TWI659075B - Curable composition, cured product, molded article, and display member - Google Patents

Abstract

An object of the present invention is to provide a curable composition having excellent surface hardness and flexibility, and a cured product thereof, a molded article having a coating film including the cured product, and a display member. Specifically, a curable composition is used which contains a urethane (meth) acrylate (X) as an essential component, and the urethane (meth) acrylate (X) is used in A polyisocyanate compound (A) having two or more isocyanate groups and a biuret structure site in a molecular structure and an isocyanate group content in a range of 15 to 27% by mass, and neopentaerythritol tri (meth) acrylate (b1) It is obtained by reacting as an essential component, and the (meth) acrylfluorenyl content is in the range of 4.0 to 8.5 mmol / g.

Description

Curable composition, cured product, molded article, and display member

The present invention relates to a curable composition having excellent surface hardness and flexibility, and a cured product thereof, a molded article having a coating film including the cured product, and a display member.

In a portable display device such as a smart phone or a tablet-type terminal device, a surface protective film made of a thin glass or plastic film is provided in order to protect the surface of the display from being damaged. With the reduction in thickness and weight of these portable display devices, the development of thinner and less susceptible materials to protect the surface of the display film has been developed. For plastic films that are lighter and thinner than glass materials Expectations are high.

In the plastic film for a surface protection film of a display, for example, a substrate film made of TAC (triethyl cellulose) or PET (polyethylene terephthalate) is used, and a UV curable coating is provided. Hard coating. For the UV-curable coating for this hard coating, in addition to requiring a hardened surface of the hardened coating film that is hard to be scratched or scratched, it is also required to have both a small hardening shrinkage and no curl deformation during hardening. It has excellent flexibility and can be used for various properties that are opposite to the surface hardness, such as roll storage and storage. In general, in order to improve the damage resistance of hard coatings, polymerizable functional groups are used to improve the UV-curable coatings. Concentration and high hardness methods, or thick coatings of hard coatings, but the hard coatings obtained by such methods have large hardening shrinkage and insufficient flexibility, so they are prone to curl deformation during hardening. Or it is easy to be damaged or cracked when the drum is coiled or punched.

As an ultraviolet-curable coating material for a hard coat layer, for example, an acrylate compound containing a biuret body containing 1,6-hexane diisocyanate, propylene glycol, and neopentaerythritol triacrylate as a main component is known. A UV-curable composition of acrylaminocarbamate oligomer obtained by the reaction (see Patent Document 1). Although the coating film composed of the ultraviolet curable composition has the characteristics of high stretchability and excellent moldability, it has low surface hardness and insufficient scratch resistance. In addition, a coating composition for UV curing using a urethane acrylate oligomer obtained by reacting neopentaerythritol triacrylate with a trimer isocyanate of 1,6-hexamethylene diisocyanate is known. (See Patent Document 2). Although the coating film composed of the aforementioned UV curing coating composition has high surface hardness and excellent scratch resistance, it has low flexibility and cannot meet recent market demands.

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2011-219660

[Patent Document 2] Japanese Patent Laid-Open No. 2013-060599

Therefore, the problem to be solved by the present invention is to provide a hardenable composition which is excellent in both the surface hardness and flexibility of a hardened material and A cured product, a molded article having a coating film including the cured product, and a display member.

As a result of intensive studies to solve the above-mentioned problems, the inventors have found a hardenable composition containing a urethane (meth) acrylate oligomer as an essential component, and the urethane The (meth) acrylate oligomer is a polyisocyanate compound having two or more isocyanate groups and biuret structure sites in a molecular structure and an isocyanate group content in a range of 15 to 27% by mass, and neopentyl tetraol. Tris (meth) acrylate is obtained by reacting as an essential component, and the content of (meth) acryl group is in the range of 4.0 to 8.5 mmol / g. The surface hardness of the hardened composition-based hardened coating film is high, so it has good scratch resistance. The present invention is excellent and has high flexibility, and thus completed the present invention.

That is, the present invention relates to a curable composition containing a urethane (meth) acrylate oligomer (X) as an essential component, and the urethane (meth) acrylate oligomer (X) Polyisocyanate compound (A) having two or more isocyanate groups and biuret structure sites in the molecular structure and an isocyanate group content in the range of 15 to 27% by mass, and neopentyl tetraol tri (methyl) ) Acrylate (b1) is obtained by reacting as an essential component, and the content of (meth) acrylofluorenyl is in the range of 4.0 to 8.5 mmol / g.

The present invention further relates to an active energy ray-curable composition containing the aforementioned curable composition and a photopolymerization initiator.

The present invention further relates to a cured product obtained by curing the curable composition.

The present invention further relates to a molded article having a coating film composed of the cured product.

The present invention further relates to a display member having a coating film made of the cured product.

According to the present invention, it is possible to provide a hardenable composition excellent in both surface hardness and flexibility of a hardened material and its hardened material, a molded article having a coating film composed of the hardened material, and a display member.

[Form of Implementing Invention]

The curable composition of the present invention is characterized in that it contains a urethane (meth) acrylate oligomer (X) having a (meth) acryl group content in the range of 4.0 to 8.5 mmol / g as an essential component. The urethane (meth) acrylate oligomer (X) has a molecular structure having two or more isocyanate groups and a biuret structure site and an isocyanate group content in a range of 15 to 27% by mass. The polyisocyanate compound (A) is obtained by reacting with neopentaerythritol tri (meth) acrylate (b1) as an essential component.

The aforementioned urethane (meth) acrylate oligomer (X) requires a polyisocyanate compound (A) having a biuret structure in the molecular structure and an isocyanate group content of 15 to 27% by mass as a necessity. Raw materials, and become a molecular skeleton with rich toughness and high flexibility. In addition, with a propylene amidino content in the range of 4.0 to 8.5 mmol / g, a crosslinked structure with a moderate density can be obtained during hardening, and surface hardness can be formed. Hardened coating film which is excellent in both flexibility and flexibility.

The polyisocyanate compound (A), which is an essential raw material of the urethane (meth) acrylate oligomer (X), has two or more isocyanate groups and a biuret structure site in the molecular structure. Examples of such a polyisocyanate compound include a diisocyanate monomer produced by a method in which a diisocyanate monomer (a1) and a biuret (a2) are reacted at a temperature of 70 to 200 ° C. Biuret modified body and so on.

Examples of the diisocyanate monomer (a1) include butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4 -Trimethylhexamethylene diisocyanate, diphenylene diisocyanate, m-tetramethyl diphenylene diisocyanate and other aliphatic diisocyanate monomers; cyclohexane-1,4-diisocyanate , isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane 4,4 '- diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, methylcyclohexane diisocyanate, isopropylidene propyl dicyclohexyl-4,4 '- diisocyanate, norbornane diisocyanate, etc. the alicyclic diisocyanate monomer; 1,5 extending naphthyl diisocyanate, 4,4' - diphenylmethane diisocyanate , 4,4 '- diphenyl dimethyl methane diisocyanate, 4,4' - dibenzyl diisocyanate, a dialkyl-diphenylmethane diisocyanate, tetraalkyl diphenyl methane diisocyanate, 1,3 -Phenylene diisocyanate, 1,4-phenylene diisocyanate, methylphenylene diisocyanate, methylphenylene diisocyanate, tetramethyl ethylene diisocyanate Dimethyl diisocyanate, etc. The aromatic diisocyanate monomers. These systems can be used individually or in combination of two or more. Among them, from the viewpoint that the obtained urethane (meth) acrylate oligomer (X) becomes more flexible, the aforementioned aliphatic diisocyanate monomer or alicyclic diisocyanate monomer is preferred. Aliphatic diisocyanate monomers are more preferred.

Examples of the biuretating agent (a2) include monovalent tertiary alcohols such as water and t-butanol, monoamine compounds such as formic acid, hydrogen sulfide, and methylamine, and methylenediamine. , Diamine compounds such as diphenylmethanediamine and the like. These systems can be used individually or in combination of two or more.

The reaction between the diisocyanate monomer (a1) and the biuretating agent (a2) can also be performed in an organic solvent. Examples of the organic solvent used here include ethylene glycol monomethyl ether acetate and ethylene diethylene glycol. Alcohol monoethyl ether acetate, ethylene glycol diacetate, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol diacetate, Ether solvents such as dipropylene glycol dimethyl ether; alkyl phosphate compounds such as trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, and the like. These systems can be used individually or in combination of two or more.

The isocyanate group content of the aforementioned polyisocyanate compound (A) is 15 in terms of obtaining a urethane (meth) acrylate oligomer (X) that is rich in toughness and has a highly flexible molecular skeleton. A range of 27% by mass, and a range of 20-25% by mass is more preferable.

The urethane (meth) acrylate oligomer (X) of the present invention is a polyisocyanate compound (A) having an isocyanate group content in the range of 15 to 27% by mass, and neopentaerythritol tri (methyl) ) Acrylic ester (b1) is obtained by reacting as an essential component.

The reaction between the polyisocyanate compound (A) and the neopentaerythritol tri (meth) acrylate (b1) includes, for example, the presence of a urethane catalyst such as tin octoate or zinc octoate. Between 40 ~ 120 ℃ The temperature range allows a method for performing the reaction and the like.

The reaction ratio between the polyisocyanate compound (A) and the neopentaerythritol tri (meth) acrylate (b1) is determined from ( The content of the meth) acryl group is controlled within a desired range based on the molar number of the isocyanate group in the polyisocyanate compound (A) and the hydroxyl group in the neopentyl tetraol tri (meth) acrylate (b1). The molar number ratio [(NCO) / (OH)] is preferably in a range of 1.0 / 0.95 to 1.0 / 1.05.

The urethane (meth) acrylate oligomer (X) of the present invention may be used in addition to the polyisocyanate compound (A) and the neopentaerythritol tri (meth) acrylate (b1). A polyisocyanate compound (A ') other than the polyisocyanate compound (A), a hydroxyl-containing compound (B') other than the neopentaerythritol tri (meth) acrylate (b1), and the like.

Examples of the other polyisocyanate compound (A ') include, for example, various diisocyanate monomers listed as raw materials of the polyisocyanate compound (A), or trimeric isocyanate modifiers and adduct modifications thereof.体 等。 Body and so on.

When the polyisocyanate compound (A) and the other polyisocyanate compound (A ') are used in combination, the effects of both the surface hardness and the flexibility of the hardened material achieved by the present invention are excellent. Of the total 100 parts by mass, the polyisocyanate compound (A) is preferably 50 parts by mass or more, and more preferably 85 parts by mass or more.

Examples of the other hydroxyl-containing compound (B ') include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl ( (Meth) acrylate, glycerol mono (meth) acrylate, glycerol di (meth) acrylate, trimethylolpropane mono (meth) acrylate, trimethylolpropane di (methyl) ) Aliphatic (meth) acrylate compounds such as acrylate, neopentaerythritol di (meth) acrylate, and dipentaerythritol penta (meth) acrylate; 4-hydroxyphenyl (meth) acrylate Β-hydroxyphenethyl (meth) acrylate, 4-hydroxyphenethyl (meth) acrylate, 1-phenyl-2-hydroxyethyl (meth) acrylate, 3-hydroxy- (meth) acrylate- Aromatic (meth) acrylate compounds such as 4-ethenylphenyl ester and 2-hydroxy-3-phenoxypropyl (meth) acrylate: Polyoxyethylene glycol, polyoxypropylene glycol, etc. Polyoxyalkylene glycol and the like. These systems can be used individually or in combination of two or more. Among them, the effects of both the surface hardness and the flexibility of the hardened material achieved by the present invention can be fully exerted. The aforementioned aliphatic (meth) acrylate compound is preferred, and flexibility can be obtained from the above. As a more excellent hardened coating film, the aforementioned neopentaerythritol di (meth) acrylate (b3) is particularly preferred.

When the aforementioned neopentaerythritol tri (meth) acrylate (b1) and other hydroxyl-containing compound (B ') are used in combination, both the surface hardness and the flexibility of the hardened material achieved by the present invention are excellent, and the effect is sufficient. In terms of performance, in the case of a total of 100 moles, the aforementioned neopentaerythritol tri (meth) acrylate (b1) is preferably 75 moles or more, and more preferably 85 moles or more.

When the other polyisocyanate compound (A ') or other hydroxyl-containing compound (B') is used in combination, the reaction ratios of various raw materials when producing the urethane (meth) acrylate oligomer (X) are based on The ratio [(NCO) / (OH)] of the total molar number of isocyanate groups of the polyisocyanate compound component to the total molar number of hydroxyl groups contained in the hydroxyl-containing compound component is A range of 1.0: 0.95 to 1.0: 1.05 is preferable.

The acrylic acid group content of the aforementioned urethane (meth) acrylate oligomer (X) is 4.0 to 8.5 mmol from the hardened coating film having excellent surface hardness and flexibility. The range of / g is more preferably in the range of 5.5 to 7.5 mmol / g.

In the present invention, the content of the acrylamide group of the urethane (meth) acrylate oligomer (X) is a value calculated from the feed amount of the reaction raw material, and specifically, the amino group The value obtained by dividing the molar number of the (meth) acrylfluorenyl group in the total raw material of the formate (meth) acrylate oligomer (X) by the total mass of the total raw material.

The weight average molecular weight (Mw) of the urethane (meth) acrylate oligomer (X) can be obtained from a cured coating film having excellent hardenability and excellent surface hardness and flexibility. In other words, a range of 5,000 to 80,000 is preferable, and a range of 7,000 to 50,000 is more preferable.

In the present invention, the weight average molecular weight (Mw) is a value measured by gel permeation chromatography (GPC) under the following conditions.

Measuring device; HLC-8220 manufactured by TOSOH Co., Ltd.

Column; TOSOH Co., Ltd. Protective Column TSK-GUARDCOLUMN SuperHZ-L

+ TOSOH Corporation TSKgel SuperHZM-M × 4

Detector; RI (Differential Refractometer)

Data processing: Multi-stage GPC-80 20modelII made by TOSOH Co., Ltd.

Measurement conditions: column temperature 40 ℃

Solvent tetrahydrofuran

Flow rate 0.35ml / min

Standard; polystyrene

Sample; 0.2% by weight of the tetrahydrofuran solution converted from the solid content of the resin was filtered by a micro filter (100 μl)

The curable composition of the present invention contains the aforementioned urethane (meth) acrylate oligomer (X) as an essential component, and may further contain other radical polymerizable compounds as necessary.

Particularly preferred among the other radically polymerizable compounds is neopentaerythritol tetra (meth) acrylate (b2). When the curable composition of the present invention contains neopentaerythritol tetra (meth) acrylate (b2), a cured coating film having a higher surface hardness can be obtained. At this time, the blending ratio of the aforementioned urethane (meth) acrylate oligomer (X) and neopentaerythritol tetra (meth) acrylate (b2) can be obtained from the surface hardness and flexibility. Both are excellent hardened coating films, and the content of the aforementioned urethane (meth) acrylate oligomer (X) is preferably in the range of 50 to 99% by mass relative to the total amount of the two. A range of 65 to 90% by mass is more preferable.

In the case where the curable composition of the present invention contains neopentaerythritol tetra (meth) acrylate (b2), as the urethane (meth) acrylate oligomer (X) As the raw material of neopentaerythritol tri (meth) acrylate (b1) used in the manufacturing process, it may also contain neopentaerythritol tri (meth) acrylate (b1) as an essential component and neopentaerythritol Tetra (meth) acrylate (b2) or neopentaerythritol poly (meth) acrylate composition (B) of neopentaerythritol di (meth) acrylate (b3).

The content of each component in the neopentaerythritol poly (meth) acrylate composition (B) is determined by (meth) acrylic acid of the urethane (meth) acrylate oligomer (X). It is easy to adjust the content of the group to a range of 4.0 to 8.5 mmol / g. In the neopentaerythritol poly (meth) acrylate composition (B), the neopentaerythritol tri (meth) acrylate (b1) ) Is preferably in the range of 50 to 85%, and the content of the aforementioned neopentaerythritol tetra (meth) acrylate (b2) is preferably in the range of 10 to 50%.

The content of each component in the neopentaerythritol poly (meth) acrylate composition (B) is a value calculated from the peak area ratio of the gas chromatography method measured under the following conditions.

Measuring device; GC-2010, manufactured by Shimadzu Corporation

Column; ZB-5 (liquid phase film thickness 0.25μm, length 30m, inner diameter 0.25mm)

Detector; FID (Hydrogen Flame Ionization Detector), 300 ° C

Measurement conditions: gasification chamber 300 ° C, 105kPa

Hold at 50 ° C for 5 minutes, heat up at 10 ° C / min, and hold at 300 ° C for 15 minutes

In addition, the hydroxyl value of the neopentaerythritol poly (meth) acrylate composition (B) is determined by (meth) acrylic acid of the urethane (meth) acrylate oligomer (X). It is easy to adjust the base content to a range of 4.0 to 8.5 mmol / g, preferably a range of 80 to 180 mgKOH / g, and more preferably a range of 100 to 170.

In addition, the radical polymerizable compound (Y) other than the urethane (meth) acrylate oligomer (X) and the neopentaerythritol tetra (meth) acrylate (b2) may be, for example, Examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, n-butyl (meth) acrylate, isopropyl Butyl (meth) acrylate, t-butyl (meth) acrylate, glycidyl (meth) acrylate, acryl Porphyrin, N-vinylpyrrolidone, tetrahydrofurfuryl acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isofluorenyl (meth) acrylate, isodecyl (Meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, Benzyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, phosphoric acid (Meth) acrylate, ethylene oxide modified phosphoric acid (meth) acrylate, phenoxy (meth) acrylate, ethylene oxide modified phenoxy (meth) acrylate, propylene oxide Modified phenoxy (meth) acrylate, nonylphenol (meth) acrylate, ethylene oxide modified nonylphenol (meth) acrylate, propylene oxide modified nonylphenol (meth) Acrylate, methoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, 2- (meth) acrylic acid Oxyethyl-2-hydroxypropylphthalic acid Ester, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acrylfluorenyloxyethyl phthalate, 2- (meth) acrylfluorenyloxypropyl Hydrogen phthalate, 2- (meth) acrylfluorenyloxypropyl hydrogen phthalate, 2- (meth) acrylfluorenyloxypropyl tetrahydrophthalate, dimethylamine Ethyl (meth) acrylate, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropropyl (meth) ) Mono (meth) acrylates such as acrylates, adamantyl mono (meth) acrylates; butanediol di (meth) acrylate, hexanediol di (meth) acrylate, ethoxylation Hexanediol di (meth) acrylate, propoxylated hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, Propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, hydroxytrimethyl acetate neopentyl glycol di (methyl) ) Bis (meth) acrylates such as acrylates; trimethylolpropane tri (meth) propane Acid ester, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, ginseng 2-hydroxyethyltrimeric isocyanate tri (methyl) ) Tris (meth) acrylates such as acrylate, glycerol tri (meth) acrylate, etc .; neopentaerythritol tri (meth) acrylate, dinepentaerythritol tri (meth) acrylate, di -Trimethylolpropane tri (meth) acrylate, neopentaerythritol tetra (meth) acrylate, di-trimethylolpropane tetra (meth) acrylate, dinepentaerythritol tetra (methyl) ) Acrylate, Dinepentaerythritol penta (meth) acrylate, Di-trimethylolpropane penta (meth) acrylate, Dinepentaerythritol hexa (meth) acrylate, Di-trimethylol 4-functional (meth) acrylates such as propane hexa (meth) acrylate and the like; and a part of the above-mentioned various multifunctional (meth) acrylates substituted with an alkyl group or ε-caprolactone ( (Meth) acrylates and the like. These systems can be used individually or in combination of two or more.

The curable composition of the present invention contains the neopentyltetraol tetra (meth) acrylate (b2) or the aforementioned urethane (meth) acrylate oligomer (X) in addition to the aforementioned urethane (meth) acrylate oligomer (X). Other radical polymerizable compounds In the case of (Y), in terms of a hardened coating film having excellent surface hardness and flexibility, the aforementioned urethane (methyl The content of the acrylate oligomer (X) is preferably in the range of 20 to 80% by mass, and more preferably in the range of 30 to 70% by mass.

In addition, the curable composition of the present invention contains the neopentaerythritol tetra (meth) acrylate (b2) in addition to the urethane (meth) acrylate oligomer (X). In the case of the other radical polymerizable compound (Y), the urethane (meth) acrylate oligomer (X) and the The total content of pentaerythritol tetra (meth) acrylate (b2) is preferably in the range of 10 to 80% by mass, and more preferably in the range of 25 to 75% by mass.

The hardenable composition of the present invention can be hardened by any one of hardening by heating or hardening by irradiation with active energy rays. In the case of curing by irradiation with active energy rays, a photopolymerization initiator is used. In light of the polymerization initiator used, based for example benzophenone, 3,3 '- dimethyl-4-methoxy benzophenone, 4,4' - bis dimethylamino benzophenone ketone, 4,4 '- bis diethyl amino benzophenone, 4,4' - dichlorobenzophenone, Michler's ketone, 3,3 ', 4,4' - four (T-butyl Peroxycarbonyl) benzophenone and other benzophenones; Ketone, 9-oxysulfur 2-methyl 9-oxysulfur , 2-chloro9-oxysulfur , 2,4-diethyl 9-oxysulfur Wait for Ketone, 9-oxysulfur ; Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and other benzoin ethers; benzyl, diethylfluorenyl and other α-diketones; tetradisulfide Sulfur compounds such as methyl thiocarbamate, p-tolyl disulfide; various benzoic acids such as 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid ethyl; 3, 3 '- carbonyl - bis (7-diethylamino) coumarin, 1-hydroxycyclohexyl phenyl ketone, 2,2' - dimethoxy-1,2-diphenylethane-1 Ketone, 2-methyl-1- [4- (methylsulfanyl) phenyl] -2-zolinolinpropane-1-one, 2-benzyl-2-dimethylamino-1- (4-taste (Phenylphenyl) -butane-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2,4,6-trimethylbenzylidene diphenylphosphine oxide , Bis (2,4,6-trimethylbenzylidene) phenylphosphine oxide, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1 -Propane-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one, 1- (4-dodecylphenyl) -2-hydroxy- 2-methyl-1-one, 4-benzoyl-4 '- methyl dimethyl sulfide, 2,2' - diethoxyacetophenone, benzyl dimethyl ketal, benzyl Base-β- Methoxyethyl acetal, o-benzylidene benzoic acid methyl ester, bis (4-dimethylaminophenyl) ketone, p-dimethylaminoacetophenone, α, α-dichloro 4-phenoxyacetophenone, pentyl-4-dimethylaminobenzoate, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2,4 -Bis-trichloromethyl-6- [di- (ethoxycarbonylmethyl) amino] phenyl-S-Mitsui, 2,4-bis-trichloromethyl-6- (4-ethoxy ) Phenyl-S-Mitsui, 2,4-bis-trichloromethyl-6- (3-bromo-4-ethoxy) phenyl-S-Mitsui anthraquinone, 2-t-butylanthraquinone, 2-pentylanthraquinone, β-chloroanthraquinone and the like. These systems can be used individually or in combination of two or more.

Among these, by using a member selected from 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1- [4- (2-hydroxyethoxy ) Phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 9-oxysulfur And 9-oxysulfur Derivatives, 2,2 '- dimethoxy-1,2-diphenylethane-1-one, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, bis (2 , 4,6-trimethylbenzylidene) phenylphosphine oxide, 2-methyl-1- [4- (methylsulfanyl) phenyl] -2-amiline-1-acetone, 2-benzyl One or two or more mixed systems of the group of 2--2-dimethylamino-1- (4-amidophenyl) -butane-1-one are for a wider range of wavelengths. Light shows activity and hardenability, so it is preferable.

Examples of commercially available products of these photopolymerization initiators include "Irgacure 184", "Irgacure 149", "Irgacure 261", "Irgacure 369", "Irgacure 500", "Irgacure 651", "Irgacure" 754, Irgacure 784, Irgacure 819, Irgacure 907, Irgacure 1116, Irgacure 1664, Irgacure 1700, Irgacure 1800, Irgacure 1850, Irgacure 2959, Irgacure 4043 "," DAROCUR 1173 "," Lucirin TPO ";" KAYACURE-DETX "," KAYACURE-MBP "," KAYACURE-DMBI "," KAYACURE-EPA "," KAYACURE-OA "manufactured by Nippon Kayaku Co., Ltd .; Stauffer. "Vicure 10" and "Vicure 55" by Chemical; "TRIGONAL P1" by AKZO; "Sandoray 1000" by Sandoz; "DEAP" by APJOHN; "Quanta cure PDO" and "Quanta cure ITX" by Ward Blenkinsop "," Quanta cure EPD ", etc.

The addition amount of the photopolymerization initiator is preferably used in a proportion ranging from 0.05 to 15 parts by mass relative to 100 parts by mass of the curable composition, and used in a proportion ranging from 0.1 to 10 parts by mass. For the better.

The curable composition of the present invention may be contained depending on the application. There are various organic solvents. Examples of the organic solvent used herein include ketone compounds such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; cyclic ether compounds such as tetrahydrofuran (THF) and dioxane; methyl acetate and acetic acid Ester compounds such as ethyl acetate and butyl acetate; aromatic compounds such as toluene and xylene; alcohol compounds such as carbitol, sirolimus, methanol, isopropanol, butanol, and propylene glycol monomethyl ether. These can be used alone or in combination of two or more.

The curable composition of the present invention may further contain various additives such as an ultraviolet absorber, an antioxidant, a silicon-based additive, a fluorine-based additive, a rheology control agent, a defoaming agent, an antistatic agent, and an anti-fogging agent.

Examples of the ultraviolet absorber include 2- [4-{(2-hydroxy-3-dodecyloxypropyl) oxy} -2-hydroxyphenyl] -4,6-bis (2,4 -Dimethylphenyl) -1,3,5-Mitsui, 2- [4-{(2-hydroxy-3-tridecyloxypropyl) oxy} -2-hydroxyphenyl] -4 , 6-bis (2,4-dimethylphenyl) -1,3,5-Mitsui etc. Mitsui derivatives, 2- (2 '- xanthene-carboxy-5' - methylphenyl) benzotriazole, 2- (2 '-o- nitro-benzyloxy-5' - methylphenyl) benzotriazole, 2- xanthene-carboxy-4-dodecyloxy benzophenone Ketones, 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone and the like.

Examples of the antioxidant include hindered phenol-based antioxidants, hindered amine-based antioxidants, organic sulfur-based antioxidants, and phosphate-based antioxidants. These can be used individually or in combination of two or more kinds.

Examples of the silicon-based additive include dimethyl polysiloxane, methylphenyl polysiloxane, cyclic dimethyl polysiloxane, methyl hydrogen polysiloxane, and polyether-modified dimethyl. Polysiloxane copolymer, polyester modified dimethyl polysiloxane copolymer, fluorine modified dimethyl polysiloxane copolymer Complexes, amine-modified dimethyl polysiloxane copolymers, such as polyorganosiloxanes with alkyl or phenyl groups, polyether-modified polydimethylsiloxanes with acrylyl groups, and polyesters Modified polydimethylsiloxane with acrylyl group. These can be used individually or in combination of two or more kinds.

Examples of the fluorine-based additive system include the "Megafac" series of DIC Corporation. These can be used individually or in combination of two or more kinds.

The amounts of the aforementioned various additives are preferably in a range in which the effects of excellent surface hardness and flexibility of the hardened material achieved by the invention of the present invention will be sufficiently exhibited, and specifically, 100 parts by mass of the hardenable composition, It is preferably used in the range of 0.01 to 40 parts by mass.

Since the hardenable composition of the present invention has the characteristics of high hardness and excellent flexibility of the surface of the hardened material, it can be suitably used as a coating for a surface protective film for protecting the surface of a molded article, a display member, or the like. Specifically, a protective film for protecting the surface of a substrate can be formed by applying the curable composition of the present invention to various substrates, and heating or irradiating the active energy rays to harden the substrate. In this case, the hardenable composition of the present invention may be directly applied to various plastic molded products, such as mobile phones, electronic products, and bumpers of automobiles, etc., and then hardened and used, or may be applied to plastic films. The hardened material is used as a surface protection film.

Examples of the plastic film include polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triethyl cellulose resin, ABS resin, AS resin, and resin. Borneene resin, cyclic olefin, polyimide resin, etc. Plastic film or plastic sheet.

Among the above plastic films, triethyl cellulose cellulose film (hereinafter referred to as "TAC film") is widely used as a base film for display members. Generally speaking, the thickness of the TAC film is 40 to 100 μm, so even if a surface protective layer made of a resin material is provided, it is difficult to sufficiently improve the surface hardness, and it is easy to cause the hardening and shrinkage of the resin material. curly. In contrast, the resin composition of the present invention has the characteristics of small hardening shrinkage and very high surface hardness of the hardened coating film. Therefore, even when a triethyl cellulose film is used as a substrate, it exhibits sufficient characteristics. The surface hardness can also reduce the occurrence of curl caused by hardening shrinkage. When a TAC film is used as a substrate, the coating amount when the curable composition of the present invention is applied is performed such that the film thickness after drying is in the range of 1 to 20 μm, and preferably in the range of 3 to 10 μm. Coating is preferred. Examples of the coating method at this time include rod coater coating, MEYER rod coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexible printing, and screen printing.

Among the above plastic films, polyester films typified by polyethylene terephthalate are inexpensive and easy to process, so they are used in various applications such as touch panel displays in the same way as TAC films. Its thickness is generally about 100 to 300 μm, but it is very soft, and it is still difficult to sufficiently improve the surface hardness even when a hard coat layer is provided. When a polyester film is used as the substrate, the coating amount when the curable composition of the present invention is applied is in a range of 1 to 20 μm, and preferably 3 to 10 μm, depending on the application. Range way to apply Better cloth. Examples of the coating method at this time include rod coater coating, MEYER rod coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexible printing, and screen printing.

Among the above plastic films, the polymethyl methacrylate film is generally about 100 to 2,000 μm thick and is relatively strong. Therefore, it is a film suitable for applications requiring high surface hardness, such as front panel applications of liquid crystal displays. In the case of using a polymethyl methacrylate film as a substrate, the coating amount when the curable composition of the present invention is applied is preferably a film thickness in the range of 1 to 20 μm after drying depending on the application, and preferably Coating is preferably performed in a range of 3 to 10 μm. Examples of the coating method at this time include rod coater coating, MEYER rod coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexible printing, and screen printing.

When the curable composition of the present invention is irradiated with an active energy ray to harden it, examples of the active energy ray include ultraviolet rays and electron rays. In the case of curing by ultraviolet rays, an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, and a metal halide lamp is used as a light source, and the light amount and the arrangement of the light sources are adjusted as necessary. When using a high-pressure mercury lamp, it is usually better to harden a lamp with a light amount in the range of 80 to 160 W / cm in a range of 5 to 50 m / min. On the other hand, when hardening by an electron beam, an electron beam acceleration device having an acceleration voltage in the range of 10 to 300 kV is usually used. The hardening is preferably performed at a transport speed of 5 to 50 m / min.

The present invention will be described in more detail with specific synthesis examples and examples below, but the present invention is not limited to these examples.

In the examples of this case, the number average molecular weight (Mn) and weight average molecular weight (Mw) were measured using a gel permeation chromatography (GPC) under the following conditions.

Measuring device; HLC-8220 manufactured by TOSOH Co., Ltd.

Column; TOSOH Co., Ltd. Protective Column TSK-GUARDCOLUMN SuperHZ-L

+ TOSOH TSKgel Supe rHZM-M × 4

Detector; RI (Differential Refractometer)

Data processing: Multi-stage GPC-8020modelII made by TOSOH Co., Ltd.

Measurement conditions: column temperature 40 ℃

Solvent tetrahydrofuran

Flow rate 0.35ml / min

Standard; polystyrene

Sample: 0.2 wt% tetrahydrofuran solution converted into solid content of resin, filtered by micro filter (100 μl)

The content of each component in the neopentaerythritol poly (meth) acrylate composition (B) was calculated from the area ratio of the gas chromatography method measured under the following conditions.

Measuring device; GC-2010, manufactured by Shimadzu Corporation

Column; ZB-5 (liquid phase film thickness 0.25μm, length 30m, inner diameter 0.25mm)

Detector; FID (Hydrogen Flame Ionization Detector), 300 ° C

Measurement conditions: gasification chamber 300 ° C, 105kPa

Hold at 50 ° C for 5 minutes, heat up at 10 ° C / min, and hold at 300 ° C for 15 minutes

Example 1 Production of hardenable composition (1)

A reaction vessel equipped with a stirring rod, an air introduction ring, a condenser, and a thermometer was charged with neopentaerythritol poly (meth) acrylate composition (B) [hydroxy value 175 mgKOH / g, neopentaerythritol diacrylate Content 7%, neopentaerythritol triacrylate content 76%, neopentaerythritol tetraacrylate content 17%] 346.5 parts by mass, 1.6 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of p-methoxyphenol, zinc octoate 0.1 mass part, and it heated up until the internal temperature became 50 degreeC. Next, 179.5 parts by mass of a biuret modified body of hexamethylene diisocyanate (isocyanate group content 23.4% by mass) was added in portions at a temperature not exceeding 80 ° C. While blowing in air and reacting at 80 ° C for 3 hours, after confirming the disappearance of the isocyanate group, 131.5 parts by mass of butyl acetate was added to obtain a urethane (meth) acrylate oligomer (X) and 657.5 parts by mass of the curable composition (1) (80% by mass of solid content) of neopentaerythritol tetraacrylate. The number average molecular weight (Mn), weight average molecular weight (Mw) of the urethane (meth) acrylate oligomer (X) contained in the curable composition (1), and the amount of the raw material to be reacted Calculated acryl group content and urethane (meth) acrylic acid relative to the total mass of the urethane (meth) acrylate oligomer (X) and neopentaerythritol tetraacrylate The content of the ester oligomer (X) is shown in Table 1.

Examples 2 to 5 Production of hardenable compositions (2) to (5)

Except for changing the composition of neopentaerythritol poly (meth) acrylate composition (B) used for production and the feed amount of each compound as shown in Table 1 In the same manner as in Production Example 1, the curable compositions (2) to (5) were obtained. The number-average molecular weight (Mn), weight-average molecular weight (Mw) of the urethane (meth) acrylate oligomer (X) contained in these, and propylene calculated from the feed amount of the reaction raw material Urethane (meth) acrylate oligomer based on the total mass of the urethane (meth) acrylate oligomer (X) and neopentaerythritol tetraacrylate ( X) content is shown in Table 1.

Notes to Table 1

[* 1] Composition ratio of neopentyl tetraol poly (meth) acrylate composition (B). "PE2A" means neopentaerythritol di (meth) acrylate.

"PE3A" means neopentaerythritol tri (meth) acrylate.

"PE4A" means neopentaerythritol tetra (meth) acrylate.

[* 2] Refers to the urethane (meth) acrylate oligomerization based on the total mass of the urethane (meth) acrylate oligomer (X) and neopentaerythritol tetraacrylate (X) content.

Comparative Production Example 1 Production of Curable Composition (1 ')

A reaction vessel provided with a stirring rod, an air introduction ring, a condenser, and a thermometer was charged with neopentyl tetraol poly (meth) acrylate composition (B) [hydroxyl value 120 mgKOH / g, neopentyl tetradiol diacrylate content 0%, neopentaerythritol triacrylate content 64%, neopentaerythritol tetraacrylate content 36%] 490.9 parts by mass, 1.6 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of p-methoxyphenol, and 0.1 of zinc octoate The mass is raised until the internal temperature becomes 50 ° C. Next, 102.8 parts by mass of a hexamethylene diisocyanate-trimeric isocyanate-modified body (isocyanate group content 21.8% by mass) was added in portions at a temperature not exceeding 80 ° C. While blowing air and reacting at 80 ° C for 3 hours, after confirming the disappearance of the isocyanate group, 170.9 parts by mass of butyl acetate was added to obtain an urethane (meth) acrylate oligomer (X) and 657.5 parts by mass of the curable composition (1 ′) (80% by mass of solid content) of neopentyl tetraol tetraacrylate. The number-average molecular weight (Mn), weight-average molecular weight (Mw) of the urethane (meth) acrylate oligomer (X) contained in the hardening composition (1 ') are fed from the reaction raw materials. The amount of acryloyl group (meth) acrylic acid based on the total mass of acrylic acid group and the total mass of urethane (meth) acrylate oligomer (X) and neopentaerythritol tetraacrylate The content of the ester oligomer (X) is shown in Table 2.

Comparative Production Example 2 Production of Curable Composition (2 ')

A reaction vessel provided with a stirring rod, an air introduction ring, a condenser, and a thermometer was charged with 179.5 parts by mass of hexamethylene diisocyanate-modified biuret (isocyanate group content: 23.4% by mass), 170.5 parts by mass of butyl acetate, 2.0 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of p-methoxyphenol, and 0.1 parts by mass of zinc octoate were heated until the internal temperature reached 50 ° C. Next, neopentylol poly (meth) acrylate composition (B) was added in portions at a temperature not exceeding 80 ° C. [hydroxyl value 120 mgKOH / g, neopentyl alcohol diacrylate content 0% , Neopentaerythritol triacrylate content 64%, neopentaerythritol tetraacrylate content 36%] 327.3 parts by mass. While blowing in air, the reaction was carried out at 80 ° C for 1 hour. Furthermore, 175.3 g of polyoxypropylene glycol (hydroxyl value 112 mgKOH / g) was added, and it was made to react at 80 degreeC for 3 hours, and the disappearance of an isocyanate group was confirmed, and the urethane-containing (meth) acrylate oligomer (X) was obtained. 852.6 parts by mass of a curable composition (2 ') (80% by mass of solid content) with neopentyltetraol tetraacrylate. The number-average molecular weight (Mn), weight-average molecular weight (Mw) of the urethane (meth) acrylate oligomer (X) contained in the hardening composition (2 ') are fed from the reaction raw materials. The amount of acrylamido group and the amount of urethane (meth) relative to the total mass of urethane (meth) acrylate oligomer (X) and neopentyl tetraol tetraacrylate The content of the acrylate oligomer (X) is shown in Table 2.

Notes to Table 2

[* 1] Composition ratio of neopentyl tetraol poly (meth) acrylate composition (B).

"PE2A" means neopentaerythritol di (meth) acrylate.

"PE3A" means neopentaerythritol tri (meth) acrylate.

"PE4A" means neopentaerythritol tetra (meth) acrylate.

[* 2] Refers to the urethane (meth) acrylate oligomerization based on the total mass of the urethane (meth) acrylate oligomer (X) and neopentaerythritol tetraacrylate (X) content.

Examples 6 to 10, Comparative Examples 1, 2

Using the previously obtained curable compositions (1) to (5), (1 '), and (2'), the active energy ray-curable composition and the test film were adjusted in the following manner. To conduct various evaluation tests. The results are shown in Table 3.

Adjustment of active energy ray hardening composition (1) to (5), (1 ') and (2')

12.5 parts by mass of the previously obtained curable composition, 0.4 parts by mass of 1-hydroxycyclohexylphenyl ketone, and 7.5 parts by mass of methyl ethyl ketone were mixed to adjust the active energy ray-curable composition.

Preparation of test film

The previously obtained active energy ray-curable composition was applied to a polyethylene terephthalate film having a thickness of 125 μm using a rod coater so as to have a dry film thickness of 5 μm, for example. The organic solvent was dried in an oven at 80 ° C. for 1 minute, and then irradiated with ultraviolet rays in an air gas environment using a high-pressure mercury lamp of 80 W / cm so that the accumulated light amount became 250 mJ / cm ^{2 to} prepare a test film.

Pencil hardness test

The pencil hardness of the active energy ray-curable composition surface of the test film was measured in accordance with JIS K5600-5-4.

Steel wool friction test

Using a Gakushin-type friction fastness tester described in JIS K5701-1, steel wool # 0000 was reciprocated 200 times with a load of 1 kg. The haze value of the test film before and after the test was measured using a haze measuring device "Haze Computer HZ-2" made by SUGA Tester Co., Ltd., and the difference was evaluated.

Flexibility test

The flexibility of the test film was evaluated in accordance with JIS K5600-5-1.

Evaluation of sclerotic shrinkage

The test film is cut out to a size of 10cm × 10cm and placed on a horizontal surface. On the surface, the four corners are measured to float from the horizontal plane, and the average value is used for evaluation.

Claims (11)

A hardening composition containing a urethane (meth) acrylate oligomer (X) as an essential component, and the urethane (meth) acrylate oligomer (X) is based on Polyisocyanate compound (A), neopentaerythritol tri (meth) acrylate (b1) having two or more isocyanate groups and biuret structure sites in the molecular structure and an isocyanate group content in the range of 15 to 27% by mass And neopentaerythritol di (meth) acrylate (b3) was obtained as an essential component and the reaction was carried out, and the (meth) acrylfluorenyl content was in the range of 4.0 to 8.5 mmol / g. The curable composition according to claim 1, wherein the polyisocyanate compound (A) is a biuret modified product of an aliphatic diisocyanate monomer. The curable composition according to claim 1, which contains neopentyl tetraol (meth) acrylate (b2) in addition to the urethane (meth) acrylate oligomer (X). The curable composition according to claim 1, wherein the weight average molecular weight (Mw) of the urethane (meth) acrylate oligomer (X) is in a range of 5,000 to 80,000. For example, the hardenable composition of claim 1 is obtained by performing a reaction with neopentyltetraol poly (meth) acrylate composition (B) and the polyisocyanate compound (A) as an essential component. The pentaerythritol poly (meth) acrylate composition (B) contains neopentaerythritol tri (meth) acrylate (b1) and neopentaerythritol di (meth) acrylate (b3) as essential components and The hydroxyl value is in the range of 80 to 180 mgKOH / g. The hardening composition according to claim 5, wherein the neopentaerythritol poly (meth) acrylate composition (B) is in addition to neopentaerythritol tri (meth) acrylate (b1) and neopentaerythritol di Those containing (meth) acrylate (b3) and neopentaerythritol tetra (meth) acrylate (b2) as an essential component. For example, the curable composition of claim 3, in addition to the urethane (meth) acrylate oligomer (X) and neopentyl tetraol (meth) acrylate (b2), Radical polymerizable compound (Y). An active energy ray-curable composition containing a curable composition as claimed in claims 1 to 7 and a photopolymerization initiator. A hardened material obtained by hardening the hardenable composition according to claims 1 to 7. A molded article having a coating film composed of a hardened article according to claim 9. A display member having a coating film composed of a hardened material as claimed in claim 9.