TW201428066A - Composition for hard coating and formed article having a hard coating layer - Google Patents

Abstract

This invention provides a composition for hard coating and formet article, which exhibits the greatest transparency, excoriation resistance, chemicals resistance and anti-blocking property of the used components, as well as controls the curling property to the minimum. The composition for hard coating comprises (A) urethane (meta)acrylate, (B) (meta)acrylate with multiple functional groups, (C) fluorine-containing (meta)acrylate resin, and (D) metal-oxide micro particles.

Description

Hard coating composition and molded article formed with hard coat layer

The present invention relates to a composition for a hard coat layer and a molded article formed with a hard coat layer, and more particularly to a good hardness, durability, chemical resistance, adhesion resistance, transparency, curling property, and adhesion. A composition for coating, and a molded article formed with a hard coat layer.

In the past, various plastics were used in various fields such as home appliances and the automotive industry. In addition to the workability and transparency, the plastic has various advantages such as light weight and low cost, but it has disadvantages such as being soft compared with materials such as glass and easily scratching the surface.

In order to improve these disadvantages, a technique of applying a hard coat material to a plastic surface and improving the scratch resistance of the surface without damaging the transparency and lightness of the plastic is used.

As such a hard coat material, for example, a thermosetting type hard coat material such as a polyfluorene type, an acrylic type, or a melamine type resin can be used. Among them, from the viewpoints of curing time, raw material cost, and the like, an acrylic resin which can be cured by light such as ultraviolet rays is advantageous, and thus has gradually become mainstream.

However, acrylic resins are resistant to conventional polyoxynoxy coatings. Badness such as scratch or abrasion resistance.

Therefore, a method of using a polyfunctional (meth) acrylate having at least two (meth)acrylic groups in a molecule or the like has been proposed (for example, JP-A-9-48934, etc.).

Further, high hardness can be obtained by adding an additive such as an inorganic material. Advanced technical literature

Patent Document 1: Japanese Patent Laid-Open No. Hei 9-48934

Such a polyfunctional (meth) acrylate or the like has a large hardening shrinkage ratio, and particularly has a problem that curling property is remarkable when it is formed into a film shape.

Further, when such a polyfunctional (meth) acrylate or the like is formed into a film shape, polyfunctional (meth) acrylates of adjacent films and the like are caused to each other due to high static frictional resistance and smoothness of the surface. It is easy to adhere and adhere closely, and it becomes a phenomenon that cannot be easily separated, that is, an adhesion phenomenon occurs. In order to prevent such an adhesive from being used as an anti-adhesive agent, cerium oxide powder is generally widely used. However, when the particle size of the cerium oxide is large, the transparency is markedly impaired. On the other hand, when the particle diameter is small, the anti-adhesive effect is not sufficiently exhibited, and there is a so-called trade off relationship. Therefore, it is required to effectively prevent adhesion and maintain high transparency.

The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a hard coat layer which is excellent in the performance of a hard coat layer such as scratch resistance and which has a minimum curling property and is excellent in adhesion resistance and transparency. Resin composition, and molded article.

The present invention encompasses the following inventions.

[1] A composition for a hard coat layer comprising: (A) ethyl urethane (meth) acrylate, (B) polyfunctional (meth) acrylate, (C) fluorine (methyl) a polymer obtained by polymerizing an acrylate, and (D) a metal oxide fine particle.

[2] The composition for a hard coat layer according to [1], wherein the (A) urethane (meth) acrylate is a polymer obtained by the reaction of the following (1) to (3): (1) A compound having a polyether as a main chain, (2) an isocyanate compound, and (3) a hydroxyl group-containing (meth) acrylate compound.

[3] The composition for a hard coat layer according to the above [1], wherein the (A) urethane (meth) acrylate comprises an urethane ethyl ester represented by the following formula (I) (Meth)acrylate oligomer: (R ¹ O-CONH-) _m -R ² -(-NHCO-OR ³ ) _n (I) In the formula (I), R ¹ O- represents a polyether as the main a dehydrogenation residue of a chain compound, -R ² - represents a deisocyanate group residue of an isocyanate compound, and R ³ O- represents a dehydrogenation residue of a hydroxyl group-containing (meth) acrylate compound, and m+n represents 1 to An integer of 50.

[4] The composition for a hard coat layer according to the above [2], wherein the (2) isocyanate compound is a diisocyanate or a polyisocyanate obtained by polycondensing a diisocyanate monomer, or Has an isocyanate group The urethane structure of the alcohol compound and/or the urea structure of the addition amine compound.

[5] The composition for a hard coat layer according to any one of [2], wherein the (3) hydroxyl group-containing (meth) acrylate compound is a hydroxyalkyl (meth) acrylate. Classes, polyol (meth) acrylates.

[6] The composition for a hard coat layer according to any one of the above [1], wherein the compound (1) having a polyether as a main chain is one or more selected from the group consisting of an alkanediol compound and A compound of the group consisting of alkylene oxide addition compounds.

[7] The composition for a hard coat layer according to [6], wherein the compound (1) having a polyether as a main chain is a mono-terminal hydroxyl group-containing polyalkane comprising an alkoxy polyalkylene glycol. An alcohol compound, a compound obtained by subjecting (meth)acrylic acid to an alkylene oxide addition or a monoalkyl (meth)acrylate of a polyalkylene glycol.

The composition for a hard coat layer according to any one of the above aspects, wherein the (C) fluorine-containing (meth)acrylic resin is substituted by (4) fluorine The (meth)acrylic acid alkyl ester monomer, the (5) alkyl (meth)acrylate monomer, and (6) the ether group-substituted alkyl (meth)acrylate monomer are reacted.

[9] The composition for a hard coat layer according to [8], wherein the (5) alkyl (meth)acrylate monomer has a C ₄ to C ₂₀ alkyl group.

[10] The composition for a hard coat layer according to [9] or [10], wherein the (6) ether group-substituted alkyl (meth)acrylate system is represented by the following formula (II); ^{_{monomer: CH 2 = C (R 21}} ) -CO-OA (II) of formula (II) is, R ²¹ represents a hydrogen atom or a methyl group, A represents a C ₁ to C ₂₀ containing alkoxy group of C ₁ to C ₂₀ An alkyl group, a mono- and poly(C ₂ to C ₂₀ alkanediol) group containing a C ₁ to C ₂₀ alkyl group.

The composition for a hard coat layer according to any one of the above aspects, wherein the (B) polyfunctional (meth) acrylate has at least two in one molecule ( A compound of methyl) acrylonitrile.

[12] A molded article obtained by using the cured polymer of the composition for a hard coat layer according to any one of the above [1] to [11] as a hard coat layer.

According to the composition for a hard coat layer of the present invention, a resin composition for a hard coat layer and a molded article can be provided, and the resin composition for a hard coat layer can maximize the performance of a hard coat layer such as scratch resistance and at the same time The curling property is minimized, and the adhesion resistance and transparency are also excellent.

The composition for a hard coat layer of the present invention mainly comprises: (A) ethyl urethane (meth) acrylate, (B) polyfunctional (meth) acrylate, (C) fluorine (meth) acrylate The polymer after the ester polymerization (hereinafter referred to as "fluorine (meth) acrylate resin)" and (D) the metal oxide fine particles.

Thus, (C) the fluorine-containing (meth) acrylate effectively exhibits anti-adhesion. Further, by using (D) metal oxide particles in combination, it is possible to ensure better anti-adhesion. Furthermore, by the action of (A) ethyl urethane (meth) acrylate, Seeking a balance between low curl and high hardness.

In addition, in the present specification, "(meth)acrylic acid" means "methacrylic acid" and/or "acrylic acid", and "(meth)acrylate" means "methacrylic acid ester" and/or "acrylic acid ester".

[(A) ethyl urethane (meth) acrylate]

(A) The ethyl urethane (meth) acrylate may be, for example, one or more hydrophilic groups (for example, a hydroxyl group, a carboxyl group, an ethylene glycol group, a propylene glycol group or the like). For example, a resin obtained by reacting an isocyanate compound, a compound having a polyether as a main chain, and/or a hydroxyl group-containing (meth) acrylate compound can be mentioned. Specifically, the resin obtained by reacting (1) a compound having a polyether as a main chain, (2) an isocyanate compound, and (3) a hydroxyl group-containing (meth) acrylate compound; (1) a polyether A resin obtained by reacting a compound of a main chain and (2) an isocyanate compound; or a resin obtained by reacting (2) an isocyanate compound with (3) a hydroxyl group-containing (meth) acrylate compound.

For example, a compound represented by the following formula (I) is exemplified as the ethyl urethane (meth) acrylate.

(R ¹ O-CONH-) _m -R ² -(-NHCO-OR ³ ) _n (I) (wherein R ¹ O- is a dehydrogenation residue of a compound having a polyether as a main chain, -R ² - a deisocyanate group residue of an isocyanate compound, R ³ O- is a dehydrogenation residue of a hydroxyl group-containing (meth) acrylate compound, and an integer of m + n = 1 to 50).

In the formula (I), m may be 0, but is preferably 1 or more. When m is 2 or more, the plural R ¹ may be the same or two or more. The molecular weight of the substituent constituting R ¹ is suitably from about 100 to about 2,000, preferably from about 100 to about 1,000. This is because if the molecular weight of the polyether chain is too large, the hardness tends to decrease.

The molecular weight of the substituent constituting R ² is suitably from about 150 to 5,000, preferably from about 500 to 3,000. This is because if the molecular weight is too large, the hardness tends to decrease.

n may be 0, but is more suitably an integer greater than 0, that is, 1 or more. When n is 2 or more, the plural R ³ may be the same or two or more.

The molecular weight of the substituent constituting R ³ is suitably from about 150 to 2,000, preferably from about 100 to 1,000. This is because if the molecular weight is too large, the hardness is lowered.

m+n is preferably 2 or more, more preferably 3 or more, 4 or more, 5 or more or 6 or more. Alternatively, m=0 and n=1, m=1 and n=0, m=2 and n=0, m=0 and n=2, m=1 or more, n=1 or more.

(1) A compound having a polyether as a main chain can be exemplified as a main chain A compound having an ether group, preferably a polyether group, and having a hydroxyl group (including a one-terminal hydroxyl group). Here, the hydroxyl group in the ether group is also included. However, it is a compound different from the (3) hydroxyl group-containing (meth) acrylate compound mentioned later. In particular, one or more compounds selected from the group consisting of alkylene glycol compounds and alkylene oxide addition compounds may be mentioned. For example, a polyalkylene glycol, an alkoxy polyalkylene glycol, a (meth) propylene oxypolyalkylene glycol, a reaction of a polyene and a polytetramethylene glycol; The epoxy compound of the oxyethylene ring is reacted with (meth)acrylic acid to obtain a hydroxyl group-containing (meth)acrylic acid derivative, and is obtained by reacting it with an alkylene oxide such as ethylene oxide or propylene oxide. (methyl) a polyether of an acrylonitrile group; an alkylene oxide addition compound of (meth)acrylic acid, and the like.

Among them, polyalkylene glycols, polyalkylene glycols having a hydroxyl group at one terminal, alkoxypolyalkylene glycols, polyethers containing (meth)acrylonitrile groups, and (meth)acrylic acid rings are preferred. The oxyalkylene addition compound is more preferably a mono-terminal hydroxyl group-containing polyalkylene glycol compound or a (meth)acrylic acid alkylene oxide addition compound.

In particular, the mono-terminal hydroxyl group-containing polyalkylene glycol compound is preferably an alkoxy polyalkylene glycol. Further, the (meth)acrylic acid alkylene oxide addition compound is preferably an epoxy group (meth)acrylic acid. An alkane or a polyalkylene glycol mono(meth)acrylate.

The carbon number of the alkylene group and the alkoxy group of the compounds is, for example, about 1 to 6, preferably about 1 to 4, and more preferably about 1 to 3.

Examples of the polyalkylene glycols include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

The alkoxy polyalkylene glycol is, for example, a polyalkylene glycol having an alkoxy group having about 1 to 6 carbon atoms (the number of carbon atoms of the alkyl group is, for example, about 1 to 6), and specifically, it may be mentioned Methoxy polyethylene glycol, methoxy polypropylene glycol, methoxy polytetramethylene glycol. The molecular weight of the alkoxypolyalkylene glycol can be arbitrarily selected, but is preferably from 100 to 2,000.

Examples of the (meth)acryloxypolyalkylene glycols include (meth)acryloxypolyethylene glycol and (meth)acryloxypolypropylene glycol.

The reactant of the polyene and the polytetramethylene glycol may, for example, be a reaction product of polyethylene and polytetramethylene glycol, or a reaction product of methoxypolyethylene and polytetramethylene glycol, (A) a reaction of a propylene oxypolyethylene with a polytetramethylene glycol.

The polyether containing (meth) acrylonitrile group contains a hydroxyl group The acrylate having an alkyl group having a carbon number of about 1 to 6 substituted may, for example, be an ethylene oxide adduct of 2-hydroxyethyl acrylate (for example, an addition molar number of about 1 to 20).

The (meth)acrylic acid alkylene oxide addition compound can be mentioned, for example An alkylene oxide (for example, a carbon number of 2 to 6) represented by ethylene oxide, propylene oxide or butylene oxide is added to (meth)acrylic acid.

(2) Isocyanate compounds are diisocyanates, polyiso Examples of the cyanate esters include polyisocyanates in which a diisocyanate monomer is polycondensed, and a urea structure having an urethane structure of an isocyanate-addition alcohol compound and/or an addition amine compound. Among them, preferred are polyisocyanates, those having an urethane structure and/or a urea structure.

Examples of the diisocyanate include 2,4-toluene diisocyanate. Acid ester, 2,6-toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, (o-, m-, p-) xylene diisocyanate, methylene double (ring) Hexyl isocyanate), trimethylhexamethylene diisocyanate, cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1,4-dimethylene isocyanate, 1,5-naphthalene diisocyanate , norbornane diisocyanate, and the like.

Polyisocyanates and/or polycondensation of diisocyanate monomers The polyisocyanate compound, for example, the polyisocyanate compound may, for example, be isophorone diisocyanate, hexamethylene diisocyanate, norbornane diisocyanate, tolyl diisocyanate, xylylene diisocyanate or diphenylmethane diisocyanate. , trimethylhexamethylene diisocyanate, hydrogenated xylene A bifunctional isocyanate such as a bis-isocyanate or a hydrogenated diphenylmethane diisocyanate; a bifunctional or a trifunctional or isocyanurate isocyanate having a trifunctional or higher isocyanurate. Among them, a polyisocyanate compound having three or more, four or more, five or more, or six or more isocyanate groups in one molecule is preferable, and for example, it contains a chain or a cyclic alkyl group or an aryl group (for example, a carbon number of 6 to The polyisocyanate compound of about 12) is particularly preferably a polyisocyanate compound such as hexamethylene diisocyanate, isophorone diisocyanate or tolyl diisocyanate.

The alcohol compound is, for example, 2 to 4 carbon atoms of 2 to 10 or so Specific examples of the valent alcohols include ethylene glycol, propylene glycol, tetramethylene glycol, glycerin, trimethylolpropane, and neopentyltetraol.

Examples of the amine compound include diaminoethane, diaminopropane, and tetramethylenediamine.

If an alcohol compound or an amine compound is added, the isocyanate can be obtained. The number of functional groups per one molecule of the acid ester compound increases. Further, from the viewpoint of increasing the scratch resistance of the hardened polymer, it is preferred to use the alcohol compound or the amine compound to have a smaller molecular weight per functional group.

(3) a hydroxyl group-containing (meth) acrylate compound and Examples of the compound having a polyether as a main chain of the component (1) include hydroxyalkyl (meth)acrylates, polyol (meth)acrylates, and epoxy resins and carboxylic acids. Derived, etc.

Examples of the (meth)acrylic acid hydroxyalkyl esters (meth) Hydroxyethyl acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyphenoxypropyl (meth)acrylate.

Polyol (meth) acrylates such as carbon number 2 to 10 Specific examples of the 2 to 4 valent polyol (meth) acrylates include glycerol di(meth)acrylate, trimethylolpropane di(meth)acrylate, and di(trishydroxyl). Propane) tris(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate.

Derived from epoxy resin and carboxylic acid, (methyl) (meth)acrylic acid adduct of glycidyl acrylate.

Further, the urethane (meth) acrylate may be used singly or in combination of two or more kinds.

The urethane (meth) acrylate of the present invention, in the formula (I), particularly preferably a combination of (2) an isocyanate compound, (1) a compound having a polyether as a main chain, and/or (3) a hydroxyl group-containing (meth) acrylate compound, wherein (2) The isocyanate compound is a polyisocyanate, and has an urethane structure of an isocyanate-addition alcohol compound; (1) a compound having a polyether as a main chain is a polyalkylene glycol or an alkoxypolyalkylene glycol And a (meth)acrylonitrile-containing polyether or (meth)acrylic acid alkylene oxide addition compound; (3) a hydroxyl group-containing (meth)acrylate compound is a (meth)acrylic acid hydroxyalkyl ester, Polyol (meth) acrylates. Among them, a combination of all of the above (1), (2), and (3) is more preferable.

The urethane (meth) acrylate of the invention is suitable For example, those having a molecular weight of about 500 to 5,000. If the molecular weight is too large, the hardness tends to decrease. Such a urethane (meth) acrylate can be produced, for example, by the method described in JP-A-2000-264936.

(A) in ethyl urethane (meth) acrylate, (1) in a poly The molar ratio of the ether as the main chain compound, for example, the mono-terminal hydroxyl group-containing polyalkylene glycol compound, is preferably lower than the molar ratio of the (3) hydroxyl group-containing (meth) acrylate compound. If the molecular weight of the polyether chain is too large, the hardness at the time of crosslinking polymerization is lowered. The more the number of functional groups of the hydroxyl group-containing (meth) acrylate compound, the higher the hardness at the time of crosslinking polymerization, and the smaller the hardness, the lower the hardness. Therefore, a hardened polymer having a suitable hardness can be obtained by adjusting the number of such functional groups. Specifically, the weight ratio of the above components (1) to (3) may be (1): (2): (3) = 0 to 50: 10 to 70: 20 to 80, preferably 10 to 30: 30 to 50: 20 to 60.

[(B) Polyfunctional (meth) acrylate]

(B) a polyfunctional (meth) acrylate-based (meth) acrylate resin containing two or more functional groups, excluding (A) a (meth) acrylate having an urethane structure as shown in (A) . A compound having two or more (meth) acrylonitrile groups in one molecule is preferred.

For example, pentaerythritol tri(meth)acrylate, neopentyltetrakis(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and dipentaerythritol five (a) Acrylate, dimethylol tricyclodecane di(meth) acrylate, trimethylolpropane (ethylene oxide adduct) tri(meth) acrylate, polyester di(methyl) Acrylate, tetraethylene glycol di(meth)acrylate, glycerol di(meth)acrylate, glycerol ethylene oxide adduct (meth)acrylate, glycerin propylene oxide adduct Acrylate; diacrylate of polyalkylene glycol such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol; polyhydric alcohol and polybasic acid a (meth) acrylate of the compound obtained by condensation, and the above polyisocyanate A compound obtained by reacting a compound obtained by reacting a hydroxyl group-containing (meth) acrylate, a hydroxyl group-containing polymer, and a hydroxyl group-containing (meth) acrylate with an isocyanate urethane. These compounds may be used singly or in combination of two or more.

Polyfunctional (meth) acrylate relative to (A) above The urethane (meth) acrylate is 100 parts by weight, preferably 10 to 500 parts by weight, 10 to 200 parts by weight, 20 to 300 parts by weight, 20 to 200 parts by weight, 20 to 100 parts by weight, 20 It is used up to 80 parts by weight, 20 to 50 parts by weight, or the like. By using in such a range, it is possible to interact with other components and effectively adjust the hardening shrinkage ratio.

[(C) fluorine-containing (meth)acrylic resin]

(C) The fluorine-containing (meth)acrylic resin may be a polymer including a structural unit derived from (meth) acrylate and containing a fluorine atom. For example, (4) a fluorine-substituted alkyl (meth)acrylate monomer, (5) an alkyl (meth)acrylate monomer, and (6) an ether group-substituted (meth)acrylic acid may be mentioned. The polymer obtained by the reaction of the ester monomer.

(4) The fluorine-substituted (meth)acrylic acid alkyl ester monomer may, for example, be a (meth) acrylate monomer having a fluoroalkyl group having 1 to 18 carbon atoms. Among them, those having a fluoroalkyl group having 2 to 18 carbon atoms are preferred.

Specific examples thereof include perfluoromethyl acrylate, perfluoroethyl acrylate, tetrafluoropropyl acrylate, perfluorooctyl acrylate, perfluoromethyl methacrylate, perfluoroethyl methacrylate, and methacrylic acid. Tetrafluoropropyl ester, perfluorooctyl methacrylate, etc., preferably perfluoromethyl methacrylate, perfluoroethyl methacrylate, tetrafluoropropyl methacrylate, perfluorooctyl methacrylate, C Perfluorooctyl enoate and the like.

(5) The (meth)acrylic acid alkyl ester monomer may, for example, be a (meth) acrylate monomer containing an alkyl group having 4 to 20 carbon atoms. Among them, a (meth) acrylate monomer having 4 to 18 carbon atoms is preferred.

Specifically, it may, for example, be n-butyl (C ₄ ), a second butyl group, a third butyl group, a n-pentyl group, a n-hexyl group, a heptyl group, a 2-ethylhexyl group, an octyl group, a decyl group or a fluorenyl group. , undecyl, dodecyl (lauryl: C ₁₂ ), tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl (stearyl: C ₁₈ ) A (meth) acrylate monomer of an alkyl group. Among them, a (meth) acrylate monomer having n-butyl group, dodecyl group, octadecyl group or the like is preferred, and n-butyl acrylate, dodecyl methacrylate, methacrylic acid is preferred. Octadecyl ester, dodecyl acrylate, octadecyl acrylate.

(6) An example of the alkyl (meth) acrylate monomer substituted with an ether group is a monomer represented by the following formula (II).

CH ₂ =C(R ²¹ )-CO-OA (II) (In the formula (II), R ²¹ represents a hydrogen atom or a methyl group, and A represents an alkyl group substituted with an ether group.)

Represents a substituted alkyl group of the ether Specifically: (i) a C ₁ to C _{20 is} substituted with alkoxy or C ₆ to C ₂₀ aryloxy group of a C ₁ to C ₂₀ alkyl group; (ii) a C ₁ to the mono-substituted C ₂₀ alkyl group (C ₂ to C ₂₀ alkylene glycol) group; (iii) in the substituted C ₁ to C ₂₀ alkoxy or C ₆ to C ₂₀ aryloxy group mono (C ₂ to C ₂₀ alkyl glycol) group; (iv) substitution of a C ₁ to C ₂₀ alkyl group of poly (C ₂ to C ₂₀ alkylene glycol) group; (V) in a C ₁ to C ₂₀ alkoxy or C ₆ to C ₂₀ aryl Oxy-substituted poly(C ₂ to C ₂₀ alkanediol) group. Further, the ether group may contain a hydroxyl group.

Wherein, preferably comprising C ₂₀ alkoxy of C ₁ to C ₁ to C ₂₀ alkyl group containing C ₁ to C ₂₀ alkyl group of the mono and poly (C ₂ to C ₂₀ alkylene glycol) group.

Here, the alkoxy group may, for example, be a methoxy group, an ethoxy group, a n-propoxy group, a n-butoxy group, a third butoxy group, a second butoxy group or a pentyloxy group.

The aryloxy group may, for example, be a phenoxy group or a benzyloxy group.

The alkoxy group and the aryloxy group may be substituted by a halogen atom.

The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Among them, a chlorine atom is preferred.

The alkyl group may be the same as described above.

The alkyl group substituted with an alkoxy group may, for example, be a methoxymethyl group, an ethoxymethyl group, a 2-methoxyethyl group, a 2-ethoxyethyl group or a (2-chloroethoxy)ethyl group. , n-propoxyethyl, butoxyethyl, cyclohexyloxyethyl, (2-cyclohexylethoxy)ethyl, (2-ethylhexyloxy)ethyl, and the like.

The alkyl group substituted with an aryloxy group may, for example, be a phenoxyethyl group or a benzyloxyethyl group.

The alkanediol may, for example, be ethylene glycol, propylene glycol or butylene glycol.

The monoalkylene glycol group substituted with an alkyl group and the polyalkylene glycol group substituted with an alkyl group may, for example, be methoxymonoethylene glycol, ethoxy monoethylene glycol or methoxydiethylene glycol. Methoxy triethylene glycol, methoxy nonaethylene glycol, methoxy polyethylene glycol, methoxy dipropylene glycol, methoxy tripropylene glycol, phenoxy diethylene glycol, phenoxy polyethylene Alcohol, ethoxy diethylene glycol, butoxy diethylene glycol and the like.

(6) The alkyl (meth)acrylate monomer substituted with an ether group, for example, butoxyethyl (meth)acrylate or methoxymethyl (meth)acrylate Ester, ethoxymethyl (meth)acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl (meth)acrylate, (2-chloroethoxy)ethyl (meth)acrylate , (2-ethylhexyloxy)ethyl (meth)acrylate, n-propoxyethyl (meth)acrylate, cyclohexyloxyethyl (meth)acrylate, (meth)acrylic acid (2- Cyclohexylethoxy)ethyl ester, phenoxyethyl (meth)acrylate, benzyloxyethyl (meth)acrylate, methoxytriethylene glycol (meth) acrylate, ethoxylated Ethylene glycol (meth) acrylate, butoxy diethylene glycol (meth) acrylate, methoxy hexaethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate Ester, methoxydiethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxy tripropylene glycol (meth) acrylate, phenoxy diethylene glycol (methyl ) acrylate, phenoxy polyethylene glycol (meth) acrylate, and the like.

Among them, the fluorine-containing (meth)acrylic resin is preferably such that (4) a resin obtained by reacting a fluorine-substituted alkyl (meth)acrylate monomer, (5) an alkyl (meth)acrylate monomer, and (6) an ether group-substituted alkyl (meth)acrylate monomer, Wherein (4) the fluorine-substituted alkyl (meth)acrylate monomer is a (meth)acrylic monomer having a fluoroalkyl group having 2 to 10 carbon atoms, and (5) the alkyl (meth)acrylate monomer is The (meth) acrylate monomer having an alkyl group having 4 to 20 carbon atoms, and (6) the alkyl (meth) acrylate monomer substituted with an ether group is an alkoxyalkyl (meth) acrylate or the like.

In fluorine-containing (meth)acrylic resin, it is derived from (4) fluorine a structural unit of an alkyl (meth) acrylate monomer, and a (meth) acrylate-substituted alkyl group derived from (5) an alkyl (meth) acrylate monomer and derived from (6) an ether group substituted The weight ratio of the structural unit of the ester is from 1 to 60:40 to 99, preferably 3 to 60:40 to 97, more preferably 1 to 30:70 to 99, 1.5 to 30:70 to 98.5, 1 to 20:80 to 99, 1.5 to 20:80 to 98.5, 2 to 20:80 to 98 people. By such a composition ratio, it is effective to impart good anti-adhesive properties, and to impart solubility and/or compatibility to the respective components, thereby obtaining a uniform and stable resin.

Fluorine-containing (meth)acrylic resin, for example, weight average The amount is preferably from 1,500 to 300,000. By being in this range, the physical properties of the obtained composition can be maintained, and a certain degree of viscosity can be maintained, so that handling is easy.

Fluorine-containing (meth)acrylic resin, relative to (A) above The urethane (meth) acrylate is 100 parts by weight, preferably 0.1 to 50 parts by weight, 0.1 to 20 parts by weight, 0.1 to 10 parts by weight, 0.5 to 20 parts by weight, 0.5 to 19 parts by weight, 0.3. It is used in an amount of 5 parts by weight, 1 to 19 parts by weight or 2 to 19 parts by weight. By using it in such a range, hardness and scratch resistance can be improved, and chemical resistance, adhesion resistance, and transparency can be imparted.

Further, the composition for a hard coat layer of the present invention preferably contains no fluorine-containing monomer or polymer other than the fluorine-containing (meth)acrylic resin, and further preferably fluorine-containing (A) The acrylic resin does not contain a fluorine-containing monomer other than (4) a fluorine-substituted alkyl (meth)acrylate.

[(D) Metal oxide microparticles]

The (D) metal oxide fine particles are not particularly limited, and those having a particle diameter of 5 nm to 50 nm are suitably used, and particularly preferably 10 nm to 20 nm. Thereby, the hardness of the film formed by the composition can be increased. In addition, the refractive index of the coating film can also be adjusted. It ensures transparency.

Metal oxide fine particles include cerium oxide and oxidation Zirconium, titanium oxide, zinc oxide, antimony pentoxide, tin oxide, aluminum oxide, indium oxide, indium tin oxide, ferric oxide, antimony oxide, antimony oxide, manganese oxide, antimony oxide, copper oxide, antimony oxide, Cobalt oxide, cobalt trioxide, triiron tetroxide, magnesium oxide, antimony oxide, antimony oxide, antimony oxide, antimony oxide, antimony oxide, antimony oxide, antimony oxide, antimony oxide, antimony oxide, antimony oxide, antimony oxide, antimony oxide, oxidation Antimony, antimony pentoxide, antimony pentoxide, antimony oxide, antimony oxide, antimony oxide, and the combined oxides of these.

For example, it is more suitable to contain a hydrazine compound represented by the following formula (IV) Or a partial hydrolyzate thereof.

R ⁹ _a R ⁸ _b Si(OR ⁷ ) _4-ab (IV)

(wherein R ⁷ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a fluorenyl group having 1 to 10 carbon atoms; R ⁸ is an alkyl group having 1 to 8 carbon atoms; and an aryl group having 6 to 8 carbon atoms; An alkenyl group having 1 to 8 carbon atoms or a mercapto group having 1 to 8 carbon atoms, and R ⁹ is a carbon number of 1 to 12 which may contain an epoxy group, a methacryl group, an acryl group, an amine group, a urea group or a fluorenyl group. The organic group, a is 0 or 1, and b is 0, 1 or 2.)

Here, the organic group may, for example, be an alkyl group, an alkenyl group, an aryl group or the like.

The alkyl group may, for example, be a methyl group, an ethyl group, a propyl group, an n-butyl group, a tert-butyl group, a second butyl group, an isobutyl group, a pentyl group, a hexyl group, a heptyl group or an octyl group.

Examples of the aryl group include a phenyl group, a tolyl group, and a xylyl group.

The alkenyl group may be a vinyl group, an allyl group, a 2-propenyl group or a propane-2-ene-1- Base.

Examples of the sulfhydryl group include a methyl group, an ethyl group, a propyl group, a butyl group, a butyl group, a pentyl group, a dimethyl group, a propylene group, a butyl group, a benzyl group, a tolylmethyl group, and an anthracene group. Base.

Specific compounds such as trimethyl methoxy hydrazine can be exemplified Alkane, triphenylmethoxy decane, diphenylmethyl methoxy decane, phenyl dimethyl methoxy decane, vinyl dimethyl ethoxy decane, dimethyl dimethoxy decane, benzene Methyl diethoxy decane, γ-mercaptopropyl trimethoxy decane, γ-glycidoxypropyl triethoxy decane, tetraethyl orthosilicate, tetramethyl phthalate, etc. A conventional hydrazine compound or a partial hydrolyzate thereof exemplified in JP-A-2006-70120.

In particular, R ⁹ is a methacrylic acid or acryl based ruthenium compound, and is preferable because the film hardness can be further increased. Such hydrazine compounds are, for example, 3-methacryloxypropylmethyldimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropyl Methyl diethoxy decane, 3-methacryloxypropyl triethoxy decane, 3-propenyl methoxy propyl trimethoxy decane, and the like.

Further, the metal oxide fine particles may be used singly or in combination of two or more kinds.

Metal oxide microparticles relative to the above (A) uric acid The ethyl ester (meth) acrylate is 100 parts by weight, and is preferably 30 to 500 parts by weight, more preferably 50 to 350 parts by weight, based on the solid content. By using such a range, it is possible to interact with other components and effectively adjust the hardening shrinkage ratio.

In addition, metal oxide microparticles can be dispersed in organic solvents. The agent is used as an organosol.

Examples of the solvent type and the alcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-methoxy-2-propanol, and isopropanol.

Ethylene glycol monomethyl ether acetate Ester, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acid ester, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl Ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether , propylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether.

Examples of the aliphatic cyclic ketones include cyclohexanone, and O-, m-, p-methylcyclohexanone and the like.

Examples of the acetates include ethyl acetate, n-propyl acetate, and n-butyl acetate.

Further, solvent naphtha, methyl ethyl ketone, methyl isobutyl ketone or the like can be used.

As the organosol, those in which the solvent is used and the solid form is in the range of 5 to 100% can be used.

The composition of the present invention may further contain (meth) propylene A compound of a methoxy group or a compound containing a vinyl group. In this case, for example, it is preferably contained in an amount of 0.1 to 50 parts by weight per 100 parts by weight of the total composition. These compounds may be used singly or in combination of two or more.

(Methyl) propylene oxime compound, for example, propylene Acid amides, alkyl (meth) acrylates, aminoalkyl (meth) acrylates, grade 4 salts of aminoalkyl (meth) acrylates, alkoxy polyalkylene glycols (methyl Acrylates, hydroxyalkyl (meth)acrylates, anhydride additions of hydroxyalkyl (meth)acrylates, polyalkylene glycol di(meth)acrylates, alkanediol di(methyl) Polyol poly(meth)acrylates of acrylates, polyol poly(meth)acrylates, and alkylene oxides. Examples of such compounds are exemplified by those described in Japanese Patent Laid-Open No. 2000-264939.

Examples of the compound containing a vinyl group include acetic acid B An ester of an enester, N-vinylacetamide, vinyl pyrrolidone, vinyl alkyl ether, vinyl sulfonic acid or vinyl sulfonic acid.

The composition of the present invention is a mixed polymerization initiator, which is rare Release agent, leveling agent, slip agent, other additives, etc.

The polymerization initiator is not particularly limited, and is preferably activated by activity. A photopolymerization initiator that generates a radical by an energy line. For example, hydroxycyclohexyl phenyl ketone, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-2-phenylacetophenone, diphenyl Ketone, 2-methyl[4-(methylthio)phenyl]-2-morpholinyl-1-propanone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl) ketone , 4-(2-propenylmethoxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 4-(2-methylpropenyloxyethoxy)phenyl-( 2-hydroxy-2-propyl)one, bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide, 2-benzyl-2-dimethylamino-1-(4) -morpholinylphenyl)-butanone-1,2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropenyl)-benzyl]-phenyl}-2-methyl Propane 1-ketone, oligo{2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone}, 1-[4-(4-benzylidenephenyl) Sulfhydryl)phenyl]-2-methyl-2-(4-methylphenylsulfonyl)propan-1-one.

The diluent may be a monoalkyl ether of an alkanediol or an alkanol. Alkyl carboxylates of the class of alkanediol monoalkanols, ketones, alkylcarboxylates of alkanols, and the like. These are described, for example, in Japanese Patent Laid-Open No. 2004-43790.

The composition for a hard coat layer of the present invention may be dissolved as needed Media. As the solvent, for example, the above-mentioned alcohols, glycols, aliphatic cyclic ketones, acetates, and the like can be used.

For the leveling agent and the slip agent, for example, polyoxyalkylene and poly a copolymer of dimethyloxane, a copolymer of a polyoxyalkylene and a fluorocarbon, and the like.

[formed product]

The composition for a hard coat layer of the present invention can be cured by irradiation with ultraviolet rays, radiation, infrared rays, X-rays, active energy rays of electron rays, or the like. The hardened polymer of the composition exerts a hard coat function on the surface of the molded article.

The molded article here is not limited to including polystyrene trees A plastic molded article comprising a general-purpose resin such as a fat, a polyolefin resin, an ABS resin, an AS resin, an AN resin, or the like, and various materials such as wood, glass, metal, ceramic, paper, cement, composite products of the like, etc. By. Further, the composition of the present invention itself may constitute a molded article. It is preferred to form the composition for a hard coat layer of the present invention as a hard coat layer on the surface thereof. In addition, the molded article may be in the form of a film, a transfer foil, or the like which constitutes a hard coat layer for the composition for a hard coat layer of the present invention.

Therefore, for example, it can be suitably used on a transparent substrate The composition for a hard coat layer of the present invention has a film shape and is a film for a transfer coating foil and a hard coat layer for a hard coat layer, and the transfer foil or film may be suitably used for the surface of a molded article.

Further, when the molded article includes a plastic, the composition for a hard coat layer of the present invention can be blended as a hard coat layer in the plastic constituting the molded article without affecting the properties desired for the molded article.

For example, coating on one or both sides of a transparent substrate The composition for a hard coat layer is formed into a hard coat layer by light irradiation or the like.

Examples of the transparent substrate include a (meth)acrylic polymer such as a polyurethane resin, an episulfide resin, a polymethyl methacrylate (PMMA), and an allyl polymer. A substrate of various synthetic resins such as diethylene glycol bisallyl carbonate, polycarbonate, MS resin, and cyclic polyolefin. The substrate may have any shape such as a flat plate shape, a curved plate shape, or a film shape.

The coating system can be, for example, by dip coating, flow coating, or spraying The coating method, the gravure coating method, the bar coating method, the spin coating method, the roll coating method, the flexographic coating method, the screen printing method, the brush coating method, and the like are carried out.

The coating thickness is suitably from about 0.01 to 100 μm after hardening.

The light irradiation may be about 100 to 1,500 mJ/cm ² by irradiation with ultraviolet rays or the like.

In addition, in order to improve the adhesion of the hard coat layer, etc., it is possible to First, a primer layer is provided on the surface of the transparent substrate or the molded article, and pretreatment such as alkali treatment, acid treatment, plasma treatment, corona treatment, flame treatment, or the like may be performed.

The undercoat layer may, for example, be an urethane resin or an acrylic resin. The thickness of the undercoat layer is preferably about 2 to 50 nm. The undercoat layer can be formed by applying the resin solution by any one of a dipping method, a spray method, a flow coating method, a roll coating method, and a spin coating method.

Example

Hereinafter, examples of the composition for a hard coat layer of the present invention will be described in detail.

Production Example 1: Production of fluorine-containing (meth)acrylic resin 1

To a vessel equipped with a reflux condenser, a thermometer, a stirrer, and a drop tank, 150 parts by weight of SOLFIT (trade name, manufactured by Kuraray Co., Ltd.) of 3-methyl-3-methoxybutanol was added thereto. The temperature is kept at 120 °C. 5 parts by weight of LIGHTESTER M-3F (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) of methyl trifluoroethyl methacrylate, 47.5 parts by weight of methyl methacrylate, and 2-hydroxyethyl acrylate, under a nitrogen atmosphere A mixed solution of 47.5 parts by weight and 1 part by weight of PERBUTYL D (trade name manufactured by Nippon Oil & Fat Co., Ltd.) was dropped into SOLFIT for about 1 hour. The reaction was carried out at 120 ° C for 2 hours to obtain a fluorine-containing (meth)acrylic copolymer liquid.

The obtained fluorine-containing (meth)acrylic copolymer liquid solution had a weight average molecular weight of 11,000 as determined by a polystyrene conversion value of colloidal permeation chromatography.

Production Example 2: Production of fluorine-containing (meth)acrylic resin 2

SOLFIT (trade name, manufactured by Kuraray Co., Ltd.) 150 weight is added to a container having a reflux condenser, a thermometer, a stirrer, and a dropping tank. Serve and keep the liquid temperature at 120 °C. 40 parts by weight of LIGHTESTER M-3F (trade name manufactured by Kyoeisha Chemical Co., Ltd.), 30 parts by weight of ethylhexyl methacrylate, 30 parts by weight of 2-hydroxyethyl acrylate, and PERBUTYL D under a nitrogen atmosphere. (trade name manufactured by Nippon Oil & Fat Co., Ltd.) 1 part by weight of the mixed solution was dropped into SOLFIT for about 1 hour. The reaction was carried out at 120 ° C for 2 hours to obtain a fluorine-containing (meth)acrylic copolymer liquid.

The obtained fluorine-containing (meth)acrylic copolymer liquid solution had a weight average molecular weight of 35,000 as determined by a polystyrene conversion value of colloidal permeation chromatography.

Production Example 3: Production of fluorine-containing (meth)acrylic resin 3

150 parts by weight of SOLFIT (trade name, manufactured by Kuraray Co., Ltd.) was placed in a container having a reflux condenser, a thermometer, a stirrer, and a dropping tank, and the liquid temperature was kept at 120 °C. Under a nitrogen atmosphere, 15 parts by weight of LIGHTESTER M-3F (trade name manufactured by Kyoeisha Chemical Co., Ltd.), 30 parts by weight of butyl methacrylate, 55 parts by weight of 2-hydroxyethyl acrylate, and PERBUTYL D (Japan) The product name of the Oils and Fats Co., Ltd.) 1 part by weight of the mixed solution was dropped into SOLFIT for about 1 hour. The reaction was carried out at 120 ° C for 2 hours to obtain a fluorine-containing (meth)acrylic copolymer liquid.

The obtained fluorine-containing (meth)acrylic copolymer liquid solution had a weight average molecular weight of 15,000 as determined by a polystyrene conversion value of colloidal permeation chromatography.

Production Example 4: Production of fluorine-containing (meth)acrylic resin 4

200 parts by weight of SOLFIT (trade name, manufactured by Kuraray Co., Ltd.) was placed in a container having a reflux condenser, a thermometer, a stirrer, and a dropping tank, and the liquid temperature was kept at 110 °C. Under a nitrogen atmosphere, 20 parts by weight of LIGHTESTER FM-108 (trade name manufactured by Kyoeisha Chemical Co., Ltd.) of fluorooctyl methacrylate, 15 parts by weight of n-butyl acrylate, and 2-hydroxyethyl acrylate. A mixed solution of 65 parts by weight of the ester and 5.0 parts by weight of PERBUTYL O (trade name, manufactured by Nippon Oil & Fat Co., Ltd.) was dropped into SOLFIT for about 1 hour. The reaction was carried out at 110 ° C for 2 hours to obtain a fluorine-containing (meth)acrylic copolymer liquid.

The obtained fluorine-containing (meth)acrylic copolymer liquid solution had a weight average molecular weight of 5,000 as determined by a polystyrene equivalent value of colloidal permeation chromatography.

Examples and comparative examples

The following composition (A) to (D) were kneaded in the composition ratio (parts by weight) shown in Table 1, and a composition for a hard coat layer containing about 30% by weight of a resin component was obtained.

(A) ethyl urethane (meth) acrylate; (B) polyfunctional (meth) acrylate; (C) fluorine-containing (meth) acrylic resin; and (D) metal oxide fine particles. ;

The ingredients of Table 1 are as follows.

Resin (A)-1: polyisocyanate (CORONATE HK) / 2-hydroxyethyl acrylate / neopentyl alcohol triacrylate (manufactured by Synthesis Example 1 of JP-A-2010-107956); A)-2: Trade name: UA-306H (manufactured by Kyoeisha Chemical Co., Ltd., pentaerythritol triacrylate hexamethylene diisocyanate urethane ethyl ester prepolymer); Resin (A)-3: Polyisocyanate (CORONATE HK) / 2-hydroxyethyl acrylate / neopentyl alcohol triacrylate / acrylic acid oxide 10 molar addition; resin (B): neopentyl alcohol triacrylate, trade name: LIGHTACRYLATE PE-3A (manufactured by Kyoeisha Chemical Co., Ltd.); resin (C)-1: fluorine-containing (meth)acrylic resin 1 produced in Production Example 1; resin (C)-2: Production Example 2 Fluorine (meth)acrylic resin 2 produced; resin (C)-3: fluorine-containing (meth)acrylic resin 3 produced in Production Example 3; resin (C)-4: manufactured in Production Example 4 Fluorine (meth)acrylic resin 4; resin (C)-5: alkyl copolymer, trade name: POLYFLOW 99C (manufactured by Kyoeisha Chemical Co., Ltd.); resin (C)-6: polyoxyl Copolymer Name: POLYFLOW KL-401 (made by Kyoeisha Chemical Co., Ltd.); Organic cerium oxide sol solution 1: In the trade name PL-2L-MEK (made by Fuso Chemical Industry Co., Ltd., particle size 10nm, solid content 20.0%) The granules are introduced into the methacrylic acid group (corresponding to R ⁹ in the formula (IV) being a methacrylic acid group); the organic cerium oxide sol solution 2 is in the PL-2L-MEK (made by Fuso Chemical Industry Co., Ltd.) Particles having a particle diameter of 10 nm and a solid content of 20.0%) are introduced into an acrylic group (corresponding to R ⁹ in the formula (IV), which is an acrylic group); an anti-adhesive filler, trade name: PL-20 (manufactured by Fuso Chemical Industry Co., Ltd.) Photopolymerization starter 1: trade name IRGACURE 184, manufactured by BASF JAPAN Co., Ltd.; photopolymerization initiator 2: trade name: LucirinTPO, manufactured by BASF JAPAN Co., Ltd.; coated substrate: 100 μm PET (unprocessed)

The composition for a hard coat layer obtained in the examples and the comparative examples was applied to a substrate, and the solvent was dried. This was placed on a conveyor belt having a speed of 6 m/min, and a high-pressure mercury lamp of 80 W/cm was irradiated twice with ultraviolet rays at a height of 10 cm to crosslink and polymerize to form a coating layer having a thickness of about 5 μm containing a hardened polymer.

The obtained coating layer was evaluated for coating state (transparency), pencil hardness, steel resistance, curling property, anti-adhesion property, adhesion, penetration rate, and haze value.

<film state>

By visual observation, there was no whitening at all, and there was almost no whitening to ○. The whitening is △, and the overall whitening is ×, which is evaluated in four stages.

<pencil hardness>

The test was carried out with a pencil hardness of 500 g and showed the pencil hardness without leaving a flaw.

<Steel resistance>

The test was carried out by rubbing the obtained coating back and forth 10 times with a steel brush (#0000) having a load of about 1 kg. When visually observed, no scratches were left as ◎, and scars were scarcely left as ○, and scars were left as Δ, and scars were left as X, and the evaluation was carried out in four stages.

<curlability>

The coated film was cut out into a square of 10 cm, and the average value of the whirling heights of the four corners was measured. The average value of the height of the float height is 10 mm or less, ○, 10 to 20 mm is ○, 20 to 30 mm is Δ, and 30 mm or more is ×, and the evaluation is performed in four stages.

<anti-adhesion>

The coated film was placed in a state of being bonded to the back surface (non-coated surface) or the coated surface in a state of 1 kg, and allowed to stand for 1 day, and it was visually confirmed whether or not the bonding surfaces were adhered to each other.

<adhesiveness>

The board test was performed, and 100/100 was ◎, 90/100 or more was ○, 50/100 or more was △, and 50/100 was ×, and the evaluation was carried out in four stages.

<Full light transmittance and haze value>

The haze value measuring machine (color measurement color meter, ULTRASCAN XE) was used to measure the total light transmittance and the haze value.

As seen from Table 1, in the examples, by the ethyl urethane The polyfunctional (meth) acrylate, the fluorine-containing (meth)acrylic resin, and the metal oxide fine particles were mixed in the acrylate, and satisfactory results were obtained in all evaluations.

On the other hand, it is understood that the anti-adhesive effect is particularly poor in the comparative example.

Example 5

The composition for a hard coat layer obtained in Example 1 and the above-mentioned coating film state (transparency), pencil hardness, steel resistance, curling property, adhesion, adhesion resistance, transmittance, and haze value The evaluation was applied to the substrate in the same manner to form a coating, and a hard coat film was produced.

The obtained film was sandwiched in an injection molding die to form an acrylic resin by injection molding. After cooling, a molded article having a hard coat layer was obtained.

Thus, the composition of the present invention can maximize the transparency, scratch resistance and durability of the acrylic resin, and can reduce the curling property. Further, by containing metal oxide fine particles, a good hard coat property can be obtained, and in particular, transmittance and/or transparency can be ensured, and a balance of polyfunctional (meth) acrylate can be achieved to exhibit good resistance. Adhesive properties. Further, the fluorine-containing (meth)acrylic resin can impart chemical resistance and stain resistance.

(industrial availability)

The composition for a hard coat layer of the present invention can be suitably used for a molded article including plastic, glass, paper, wood, etc., and durability of such a molded article in terms of adhesion, transparency, scratch resistance, moisture resistance, and the like. In terms of chemical resistance, anti-adhesiveness, etc., it is possible to impart a stable and excellent coating over a long period of time, and also to reduce the curling property of the composition for a hard coat layer, that is, to reduce the hardening shrinkage ratio and maintain the anti-adhesion property. A good coating is available. So available for Parts and molded articles of these characteristics are required.

Claims (12)

A composition for a hard coat layer comprising: (A) ethyl urethane (meth) acrylate, (B) polyfunctional (meth) acrylate, (C) fluorine (meth) acrylate Polymer after polymerization, and (D) metal oxide fine particles. The composition for a hard coat layer according to the above aspect of the invention, wherein the (A) urethane (meth) acrylate is a polymer obtained by the reaction of the following (1) to (3): (1) A compound having a polyether as a main chain, (2) an isocyanate compound, and (3) a hydroxyl group-containing (meth) acrylate compound. The composition for a hard coat layer according to the above aspect, wherein the (A) ethyl urethane (meth) acrylate comprises an urethane represented by the following formula (I) (A) Acrylate oligomer: (R ¹ O-CONH-) _m -R ² -(-NHCO-OR ³ ) _n (I) In the formula (I), R ¹ O- represents a polyether as a main chain a dehydrogenation residue of the compound, -R ² - represents a deisocyanate group residue of the isocyanate compound, R ³ O- represents a dehydrogenation residue of the hydroxyl group-containing (meth) acrylate compound, and m+n represents 1 to 50 Integer. The composition for a hard coat layer according to claim 2, wherein the (2) isocyanate compound is a diisocyanate or A polyisocyanate after polycondensation of a diisocyanate monomer, or a urea structure having an urethane structure and/or an addition amine compound in an isocyanate-addition alcohol compound. The composition for a hard coat layer according to any one of claims 2 to 4, wherein the (3) hydroxyl group-containing (meth) acrylate compound is a hydroxyalkyl (meth) acrylate, Polyol (meth) acrylates. The composition for a hard coat layer according to any one of the above aspects, wherein the compound (1) having a polyether as a main chain is one or more selected from the group consisting of an alkanediol compound and an epoxy resin. A compound in the group of alkane addition compounds. The composition for a hard coat layer according to the above aspect of the invention, wherein the compound (1) having a polyether as a main chain is a single-end hydroxyl group-containing polyalkane comprising an alkoxy polyalkylene glycol. An alcohol compound, a compound obtained by subjecting (meth)acrylic acid to an alkylene oxide addition or a monoalkyl (meth)acrylate of a polyalkylene glycol. The composition for a hard coat layer according to any one of claims 1 to 7, wherein the (C) fluorine-containing (meth)acrylic resin is the following (4) to (6) The reaction is obtained by: (4) a fluorine-substituted (meth)acrylic acid alkyl ester monomer, (5) an alkyl (meth)acrylate monomer, and (6) an ether group-substituted (meth) group. Alkyl acrylate monomer. The composition for a hard coat layer according to Item 8, wherein the (5) alkyl (meth) acrylate monomer has a C ₄ to C ₂₀ alkyl group. The composition for a hard coat layer according to the above item (8), wherein the (6) ether group-substituted alkyl (meth)acrylate single system is a monomer represented by the following formula (II). ^{_{: CH 2 = C (R 21}} ) -CO-OA (II) of formula (II) is, R ²¹ represents a hydrogen atom or a methyl group, A represents a C ₁ to C ₂₀ containing alkoxy groups a C ₁ to C ₂₀ alkyl group And a poly(C ₂ to C ₂₀ alkanediol) group containing a C ₁ to C ₂₀ alkyl group. The composition for a hard coat layer according to any one of claims 1 to 10, wherein the (B) polyfunctional (meth) acrylate has at least two in one molecule (methyl group). a compound of an acrylonitrile group. A molded article is formed by using a hardened polymer of a composition for a hard coat layer according to any one of claims 1 to 11 as a hard coat layer.