TWI715751B - Active energy ray curable composition and coating film - Google Patents

Abstract

The problem to be solved by the present invention is to provide a hard coating, which has high adhesion to cyclic olefins and excellent scratch resistance. Therefore, it is particularly suitable for cyclic olefin resins as a substitute for cellulose triacetate film. The film is hard-coated, and the cellulose triacetate film is a polarizing plate used in liquid crystal display devices and the like. The solution of the present invention is to use an active energy ray hardening composition, in which: when the total solid content is diluted to 80% by weight with toluene, the E-type viscosity at 25°C is 300～10000mPa‧s ; Relative to all organic solids, the active energy ray curable composition contains 15 to 80% by weight of the active energy ray curable oligomer (A); and the (A) component has a (meth)acrylic acid group , Polypentaerythritol skeleton, isocyanurate group and/or biuret group, weight average molecular weight (Mw) is 3000～100000, urethane bond equivalent is 350～2000g/eq, (meth)acrylic acid group equivalent is 120～250g/eq.

Description

Active energy ray curable composition and coating film

The present invention relates to an active energy ray hardening type composition and a coating film.

In the past, the polarizing plate used in the liquid crystal display device was a cellulose triacetate film (TAC film) laminated on both sides of the polarizer as a protective film, and the surface was further coated with a transparent photo-curing resin composition, and It is hardened to form a high-hardness coating (hard coating) and protected from damage. The polarizer is obtained by adsorbing iodine and the like on the polyvinyl alcohol film and orienting it by stretching. As a material for forming such a cured film, an active energy ray-curable resin composition is known which uses a polyfunctional (meth)acrylate (Patent Document 1).

In recent years, due to the increase in size and quality of liquid crystal devices, and the expansion of the use of mobile devices, it is required to be able to withstand more severe use environments, and it is understood that TAC films have their limits in terms of characteristics. Under such circumstances, various studies have been conducted on the material of the protective film, and it is currently optimistic that TAC films should be replaced with cyclic olefin resin films. The cyclic olefin resin film is excellent in transparency, low birefringence, dimensional stability, etc., and has the performance required as an optical film. Furthermore, low moisture permeability is also a major feature, and for this, it has become a major factor in replacing TAC films. However, the cyclic olefin resin film has a problem that it is difficult to form a hard coating layer with high adhesion on the surface.

In the past, the cyclic olefin resin film was coated with a primer layer or electrical treatment (corona discharge treatment, atmospheric pressure slurry treatment) to improve the adhesion between the substrate and the hard coating layer (Patent Document 2) . [Prior Art Document] (Patent Document)

Patent Document 1: Japanese Patent Application Publication No. 2009-286924 Patent Document 2: Japanese Patent Application Publication No. 2014-189566

[Problem to be Solved by the Invention] However, in the aforementioned method, a processing step for improving the adhesion to the substrate is required when producing a coated film, which causes a problem of high cost. In addition, electrical processing causes changes in the processing surface over time, so there is a limitation that the hard coating layer must be applied quickly after processing.

The object of the present invention is to provide an active energy ray curable composition and a coating film formed using the active energy ray curable composition. The active energy ray curable composition has good coating properties, especially for ring-shaped High adhesion and scratch resistance of olefin substrate. [Technical means to solve the problem]

In order to solve the aforementioned problems, the inventors have devoted themselves to research and found that the aforementioned problems can be solved by using a reactant with a specific structure introduced, thereby completing the present invention.

That is, according to the present invention, the following items are provided.

(Item 1) An active energy ray hardening composition, wherein: when the total solid content is diluted to 80% by weight with toluene, the E-type viscosity at 25°C is 300 to 10000 mPa‧s; All organic solids, the active energy ray hardening composition contains 15 to 80% by weight of active energy ray hardening oligomer (A); and the (A) component has (1) (meth)acryloyl group , (2) Polypentaerythritol skeleton, and (3) isocyanurate group and/or biuret group, weight average molecular weight (Mw) is 3000-100000, urethane bond equivalent is 350-2000g/eq, (former The base) acryl equivalent is 120 to 250 g/eq. (Item 2) The active energy ray curable composition according to the above item 1, wherein the active energy ray curable composition is used for a cyclic olefin resin film. (Item 3) The active energy ray curable composition as described in item 1 or 2, which contains a photopolymerization initiator (B). (Item 4) A coating film formed by forming a cured film of the active energy ray curable composition according to any one of items 1 to 3 on at least one side of a substrate. (Item 5) The coating film according to any one of the above items, wherein the substrate is made of cyclic olefin resin. (Item 6) The coating film according to any one of the above items, wherein the substrate is not subjected to easy adhesion treatment. [Effect of Invention]

According to the present invention, it is suitable as a hard coating agent. It has high adhesion to cyclic olefins and excellent scratch resistance. Therefore, it is particularly suitable for cyclic olefin resins as a substitute for cellulose triacetate (TAC) films. The TAC film is used as a polarizing plate for liquid crystal display devices and the like for hard coating.

In one of the embodiments, the active energy ray-curable composition of the present invention, when the total solid content is diluted to 80% by weight with toluene, the E-type viscosity at 25°C is 300 to 10000 mPa·s , The active energy ray hardening composition contains 15 to 80% by weight of the active energy ray hardening oligomer (A) (hereinafter also referred to as "(A) component") relative to all organic solids; and (A) Component has (1) (meth)acrylic acid group, (2) polypentaerythritol skeleton, and (3) isocyanurate group and/or biuret group, and the weight average molecular weight (Mw) is 3000～ 100000, the equivalent of amine ester bond is 350-2000g/eq, and the equivalent of (meth)acrylic acid is 120-250g/eq. The above composition can be used as a cyclic olefin resin film. In addition, examples of active energy rays include ultraviolet rays, electron beams, and radiation. Furthermore, in the present invention, "(meth)acryloyl group" means to include both acryloyl group and methacryloyl group collectively, and similarly, "(meth)acrylate" means to include all Both acrylate and methacrylate.

As a component contained in the component (A), it has a polypentaerythritol skeleton and (3) an isocyanurate group and/or a biuret group, thereby curing the active energy ray containing the component (A) The cured product (coating film) obtained from the composition has sufficient adhesion and scratch resistance.

As the above-mentioned (A) component, for example, a reaction product of an isocyanate compound having a biuret structure and polypentaerythritol poly(meth)acrylate, an isocyanate compound having an isocyanurate structure and a dipentaerythritol poly(meth)acrylate Base) acrylate reactants, etc. Specifically, for example, the biuret modified product of hexamethylene diisocyanate and the reaction product of dipentaerythritol hexaacrylate, the isocyanurate modified product of hexamethylene diisocyanate and dipentaerythritol hexaacrylate The reactant of the ester.

Examples of the isocyanate compound having a biuret structure include: biuret modification products of aliphatic isocyanates such as 1,6-hexamethylene diisocyanate; esters such as hydrogenated xylene diisocyanate and isophorone diisocyanate Biuret-modified cyclic isocyanate; biuret-modified aromatic isocyanate such as xylene diisocyanate, etc.

Examples of the isocyanate compound having an isocyanurate structure include: isocyanurate modified products of aliphatic isocyanates such as 1,6-hexamethylene diisocyanate; hydrogenated xylene diisocyanate, isophos Isocyanurate modified products of alicyclic isocyanates such as ketone diisocyanate; isocyanurate modified products of aromatic isocyanates such as xylene diisocyanate, etc.

Examples of the compound having a polypentaerythritol skeleton include: dipentaerythritol pentaacrylate, ethylene oxide modified product of dipentaerythritol pentaacrylate, caprolactone modified product of dipentaerythritol pentaacrylate, polypentaerythritol polyacrylate, The ethylene oxide modified product of polypentaerythritol polyacrylate, the caprolactone modified product of polypentaerythritol polyacrylate, and a mixture of two or more of these compounds.

As a method of producing the above-mentioned reactant, for example, the following methods can be cited: triethylenediamine, 1,8-diazabicyclo[5.4.0]undecane-7-ene, tin octoate, lead octoate, etc. In the presence of an amine esterification catalyst, the above-mentioned isocyanate compound is reacted with a compound having a dipentaerythritol skeleton in a temperature range of 40 to 90°C.

As an example of the upper limit of the E-type viscosity at 25°C when the active energy ray hardening composition containing the above-mentioned component (A) is diluted with toluene to 80% by weight in terms of solid content, the upper limit of the E-type viscosity at 25°C is 10,000 , 9000, 8000, 7000, 6000, 5000, 4000, 3000, 2000, 1000, 900, 800, 700, 600, 500, 400mPa‧s, etc.; as an example of the lower limit of the E-type viscosity, you can include: 9000, 8000, 7000, 6000, 5000, 4000, 3000, 2000, 1000, 900, 800, 700, 600, 500, 400, 300mPa‧s etc. The range of the aforementioned E-type viscosity can be appropriately set (selected from, for example, the aforementioned upper limit and lower limit). In one of the embodiments, from the viewpoint of coatability, the range of the above-mentioned E-type viscosity is 300 to 10000 mPa·s, preferably 450 to 2000 mPa·s. The active energy ray hardening composition containing the above component (A) can be diluted with toluene to a solution of 80% solid content, and about 0.4 mL of this solution can be used as a measurement sample, and the E-type viscosity meter at 25°C (Manufactured by Toki Sangyo Co., Ltd., product model: TV-22, 3°cone), the above-mentioned E-type viscosity (mPa‧s) was measured at a rotation speed of 0.5-100 rpm and a rotation of 5 minutes. The active energy ray-curable composition of the present invention also contains other components such as monomers remaining in the step of producing the component (A) or a polymerization initiator described later.

As an example of the upper limit of the weight average molecular weight (Mw) (measured by colloid permeation chromatography in terms of polystyrene) of the component (A), the upper limit includes: 100,000, 90000, 80,000, 70,000, 60,000, 50000, 46000, 40000, 30000, 20000, 15600, 13500, 11000, 10500, 10000, 8500, 8000, 5000, etc.; examples of the lower limit of the weight average molecular weight include: 90000, 80000, 70000, 60000, 50000, 46000 , 40000, 30000, 20000, 15600, 13500, 11000, 10500, 10000, 8500, 8000, 5000, 3000, etc. The range of the weight average molecular weight (Mw) can be set appropriately (selected from, for example, the above upper limit and lower limit). In one embodiment, the weight average molecular weight (Mw) ranges from 3000 to 100,000 from the viewpoint of adhesion to the substrate, paint stability, and printability. Preferably it is 5,000 to 80,000, more preferably 8,000 to 50,000.

Examples of the upper limit of the amine ester bond equivalent weight of the component (A) include: 1500, 1400, 1300, 1200, 1100, 1000, 976, 900, 800, 750, 748, 735, 725, 700, 612, 600, 500, 400g/eq, etc.; as examples of the lower limit of the amine ester bond equivalent weight, 1400, 1300, 1200, 1100, 1000, 976, 900, 800, 750, 748, 735, 725, 700, 612, 600, 500, 400g/eq, etc. The range of the amine ester bond equivalent can be appropriately set (selected from, for example, the above upper limit and lower limit). In one embodiment, from the viewpoint of scratch resistance and adhesion, the range of the urethane bond equivalent is 350 to 2000 g/eq, preferably 350 to 1500 g/eq, and more preferably 600 to 1000 g/eq. eq. The urethane bond equivalent refers to the value calculated from the input amount of the reaction raw materials. Specifically, it is the total weight of all raw materials divided by the isocyanic acid component (A) contained in all raw materials that can react with the hydroxyl group The value derived from the molar number of the base.

Examples of the upper limit of the (meth)acrylic equivalent of the component (A) include: 250, 240, 230, 220, 210, 200, 196, 190, 180, 170, 160, 156, 150, 147, 145, 140, 130g/eq, etc.; as examples of the lower limit of the (meth)acrylic acid equivalent, 240, 230, 220, 210, 200, 196, 190, 180, 170, 160, 156, 150, 147, 145, 140, 130g/eq, etc. The range of the (meth)acrylic acid equivalent can be appropriately set (selected from, for example, the above upper limit and lower limit). In one embodiment, from the viewpoint of industrial synthesis and scratch resistance, the range of the (meth)acrylic equivalent is preferably 120 to 250 g/eq, more preferably 120 to 200 g/eq. The (meth)acrylic acid equivalent refers to the value calculated from the input amount of the reaction raw materials, specifically, the total weight of all raw materials divided by the (meth) of the component (A) contained in all raw materials The value derived from the number of moles of acrylic base.

It is preferable that the ratio of the said (A) component is 50 weight% or more with respect to 100 weight% of the active energy ray-curable oligomer which has a functional group derived from an isocyanate group. This can show good adhesion. More preferably, it is 75 to 100% by weight. Moreover, when both an isocyanurate group and a biuret group are contained, each ratio of the functional group may be arbitrary ratios.

Examples of the upper limit of the content of the component (A) contained in the active energy ray-curable composition of the present invention with respect to the total organic solid content include: 80, 70, 60, 58, 50, 49, 43, 40, 39, 34, 30, 20, 17% by weight, etc.; as examples of the lower limit of the content rate, 70, 60, 58, 50, 49, 43, 40, 39, 34, 30, 20, 17, 15% by weight, etc. The range of the content of the (A) component relative to the total organic solid content can be appropriately set (selected from, for example, the above upper limit and lower limit). In one of the embodiments, from the viewpoint of coatability and adhesion to the substrate, the component (A) is contained 15 to 80% by weight, preferably 15 to 50%, relative to the total organic solid content. weight%. Here, the so-called "solid content" refers to the components excluding the solvent; the so-called "all organic solid content" refers to the solid content excluding the solid content of inorganic substances such as silica filler from the total solid content.

In addition, a coating film is also one of the present invention, and is formed by forming a cured film of the active energy ray curable composition of the present invention on at least one side of a substrate. For a cyclic olefin resin film with high transparency and low moisture permeability, the active energy ray-curable composition for a cyclic olefin resin film of the present invention is used to ensure high adhesion to the substrate, and to achieve resistance A coating with excellent scratching properties, so it can be suitably used as a protective film for polarizing plates.

The above-mentioned substrates include: cyclic olefin resin, cellulose triacetate, polycarbonate, polymethylmethacrylate, polystyrene, polyester, melamine resin, epoxy resin, acrylonitrile-butadiene- Styrene (ABS) resin, norbornene resin, polyimide resin, etc. Among them, when a cyclic olefin resin is used as a base material, it has high adhesion and is therefore preferred. More preferably, the substrate has not been subjected to easy adhesion treatment. By using this substrate, it is possible to reduce production costs or remove restrictions on manufacturing steps.

Examples of the easy adhesion treatment include surface unevenness treatment (sandblasting method, solvent treatment method), electrical treatment (corona discharge treatment, atmospheric pressure slurry treatment), flame treatment, electron beam irradiation treatment, and the like.

The active energy ray-curable composition of the present invention may contain (meth)acrylate components other than the (A) component in addition to the above-mentioned (A) component within the range that does not impair the efficacy of the present invention; Various well-known additives such as photosensitizers, antioxidants, light stabilizers, leveling agents, and pigments; and, photopolymerization initiator (B) (hereinafter also referred to as "(B) component") and the like. Here, the aforementioned additives mean preparations other than the following components: the aforementioned (A) component, the (meth)acrylate component other than the (A) component, and the (B) component; relative to 100 parts by weight of the composition, Examples of the content in the composition include: less than 10 parts by weight, less than 1 part by weight, less than 0.1 parts by weight, less than 0.01 parts by weight, etc.; but it is not limited thereto.

The (meth)acrylate component other than the (A) component is not particularly limited, and examples thereof include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and di(trimethylolpropane) ) Tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide modified trimethylolpropane tri(meth)acrylate, propylene oxide modified trimethylol Propane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol poly(meth)acrylate, pentaerythritol poly(meth)acrylate, isotris Ginseng polycyanate (2-hydroxyethyl) ester trimethyl (meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,4-nonanediol di(meth)acrylate , 2-hydroxyethyl acrylate, benzyl acrylate, tridecyl (meth)acrylate, dodecyl (meth)acrylate, etc. When blending (meth)acrylate components other than (A) component, the weight ratio of (A) component to the blended (meth)acrylate components other than (A) component ((A) component /(Meth)acrylate component other than (A) component), 0.7-9 etc. are mentioned, but it is not limited to this numerical value.

There is no restriction|limiting in particular as said (B) component, A well-known component can be used. Specifically, for example, 1-hydroxy-cyclohexyl-phenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-cyclohexyl phenyl ketone, 2 -Hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan- 1-ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-(N-morpholinyl)propan-1-one, 2-benzyl-2-dimethylamine Base-1-(4-(N-morpholinyl)phenyl)-butan-1-one, bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide, 2,4, 6-Trimethylbenzyl-diphenyl-phosphine oxide, 4-methyldiphenyl ketone, etc. These components may be used individually by 1 type, and may mix and use 2 or more types. In addition, the component (B) is used when performing ultraviolet curing, and when performing electron beam curing, the component (B) is not necessarily required. As an example of the usage amount when using (B) component, about 1-10 weight part etc. are generally mentioned with respect to 100 weight part of total amounts of (A) component, but it is not limited to this value.

The method of forming a cured film formed by using the active energy ray-curable resin composition of the present invention generally involves coating the active energy ray-curing resin composition with a plastic film or plastic sheet used as a substrate and making the active energy The linear-curable resin composition is dried and then irradiated with active energy rays to generate a curing reaction on the surface of the film, as long as a cured film can be formed.

Examples of the above-mentioned coating methods include: bar coater coating, wire bar coating, Meyer bar coating, air knife coating, Gravure coating, reverse gravure coating, offset printing, flexographic printing, screen printing, etc.

The above-mentioned coating amount is not particularly limited. Generally, the weight after drying is preferably about 0.1 to 30 g/m ² , and more preferably 1 to 20 g/m ² .

Examples of the active energy rays used for the curing reaction include ultraviolet rays and electron beams. As a light source of ultraviolet light, an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, and a metal halide lamp can be used. Furthermore, the amount of light, the configuration of the light source, the delivery speed, etc. can be adjusted as needed. For example, when a high-pressure mercury lamp is used, it is better to use a delivery speed of 5 with respect to a lamp that generally has a light amount of about 80 to 160 W/cm. ~50m/min for curing. On the other hand, in the case of electron beams, it is preferable to use an electron beam acceleration device generally having an acceleration voltage of about 10 to 30 kV and perform curing at a conveying speed of about 5 to 50 m/min. [Example]

Hereinafter, examples and comparative examples are given to further explain the present invention in detail. Of course, the present invention is not limited to these examples and comparative examples. Furthermore, in the examples, unless otherwise specified, parts or% are based on weight.

In addition, in this embodiment, the weight average molecular weight is expressed by a colloidal permeation chromatography (manufactured by Tosoh Co., Ltd., trade name "HLC-8220", column: manufactured by Tosoh Co., Ltd., trade name " TSKgel superHZ2000" and "TSKgel superHZM-M") are measured.

(Production of active energy ray-curable resin) (Example 1) Into a reaction vessel equipped with a stirring device, a cooling tube, a dropping funnel, and a nitrogen introduction tube, 210 parts of isocyanurate of hexamethylene diisocyanate were introduced Modified substance (CORONATE HXR, manufactured by Tosoh Corporation) (hereinafter referred to as HDI isocyanurate), 0.6 parts of tin octoate, 1500 parts of mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (mixing ratio is 35: After 65), it took about 1 hour to raise the temperature in the system to about 80°C. Then, the reaction system was kept at the same temperature for 2 hours and then cooled to obtain a mixture of active energy ray-curable oligomer (A-1) and remaining monomer (solid content 100% by weight). (A-1) The (meth)acrylic acid equivalent of the component is 147g/eq, the urethane bond equivalent is 735g/eq, the weight average molecular weight is 15,600, and the oligomer content in 100% by weight of solid content is 43% by weight (calculated value). Based on the solid content ratio, 5 parts of 1-hydroxy-cyclohexyl-phenyl ketone (manufactured by BASF Co., Ltd., Japan, trade name "Irugacure-184", hereinafter referred to as HCPK) is blended with respect to 100 parts of this mixture. Toluene was diluted to prepare an active energy ray curable composition, the solid content of which was 40% by weight, and the content of the (A) component to the total organic solids was 41%.

(Examples 2 to 6) (A-1) to (A-3) were blended in the manner described in Table 1. In the same manner as in Example 1, an active energy ray curable composition having a solid content of 40% by weight was prepared Things. The details are explained below.

(Example 2) According to the solid content ratio, relative to 90 parts of the above-mentioned (A-1) component, 10 parts of dipentaerythritol hexaacrylate and 5 parts of HCPK were blended and diluted with toluene to prepare an active energy ray hardening type The composition had a solid content of 40% by weight, and the content of the (A) component relative to the total organic solid content was 37%.

(Example 3) According to the solid content ratio, relative to 90 parts of the above (A-1) component, 10 parts of pentaerythritol tetraacrylate and 5 parts of HCPK were blended and diluted with toluene to prepare an active energy ray hardening composition The solid content is 40% by weight, and the content of the (A) component relative to the total organic solid content is 37%.

(Example 4) According to the solid content ratio, relative to 80 parts of the above (A-1) component, 20 parts of dipentaerythritol hexaacrylate and 5 parts of HCPK were blended and diluted with toluene to prepare an active energy ray hardening type The composition had a solid content of 40% by weight, and the content of the (A) component relative to the total organic solid content was 33%.

(Example 5) In the above-mentioned reaction vessel equipped with a stirring device, a cooling tube, a dropping funnel, and a nitrogen introduction tube, 200 parts of a biuret modification of hexamethylene diisocyanate (Desmodur N3200A, manufactured by Sumitomo Bayer Polyurethane Co., Ltd.) ) (Hereinafter referred to as HDI biuret), 0.6 parts of tin octoate, 1500 parts of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (mixing ratio is 35:65), it takes about 1 hour to set the temperature in the system The temperature is raised to about 80°C. Then, the reaction system was kept at the same temperature for 2 hours, and then cooled to obtain a mixture of active energy ray-curable oligomer (A-2) and remaining monomer (solid content 100% by weight). (A-2) The (meth)acrylic acid equivalent of the component is 145g/eq, the urethane bond equivalent is 725g/eq, the weight average molecular weight is 11000, and the content of the oligomer component in 100% by weight of the solid content is 43% by weight. According to the solid content ratio, 5 parts of HCPK were blended with respect to 100 parts of this mixture, and diluted with toluene to prepare an active energy ray hardening composition, the solid content of which is 40% by weight and the (A) component is relative to all The solid content of organic matter was 41%.

(Example 6) In a reaction vessel equipped with a stirring device, a cooling tube, a dropping funnel, and a nitrogen introduction tube, 670 parts of isocyanurate modified substance of isophorone diisocyanate (VESTANAT T1890/100, win Created by a company) (hereinafter referred to as IPDI isocyanurate), 0.6 parts of tin octoate, 4,500 parts of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (mixing ratio is 35:65), the cost is about 1 Hours, the temperature in the system was raised to about 80°C. Then, the reaction system was kept at the same temperature for 2 hours, and then cooled to obtain a mixture of active energy ray hardening oligomer (A-3) and remaining monomer (100% solid content). (A-3) The (meth)acrylic acid equivalent of the component is 150g/eq, the urethane bond equivalent is 748g/eq, the weight average molecular weight is 8500, and the oligomer content in 100% solid content is 43 weight%. According to the solid content ratio, 5 parts of HCPK were blended with respect to 100 parts of this mixture, and diluted with toluene to prepare an active energy ray hardening composition, the solid content of which is 40% by weight and the (A) component is relative to all The solid content of organic matter was 41%.

(Example 7) According to the solid content ratio, relative to 40 parts of component (A-1), 60 parts of dipentaerythritol hexaacrylate and 5 parts of HCPK are blended as other components, and diluted with toluene to prepare an active energy The linear hardening type composition has a solid content of 40% by weight, and the content of the (A) component relative to the total organic solid content is 16%.

(Example 8) In a reaction vessel equipped with a stirring device, a cooling tube, a dropping funnel, and a nitrogen introduction tube, 200 parts of HDI biuret, 0.6 parts of tin octoate, 750 parts of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylic acid were put into a reaction vessel After the ester mixture (mixing ratio is 35:65), 240 parts of the mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (mixing ratio is 62:38), it takes about 1 hour to raise the temperature in the system to about 80°C. Then, the reaction system was kept at the same temperature for 2 hours, and then cooled to obtain a mixture of active energy ray hardening oligomer (A-4) and remaining monomer (100% by weight of solid content). (A-4) The (meth)acrylic acid equivalent of the component is 156g/eq, the urethane bond equivalent is 612g/eq, the weight average molecular weight is 10500, and the content of the oligomer component in 100% by weight of solid content is 58% by weight. According to the solid content ratio, 5 parts of HCPK were blended with respect to 100 parts of this mixture, and diluted with toluene to prepare an active energy ray hardening composition, the solid content of which is 40% by weight and the (A) component is relative to all The solid content of organic matter is 55%.

(Example 9) Into a reaction vessel equipped with a stirring device, a cooling tube, a dropping funnel and a nitrogen introduction tube, 205 parts of HDI isocyanurate modified polymer (CORONATE HK, manufactured by Tosoh Corporation), After 0.6 parts of tin octoate, 1500 parts of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate mixture (mixing ratio is 35:65), it takes about 1 hour to increase the temperature in the system to about 80°C. Then, the reaction system was kept at the same temperature for 2 hours, and then cooled to obtain a mixture of active energy ray hardenable oligomer (A-5) and remaining monomer (solid content 100% by weight). (A-5) The (meth)acrylic acid equivalent of the component is 150g/eq, the urethane bond equivalent is 750g/eq, the weight average molecular weight is 46,000, and the content of the oligomer component in 100% by weight of solid content is 43% by weight. According to the solid content ratio, 5 parts of HCPK were blended with respect to 100 parts of this mixture, and diluted with toluene to prepare an active energy ray hardening composition, the solid content of which is 40% by weight and the (A) component is relative to all The solid content of organic matter was 41%.

(Example 10) In a reaction vessel equipped with a stirring device, a cooling tube, a dropping funnel, and a nitrogen introduction tube, 670 parts of HDI biuret, 0.6 parts of tin octoate, 1728 parts of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylic acid were put into a reaction vessel After adding 2 moles of caprolactone to the dipentaerythritol pentaacrylate of a mixture of esters (mixing ratio of 35:65), the temperature in the system was increased to about 80°C in about 1 hour. Then, the reaction system was kept at the same temperature for 2 hours, and then cooled to obtain a mixture of active energy ray-curable oligomer (A-6) and remaining monomer (solid content 100% by weight). (A-6) The (meth)acrylic acid equivalent of the component is 196g/eq, the urethane bond equivalent is 976g/eq, the weight average molecular weight is 13,500, and the content of the oligomer component in 100% by weight of the solid content is 49% by weight. According to the solid content ratio, 5 parts of HCPK were blended with respect to 100 parts of this mixture, and diluted with toluene to prepare an active energy ray hardening composition, the solid content of which is 40% by weight and the (A) component is relative to all The solid content of organic matter was 47%.

(Comparative Example 1) According to the solid content ratio, relative to 20 parts of (A-1) component, 80 parts of dipentaerythritol hexaacrylate and 5 parts of HCPK are blended as other components and diluted with toluene to prepare an active energy The linear hardening composition has a solid content of 40% by weight, and the content of the (A) component relative to the total organic solid content is 8%.

(Comparative Examples 2 to 7) (A-2) and (A'-7) to (A'-11) were blended as described in Table 1. In addition, 40% by weight of solid content was prepared in the same manner as in Comparative Example 1. Active energy ray hardening composition. The details are explained below.

(Comparative Example 2) In a reaction vessel equipped with a stirring device, a cooling tube, a dropping funnel, and a nitrogen introduction tube, 200 parts of HDI biuret, 0.6 parts of tin octoate, 480 parts of pentaerythritol triacrylate and pentaerythritol tetraacrylate After mixing (mixing ratio is 62:38), it takes about 1 hour to raise the temperature in the system to about 80°C. Then, the reaction system was kept at the same temperature for 2 hours and then cooled to obtain a mixture of active energy ray-curable oligomer (A'-7) and remaining monomer (solid content 100% by weight). (A'-7) The (meth)acrylic acid equivalent of the component is 166g/eq, the urethane bond equivalent is 498g/eq, the weight average molecular weight is 8000, and the content of the oligomer component in 100% by weight of solid content It is 73% by weight. According to the solid content ratio, 5 parts of HCPK were blended with respect to 100 parts of this mixture, and diluted with toluene to prepare an active energy ray hardening composition, the solid content of which is 40% by weight and the (A) component is relative to all The solid content of organic matter is 0%.

(Comparative example 3) After putting 200 parts of HDI isocyanurate, 0.6 parts of tin octoate, and 150 parts of 2-hydroxyethyl acrylate into a reaction vessel equipped with a stirring device, a cooling tube, a dropping funnel and a nitrogen introduction tube , It took about 1 hour to raise the temperature in the system to about 80°C. Then, the reaction system was kept at the same temperature for 2 hours and then cooled to obtain a mixture of active energy ray-curable oligomer (A'-8) and remaining monomer (solid content 100% by weight). (A'-8) The (meth)acrylic acid equivalent of the component is 344g/eq, the urethane bond equivalent is 344g/eq, the weight average molecular weight is 2300, and the content of the oligomer component in 100% by weight of solid content It is 98% by weight. According to the solid content ratio, 5 parts of HCPK were blended with respect to 100 parts of this mixture, and diluted with toluene to prepare an active energy ray hardening composition, the solid content of which is 40% by weight and the (A) component is relative to all The solid content of organic matter is 0%.

(Comparative Example 4) In a reaction vessel equipped with a stirring device, a cooling tube, a dropping funnel, and a nitrogen introduction tube, 210 parts of HDI isocyanurate, 0.6 parts of tin octoate, 110 parts of 2-hydroxyethyl acrylate, After 180 parts of 5-mole caprolactone adduct of 2-hydroxyethyl acrylate, it took about 1 hour to raise the temperature in the system to about 80°C. Then, the reaction system was kept at the same temperature for 2 hours and then cooled to obtain a mixture of active energy ray-curable oligomer (A'-9) and remaining monomer (solid content 100% by weight). (A'-9) The (meth)acrylic acid equivalent of the component is 490g/eq, the urethane bond equivalent is 490g/eq, the weight average molecular weight is 4300, and the content of the oligomer component in 100% by weight of solid content It is 98% by weight. Based on the solid content ratio, 5 parts of 1-hydroxy-cyclohexyl-phenyl ketone (manufactured by BASF Co., Ltd., Japan, trade name "Irugacure-184", hereinafter referred to as HCPK) is blended with respect to 100 parts of this mixture. Toluene was diluted to prepare an active energy ray curable composition whose solid content was 40% by weight and the content of (A) component with respect to all organic solids was 0%.

(Comparative Example 5) Into a reaction vessel equipped with a stirring device, a cooling tube, a dropping funnel, and a nitrogen introduction tube, 260 parts of hexamethylene diisocyanate allophanate (TAKENATE D-178NL, manufactured by Mitsui Chemicals Co., Ltd.) ) (Hereinafter referred to as HDI urethane), 0.6 parts of tin octoate, 1500 parts of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (mixing ratio is 35:65), it takes about 1 hour to transfer the system The temperature was raised to about 80°C. Then, the reaction system was kept at the same temperature for 2 hours and then cooled to obtain a mixture of active energy ray-curable oligomer (A'-10) and remaining monomer (solid content 100% by weight). (A'-10) The (meth)acrylic acid equivalent of the component is 157g/eq, the urethane bond equivalent is 785g/eq, the weight average molecular weight is 4000, and the content of the oligomer component in 100% by weight of solid content It is 45% by weight. According to the solid content ratio, 5 parts of HCPK were blended with respect to 100 parts of this mixture, and diluted with toluene to prepare an active energy ray hardening composition, the solid content of which is 40% by weight and the (A) component is relative to all The solid content of organic matter is 0%.

(Comparative Example 6) Into a reaction vessel equipped with a stirring device, a cooling tube, a dropping funnel, and a nitrogen introduction tube, 170 parts of hexamethylene diisocyanate, 0.6 parts of tin octoate, 1500 parts of dipentaerythritol pentaacrylate and dipentaerythritol were charged After the mixture of hexaacrylate (mixing ratio is 35:65), it takes about 1 hour to raise the temperature in the system to about 80°C. Then, the reaction system was kept at the same temperature for 2 hours, and then cooled to obtain a mixture of active energy ray hardening oligomer (A'-11) and remaining monomer (100% by weight of solid content). (A'-11) The (meth)acrylic acid equivalent of the component is 122g/eq, the urethane bond equivalent is 610g/eq, the weight average molecular weight is 3200, and the content of the oligomer component in 100% by weight of solid content It is 42% by weight. According to the solid content ratio, 5 parts of HCPK were blended with respect to 100 parts of this mixture, and diluted with toluene to prepare an active energy ray hardening composition, the solid content of which is 40% by weight and the (A) component is relative to all The solid content of organic matter is 0%.

(Comparative Example 7) According to the solid content ratio, 25 parts of (A-2) component, 75 parts of (A'-10) component, 5 parts of HCPK were blended, and diluted with toluene to prepare an active energy ray hardening The solid content of the type composition is 40% by weight, and the content of the (A) component relative to the total organic solid content is 10%.

<E-type viscosity of the composition diluted with toluene> For a mixture (that is, a mixture containing the following components: (1) each implementation) Example and Comparative Example: A mixture of active energy ray hardening composition and excess monomers, (2) other solid components that can be contained in active energy ray hardening composition such as HCPK), diluted with toluene to a solid content of 80 % Solution, and then measure the viscosity of the solution at 25°C with an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., product model: TV-22, 3° cone). The measurement method is to use about 0.4mL of this solution as the measurement sample, and measure the E-type viscosity of the composition diluted with toluene (mPa‧s) at a rotation speed of 0.5-100 rpm and rotation for 5 minutes.

<Preparation of a cured film> On a cyclic olefin resin film with a thickness of 100μm, each active energy ray-curable composition is coated with a #10 bar coater so that the thickness of the cured film becomes 5μm. It was dried at 70°C for 1 minute to produce a film. Then, for the obtained film, an ultraviolet curing device (product name: UBT-080-7A/BM, manufactured by Multiply Co., Ltd., high-pressure mercury lamp 600 mJ/cm ² ) was used to obtain a plastic film with a cured film. The resin compositions of Examples 2 to 10 and Comparative Examples 1 to 7 were also formed into thin films in the same manner, and the cured films were evaluated in the following manner. The results are shown in Table 1 and Table 2.

<Evaluation of the cured film> (1) Coatability The evaluation film obtained above was visually observed to confirm whether or not cissing of the coating liquid occurred. ○: No shrinkage △: Partially observed shrinkage of the coating solution ×: Shrinkage observed on the entire surface

(2) Adhesiveness With respect to the evaluation film obtained above, the adhesiveness of the cured film was evaluated by a 100-square peel test in accordance with Japanese Industrial Standards (JIS) K5600-5-4. The result is expressed as (number of squares remaining in the peel test/100).

(3) Scratch resistance: For the evaluation film obtained above, a weight of steel wool (#0000, 10mm×10mm) was attached to the bottom and rubbed back and forth 10 times, and the coating was evaluated visually according to the following criteria Exterior. ○: No damage ○ -: Less than 5 damages △: More than 6 damages and less than 20 damages ×: Many damages are generated

[表2]

[Table 1]

[Table 2]

In Table 1 and Table 2, the composition values indicate parts by weight. HDI isocyanurate: isocyanurate modified product of hexamethylene diisocyanate HDI biuret: biuret modified product of hexamethylene diisocyanate HDI urethane: hexamethylene diisocyanate Allophanate modification of diisocyanate IPDI isocyanurate: Isocyanurate modification of isophorone diisocyanate

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Claims (5)

An active energy ray hardening composition, in which: when the total solid content is diluted to 80% by weight with toluene, the E-type viscosity at 25°C is 300~10000mPa‧s; relative to all organic solids The active energy ray curable composition contains 15 to 80% by weight of the active energy ray curable oligomer (A), the polymerization initiator (B), and the monomer remaining in the step of producing the component (A) And, the (A) component has (1) (meth)acrylic acid group, (2) polypentaerythritol skeleton, and (3) isocyanurate group and/or biuret group, and the weight average molecular weight Mw is 3000~100000, urethane bond equivalent is 350~2000g/eq, (meth)acrylic acid equivalent is 120~250g/eq, this component (A) is diisocyanate with isocyanurate group and/or A reaction product of a biuret-based isocyanate and a compound having a polypentaerythritol skeleton and a (meth)acryloyl group. The active energy ray curable composition according to claim 1, wherein the active energy ray curable composition is used for a cyclic olefin resin film. A coating film formed by forming a cured film of the active energy ray curable composition according to claim 1 or 2 on at least one side of a substrate. The coating film according to claim 3, wherein the aforementioned base The material is made of cyclic olefin resin. The coating film according to claim 3 or 4, wherein the substrate is not subjected to easy adhesion treatment.