TW201807113A - Active energy ray curable composition and coating film - Google Patents

Abstract

To provide a hard coating agent for a cyclic olefin resin-based film as a substituent for a TAC film, used for especially a polarizer of a liquid crystal display device or the like as adhesion to specially cyclic olefin is high and scratch resistance is excellent. There is used an active energy ray curable composition having E type viscosity at 25 DEG C when all solid component is diluted by toluene to solid component of 80 wt.% of 300 to 10000 mPa.s and containing an active energy ray curable oligomer (A) of 15 to 80 wt.% based on all organic solid component, the (A) component has a (meth)acryloyl group, a polypentaerythritol skeleton, an isocyanate group and/or a biuret group, weight average molecular weight (Mw) of 3000 to 100000, urethane bond equivalent of 350 to 2000 g/eq and (meth)acryloyl equivalent of 120 to 250 g/eq.

Description

Active energy ray hardening composition and coating film

The present invention relates to an active energy ray-curable composition and a coating film.

Conventionally, a polarizing plate used for a liquid crystal display device is a cellulose triacetate film (TAC film) laminated on both sides of a polarizer as a protective film, and a transparent photocurable resin composition is further applied to the surface of the polarizer. The polarizer is hardened to form a high-hardness film (hard coating layer) and protected from damage. The polarizer is obtained by adsorbing iodine or the like on a polyvinyl alcohol film and orienting it by stretching or the like. 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 the size and quality of liquid crystal devices and the expansion of mobile device applications, 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 promising to replace the TAC film with a cyclic olefin resin-based film. The cyclic olefin resin-based film is excellent in transparency, low birefringence, dimensional stability, and the like, and has properties required as an optical film. Furthermore, having low moisture permeability is also a major feature, and for this reason, it has become a major factor in replacing TAC films. However, the cyclic olefin resin-based film has a problem that it is difficult to form a hard coating layer having high adhesion on the surface.

Conventionally, the adhesion of a substrate and a hard coating layer has been improved by applying a primer layer or an electrical treatment (corona discharge treatment, atmospheric piezoelectric paste treatment) to a cyclic olefin resin-based film (Patent Document 2) . [Prior Art Literature] (Patent Literature)

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

[Problems to be Solved by the Invention] However, in the aforementioned method, a processing step for improving adhesion to a substrate is required when producing a coating film, and there is a problem that it causes high cost. In addition, electrical treatment changes with time on the treated surface, so there is a limitation that a hard coating layer must be applied quickly after the treatment.

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

The present inventors made intensive research in order to solve the aforementioned problems, and as a result, found that the use of a reactant having a specific structure introduced therein can solve the aforementioned problems, thereby completing the present invention.

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

(Item 1) An active energy ray-curable composition, in which when the entire solid content is diluted to 80% by solid content in toluene, the E-type viscosity at 25 ° C is 300-10000 mPa‧s; relative to All organic solid components, 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 (1) (meth) acrylfluorenyl group , (2) a polypentaerythritol skeleton, and (3) an isotrimeric cyano group and / or a biuret group, the weight average molecular weight (Mw) is 3000 to 100,000, and the amine ester bond equivalent is 350 to 2000 g / eq. The acryl fluorenyl 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 according to item 1 or 2 above, which contains a photopolymerization initiator (B). (Item 4) A coating film obtained 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 a cyclic olefin resin. (Item 6) The coating film according to any one of the above items, wherein the substrate is not subjected to an easy-adhesion treatment. [Effect of the invention]

According to the present invention, it is suitable as a hard coating agent, 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 (TAC) films. The TAC film is a hard film, and this TAC film is a polarizing plate used for a liquid crystal display device and the like.

In one embodiment, the active energy ray-curable composition of the present invention has an E-type viscosity at 25 ° C. of 300 to 10,000 mPa · s when the entire solid content is diluted to 80% by weight based on toluene. The active energy ray-curable composition contains 15 to 80% by weight of the active energy ray-curable oligomer (A) (hereinafter also referred to as "(A) component") with respect to all organic solid components; and, the (A) The component has (1) (meth) acrylfluorenyl group, (2) polypentaerythritol skeleton, and (3) isotrimeric cyano group and / or biuret group, and weight average molecular weight (Mw) is 3000- 100,000, amine ester bond equivalent is 350-2000 g / eq, and (meth) acrylfluorenyl equivalent is 120-250 g / eq. The composition can be used as a cyclic olefin resin film. Examples of the active energy rays include ultraviolet rays, electron rays, and radiation. In addition, in the present invention, "(meth) acrylfluorenyl" means collectively including both acrylfluorenyl and methacrylfluorenyl, and likewise, "(meth) acrylic acid ester" means collectively including Both acrylate and methacrylate.

As a component contained in the component (A), it has a polypentaerythritol skeleton and (3) an isocyanuric group and / or a biuret group, and thereby the active energy ray hardening type containing the component (A) The hardened | cured material (coating film) obtained by the composition has sufficient adhesiveness and abrasion resistance.

Examples of the component (A) include a reaction product of an isocyanate compound having a biuret structure and polypentaerythritol poly (meth) acrylate, an isocyanate compound having an isotricyanate structure, and dipentaerythritol poly (methyl Group) acrylate reactants and the like. Specifically, examples thereof include a reaction product of a biuret modification product of hexamethylene diisocyanate and dipentaerythritol hexaacrylate, and an isotricyanate modification product of hexamethylene diisocyanate and dipentaerythritol hexaacrylic acid. Ester reactants.

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

Examples of the isocyanate compound having an isotricyanate structure include an isotricyanate modified product of an aliphatic isocyanate such as 1,6-hexamethylene diisocyanate, hydrogenated xylene diisocyanate, isophor Isocyanurate modified products of alicyclic isocyanates such as ketone diisocyanate; Isocyanate modified products of aromatic isocyanates such as xylene diisocyanate and the like.

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, Modified ethylene oxide of polypentaerythritol polyacrylate, modified caprolactone of polypentaerythritol polyacrylate, and a mixture of two or more of these compounds.

Examples of the method for producing the reactant include the following methods: triethylene glycol, 1,8-diazabicyclo [5.4.0] undecane-7-ene, tin octoate, lead octoate, and the like In the presence of an amine esterification catalyst, the 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-curable composition containing the above-mentioned (A) component is diluted with toluene to 80% of the solid content by weight% of solid content, 10,000 , 9000, 8000, 7000, 6000, 5000, 4000, 3000, 2000, 1000, 900, 800, 700, 600, 500, 400mPa‧s, etc. As examples of the lower limit of the E-type viscosity, 9000, 8000, 7000, 6000, 5000, 4000, 3000, 2000, 1000, 900, 800, 700, 600, 500, 400, 300mPa‧s, etc. The range of the E-type viscosity may be appropriately set (selected from, for example, the upper limit and the lower limit). In one embodiment, the E-type viscosity ranges from 300 to 10,000 mPa · s, and preferably from 450 to 2000 mPa · s from the viewpoint of coating properties. The active energy ray-curable composition containing the component (A) can be diluted with toluene to form a 80% solid solution, and about 0.4 mL of the solution can be used as a measurement sample at 25 ° C as an E-type viscosity meter. (Manufactured by Toki Sangyo Co., Ltd., product model: TV-22, 3 ° cone), the E-type viscosity (mPa · s) was measured under conditions of a rotation speed of 0.5 to 100 rpm and a rotation of 5 minutes. The active energy ray-curable composition of the present invention also contains other components such as a monomer remaining in the step of producing the component (A) or a polymerization initiator described later.

Examples of the upper limit of the weight average molecular weight (Mw) of the component (A) (value measured in terms of polystyrene measured by colloidal permeation chromatography) include 100,000, 90,000, 80,000, 70,000, 60,000, 50000, 46000, 40,000, 30,000, 20000, 15600, 13500, 11000, 10500, 10000, 8500, 8000, 5000, etc. As examples of the lower limit of the weight average molecular weight, there can be listed: 90,000, 80,000, 70,000, 60,000, 50000, 46000 , 40,000, 30,000, 20000, 15600, 13500, 11000, 10500, 10000, 8500, 8000, 5000, 3000, etc. The range of the weight average molecular weight (Mw) can be appropriately set (selected from, for example, the above upper and lower limits). In one embodiment, the weight average molecular weight (Mw) ranges from 3,000 to 100,000 from the viewpoints of adhesion to the substrate, paint stability, and printability. It is preferably 5,000 to 80,000, and more preferably 8,000 to 50,000.

Examples of the upper limit of the amine ester bond equivalent 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, 1400, 1300, 1200, 1100, 1000, 976, 900, 800, 750, 748, 735, 725, 700, 612, 600, 500, 400g / eq and so on. 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 viewpoints of scratch resistance and adhesion, the range of the amine ester bond equivalent is 350 to 2000 g / eq, preferably 350 to 1500 g / eq, and more preferably 600 to 1000 g / eq. The amine ester bond equivalent is a value calculated from the input amount of the reaction raw materials, and specifically, it is the total weight of all raw materials divided by the isocyanate of the component (A) capable of reacting with hydroxyl groups contained in all the raw materials. Moore number of the base.

Examples of the upper limit of the (meth) acrylfluorene equivalent of the (A) component 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) acrylfluorenyl equivalent, 240, 230, 220, 210, 200, 196, 190, 180, 170, 160, 156, 150, 147, 145, 140, 130g / eq and so on. The range of the (meth) acrylfluorenyl equivalent may be appropriately set (selected from, for example, the upper limit and the lower limit). In one embodiment, from the viewpoint of industrial synthesis and scratch resistance, the range of the (meth) acrylfluorenyl equivalent is preferably 120 to 250 g / eq, and more preferably 120 to 200 g / eq. The (meth) acrylfluorenyl equivalent is a value calculated from the input amount of the reaction raw materials, and specifically, is the total weight of all raw materials divided by the (methyl) component (A) contained in all the raw materials. Molar number of acryl fluorenyl group.

The proportion of the component (A) is preferably 50% by weight or more with respect to 100% by weight of the active energy ray-curable oligomer having a functional group derived from an isocyanate group. Thereby, good adhesiveness can be expressed. It is more preferably 75 to 100% by weight. When both isocyanuric group and biuret group are included, the ratio of each functional group may be any ratio.

Examples of the upper limit of the content rate of the component (A) contained in the active energy ray-curable composition of the present invention with respect to all organic solid components 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 ratio, 70, 60, 58, 50, 49, 43, 40, 39, 34, 30, 20, 17, 15% by weight, etc. The range of the content rate of (A) component with respect to the solid content of all organic substances can be set suitably (selected from the said upper limit and lower limit, for example). In one embodiment, from the viewpoints of coatability and adhesion to the substrate, the (A) component contains 15 to 80% by weight, and preferably 15 to 50%, based on the total organic solid content. weight%. Here, the "solid content" means a component except a solvent, and the "all organic solid content" means a solid content in which an inorganic solid component such as a silica filler is excluded from all solid components.

The coating film is also one of the present invention, and is formed by forming a cured coating of the active energy ray-curable composition of the present invention on at least one side of a substrate. For the cyclic olefin resin film having high transparency and low moisture permeability, the active energy ray-curable composition for a cyclic olefin resin film of the present invention is used, thereby ensuring high adhesion to a substrate and achieving resistance to the substrate. Since the coating is excellent in abrasion resistance, it can be suitably used as a protective film for a polarizing plate.

Examples of the substrate include cyclic olefin resin, cellulose triacetate, polycarbonate, polymethyl methacrylate, polystyrene, polyester, melamine resin, epoxy resin, and acrylonitrile-butadiene- Styrene (ABS) resin, norbornene resin, polyimide resin, and the like. Among these, when a cyclic olefin resin is used as a base material, it is preferable because it has high adhesion. More preferred is a substrate that has not been subjected to an 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 piezoelectric slurry treatment), flame treatment, and electron beam irradiation treatment.

The active energy ray-curable composition of the present invention may contain, in addition to the above-mentioned (A) component, a (meth) acrylic acid ester component other than the (A) component, as long as the effect of the present invention is not impaired. Various well-known additives such as a photosensitizer, an antioxidant, a light stabilizer, a leveling agent, and a pigment; and a photopolymerization initiator (B) (hereinafter also referred to as "(B) component") and the like. Here, the above-mentioned additive means a preparation other than the following components: the (A) component, the (meth) acrylate component other than the (A) component, and the (B) component; with respect 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 part by weight, less than 0.01 part by weight, and the like;

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 bis (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 Poly (2-hydroxyethyl) cyanate tri (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, and the like. When the (meth) acrylate component other than the (A) component is blended, the weight ratio of the (A) component to the (meth) acrylate component other than the (A) component is blended ((A) component (The (meth) acrylic acid ester component other than the (A) component) includes 0.7 to 9 and the like, but is not limited to this value.

The component (B) is not particularly limited, and a known component can be used. Specific examples include 1-hydroxy-cyclohexyl-phenyl ketone, 2,2-dimethoxy-1,2-diphenylethyl-1-one, 1-cyclohexylphenyl ketone, 2 -Hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan- 1-one, 2-methyl-1- [4- (methylthio) phenyl] -2- (N-morpholinyl) propan-1-one, 2-benzyl-2-dimethylamine -1- (4- (N-morpholinyl) phenyl) -butan-1-one, bis (2,4,6-trimethylbenzyl) -phenylphosphine oxide, 2,4, 6-trimethylbenzylidene-diphenyl-phosphine oxide, 4-methyldiphenylmethanone and the like. These components may be used individually by 1 type, and may mix and use 2 or more types. The component (B) is used when performing ultraviolet curing, and the component (B) is not necessarily required when performing electron beam curing. As an example of the amount used when the component (B) is used, about 1 to 10 parts by weight is generally mentioned with respect to 100 parts by weight of the total amount of the component (A), but it is not limited to this value.

The method for forming a hardened film using the active energy ray-curable resin composition of the present invention is generally to apply an active energy ray-curable resin composition to a plastic film or a plastic sheet used as a base material and make the active energy The wire-curable resin composition is dried and then irradiated with active energy rays to generate a hardening reaction on the surface of the film as long as a hardened film can be formed.

Examples of the coating method include: bar coater coating, wire bar coating, Meyer bar coating, air knife coating, Gravure coating, reverse gravure coating, offset printing, flexographic printing, screen printing, and the like.

The 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 rays. As an ultraviolet light source, an ultraviolet irradiation device including a xenon lamp, a high-pressure mercury lamp, and a metal halide lamp can be used. In addition, the light quantity, light source configuration, and conveyance speed can be adjusted according to needs. For example, when using a high-pressure mercury lamp, it is preferable that the conveyance speed is 5 with respect to a lamp that generally has a light quantity of about 80 to 160 W / cm. It is hardened at about 50 m / min. On the other hand, in the case of an electron beam, it is preferable to use an electron beam acceleration device generally having an acceleration voltage of about 10 to 30 kV to perform hardening at a conveying speed of about 5 to 50 m / min. [Example]

Hereinafter, the present invention will be described in more detail with examples and comparative examples. However, the present invention is not limited to these examples and comparative examples. In the examples, parts or% are based on weight unless otherwise specified.

In addition, in this example, the weight average molecular weight means that by colloidal permeation chromatography (manufactured by Tosoh Corporation, trade name "HLC-8220", column: manufactured by Tosoh Corporation, trade name " TSKgel superHZ2000 "," TSKgel superHZM-M ").

(Production of active energy ray-curable resin) (Example 1) In a reaction vessel provided with a stirring device, a cooling tube, a dropping funnel, and a nitrogen introduction tube, 210 parts of hexamethylene diisocyanate isocyanate was charged. Modified product (CORONATE HXR, manufactured by Tosoh Corporation) (hereinafter referred to as HDI isocyanurate), 0.6 parts of tin octoate, 1500 parts of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (mixing ratio is 35: 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 (solid content 100% by weight) of the active energy ray-curable oligomer (A-1) and the remaining monomers. The (meth) acrylfluorenyl equivalent of the component (A-1) is 147 g / eq, the amine ester equivalent is 735 g / eq, the weight average molecular weight is 15600, and the content of the oligomer component in 100% by weight of the solid content is 43% by weight (calculated). According to the solid content ratio, 5 parts of 1-hydroxy-cyclohexyl-phenyl ketone (made by BASF Corporation of Japan, trade name "Irugacure-184", hereinafter referred to as HCPK) is added to 100 parts of the mixture, and Toluene was diluted to prepare an active energy ray-curable composition having a solid content of 40% by weight and a content of (A) component with respect to the total organic solid content of 41%.

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

(Example 2) According to the solid content ratio, with respect to 90 parts of the above (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 has a solid content of 40% by weight and a content of the component (A) with respect to the total organic solid content of 37%.

(Example 3) According to the solid content ratio, with respect 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-curable composition. The solid content was 40% by weight and the content of the component (A) relative to the total solid content of the organic matter was 37%.

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

(Example 5) 200 parts of a hexamethylene diisocyanate-modified biuret modified product (Desmodur N3200A, manufactured by Sumitomo Bayer Polyurethane Co., Ltd.) was placed in the above-mentioned reaction vessel equipped with a stirring device, a cooling pipe, a dropping funnel, and a nitrogen introduction pipe. ) (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 reduce the temperature in 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-2) and the remaining monomers (solid content: 100% by weight). The (meth) acrylfluorenyl equivalent of the component (A-2) is 145 g / eq, the amine ester equivalent is 725 g / eq, the weight average molecular weight is 11,000, 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, with respect to 100 parts of the mixture, 5 parts of HCPK is blended and diluted with toluene to prepare an active energy ray hardening composition, the solid content is 40% by weight and the (A) component is relative to all The organic matter solid content 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 isophorone diisocyanate modified product (VESTANAT T1890 / 100, win (Manufactured by Soka Co., Ltd.) (hereinafter referred to as IPDI isocyanurate), 0.6 parts of tin octoate, 4500 parts of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (mixing ratio is 35:65), it takes about 1 The temperature in the system was raised to about 80 ° C for hours. Then, the reaction system was kept at the same temperature for 2 hours, and then cooled to obtain a mixture (solid content: 100%) of the active energy ray-curable oligomer (A-3) and the remaining monomers. The (meth) acrylfluorenyl equivalent of the component (A-3) is 150 g / eq, the amine ester equivalent is 748 g / eq, the weight average molecular weight is 8500, and the content of the oligomer component in 100% of the solid content is 43. weight%. According to the solid content ratio, with respect to 100 parts of the mixture, 5 parts of HCPK is blended and diluted with toluene to prepare an active energy ray hardening composition, the solid content is 40% by weight and the (A) component is relative to all The organic matter solid content was 41%.

(Example 7) According to the solid content ratio, 60 parts of dipentaerythritol hexaacrylate and 5 parts of HCPK were blended into other ingredients with respect to 40 parts of (A-1) component, and diluted with toluene to prepare an active energy. The linear curing composition has a solid content of 40% by weight and a content of the component (A) with respect to the total organic solid content of 16%.

(Example 8) In a reaction vessel provided with a stirring device, a cooling pipe, a dropping funnel, and a nitrogen introduction pipe, 200 parts of HDI biuret, 0.6 parts of tin octoate, 750 parts of dipentaerythritol pentaacrylate, and dipentaerythritol hexaacryl were charged. After a mixture of esters (mixing ratio is 35:65) and a mixture of 240 parts of pentaerythritol triacrylate and pentaerythritol tetraacrylate (mixing ratio: 62:38), 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-4) and the remaining monomer (solid content: 100% by weight). The (meth) acrylfluorenyl equivalent of the component (A-4) is 156 g / eq, the amine ester equivalent is 612 g / eq, the weight average molecular weight is 10,500, and the content of the oligomer component in 100% by weight of the solid content is 58% by weight. According to the solid content ratio, with respect to 100 parts of the mixture, 5 parts of HCPK is blended and diluted with toluene to prepare an active energy ray hardening composition, the solid content is 40% by weight and the (A) component is relative to all The organic matter solid content was 55%.

(Example 9) In a reaction vessel including a stirring device, a cooling tube, a dropping funnel, and a nitrogen introduction tube, 205 parts of a polymer of HDI isocyanurate modified product (CORONATE HK, manufactured by Tosoh Corporation), After 0.6 parts of tin octoate, 1500 parts of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (mixing ratio is 35:65), 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-5) and the remaining monomer (solid content: 100% by weight). The (meth) acrylfluorenyl equivalent of the component (A-5) is 150 g / eq, the amine ester equivalent is 750 g / eq, the weight average molecular weight is 46,000, 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, with respect to 100 parts of the mixture, 5 parts of HCPK is blended and diluted with toluene to prepare an active energy ray hardening composition, the solid content is 40% by weight and the (A) component is relative to all The organic matter solid content 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 hexaacryl were charged. After the dipentaerythritol pentaacrylate of the ester mixture (the mixing ratio is 35:65) is added with 2 mol caprolactone, 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-6) and the remaining monomer (solid content: 100% by weight). The (meth) acrylfluorenyl equivalent of the component (A-6) is 196 g / eq, the amine ester equivalent is 976 g / 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, with respect to 100 parts of the mixture, 5 parts of HCPK is blended and diluted with toluene to prepare an active energy ray hardening composition, the solid content is 40% by weight and the (A) component is relative to all The organic matter solid content was 47%.

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

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

(Comparative Example 2) In a reaction vessel equipped with a stirring device, a cooling pipe, a dropping funnel, and a nitrogen introduction pipe, 200 parts of HDI biuret, 0.6 parts of tin octoate, 480 parts of pentaerythritol triacrylate, and pentaerythritol tetraacrylate were charged. After the mixture (mixing ratio was 62:38), 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'-7) and the remaining monomers (solid content: 100% by weight). The (meth) acrylfluorenyl equivalent of the (A'-7) component is 166 g / eq, the amine ester equivalent is 498 g / eq, the weight average molecular weight is 8000, and the content of the oligomer component in 100% by weight of the solid content It is 73% by weight. According to the solid content ratio, with respect to 100 parts of the mixture, 5 parts of HCPK is blended and diluted with toluene to prepare an active energy ray hardening composition, the solid content is 40% by weight and the (A) component is relative to all The organic matter solid content was 0%.

(Comparative Example 3) After putting 200 parts of HDI isotricyanate, 0.6 parts of tin octoate, and 150 parts of 2-hydroxyethyl acrylate into a reaction vessel equipped with a stirring device, a cooling pipe, a dropping funnel, and a nitrogen introduction pipe, 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 the remaining monomer (solid content: 100% by weight). The (meth) acrylfluorenyl equivalent of the (A'-8) component is 344 g / eq, the amine ester equivalent is 344 g / eq, the weight average molecular weight is 2300, and the content of the oligomer component in 100% by weight of the solid content It is 98% by weight. According to the solid content ratio, with respect to 100 parts of the mixture, 5 parts of HCPK is blended and diluted with toluene to prepare an active energy ray hardening composition, the solid content is 40% by weight and the (A) component is relative to all The organic matter solid content was 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 isotricyanate, 0.6 parts of tin octoate, 110 parts of 2-hydroxyethyl acrylate, After 180 parts of the 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 the remaining monomers (solid content: 100% by weight). The (meth) acrylfluorenyl equivalent of the (A'-9) component is 490 g / eq, the amine ester equivalent is 490 g / eq, the weight average molecular weight is 4300, and the content of the oligomer component in 100% by weight of the solid content It is 98% by weight. According to the solid content ratio, 5 parts of 1-hydroxy-cyclohexyl-phenyl ketone (made by BASF Corporation of Japan, trade name "Irugacure-184", hereinafter referred to as HCPK) is added to 100 parts of the mixture, and Toluene was diluted to prepare an active energy ray-curable composition having a solid content of 40% by weight and a content of the component (A) with respect to the total organic solid content of 0%.

(Comparative Example 5) In a reaction vessel provided with a stirring device, a cooling tube, a dropping funnel, and a nitrogen introduction tube, 260 parts of hexamethylene diisocyanate urethane (TAKENATE D-178NL, manufactured by Mitsui Chemicals Co., Ltd.) was charged. ) (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), and it takes about 1 hour. The temperature rose 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 the remaining monomers (solid content: 100% by weight). The (meth) acrylfluorenyl equivalent of the (A'-10) component is 157 g / eq, the amine ester equivalent is 785 g / eq, the weight average molecular weight is 4000, and the content of the oligomer component in 100% by weight of the solid content It is 45% by weight. According to the solid content ratio, with respect to 100 parts of the mixture, 5 parts of HCPK is blended and diluted with toluene to prepare an active energy ray hardening composition, the solid content is 40% by weight and the (A) component is relative to all The organic matter solid content was 0%.

(Comparative Example 6) In 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 (the mixing ratio is 35:65), 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'-11) and the remaining monomer (solid content: 100% by weight). The (meth) acrylfluorenyl equivalent of the (A'-11) component is 122 g / eq, the amine ester equivalent is 610 g / eq, the weight average molecular weight is 3200, and the content of the oligomer component in 100% by weight of the solid content It is 42% by weight. According to the solid content ratio, with respect to 100 parts of the mixture, 5 parts of HCPK is blended and diluted with toluene to prepare an active energy ray hardening composition, the solid content is 40% by weight and the (A) component is relative to all The organic matter solid content was 0%.

(Comparative Example 7) An active energy ray hardening was prepared by blending 75 parts (A'-10) and 5 parts of HCPK with 25 parts of (A-2) component and diluting with toluene according to the solid content ratio. The solid composition has a solid content of 40% by weight and the content of the component (A) with respect to the total solid content of the organic matter is 10%.

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

<Creating a hardened coating> On a cyclic olefin resin film having a film thickness of 100 μm, each active energy ray-curable composition was coated with a # 10 bar coater so that the film thickness of the cured film became 5 μm. And it dried at 70 degreeC for 1 minute, and produced the film. Then, 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 for the obtained film to obtain a plastic film having a cured film. The resin compositions of Examples 2 to 10 and Comparative Examples 1 to 7 were also formed into thin films, and the cured films were evaluated in the following manner. The results are shown in Tables 1 and 2.

<Evaluation of hardened film> (1) Coating property The film for evaluation obtained above was visually observed, and it was confirmed whether the coating liquid was cissing. ○: No shrinkage △: Shrinkage of the coating liquid was partially observed ×: Shrinkage was observed on the entire surface

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

(3) Scratch resistance For the obtained evaluation film, a steel wool (# 0000, 10mm × 10mm) weight was rubbed back and forth 10 times with a bottom attached, and the coating was visually evaluated according to the following criteria Exterior. ○: No damage ○-: 5 or less damage occurred △: 6 or more damage or less ×: Most damage occurred

[Table 1] [Table 2]

In Tables 1 and 2, composition values indicate parts by weight. HDI isotricyanate: isotricyanate modification of hexamethylene diisocyanate HDI biuret: biuret modification of hexamethylene diisocyanate HDI urethane: hexamethylene Diisocyanate Urea Formate Modified IPDI Isocyanurate: Isophorone Diisocyanate Modified Isocyanate

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Claims (6)

An active energy ray hardening composition, wherein: when all the solid components are diluted to 80% by weight in toluene, the E-type viscosity at 25 ° C. is 300-10000 mPa‧s; relative to all organic solid components 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 (1) (meth) acrylic acid fluorene group, (2) Polypentaerythritol skeleton and (3) isotricyanic acid group and / or biuret group, weight average molecular weight, that is, Mw is 3000 to 100,000, amine ester bond equivalent is 350 to 2000 g / eq, (meth) acrylic acid The base equivalent is 120 to 250 g / eq. 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. The active energy ray-curable composition according to claim 1 or 2, further comprising a photopolymerization initiator (B). A coating film formed by forming a cured film of the active energy ray-curable composition according to any one of claims 1 to 3 on at least one side of a substrate. The coating film according to claim 4, wherein the substrate is made of a cyclic olefin resin. The coating film according to claim 4 or 5, wherein the substrate is not subjected to an easy-adhesion treatment.