrate.

Further, the thickness of the substrate is 100 μm to 250 μm, preferably 100 μm to 188 μm, and most preferably 188 μm.

Further, the thickness of the hardening layer is 3-10 μm. The thickness is the dry coating thickness of the hardened layer, and the wet coating thickness of the hardened layer is generally about 8 μm to 25 μm.

Further, the thickness of the hardening layer is 4-10 μm.

The invention obtains the hardened film which has high wear resistance, high light transmittance, excellent flash point performance and excellent writing performance.

Drawings

Fig. 1 is a schematic structural diagram of a hardened film provided by the present invention.

Detailed Description

In order to make the structure and features of the invention easier to understand, preferred embodiments of the invention will be described in detail below with reference to the drawings.

As shown in fig. 1, the hardened film provided by the present invention includes a substrate 3 and a hardened layer 1, and the hardened layer is formed by curing the hardened layer coating liquid provided by the present invention. In order to improve the adhesion of the hardened layer 1 to the substrate 3, the substrate 3 is provided with a primer layer 2, and the hardened layer 1 is coated on the primer layer 2. The substrate is a PET substrate.

In the raw materials of the hardened layer coating liquid provided by the embodiment of the invention, the six-functional group polyurethane acrylic resin oligomer, the four-functional group polyurethane acrylic resin oligomer and the acrylate monomer are produced by the Guangzhou Shenwei company, the silicon dioxide inorganic particles are produced by the Fuji silicon chemical company, the leveling agent is produced by the Pico chemical company, and the propylene glycol methyl ether is produced by the Hangzhou high-crystalline company.

In the hardened film provided by the embodiment of the invention,

1. base film material: highly transparent substrate, poly (p-xylylene glycol) (PET)

Thickness: 100 to 250 μm, preferably 188 μm

A base film manufacturer: the Dongli PL2-188 μm base film comprises a base material layer and a pretreatment layer, wherein the pretreatment layer is arranged on the surface of the base material layer and is a chemical base, and the adhesion between a hardening layer and the base material layer can be improved.

2. Process conditions for curing the hardened layer and coating thickness of the hardened layer:

temperature: at the temperature of 85 ℃ for 5min,

light curing energy: 400 to 600mj/cm²，

Coating thickness: 3-10 μm (within the thickness range, the anti-glare and wear-resistant properties can be ensured, and the thickness is thinner).

Before coating the hardened layer coating liquid on the surface of the substrate, the hardened layer coating liquid is prepared and stands for 30 min.

The test instrument and the test method for the hardened film provided by the embodiment of the invention are as follows:

1. light transmittance and haze test: the cured film was tested for total light transmittance and haze according to JIS K-7150 using the Japanese electrochromic NDH-2000N.

2. And (3) wear resistance test: kunshijing Jia instrument A20-339 adopts 0000# steel wool, 1000gf/cm according to JISK-5600 standard²And (5) carrying out load application, wiping the surface of the hardened film back and forth, and detecting whether the film surface is scratched or not at the maximum limit times. The abrasion resistance times are more than 1500 times, and no scratch exists, so the wear resistance is called as high wear resistance.

3. And (3) testing pencil hardness: according to the JIS K-5600 standard, the Japanese Elcometer 3086 uses Mitsubishi type 1H-9H pencils, and the highest pencil type is used for marking 5 lines on the surface of the hardened film by a load of 750g and detecting whether the film surface is scratched.

4. Testing the adhesion force of the hardened layer: the surface of the hardened layer was tested for adhesion according to the JISK-5600 standard, wherein 100/100 represents no exfoliation and 0/100 represents complete exfoliation.

5. And (3) testing the writing performance: under the same condition, after the white chalk writes on the surface of the hardened film, the color of the font becomes white, the writing performance is excellent, the color of the font is grey, the writing performance is good, and the color of the font is grey or has no font color, the writing performance is poor. When the writing performance was evaluated to be excellent, the writing feeling was said to be good.

6. Flash point performance test: the hard film is tightly attached to the background of a pure green display screen, the diameter of the shiny particles is observed through an electron microscope, the average diameter of the shiny particles on the film surface is larger than or equal to 3 microns, the flash point performance is poor, the average diameter of the shiny particles on the film surface is 1-3 microns, the flash point performance is general, and the average diameter of the shiny particles on the film surface is smaller than or equal to 1 micron, the flash point performance is excellent. When the flash point property is evaluated to be excellent, it is called low flash point.

7. And (3) thickness testing: a100 mm by 100mm hardened film was cut out and the thickness thereof was measured with a micrometer.

Example 1

The invention provides a hardened layer coating liquid and a hardened film, wherein the hardened layer coating liquid comprises a hexafunctional group polyurethane acrylic resin oligomer, a tetrafunctional group polyurethane acrylic resin oligomer, an acrylate monomer, silica inorganic large particles, silica inorganic small particles, a leveling agent, a photoinitiator and propylene glycol methyl ether. The weight percentages of the components are shown in table 1.

The hardened film comprises a substrate and a hardened layer, the substrate is a PET substrate, and the hardened layer is formed after the hardened layer coating liquid is solidified. The thickness of the substrate and the thickness of the hardened layer are shown in table 1.

Examples 2 to 7

The coating liquid for a hardened layer and the hardened film provided in example 1 have the technical characteristics shown in table 1.

TABLE 1 technical characteristics of the coating liquid formulations for hardened layers and the hardened films provided in examples 1 to 7

Comparative example 1

The comparative example provides a hardened layer coating liquid and a hardened film, wherein the hardened layer coating liquid comprises a hexafunctional group polyurethane acrylic resin oligomer, a tetrafunctional group polyurethane acrylic resin oligomer, an acrylate monomer, silica inorganic large particles, silica inorganic small particles, a leveling agent, a photoinitiator and propylene glycol methyl ether. The weight percentages of the components are shown in table 2.

The hardened film comprises a substrate and a hardened layer, the substrate is a PET substrate, and the hardened layer is formed after the hardened layer coating liquid is solidified. The thickness of the substrate and the thickness of the hardened layer are shown in table 2.

Comparative examples 2 to 3

The coating liquid for a hardened layer and the hardened film as provided in comparative example 1 have the technical characteristics as shown in table 2.

TABLE 2 formulation of coating liquid for hard coat and technical characteristics of hard coat film provided in comparative examples 1 to 3

TABLE 3 measurement results of main properties of the cured films provided in examples 1 to 7 of the present invention and comparative examples 1 to 3

From the experimental data shown in table 3 above, it can be found that the addition amount of the silica inorganic large particles directly affects the wear resistance and writing performance, and the addition amount of the silica inorganic small particles directly affects the flash point performance. When the addition amount of the large inorganic silica particles is 0.5% and the addition amount of the small inorganic silica particles is 0.6%, the wear-resistant frequency is low (the wear resistance is poor), the writing performance is poor, and the flash point performance is poor. When the addition amount of the inorganic large silica particles is increased to 3% and the addition amount of the inorganic small silica particles is increased to 2%, the abrasion resistance times are obviously increased, and the writing performance and the flash point performance are also excellent. When the addition amount of the inorganic large silica particles is 6% and the addition amount of the inorganic small silica particles is 8%, the haze is obviously increased, the light transmittance of the product is influenced, the wear-resistant times are obviously reduced, and the writing performance and the flash point performance are good.

The coating thickness of the hardened film is also related to the wear resistance, and when the coating thickness reaches 7-10 mu m, the performance is generally better than that of 3-5 mu m. The addition amount of the inorganic silica particles also has a certain influence on the wear resistance, when the addition amount of the large silica particles is 0.5% and the addition amount of the small silica particles is 0.6%, the wear resistance is reduced because the surface of the hardened film is too smooth, and when the addition amount of the large silica particles is 6% and the addition amount of the small silica particles is 8%, the surface of the hardened film is too rough and the particles are directly ground flat, so that the wear resistance is reduced.

The hardened film provided by the invention has the advantages of good wear resistance, low flash point and good writing performance. In particular, examples 4 to 6 of the present application provide a cured film having a better combination of properties.

The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. All equivalent changes and modifications made according to the disclosure of the present invention are covered by the scope of the claims of the present invention.