TW201546203A - Curable composition, cured product thereof, molded article, and display member - Google Patents

Abstract

The purpose of the present invention is to provide: a curable composition having both surface hardness and flexibility in a cured product; a cured product thereof; a molded article having a coating film comprising said cured product; and a display member. Specifically, a curable composition is used that contains, as an essential component thereof, urethane (meth) acrylate (X) obtained by reacting, as essential components thereof: a polyisocyanate compound (A) having at least two isocyanate groups and a biuret structural site, in the molecular structure thereof, and having an isocyanate group content of 15-27 mass%; and a pentaerythritol tri(meth) acrylate (b1). The (meth) acryloyl group content of the urethane (meth) acrylate (X) is 4.0-8.5 mmol/g.

Description

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

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

In a portable display device such as a smart phone or a tablet terminal device, a surface protective film made of a thin glass or a plastic film is provided to protect the display surface from scratches. With the thinner and lighter weight of these portable display devices, the development of materials that are thinner and less susceptible to damage on the surface of the display is a lightweight and easy-to-film plastic film compared to glass materials. The expectation is high.

In the plastic film for protecting the film on the surface of the display, for example, a substrate film made of TAC (triethylene glycol) or PET (polyethylene terephthalate) is provided with an ultraviolet curable paint. Hard coater. For the ultraviolet curable coating for the hard coat layer, in addition to requiring the hardened coating film to have a high surface hardness and being hard to be scratched or scratched, it is also required to have a small hardening shrinkage during hardening and no curling deformation, and the obtained plastic film can be used. It is excellent in flexibility and can be used in various properties such as drum winding and storage, which are opposite in surface hardness. Generally, in order to improve the scratch resistance of the hard coat layer, it is possible to improve the polymerizable functional group in the ultraviolet curable coating material. A method of increasing the hardness and increasing the hardness, or a method of thickening a hard coat layer, but the hard coat layer obtained by such a method has a large hardening shrinkage and insufficient flexibility, so that curling deformation easily occurs during hardening. It may be prone to breakage or cracking during drum winding or punching.

As the ultraviolet curable coating material for a hard coat layer, for example, an acrylate compound containing a biuret, propylene glycol, and pentaerythritol triacrylate as a main component of 1,6-hexane diisocyanate is known. The ultraviolet curable composition of the acrylonitrile urethane oligomer obtained by the reaction (refer patent document 1). The coating film composed of the ultraviolet curable composition described above has a high degree of stretch and is excellent in moldability, but has a low surface hardness and insufficient scratch resistance. Further, it is known to use a coating composition for UV curing of a urethane acrylate oligomer obtained by reacting pentaerythritol triacrylate with a trimer isocyanate of 1,6-hexamethylene diisocyanate. (Refer to Patent Document 2). The coating film composed of the coating composition for UV curing described above has high surface hardness and excellent scratch resistance, but has low flexibility and cannot meet the recent market demand.

[Previous Technical Literature] [Patent Literature]

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

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

Therefore, the object of the present invention is to provide a hardenable composition which is excellent in both surface hardness and flexibility of a cured product and A cured product, a molded article having a coating film containing the cured product, and a display member.

As a result of intensive studies to solve the above problems, the present inventors have found a curable composition containing a urethane (meth) acrylate oligomer as an essential component, and the urethane is a urethane. The (meth) acrylate oligomer is a polyisocyanate compound having a ratio of two or more isocyanate groups and biuret structures in a molecular structure and having an isocyanate group content of 15 to 27% by mass, and pentaerythritol. Trimethyl (meth) acrylate is obtained by reacting as an essential component, and the (meth) acrylonitrile group content is in the range of 4.0 to 8.5 mmol/g, and the curable composition is a hardened coating film having a high surface hardness and thus is resistant to scratches. It is excellent, and has high flexibility, and thus the present invention has been completed.

That is, the present invention relates to a curable composition containing a urethane (meth) acrylate oligomer (X) as an essential component, the urethane (meth) acrylate oligomer (X) is a polyisocyanate compound (A) having a ratio of two or more isocyanate groups and biuret structures in a molecular structure and an isocyanate group content of 15 to 27% by mass, and pentaerythritol tris(methyl) The acrylate (b1) is obtained by reacting as an essential component, and the (meth) acrylonitrile group content 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 curable composition and a photopolymerization initiator.

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

The present invention is further directed to a molded article having a coating film composed of the above-mentioned cured product.

The present invention is further directed to a display member having a coating film composed of the above-described cured product.

According to the present invention, it is possible to provide a curable composition excellent in both surface hardness and flexibility of a cured product, a cured product thereof, a molded article having a coating film composed of the cured product, and a display member.

[Formation of the Invention]

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

The urethane (meth) acrylate oligomer (X) is required to have a polyisocyanate compound (A) having a biuret structure in a molecular structure and an isocyanate group content of 15 to 27% by mass. As a raw material, it becomes a molecular skeleton with high toughness and flexibility. Further, by having a propylene sulfhydryl group content of 4.0 to 8.5 mmol/g, a crosslinked structure having a moderate density can be obtained at the time of hardening, and surface hardness can be formed. A hardened coating film which is excellent both in 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 biuret structural sites in a molecular structure. The polyisocyanate compound is, for example, a diisocyanate monomer produced by a method in which a diisocyanate monomer (a1) and a biuretizing agent (a2) are reacted at a temperature of 70 to 200 ° C. a biuret modified body or the like.

The diisocyanate monomer (a1) may, for example, be butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4. An aliphatic diisocyanate monomer such as trimethylhexamethylene diisocyanate, benzoyl diisocyanate or m-tetramethylxylylene diisocyanate; cyclohexane-1,4-diisocyanate , isophorone diisocyanate, leucine diisocyanate, dicyclohexylmethane-4,4 ' -diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane, methylcyclohexane diisocyanate, iso-Asia An alicyclic diisocyanate monomer such as propyl dicyclohexyl-4,4 ' -diisocyanate or norbornane diisocyanate; 1,5-anthranyl diisocyanate, 4,4 ' -diphenylmethane diisocyanate 4,4 ' -diphenyldimethylmethane diisocyanate, 4,4 ' -dibenzyl diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3 -phenylene diisocyanate, 1,4-phenylene diisocyanate, methylphenyl diisocyanate, benzoyl diisocyanate, tetramethyl extension Dimethyl diisocyanate, etc. The aromatic diisocyanate monomers. These may be used alone or in combination of two or more. Among them, the above-mentioned aliphatic diisocyanate monomer or alicyclic diisocyanate monomer is preferred because the obtained urethane (meth) acrylate oligomer (X) is more excellent in flexibility. The aliphatic diisocyanate monomer is more preferred.

The diuretating agent (a2) may, for example, be a monovalent tertiary alcohol such as water or t-butanol, a monoamine compound such as formic acid, hydrogen sulfide or methylamine, or a methylenediamine. a diamine compound such as diphenylmethanediamine or the like. These may be used alone or in combination of two or more.

The reaction of the diisocyanate monomer (a1) with the biuretizing agent (a2) may also be carried out in an organic solvent. The organic solvent used herein may, for example, be ethylene glycol monomethyl ether acetate or ethylene. Alcohol monoethyl ether acetate, ethylene glycol diacetate, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol diacetate, An ether solvent such as dipropylene glycol dimethyl ether; an alkyl phosphate compound such as trimethyl phosphate, triethyl phosphate, tripropyl phosphate or tributyl phosphate. These may be used alone or in combination of two or more.

The content of the isocyanate group of the polyisocyanate compound (A) is 15 by obtaining a urethane (meth) acrylate oligomer (X) having a tough, highly flexible molecular skeleton. The range of ~27% by mass is more preferably in the range of 20 to 25% by mass.

The urethane (meth) acrylate oligomer (X) of the present invention is a polyisocyanate compound (A) having an isocyanate group content of 15 to 27% by mass, and pentaerythritol tris(methyl) The acrylate (b1) is obtained as an essential component by carrying out a reaction.

The reaction of the polyisocyanate compound (A) with the neopentyl alcohol tris(meth)acrylate (b1) is, for example, in the presence of a urethane catalyst such as tin octylate or zinc octylate. At 40~120°C The temperature range allows the reaction to proceed.

The reaction ratio of the above polyisocyanate compound (A) to the aforementioned neopentyl alcohol tri(meth)acrylate (b1) is easily obtained by the obtained urethane (meth) acrylate oligomer (X) ( The methyl group propylene sulfhydryl group content is controlled within the desired range, and the number of moles of the isocyanate group in the polyisocyanate compound (A) and the hydroxyl group in the pentaerythritol tri(meth) acrylate (b1) The molar ratio [(NCO)/(OH)] is preferably in the 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 combination with the above polyisocyanate compound (A) and the neopentyl alcohol tri(meth) acrylate (b1). The polyisocyanate compound (A') other than the polyisocyanate compound (A) or the other hydroxyl group-containing compound (B') other than the neopentyl alcohol tri(meth)acrylate (b1).

The other polyisocyanate compound (A') may, for example, be various diisocyanate monomers listed as raw materials of the polyisocyanate compound (A), or such trimer isocyanate modified products, and modified with an adduct. Body and so on.

When the polyisocyanate compound (A) and the other polyisocyanate compound (A') are used in combination, the effect of both the surface hardness and the flexibility of the cured product obtained by the present invention is sufficiently exhibited, both of which are In the total of 100 parts by mass, the polyisocyanate compound (A) is preferably 50 parts by mass or more, more preferably 85 parts by mass or more.

The other hydroxyl group-containing compound (B') may, for example, be hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate or hydroxybutyl ( Methyl) acrylate, glycerol mono(meth) acrylate, glycerol di(meth) acrylate, trimethylolpropane mono (meth) acrylate, trimethylolpropane bis (methyl) An aliphatic (meth) acrylate compound such as acrylate, pentaerythritol di(meth) acrylate, dipentaerythritol penta (meth) acrylate or the like; 4-hydroxyphenyl (meth) acrylate , β-hydroxyphenylethyl (meth)acrylate, 4-hydroxyphenethyl (meth)acrylate, 1-phenyl-2-hydroxyethyl (meth)acrylate, 3-hydroxy-(meth)acrylate- An aromatic (meth) acrylate compound such as 4-ethenyl phenyl ester or 2-hydroxy-3-phenoxypropyl (meth) acrylate: polyoxyethylene glycol or polyoxypropylene glycol Polyoxyalkylene glycol and the like. These may be used alone or in combination of two or more. Further, in addition, the effect of the surface hardness and the flexibility of the cured product achieved by the present invention is excellent, and the aliphatic (meth) acrylate compound is preferably used, and flexibility is obtained. The more excellent hard coat film is particularly preferably the above neopentyl alcohol di(meth)acrylate (b3).

When the neopentyl alcohol tri(meth)acrylate (b1) and the other hydroxyl group-containing compound (B') are used in combination, the effect of both surface hardness and flexibility in the cured product obtained by the present invention can be sufficiently obtained. In general, it is preferable that the neopentyltetraol tri(meth)acrylate (b1) is 75 mol or more, and more preferably 85 mol or more.

When the other polyisocyanate compound (A') or other hydroxyl group-containing compound (B') is used in combination, the reaction ratio of each raw material in the case of producing the urethane (meth)acrylate oligomer (X) is contained. The ratio of the total number of moles of the isocyanate group of the polyisocyanate compound component to the total number of moles of the hydroxyl group contained in the hydroxyl group-containing compound component [(NCO)/(OH)] is The range of 1.0:0.95~1.0:1.05 is better.

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

Further, in the present invention, the acrylamide group content of the urethane (meth) acrylate oligomer (X) is a value calculated from the feed amount of the reaction raw material, specifically, an amine group. The number of moles of (meth)acryl fluorenyl group contained in the total raw material of the formate (meth) acrylate oligomer (X) divided by the total mass of the total raw materials.

In addition, the weight average molecular weight (Mw) of the urethane (meth) acrylate oligomer (X) is excellent in curability, and is excellent in both surface hardness and flexibility. The range is preferably between 5,000 and 80,000, and the range of 7,000 to 50,000 is better.

Further, in the invention of the present invention, the weight average molecular weight (Mw) is a value measured by gel permeation chromatography (GPC) according to the following conditions.

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

Pipe column; TSK-GUARDCOLUMN made by TOSOH Co., Ltd. TSKgel SuperHZM-M×4 made by SuperHZ-L+TOSOH Co., Ltd.

Detector; RI (differential refractometer)

Data Processing: TOSOH Co., Ltd. Multi-stage GPC-80 20modelII

Measurement conditions: column temperature 40 ° C

Solvent tetrahydrofuran

Flow rate 0.35ml / min

Standard; polystyrene

Sample; a tetrahydrofuran solution converted to a resin solid content of 0.2% by weight in a microfilter (100 μl)

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

As a particularly preferable one of the other radical polymerizable compounds, pentaerythritol tetra(meth)acrylate (b2) is mentioned. When the curable composition of the present invention contains pentaerythritol tetra(meth)acrylate (b2), a cured coating film having a higher surface hardness can be obtained. At this time, the ratio of the aforementioned urethane (meth) acrylate oligomer (X) to pentaerythritol tetra (meth) acrylate (b2) is obtained by the surface hardness and flexibility. The content of the urethane (meth) acrylate oligomer (X) in the total amount of the hardened coating film which is excellent in both of them is preferably in the range of 50 to 99% by mass. It is preferably in the range of 65 to 90% by mass.

Further, when the curable composition of the present invention contains pentaerythritol tetra(meth)acrylate (b2), it is contained in the urethane (meth)acrylate oligomer (X). The raw material of the pentaerythritol tri(meth)acrylate (b1) used in the production step may also use neopentyl alcohol tris(meth)acrylate (b1) as an essential component and contain pentaerythritol. A neopentyl alcohol poly(meth) acrylate composition (B) of tetra (meth) acrylate (b2) or pentaerythritol di(meth) acrylate (b3).

The content of each component in the neopentyl alcohol poly(meth) acrylate composition (B) is determined by the (meth) acrylonitrile of the urethane (meth) acrylate oligomer (X). The basis content is adjusted to a range of 4.0 to 8.5 mmol/g. In the neopentyl alcohol poly(meth) acrylate composition (B), the neopentyl alcohol tri(meth) acrylate (b1) is easily used. The content is in the range of 50 to 85%, and the content of the neopentyltetrakis(meth)acrylate (b2) is preferably in the range of 10 to 50%.

The content of each component in the pentaerythritol 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; Shimadzu Corporation CO., Ltd. GC-2010

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

Detector; FID (hydrogen ionization type detector), 300 ° C

Measurement conditions: gasification chamber 300 ° C, 105 kPa

50 ° C for 5 minutes, 10 ° C / min for temperature, 300 ° C for 15 minutes

Further, the hydroxyl value of the neopentyl alcohol poly(meth) acrylate composition (B) is derived from the (meth) acrylonitrile of the urethane (meth) acrylate oligomer (X). The range in which the basis content is adjusted to 4.0 to 8.5 mmol/g is preferably in the range of 80 to 180 mgKOH/g, more preferably in the range of 100 to 170.

Further, the urethane (meth) acrylate oligomer (X) and the radical polymerizable compound (Y) other than the neopentyltetrakis(meth) acrylate (b2) may be, for example, For example, 2-hydroxyethyl ( Methyl) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate , t-butyl (meth) acrylate, glycidyl (meth) acrylate, propylene sulfenyl porphyrin, N-vinyl pyrrolidone, tetrahydrofurfuryl acrylate, cyclohexyl (meth) acrylate Ester, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (methyl) Acrylate, hexadecyl (meth) acrylate, stearyl methacrylate, 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, nonyl phenol (meth) acrylate, epoxy Ethyl modified nonylphenol (methyl) propylene Acid ester, propylene oxide modified nonylphenol (meth) acrylate, methoxy diethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, methoxy propylene glycol (Meth)acrylate, 2-(methyl)propenyloxyethyl-2-hydroxypropyl phthalate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (Methyl) propylene decyloxyethyl decanoate, 2-(methyl) propylene hydroxy propyl hydroxy phthalate, 2-(methyl) propylene methoxy propyl hexahydro hydrazine Acid hydrogen ester, 2-(methyl)propenyloxypropyl tetrahydrofurfurate, dimethylaminoethyl (meth) acrylate, trifluoroethyl (meth) acrylate, four Fluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropropyl (meth) acrylate, octafluoropropyl (meth) acrylate, adamantyl mono (methyl) a single (meth) acrylate such as acrylate; Butanediol di(meth)acrylate, hexanediol di(meth)acrylate, ethoxylated hexanediol di(meth)acrylate, propoxylated hexanediol di(meth)acrylic acid Ester, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethoxylate Di(meth)acrylate such as neopentyl glycol di(meth)acrylate, hydroxytrimethylacetic acid neopentyl glycol di(meth)acrylate; trimethylolpropane tri(meth)acrylic acid Ester, ethoxylated trimethylolpropane tri(meth) acrylate, propoxylated trimethylolpropane tri(meth) acrylate, gin-2-hydroxyethyl trimeric isocyanate tri(methyl) Tris(meth)acrylate such as acrylate, glycerol tri(meth)acrylate, neopentyl alcohol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, di- Trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(methyl) Acrylate, dipentaerythritol Penta(meth)acrylate, di-trimethylolpropane penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, di-trimethylolpropane hexa(meth)acrylate And a (meth) acrylate having a tetrafunctional or higher functional group; and a (meth) acrylate having a part of the above various polyfunctional (meth) acrylates substituted with an alkyl group or ε-caprolactone. These may be used alone or in combination of two or more.

The curable composition of the present invention contains the neopentyltetrakis(meth)acrylate (b2), or the aforementioned, in addition to the urethane (meth)acrylate oligomer (X). Other radical polymerizable compounds In the case of (Y), the above-mentioned urethane (methyl group) of the total of the compound containing a radical polymerizable group is obtained from the cured coating film which is excellent in both surface hardness and flexibility. The content of the acrylate oligomer (X) is preferably in the range of 20 to 80% by mass, preferably in the range of 30 to 70% by mass.

Further, the curable composition of the present invention contains the above neopentyltetrakis(meth)acrylate (b2) in addition to the urethane (meth)acrylate oligomer (X). In the case of both the other radical polymerizable compound (Y), the urethane (meth) acrylate oligomer (X) and the aforementioned new one with respect to the total amount of the radical polymerizable group-containing compound The total content of pentaerythritol tetra(meth)acrylate (b2) is preferably in the range of 10 to 80% by mass, and preferably in the range of 25 to 75% by mass.

The curable composition of the present invention can be cured by any of methods such as hardening by heating or hardening by irradiation with an active energy ray. In the case where it is hardened by irradiation with an active energy ray, 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 ' -bisdiethylaminobenzophenone, 4,4 ' -dichlorobenzophenone, Michler's ketone, 3,3 ' ,4,4 ' -tetra (t-butyl) Various benzophenones such as peroxycarbonyl)benzophenone; Ketone, 9-oxosulfur 2-methyl 9-oxosulfur 2-chloro 9-oxosulfur 2,4-diethyl 9-oxosulfur Wait for Ketone, 9-oxosulfur ; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and other oxalate ethers; benzyl, diethyl ketone and the like α-diketone; a sulfide of methyl methyl carbamide, p-tolyl disulfide, or the like; a variety of benzoic acid such as 4-dimethylamino benzoic acid, 4-dimethylamino benzoic acid ethyl; 3 ' -carbonyl-bis(7-diethylamino)coumarin, 1-hydroxycyclohexyl phenyl ketone, 2,2 ' -dimethoxy-1,2-diphenylethane-1- Ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinepropan-1-one, 2-benzyl-2-dimethylamino-1-(4-flavor Phenylphenyl)-butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide , bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1 -propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-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, methyl o-benzylidene benzoate, 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-tripper, 2,4-bis-trichloromethyl-6-(4-ethoxyl phenyl-S-tripa, 2,4-bis-trichloromethyl-6-(3-bromo-4-ethoxy)phenyl-S-tripholed, 2-t-butylhydrazine, 2-pentyl hydrazine, β-chloropurine, and the like. These systems may be used alone or in combination of two or more.

Among these, by using 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy) Phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 9-oxosulfur And 9-oxosulfur Derivative, 2,2 ' -dimethoxy-1,2-diphenylethane-1-one, 2,4,6-trimethylbenzhydryldiphenylphosphine oxide, double (2 ,4,6-trimethylbenzylidene)phenylphosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-sodium phthalate-1-propanone, 2-benzyl One or a mixture of two or more of the group of 2--2-aminoamino-1-(4-morpholinylphenyl)-butan-1-one, because of a wider range of wavelengths Light shows activity and hardenability is improved, so it is preferred.

Commercial products of such photopolymerization initiators include, for example, "Irgacure 184", "Irgacure 149", "Irgacure 261", "Irgacure 369", "Irgacure 500", "Irgacure 651", "Irgacure", manufactured by BASF Corporation. 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. Chemical company "Vicure 10", "Vicure 55"; AKZO company "TRIGONAL P1"; Sandoz company "Sandoray 1000"; APJOHN company "DEAP"; Ward Blenkinsop company "Quanta cure PDO", "Quanta cure ITX ", "Quanta cure EPD" and so on.

The amount of the photopolymerization initiator to be added is preferably from 0.05 to 15 parts by mass based on 100 parts by mass of the curable composition, and is used in a ratio of 0.1 to 10 parts by mass. For better.

The curable composition of the present invention may also be included in accordance with the use. There are various organic solvents. The organic solvent to be used herein may, for example, be a ketone compound such as acetone, methyl ethyl ketone or methyl isobutyl ketone; a cyclic ether compound such as tetrahydrofuran (THF) or dioxane; methyl acetate or acetic acid; An ester compound such as ethyl ester or butyl acetate; an aromatic compound such as toluene or xylene; an alcohol compound such as carbitol, celecoxime, methanol, isopropanol, butanol or propylene glycol monomethyl ether. These may 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 lanthanide additive, a fluorine-based additive, a rheology control agent, a defoaming agent, an antistatic agent, and an antifogging agent.

The above ultraviolet absorber may, for example, be 2-[4-{(2-hydroxy-3-dodecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis (2,4) -Dimethylphenyl)-1,3,5-tripper, 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 Ketone, 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone, and the like.

Examples of the antioxidant include a hindered phenol-based antioxidant, a hindered amine-based antioxidant, an organic sulfur-based antioxidant, and a phosphate-based antioxidant. These may be used alone or in combination of two or more.

The lanthanide additive may, for example, be dimethyl polyoxy siloxane, methyl phenyl polyoxy siloxane, cyclic dimethyl polyoxy siloxane, methyl hydrogen polyoxy siloxane, polyether modified dimethyl group. Polyoxyalkylene copolymer, polyester modified dimethyl polyoxyalkylene copolymer, fluorine modified dimethyl polyoxyalkylene copolymer a complex, amine-modified dimethyl polyoxyalkylene copolymer such as a polyorganosiloxane having an alkyl group or a phenyl group, a polyether-modified polydimethyl siloxane having an acryl fluorenyl group, and a polyester A modified polydimethyl methoxy alkane having an acrylonitrile group or the like. These may be used alone or in combination of two or more.

The fluorine-based additive may, for example, be a "Megafac" series of DIC Corporation. These may be used alone or in combination of two or more.

The amount of use of the various additives described above is preferably in a range in which the surface hardness and the flexibility of the cured product achieved by the present invention are sufficiently exhibited, and specifically, 100 parts by mass of the curable composition. It is preferably used in the range of 0.01 to 40 parts by mass.

Since the curable composition of the present invention has a feature that the surface hardness of the cured product is high and the flexibility is excellent, it can be suitably used as a coating material for a surface protective film for protecting the surface of a molded article or a display member. Specifically, the protective film of the surface of the protective substrate can be formed by applying the curable composition of the present invention to various substrates and heating or irradiating the active energy ray to cure it. In this case, the curable composition of the present invention may be directly applied to various plastic molded articles, such as mobile phones, electric household products, automobile bumpers, etc., and used for hardening or coating on plastic films. The hardened material is used as a surface protective film.

The plastic film may, for example, be polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetone cellulose resin, ABS resin, AS resin, or lower. a borneol-based resin, a cyclic olefin, a polyimide resin, or the like Plastic film or plastic sheet.

Among the above plastic films, a triacetyl cellulose film (hereinafter abbreviated as "TAC film") is widely used as a base film for a display member. In general, since the thickness of the TAC film is 40 to 100 μm, even if a surface protective layer made of a resin material is provided, it is difficult to sufficiently increase the surface hardness, and the curing of the resin material is likely to occur. curly. On the other hand, the resin composition of the present invention has a characteristic that the curing shrinkage is small and the surface hardness of the cured coating film is also extremely high. Therefore, even when the triethylene fluorene cellulose film is used as a substrate, it is sufficiently exhibited. The surface hardness can also reduce the occurrence of curl caused by hardening shrinkage. When the TAC film is used as a substrate, the coating amount when the curable composition of the present invention is applied is such that the film thickness after drying is in the range of 1 to 20 μm, preferably 3 to 10 μm. Coating is preferred. The coating method at this time may, for example, be a bar coater coating, a MEYER bar coating, an air knife coating, a gravure coating, a reverse gravure coating, an offset printing, a flexographic printing, a screen printing method, or the like.

Among the above-mentioned plastic films, polyester films typified by polyethylene terephthalate are used in various applications such as touch panel displays in the same manner as TAC films because they are inexpensive and easy to process. The thickness is generally about 100 to 300 μm, but it is very soft, and it is difficult to sufficiently increase the surface hardness even in the case where a hard coat layer is provided. When the polyester film is used as the substrate, the coating amount when the curable composition of the present invention is applied is such that the film thickness after drying is in the range of 1 to 20 μm, preferably 3 to 10 μm, depending on the application. Scope of the coating Cloth is better. The coating method at this time may, for example, be a bar coater coating, a MEYER bar coating, an air knife coating, a gravure coating, a reverse gravure coating, an offset printing, a flexographic printing, a screen printing method, or the like.

Among the above-mentioned plastic films, since the polymethyl methacrylate film is generally strong in thickness of about 100 to 2,000 μm, it is a film suitable for use in applications requiring high surface hardness, such as a front panel use of a liquid crystal display. When a polymethyl methacrylate film is used as the substrate, the coating amount in the case of applying the curable composition of the present invention is preferably in the range of 1 to 20 μm, preferably in the range of 1 to 20 μm, depending on the application. It is preferable to carry out coating in a range of 3 to 10 μm. The coating method at this time may, for example, be a bar coater coating, a MEYER bar coating, an air knife coating, a gravure coating, a reverse gravure coating, an offset printing, a flexographic printing, a screen printing method, or the like.

In the case where the curable composition of the present invention is irradiated with an active energy ray to be cured, the active energy ray may, for example, be an ultraviolet ray or an electron ray. In the case where it is hardened by ultraviolet rays, an ultraviolet irradiation device having a xenon lamp, a high pressure mercury lamp, or a metal halide lamp is used as a light source, and the amount of light, the arrangement of the light source, and the like are adjusted as needed. When a high-pressure mercury lamp is used, it is usually preferable to use a lamp having a light amount 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, it is preferable to harden by the electron beam acceleration apparatus which has the acceleration voltage of the range of 10-300 kV in the range of 5-50 m/min.

Hereinafter, the present invention will be described in more detail with reference to specific synthetic examples and examples, but the present invention is not limited to the examples.

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

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

Pipe column; TSK-GUARDCOLUMN made by TOSOH Co., Ltd. TSKgel SuperHZM-M×4 made by SuperHZ-L+TOSOH Co., Ltd.

Detector; RI (differential refractometer)

Data Processing: TOSOH Co., Ltd. Multi-stage GPC-8020modelII

Measurement conditions: column temperature 40 ° C

Solvent tetrahydrofuran

Flow rate 0.35ml / min

Standard; polystyrene

Sample; the resin solid content was converted into a 0.2% by weight tetrahydrofuran solution as a microfilter (100 μl)

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

Measuring device; Shimadzu Corporation CO., Ltd. GC-2010

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

Detector; FID (hydrogen ionization type detector), 300 ° C

Measurement conditions: gasification chamber 300 ° C, 105 kPa

50 ° C for 5 minutes, 10 ° C / min for temperature, 300 ° C for 15 minutes

Example 1 Production of Curable Composition (1)

In a reaction vessel equipped with a stir bar, an air introduction ring, a condenser, and a thermometer, a neopentyl alcohol poly(meth) acrylate composition (B) [hydroxyl price 175 mg KOH/g, neopentyl alcohol diacrylate) was charged. Content 7%, neopentyl alcohol triacrylate content 76%, pentaerythritol tetraacrylate content 17%] 346.5 parts by mass, dibutylhydroxytoluene 1.6 parts by mass, p-methoxyphenol 0.3 parts by mass, zinc octoate 0.1 part by mass, and the temperature was raised until the internal temperature became 50 °C. Next, 179.5 parts by mass of a biuret modified product (isocyanate group content: 23.4% by mass) of hexamethylene diisocyanate was added in portions at a rate not exceeding 80 ° C in the system. While blowing 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 The curable composition (1) (solid content: 80% by mass) of pentaerythritol tetraacrylate was 657.5 parts by mass. The number average molecular weight (Mn), the weight average molecular weight (Mw) of the urethane (meth) acrylate oligomer (X) contained in the curable composition (1), and the amount of the feed from the reaction raw material Calculated methacrylic acid group content, and urethane (meth)acrylic acid relative to the total mass of urethane (meth) acrylate oligomer (X) and neopentyl alcohol tetraacrylate The content of the ester oligomer (X) is shown in Table 1.

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

The composition of the neopentyl alcohol poly(meth)acrylate composition (B) used for the production and the feed amount of each compound were changed 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), the weight average molecular weight (Mw) of the urethane (meth) acrylate oligomer (X) contained in these, and the propylene oxime calculated from the feed amount of the reaction raw material. Base content, and urethane (meth) acrylate oligomer relative to the total mass of urethane (meth) acrylate oligomer (X) and pentaerythritol tetra acrylate ( The content of X) is shown in Table 1.

Notes to Table 1

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

"PE3A" means pentaerythritol tri(meth)acrylate.

"PE4A" means pentaerythritol tetra (meth) acrylate.

[*2] means oligomerization of urethane (meth) acrylate relative to the total mass of urethane (meth) acrylate oligomer (X) and neopentyl alcohol tetraacrylate The content of the substance (X).

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

The neopentyl alcohol poly(meth) acrylate composition (B) is charged in a reaction vessel equipped with a stir bar, an air introduction ring, a condenser, and a thermometer [hydroxyl price 120 mg KOH/g, neopentyl alcohol diacrylate content 0%, neopentyl alcohol triacrylate content 64%, pentaerythritol tetraacrylate content 36%] 490.9 parts by mass, dibutylhydroxytoluene 1.6 parts by mass, p-methoxyphenol 0.3 parts by mass, zinc octoate 0.1 The mass fraction was raised until the temperature in the system became 50 °C. Next, 102.8 parts by mass of a trimer isocyanate modified product (isocyanate group content: 21.8% by mass) of hexamethylene diisocyanate was added in portions at a rate not exceeding 80 ° C in the system. 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 The curable composition (1') (solid content: 80% by mass) of pentaerythritol tetraacrylate was 657.5 parts by mass. 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 feed from the reaction raw material The calculated propylene sulfonate content and the urethane (meth) acrylate relative to the total mass of the urethane (meth) acrylate oligomer (X) and neopentyl alcohol tetraacrylate The content of the ester oligomer (X) is shown in Table 2.

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

In a reaction vessel equipped with a stirring bar, an air introduction ring, a condenser, and a thermometer, a biuret modified product of hexamethylene diisocyanate (isocyanate group content: 23.4% by mass), 179.5 parts by mass, and butyl acetate (170.5 parts by mass) were charged. 2.0 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of p-methoxyphenol, and 0.1 parts by mass of zinc octoate, the temperature was raised until the internal temperature became 50 °C. Next, the neopentyl alcohol poly(meth) acrylate composition (B) is added in portions at a rate not exceeding 80 ° C in the system (hydroxyl price 120 mg KOH/g, neopentyl alcohol diacrylate content 0%) The neopentyl alcohol triacrylate content was 64%, and the neopentyl alcohol tetraacrylate content was 36%] 327.3 parts by mass. Air was blown in while reacted at 80 ° C for 1 hour. Further, 175.3 g of polyoxypropylene glycol (hydroxyl group 112 mgKOH/g) was added, and the mixture was reacted at 80 ° C for 3 hours to confirm the disappearance of the isocyanate group, thereby obtaining an amino group-containing (meth)acrylate oligomer (X). The curable composition (2') (solid content: 80% by mass) of pentaerythritol tetraacrylate was 852.6 parts by mass. The number average molecular weight (Mn), weight average molecular weight (Mw) of the urethane (meth) acrylate oligomer (X) contained in the curable composition (2'), and the feed from the reaction raw material The calculated amount of propylene sulfhydryl group and the urethane (methyl) relative to the total mass of the urethane (meth) acrylate oligomer (X) and pentaerythritol tetraacrylate The content of the acrylate oligomer (X) is shown in Table 2.

Notes to Table 2

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

"PE2A" means pentaerythritol di(meth)acrylate.

"PE3A" means pentaerythritol tri(meth)acrylate.

"PE4A" means pentaerythritol tetra (meth) acrylate.

[*2] means oligomerization of urethane (meth) acrylate relative to the total mass of urethane (meth) acrylate oligomer (X) and neopentyl alcohol tetraacrylate The content of the substance (X).

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 according to the following procedures. , conducting various evaluation tests. The results are shown in Table 3.

Adjustment of active energy ray-curable compositions (1) to (5), (1') and (2')

The active energy ray-curable composition was adjusted by mixing 12.5 parts by mass of the curable composition obtained previously, 0.4 parts by mass of 1-hydroxycyclohexyl phenyl ketone, and 7.5 parts by mass of methyl ethyl ketone.

Test film

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

Pencil hardness test

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

Steel wool friction test

The steel wool #0000 was reciprocated 200 times at a load of 1 kg with a vibration-type friction fastness tester described in JIS K5701-1. The haze value of the test film before and after the test was measured using a haze measuring instrument "Haze Computer HZ-2" manufactured by SUGA Testing Machine Co., Ltd., and evaluated by the difference between the two values.

Flexibility test

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

Assessment of hardening shrinkage

The test film was cut out to a size of 10 cm × 10 cm and placed at a level. On the surface, the four corners were measured from the horizontal plane and evaluated by the average value.

Claims (12)

A curable composition containing a urethane (meth) acrylate oligomer (X) as an essential component, and the urethane (meth) acrylate oligomer (X) is Polyisocyanate compound (A) having a ratio of two or more isocyanate groups and biuret structures in the molecular structure and having an isocyanate group content of 15 to 27% by mass, and pentaerythritol tri(meth)acrylate (b1) The reaction is carried out as an essential component, and the (meth)acrylonitrile group content is in the range of 4.0 to 8.5 mmol/g. The hardenable composition of claim 1, wherein the polyisocyanate compound (A) is a biuret modified body of an aliphatic diisocyanate monomer. The curable composition of claim 1, which further contains pentaerythritol tetra(meth)acrylate (b2) in addition to the urethane (meth)acrylate oligomer (X). The hardenable composition of claim 1, wherein the urethane (meth) acrylate oligomer (X) is the polyisocyanate compound (A), neopentyl alcohol tri(meth) acrylate (b1) and pentaerythritol di(meth)acrylate (b3) are obtained as an essential component to carry out a reaction. The hardenable composition of claim 1, wherein the urethane (meth) acrylate oligomer (X) has a weight average molecular weight (Mw) in the range of 5,000 to 80,000. The curable composition of claim 1, which is obtained by reacting a neopentyl alcohol poly(meth) acrylate composition (B) with the polyisocyanate compound (A) as an essential component, wherein the new The pentaerythritol poly(meth)acrylate composition (B) contains pentaerythritol tri(meth)acrylate (b1) as an essential component and has a hydroxyl value of 80 to 180 mgKOH/g. The sclerosing composition of claim 6, wherein the neopentyl alcohol poly(meth) acrylate composition (B) contains new pentane in addition to pentaerythritol tri(meth) acrylate (b1) Tetrahydrin tetra(meth)acrylate (b2) or pentaerythritol di(meth)acrylate (b3) is an essential component. The curable composition of claim 3, which comprises, in addition to the urethane (meth) acrylate oligomer (X) and pentaerythritol tetra (meth) acrylate (b2), Radical polymerizable compound (Y). An active energy ray-curable composition comprising the curable composition as claimed in claims 1 to 8 and a photopolymerization initiator. A cured product obtained by hardening a hardenable composition as claimed in claims 1 to 8. A molded article having a coating film comprising the cured product of claim 10. A display member having a coating film composed of a cured product of claim 10.