KR20150092202A - Composition for hardcoat and molded article with hardcoat layer - Google Patents

Abstract

It is an object of the present invention to provide a hard coat composition and a molded article which can maximize the transparency, scratch resistance, chemical resistance and anti-blocking property of a component to be used and also can prevent the crimpability to a minimum. A composition for a hard coat comprising (A) urethane (meth) acrylate, (B) a polyfunctional (meth) acrylate, (C) a fluorine-containing (meth) acrylic resin and (D) metal oxide fine particles.

Description

TECHNICAL FIELD [0001] The present invention relates to a composition for a hard coat and a molded article having a hard coat layer formed thereon,

More particularly, the present invention relates to a composition for a hard coat and a hard coat layer having good durability, chemical resistance, anti-blocking property, transparency, crimpability and adhesion, To a formed article.

BACKGROUND ART Conventionally, various plastics have been used in various fields such as home appliances and automobiles. Plastic has various advantages such as processability and transparency, and is light and inexpensive. However, it has drawbacks such as being soft compared to a material such as glass, and easily scratched on the surface.

In order to improve these drawbacks, there has been used a technique of coating a hard coat material on a plastic surface and improving the scratch resistance of the surface without impairing the transparency and light weight of the plastic.

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

However, acrylic resins generally have poor scratch resistance and abrasion resistance as compared with silicone paints.

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

In addition, high hardness is achieved by adding an additive such as an inorganic material.

Such a polyfunctional (meth) acrylate has a large curing shrinkage ratio, and in particular, when it is molded into a thin film shape, there is a problem that crimpability is remarkable.

Further, when such a polyfunctional (meth) acrylate or the like is molded into a film shape, the polyfunctional (meth) acrylates of adjacent films or the like stick to each other due to high static friction resistance and surface smoothness, So that a phenomenon of becoming a state in which it can not be easily dropped, that is, a blocking phenomenon may occur. As an anti-blocking agent used to prevent such blocking phenomenon, silica powder is generally widely used. However, there is a trade-off relationship in that when the particle size of the silica is large, the transparency is remarkably impaired while when the particle size is small, the anti-blocking effect can not be sufficiently exhibited. Therefore, it is required to maintain high transparency while effectively preventing the occurrence of the blocking phenomenon.

The present invention has been made in order to solve the above problems, and an object of the present invention is to provide a hardcoat resin composition and a molded article for a hardcoat which exhibit hard coat performance such as abrasion resistance to a maximum extent and at the same time, And to provide the above objects.

The present invention includes the following inventions.

[1] A curable composition comprising (A) a urethane (meth)

(B) a polyfunctional (meth) acrylate,

(C) a polymer obtained by polymerizing a fluorine-containing (meth) acrylate,

(D) a metal oxide fine particle.

[2] The positive resist composition according to [1], wherein the urethane (meth)

(1) a compound having a polyether as a main chain,

(2) an isocyanate compound,

(3) a polymer obtainable by a reaction with a hydroxyl group-containing (meth) acrylate compound.

[3] The composition according to [1], wherein the urethane (meth) acrylate (A)

(In the formula (I), R ¹ O- represents a dehydroxyl residue of a compound having a polyether as a main chain,

-R ² - is a deisocyanate group residue of the isocyanate compound,

R ³ O- is a dehydroxyl residue of a hydroxyl group-containing (meth) acrylate compound,

and m + n = an integer of 1 to 50. The composition for a hard coat according to [1] or [2], further comprising a urethane (meth) acrylate oligomer.

[4] The positive resist composition as described in [1] or [2], wherein the isocyanate compound (2) is a polycondensation product of a diisocyanate or a diisocyanate monomer, or a urethane structure in which an alcohol compound is added to an isocyanate group and / ] Or [3].

[5] The composition for a hard coat according to any one of [2] to [4], wherein the hydroxyl group-containing (meth) acrylate compound is the hydroxyalkyl (meth) acrylate and the polyol (meth) acrylate.

[6] The hard coat according to any one of [3] to [5], wherein the compound (1) wherein the polyether is the main chain is at least one compound selected from the group consisting of an alkylene glycol compound and an alkylene oxide adduct / RTI >

[7] The method for producing a polyalkylene glycol-based resin composition according to any one of [1] to [7], wherein the compound having a polyether as a main chain is at least one compound selected from the group consisting of a polyalkylene glycol compound having a hydroxyl group at one end and an alkoxypolyalkylene glycol, (Meth) acrylate. [6] The composition for a hard coat according to [6].

[8] The fluorine-containing (meth) acrylic resin composition according to any one of [

(4) a fluorine-substituted alkyl (meth) acrylate monomer,

(5) an alkyl (meth) acrylate monomer,

(6) The composition for a hard coat according to any one of [1] to [7], which is a resin obtained by reaction with an ether group-substituted alkyl (meth) acrylate monomer.

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

[10] The process according to [10], wherein the ether group-substituted alkyl (meth) acrylate monomer (6)

(In the formula (II), R ²¹ represents a hydrogen atom or a methyl group

A is a monomer represented by represents a C ₁ ~ C ₂₀ alkoxy group containing C ₁ ~ alkyl group-containing mono and poly C ₂₀ alkyl group, C ₁ ~ C ₂₀ of (C ₂ ~ C ₂₀ alkylene glycol).) [ 9] or [10].

[11] The hard coat composition according to any one of [1] to [10], wherein the polyfunctional (meth) acrylate (B) is a compound having at least two (meth) acryloyl groups in one molecule.

[12] A molded article, characterized in that the hard coat polymer of the composition for hard coat according to any one of [1] to [11] is formed from a hard coat layer.

According to the composition for a hard coat of the present invention, it is possible to provide a resin composition for a hard coat and a molded article which exhibits hard coat performance such as abrasion resistance at the maximum, at the same time, and which has a minimum crimpability and also excellent anti-blocking property and transparency .

The composition for a hard coat of the present invention mainly comprises,

(A) a urethane (meth) acrylate,

(B) a polyfunctional (meth) acrylate,

(C) a polymer obtained by polymerizing a fluorine-containing (meth) acrylate (hereinafter may be referred to as "fluorine-containing (meth) acrylate-based resin"

(D) metal oxide fine particles.

Thus, the fluorine-containing (meth) acrylate (C) is effective for exhibiting anti-blocking properties. In addition, by using (D) metal oxide particles in combination, it is possible to secure even better anti-blocking properties. Further, by the action of (A) urethane (meth) acrylate, balance of low crimp and high hardness can be achieved.

In the present specification, "(meth) acryl" refers to "methacryl" and / or "acrylic" and "(meth) acrylate" refers to "methacrylate" and / or "acrylate".

[(A) urethane (meth) acrylate]

(A) The urethane (meth) acrylate may be one having at least one hydrophilic group (for example, a hydroxyl group, a carboxyl group, an ethylene glycol group, a propylene glycol group or the like). For example, a resin that can be obtained by the reaction of an isocyanate compound with a compound having a polyether as a main chain and / or a hydroxyl group-containing (meth) acrylate compound can be given. Specifically,

(1) a compound having a polyether as a main chain,

(2) an isocyanate compound,

(3) a resin obtained by a reaction with a hydroxyl group-containing (meth) acrylate compound,

(1) a compound having a polyether as a main chain,

(2) a resin obtainable by reaction with an isocyanate compound, or

(2) an isocyanate compound,

(3) a resin obtained by a reaction with a hydroxyl group-containing (meth) acrylate compound.

For example, as an example of urethane (meth) acrylate, the following formula (I)

(Wherein R ¹ O- is a dehydroxyl residue of a compound having a polyether as a main chain, -R ² - is a deisocyanate group residue of an isocyanate compound, R ³ O- is a dehydroxyl residue of a hydroxyl group-containing (meth) 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, a plurality of R ^{1 s} may be the same or two or more. The molecular weight of the substituent constituting R ¹ is preferably about 100 to 2,000, and preferably about 100 to 1,000. 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 preferably about 150 to 5,000, and preferably about 500 to 3,000. If the molecular weight is too large, the hardness tends to decrease.

n may be 0, but an integer larger than 0, that is, 1 or more, is suitable. When n is 2 or more, a plurality of R ³ may be the same or two or more.

The molecular weight of the substituent constituting R ³ is preferably about 150 to 2,000, and preferably about 100 to 1,000. If the molecular weight is too large, the hardness decreases.

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

(1) Examples of the compound having a polyether as a main chain include a compound having an ether group, preferably a polyether group as a main chain and a hydroxyl group (including a hydroxyl group-containing compound at one end). Here, the ether group includes a hydroxyl group. However, it is a compound different from the hydroxyl group-containing (meth) acrylate compound (3) described later. In particular, at least one compound selected from the group consisting of alkylene glycol compounds and alkylene oxide adducts may be mentioned. (Meth) acryloxypolyalkylene glycols, a reaction product of a polyalkylene and a polytetramethylene glycol, an epoxy compound having an oxirane ring and a (meth) acryloxypolyalkylene glycol, (Meth) acryloyl group-containing polyethers obtained by reacting a (meth) acrylic acid derivative containing a hydroxyl group obtained by addition reaction of acrylic acid with an alkylene oxide such as ethylene oxide or propylene oxide, a (meth) acrylic acid alkylene oxide- .

Among them, polyalkylene glycols, polyalkylene glycols having one terminal hydroxyl group, alkoxypolyalkylene glycols and (meth) acryloyl group-containing polyethers and (meth) acrylic acid alkylene oxide adducts are preferable, Also preferred are a polyalkylene glycol compound having a hydroxyl group at one end or a (meth) acrylic acid alkylene oxide addition compound.

Particularly, the polyalkylene glycol compound having one terminal hydroxyl group is preferably an alkoxypolyalkylene glycol, and the (meth) acrylic acid alkylene oxide addition compound is preferably a compound obtained by adding (meth) acrylic acid to an alkylene oxide, It is preferable that monoglyme (meth) acrylate of phenol is used.

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

Polyalkylene glycols include, for example, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

Examples of the alkoxypolyalkylene glycols include polyalkylene glycols having an alkoxy group of about 1 to 6 carbon atoms (the number of carbon atoms of the alkylene is, for example, about 1 to 6), specifically, methoxy Polyethylene glycol, methoxypolypropylene glycol, and methoxypolytetramethylene glycol. The molecular weight of the alkoxypolyalkylene glycols may be optionally selected, but is preferably from 100 to 2,000.

(Meth) acryloxypolyalkylene glycols include, for example, (meth) acryloxypolyethylene glycol and (meth) acryloxypolypropylene glycol.

The reaction product of the polyalkylene and the polytetramethylene glycol is, for example, a reaction product of polyethylene and polytetramethylene glycol, a reaction product of methoxypolyethylene and polytetramethylene glycol, a reaction product of (meth) acryloxypolyethylene and polytetramethylene glycol .

The (meth) acryloyl group-containing polyether is an acrylate containing an alkyl group having about 1 to 6 carbon atoms substituted with a hydroxy group, for example, an ethylene oxide adduct of 2-hydroxyethyl acrylate (for example, Addition mole number is about 1 to 20).

(Meth) acrylic acid alkylene oxide adduct is obtained by adding an alkylene oxide represented by ethylene oxide, propylene oxide or butylene oxide (for example, having about 2 to 6 carbon atoms) to (meth) acrylic acid .

(2) Examples of the isocyanate compound include diisocyanates, polyisocyanates such as polyisocyanates obtained by polycondensation of a diisocyanate monomer, urethane structures in which an alcohol compound is added to an isocyanate group and / or urea structures added with an amine compound And the like. Among them, those having polyisocyanates, a urethane structure and / or a urea structure are preferable.

The diisocyanates include, for example, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, (ortho, meta, para) Isocyanate, cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1,4-dimethylene isocyanate, 1,5-naphthalene diisocyanate, Isocyanate and the like.

The polycondensation polyisocyanates of polyisocyanates and / or diisocyanate monomers include, for example, polyisocyanate compounds such as isophorone diisocyanate, hexamethylene diisocyanate, norbornene diisocyanate, tolylene diisocyanate, xylene diisocyanate, Bifunctional isocyanates such as diphenylmethane diisocyanate, trimethylhexamethylene diisocyanate, hydrogenated xylylene diisocyanate and hydrogenated diphenylmethane diisocyanate, and bifunctional or nuorificated trifunctional or higher isocyanates. Among them, a polyisocyanate compound having three or more, four or more, five or more, and six or more isocyanate groups in a molecule, such as a chain or cyclic alkyl or aryl group (e.g., , And especially nylate compounds such as hexamethylene diisocyanate, isophorone diisocyanate and tolylene diisocyanate are preferable.

The alcohol compounds include, for example, alcohols having 2 to 4 carbon atoms of about 2 to 10 carbon atoms, specifically, ethylene glycol, propylene glycol, tetramethylene glycol, glycerin, trimethylol propane and pentaerythritol.

The amine compound includes, for example, diaminoethane, diaminopropane, and tetramethylene diamine.

When an alcohol compound or an amine compound is added, the number of functional groups per molecule of the isocyanate compound can be increased. Further, from the viewpoint of enhancing the scratch resistance of the cured polymer, these alcohol compounds and amine compounds are preferably used with a small molecular weight per functional group.

(3) The hydroxyl group-containing (meth) acrylate compound is a compound different from the compound having the polyether of the above-mentioned component (1) as a main chain and includes, for example, hydroxyalkyl (meth) acrylates, ) Acrylates, and those derived from an epoxy resin and carboxylic acid.

Examples of the hydroxyalkyl (meth) acrylates include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyphenoxypropyl Acrylate.

Examples of the polyol (meth) acrylate include 2- to 4-valent polyol (meth) acrylates having about 2 to 10 carbon atoms, specifically, glycerin di (meth) acrylate, trimethylolpropane di Acrylate, ditrimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate.

(Meth) acrylic acid adduct of glycidyl (meth) acrylate derived from an epoxy resin and carboxylic acid.

The urethane (meth) acrylate may be used alone or in combination of two or more.

The urethane (meth) acrylate of the present invention is preferably a urethane (meth) acrylate of the formula (1), in particular, (2) a polyisocyanate compound having an isocyanate compound and an urethane structure in which an alcohol compound is added to an isocyanate group, (Meth) acrylic acid alkylene oxide adduct and / or (3) a hydroxyl group-containing (meth) acrylate compound having at least one functional group selected from the group consisting of polyalkylene glycols, alkoxypolyalkylene glycols and (meth) acryloyl group- As the compound, a combination with a hydroxyalkyl (meth) acrylate and a polyol (meth) acrylate is preferable. Among them, a combination having all of (1), (2) and (3) described herein is more preferable.

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

(Meth) acrylate having a hydroxyl group, the molar ratio of (1) a compound having a polyether as a main chain, for example, a polyalkylene glycol compound having an end hydroxyl group is (3) Is preferably not more than the molar ratio of the compound. The larger the molecular weight of the polyether chain, the lower the hardness when crosslinked. The greater the number of functional groups of the hydroxyl group-containing (meth) acrylate compound, the higher the hardness when crosslinked and the lower the hardness, the lower the hardness. Therefore, by adjusting these, a hardened polymer having appropriate hardness can be obtained. Concretely, the weight ratio of the components (1) to (3) is set to be (1) :( 2) :( 3) = 0 to 50:10 to 70:20 to 80, 30:30 to 50:20 to 60 is preferable.

[(B) polyfunctional (meth) acrylate]

(B) The multifunctional (meth) acrylate is a (meth) acrylate resin containing two or more functional groups and is other than (meth) acrylate having a urethane structure represented by (A). A compound having two or more (meth) acryloyl groups in one molecule is preferable.

(Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (metha) acrylate, dipentaerythritol penta (meth) acrylate, dimethylol tricyclo Acrylate, trimethylolpropane (ethylene oxide adduct) tri (meth) acrylate, polyester di (meth) acrylate, tetraethylene glycol di (meth) acrylate, glycerin di (meth) (Meth) acrylate of glycerin ethylene oxide adduct, (meth) acrylate of glycerin propylene oxide adduct, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetra Diacrylates of polyalkylene glycols such as propylene glycol, polyvalent alcohols (Meth) acrylate of a compound obtained by condensing a polyol and a polybasic acid, and a compound obtained by the reaction of the polyisocyanate and the hydroxyl group-containing (meth) acrylate, a hydroxyl group-containing polymer and a hydroxyl group- And a compound obtained by the reaction. These compounds may be used alone or in combination of two or more.

The polyfunctional (meth) acrylate is used in an amount of 10 to 500 parts by weight, 10 to 200 parts by weight, 20 to 300 parts by weight, 20 to 200 parts by weight based on 100 parts by weight of the (A) urethane (meth) 20 to 100 parts by weight, 20 to 80 parts by weight, and 20 to 50 parts by weight. With this range, the hardening shrinkage ratio can be adjusted effectively in combination with other components.

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

The fluorine-containing (meth) acrylic resin (C) may be a polymer containing 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,

(6) an ether group-substituted alkyl (meth) acrylate monomer.

(4) The fluorine-substituted alkyl (meth) acrylate monomer includes, for example, 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 preferable.

Specific examples thereof include perfluoroalkyl acrylates such as perfluoromethyl acrylate, perfluoroethyl acrylate, tetrafluoropropyl acrylate, perfluorooctyl acrylate, perfluoromethyl methacrylate, perfluoroethyl methacrylate, tetrafluoro Propyl methacrylate, perfluorooctyl methacrylate, and the like, and examples thereof include perfluoromethyl methacrylate, perfluoroethyl methacrylate, tetrafluoropropyl methacrylate, perfluorooctyl methacrylate , Perfluorooctyl acrylate, and the like.

(5) The alkyl (meth) acrylate monomer includes, for example, (meth) acrylate monomers containing an alkyl group having 4 to 20 carbon atoms. Among them, a (meth) acrylate monomer having 4 to 18 carbon atoms is preferable.

Specific examples include n-butyl (C ₄ ), sec-butyl, tert-butyl, n-pentyl, n-hexyl, heptyl, 2-ethylhexyl, octyl, C _12), tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl (stearyl: there may be mentioned the (meth) acrylate monomers having an alkyl group such as C ₁₈₎ group. Among them, (meth) acrylate monomers having n-butyl, dodecyl, octadecyl and the like are preferable, and n-butyl acrylate, dodecyl methacrylate, octadecyl methacrylate, dodecyl acrylate, Decyl acrylate is more preferable.

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

(In the formula (II), R ²¹ represents a hydrogen atom or a methyl group,

And A represents an ether group substituted alkyl group.

In an ether group-substituted alkyl group are, specifically, (i) C ₁ ~ alkyl group of C ₂₀ alkoxy group or a C ₁ ~ C ₂₀ with C ₁ ~ C ₂₀ substituted with an aryloxy group _{of, (ⅱ) C 1 ~ C} 20 the mono-substituted with an alkyl group (C ₂ ~ C ₂₀ alkylene glycol) _{group, (ⅲ) C 1 ~ C} 20 alkoxy group or a C ₁ ~ C ₂₀ aryloxy mono (C ₂ ~ C is substituted with ₂₀ alkylene glycol) group, (iv) C ₁ ~ C poly substituted with ₂₀ alkyl group (C ₂ ~ C ₂₀ alkylene glycol) group, (v) C ₁ ~ alkoxy group of C ₂₀ or C ₁ ~ aryloxy of C ₂₀ (C ₂ -C ₂₀ alkylene glycol) group substituted with a group represented by the formula: The ether group may contain a hydroxyl group.

Among them, the group of C ₁ ~ C ₂₀ alkoxy group containing C ₁ ~ C ₂₀ alkyl group-containing mono or polyester of an alkyl group, C ₁ ~ C ₂₀ of (C ₂ ~ C ₂₀ alkylene glycol) is preferred.

Examples of the alkoxy group include a methoxy group, ethoxy group, n-propoxy group, n-butoxy group, tert-butoxy group, sec-butoxy group and pentyloxy group.

Examples of the aryloxy group include a phenoxy group and a benzyloxy group.

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

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among them, a chlorine atom is preferable.

Examples of the alkyl group include those described above.

Examples of the alkyl group substituted with an alkoxy group include methoxymethyl, ethoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, (2-chlorethoxy) ethyl, n- , (2-cyclohexylethoxy) ethyl, (2-ethylhexyloxy) ethyl and the like.

Examples of the alkyloxy group substituted with an aryloxy group include phenoxyethyl and benzyloxyethyl.

Examples of the alkylene glycol include ethylene glycol, propylene glycol, and butylene glycol.

Examples of the alkyl group-substituted monoalkylene glycol group and the alkyl group-substituted polyalkylene glycol) group include methoxymonoethylene glycol, ethoxymonoethylene glycol, methoxydiethylene glycol, methoxytriethylene glycol, methoxynonoethylene Glycols, methoxypolyethylene glycol, methoxy dipropylene glycol, methoxy tripropylene glycol, phenoxy diethylene glycol, phenoxypolyethylene glycol, ethoxy diethylene glycol, butoxy diethylene glycol and the like.

(6) Examples of the ether group-substituted alkyl (meth) acrylate monomer include butoxy ethyl (meth) acrylate, methoxymethyl (meth) acrylate, ethoxymethyl (meth) Ethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, (2-chlorethoxy) ethyl (Meth) acrylate, cyclohexyloxyethyl (meth) acrylate, (2-cyclohexylethoxy) ethyl (meth) acrylate, phenoxyethyl (meth) acrylate, benzyloxyethyl (Meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, triethylene glycol (meth) acrylate, ethoxydiethylene glycol Methoxydiethyl (Meth) acrylate, methoxy dipropylene glycol (meth) acrylate, methoxy tripropylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate and phenoxypolyethylene glycol .

Among them, the fluorine-containing (meth) acrylic resin is preferably a (meth) acrylic monomer having a fluoroalkyl group having 2 to 10 carbon atoms as the fluorine-substituted alkyl (meth) acrylate monomer, (5) (Meth) acrylate monomer containing an alkyl group having 4 to 20 carbon atoms as a monomer, and (6) an alkoxyalkyl (meth) acrylate as an ether group-substituted alkyl (meth) acrylic monomer.

The fluorine-containing (meth) acrylic resin is obtained by copolymerizing (4) a structural unit derived from a fluorine-substituted alkyl (meth) acrylate monomer, (5) an alkyl (meth) acrylate monomer, and The weight ratio of the structural unit derived from the monomer is preferably 1 to 60:40 to 99 and 3 to 60:40 to 97, more preferably 1 to 30:70 to 99, 1.5 to 30:70 to 98.5, and 1 to 20:80 More preferably from 0.5 to 20:80 to 98.5, and from 2 to 20:80 to 98. By providing such a composition ratio, it is possible to effectively obtain a good anti-blocking property, to give solubility and / or compatibility of each component, and to obtain a uniform and stable resin.

The fluorine-containing (meth) acrylic resin preferably has a weight average molecular weight of 1,500 to 300,000, for example. By setting this range, the properties of the resulting composition can be maintained, and viscosity can be maintained, thereby facilitating handling.

The fluorine-containing (meth) acrylic resin is used in an amount of from 0.1 to 50 parts by weight, from 0.1 to 20 parts by weight, from 0.1 to 10 parts by weight, from 0.5 to 20 parts by weight, based on 100 parts by weight of the (A) urethane (meth) 0.5 to 19 parts by weight, 0.3 to 5 parts by weight, 1 to 19 parts by weight or 2 to 19 parts by weight. By using in this range, hardness and scratch resistance can be improved, and chemical resistance, anti-blocking property and transparency can be imparted.

The composition for a hard coat of the present invention preferably contains no fluorine-containing monomer or polymer other than the above-mentioned fluorine-containing (meth) acrylic resin. Among the fluorine-containing (meth) acrylic resins, Other than the substituted alkyl (meth) acrylate, it is preferable not to have a fluorine-containing monomer.

[(D) Metal oxide fine particles]

The metal oxide fine particles (D) are not particularly limited, and those having a particle diameter of 5 nm to 50 nm are suitable, and particularly preferably 10 nm to 20 nm. Thus, the hardness of the film formed by the composition can be increased. In addition, it is possible to adjust the refractive index of the coating film and to ensure transparency.

The metal oxide fine particles include silicon oxide, zirconium oxide, titanium oxide, zinc oxide, antimony pentoxide, tin oxide, aluminum oxide, indium oxide, indium tin oxide, ferric oxide, cerium oxide, , Cobalt oxide, cobalt oxide, cobalt trioxide, magnesium oxide, magnesium oxide, lanthanum oxide, praseodymium oxide, neodymium oxide, samarium oxide, oxidized gadolinium, terbium oxide, dysprosium oxide, erbium oxide Thulium oxide, ytterbium oxide, ruthenium oxide, scandium oxide, tantalum pentoxide, niobium pentoxide, iridium oxide, rhodium oxide, ruthenium oxide, and complex oxides obtained by bonding them.

For example, a silicon compound represented by the following formula (IV) or a partial hydrolyzate thereof.

(Wherein,

R ⁷ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an acyl group having 1 to 10 carbon atoms,

R ⁸ represents an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms, an acyl group having 1 to 8 carbon atoms,

R ⁹ is an organic group having 1 to 12 carbon atoms which may contain an epoxy group, a methacrylic group, an acrylic group, an amino group, a ureido group or a mercapto group,

a is 0 or 1, and b is 0, 1 or 2.)

Examples of the organic group include alkyl, alkenyl, aryl and the like.

Examples of the alkyl group include methyl, ethyl, propyl, n-butyl, t-butyl, sec-butyl, isobutyl, pentyl, hexyl, heptyl and octyl groups.

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

Examples of the alkenyl group include vinyl, aryl, 2-propenyl, prop-2-en-1-yl and the like.

Examples of the acyl group include formyl, acetyl, propionyl, butyryl, valeryl, oxalyl, malonyl, succinyl, benzoyl, trioyl, and phthaloyl.

Specific examples of the compound include trimethylmethoxysilane, triphenylmethoxysilane, diphenylmethylmethoxysilane, phenyldimethylmethoxysilane, vinyldimethylethoxysilane, dimethyldimethoxysilane, phenylmethyldiethoxysilane, gamma -Mercaptopropyltrimethoxysilane,? -Glycidoxypropyltriethoxysilane, tetraethylorthosilicate, tetramethylorthosilicate, and other known silicon compounds exemplified in JP-A-2006-70120, or a partial hydrolyzate thereof .

Particularly, a silicon compound in which R ⁹ is a methacryl group or an acrylic group is preferable because it further increases the hardness of the film. Examples of such silicon compounds include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltri Ethoxy silane, 3-acryloxypropyl trimethoxy silane, and the like.

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

The metal oxide fine particles are preferably used in an amount of 30 to 500 parts by weight, more preferably 50 to 350 parts by weight, based on 100 parts by weight of the (A) urethane (meth) acrylate as solid content. By using in this range, the hardening shrinkage ratio can be adjusted together with other components.

The metal oxide fine particles may be dispersed in an organic solvent and used as an organosol.

Examples of the solvent include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-methoxy-2-propanol and isopropyl alcohol.

Examples of the glycols include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 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 moiety It may be mentioned ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether.

Examples of the aliphatic cyclic ketones include cyclohexanone, ortho, meta, and paramethylcyclohexanone.

The acetic acid esters include, for example, n-propyl acetate and n-butyl acetate.

Solvent naphtha, methyl ethyl ketone, methyl isobutyl ketone and the like may also be used.

The organosols having a solid content in the range of 5 to 100% concentration can be used by using these solvents.

The composition of the present invention may further contain a (meth) acrylic acid compound or a vinyl group-containing compound. In this case, it is preferable that 0.1 to 50 parts by weight, for example, be contained in 100 parts by weight of the total composition. These compounds may be used alone, or two or more of them may be used in combination.

Examples of the (meth) acrylic acid compound include acrylic acid amides, alkyl (meth) acrylates, aminoalkyl (meth) acrylates, quaternary salts of aminoalkyl (meth) acrylate, alkoxypolyalkylene glycol (Meth) acrylates, hydroxyalkyl (meth) acrylates, acid anhydride adducts of hydroxyalkyl (meth) acrylates, polyalkylene glycol di (meth) acrylates, alkyldiol di Polyol poly (meth) acrylates, and alkylene oxide-added polyol poly (meth) acrylates. These compounds are described, for example, in JP-A-2000-264939.

Examples of the vinyl group-containing compound include vinyl acetate, N-vinylacetamide, vinyl pyrrolidone, vinyl alkyl ethers, vinyl sulfonic acid, and salts of vinyl sulfonic acid.

The composition of the present invention may contain a polymerization initiator, a diluent, a leveling agent, a lubricity-imparting agent, and other additives.

The polymerization initiator is not particularly limited, but a photopolymerization initiator that generates a radical by an active energy ray is preferable. For example, hydroxycyclohexyl phenyl ketone, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-2-phenylacetophenone, benzophenone, 2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) (2-hydroxy-2-propyl) ketone, 4- (2-acryloyloxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, bis (2,4,6-trimethylbenzoyl) phenyl (4-morpholinophenyl) -butanone-1,2-hydroxy-1- {4- [4- (2- Methylpropionyl) -benzyl] -phenyl} -2-methylpropan-1-one, oligo {2-hydroxy- Methyl-2- (4-methylphenylsulfonyl) propane-1-yl] 1-one.

Examples of diluents include monoalkyl ethers of alkylene glycols, alkyl alcohols, alkylcarboxylic esters of alkylene glycol monoalkyl alcohols, ketones, alkylcarboxylic esters of alkyl alcohols and the like. These are exemplified, for example, in JP-A-2004-43790.

The composition for a hard coat of the present invention may contain a solvent as required. As the solvent, there can be used the above-mentioned alcohols, glycols, aliphatic cyclic ketones, acetic acid esters, and the like.

Examples of the leveling agent and lubricity imparting agent include a copolymer of polyoxyalkylene and polydimethylsiloxane, and a copolymer of polyoxyalkylene and fluorocarbon.

[Molded article]

The composition for a hard coat of the present invention can be cured by irradiating active energy rays of ultraviolet rays, radiation rays, infrared rays, X rays, and electron rays. The cured polymer of this composition exerts a hard coat function on the surface of the molded article.

The molded article here is not limited to a plastic molded article made of a general-purpose resin such as polystyrene resin, polyolefin resin, ABS resin, AS resin and AN resin, but may be a molded article made of wood, glass, metal, ceramics, paper, cement, Including those molded from various materials. In addition, a molded article may be constituted by the composition of the present invention itself. Preferably, the hard coat composition of the present invention is formed as a hard coat layer on its surface. In addition, as the molded article, the composition for a hard coat of the present invention may be in the form of a film constituting the hard coat layer, a transfer foil or the like.

Thus, for example, the composition for a hard coat of the present invention may be applied to a transparent substrate to form a film, and a transfer film for hard coating or a film for hard coat may be used. It may be applied.

In the case where the molded article is made of plastic, the hard coat composition of the present invention may be mixed with the plastic constituting the molded article to form a hard coat layer as long as the plastic molded article does not affect the intended properties.

For example, a hard coat layer is formed by applying a composition for a hard coat to one or both surfaces of a transparent substrate, irradiating the coating film with light, and the like.

Examples of the transparent substrate include polyurethane resin, polyepisulfide resin, (meth) acrylic polymer such as polymethyl methacrylate (PMMA), aryl polymer, diethylene glycol bisaryl carbonate, polycarbonate, MS resin, cyclic polyolefin And a substrate made of various synthetic resins. The base material may be any of a flat plate shape, a curved plate shape, and a film shape.

The coating can be carried out by, for example, dip coating, flow coating, spray coating, gravure coating, bar coating, spin coating, roll coating, flexographic printing, screen printing, .

The thickness of the coating is preferably about 0.01 to 100 mu m after curing.

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

In addition, in order to improve the adhesion of the hard coat layer, a primer layer may be provided on the surface of the transparent substrate or the molded product in advance, or a pretreatment such as alkali treatment, acid treatment, plasma treatment, corona treatment or flame treatment may be performed.

Examples of the primer layer include a urethane resin and an acrylic resin. The thickness of the primer layer is preferably about 2 to 50 nm. The primer layer can be formed by applying these resin solutions by one of a dipping method, a spraying method, a flow coating method, a roll coating method and a spin coating method.

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

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

To the vessel equipped with a reflux condenser, a thermometer, a stirrer and a dropping tank, 150 parts by weight of 3-methyl-3-methoxybutanol Solfit (manufactured by Kuraray Co., Ltd.) was added and the liquid temperature was kept at 120 占 폚. 5 parts by weight of LIGHTEESTER M-3F (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) as a trifluoroethyl methacrylate, 47.5 parts by weight of methyl methacrylate, 47.5 parts by weight of 2-hydroxyethyl acrylate , And 1 part by weight of Pabutil D (trade name, manufactured by Nippon Oil & Fats Co., Ltd.) was added dropwise to the sole pit over about 1 hour. And the mixture was reacted at 120 DEG C for 2 hours to obtain a fluorine-containing (meth) acrylic copolymer liquid.

The weight average molecular weight of the resulting fluorine-containing (meth) acrylic copolymer solution was determined by gel permeation chromatography to be 11000 in terms of polystyrene.

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

150 parts by weight of Solfit (trade name, manufactured by Kuraray Co., Ltd.) was placed in a container equipped with a reflux condenser, a thermometer, a stirrer and a dropping funnel, and the liquid temperature was kept at 120 캜. 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, 30 parts by weight of perbutyl D (Trade name, manufactured by KYOTO K.K.) was added dropwise to the sole pit over a period of about 1 hour. And the mixture was reacted at 120 DEG C for 2 hours to obtain a fluorine-containing (meth) acrylic copolymer liquid.

The weight average molecular weight of the obtained fluorine-containing (meth) acrylic copolymer liquid was determined by gel permeation chromatography, which was found to be 35000 in terms of polystyrene.

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 equipped with a reflux condenser, a thermometer, a stirrer and a dropping funnel, and the liquid temperature was kept at 120 캜. 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, (Trade name, manufactured by Mitsubishi Chemical Corporation) was added dropwise to the sole pit over a period of about 1 hour. And the mixture was reacted at 120 DEG C for 2 hours to obtain a fluorine-containing (meth) acrylic copolymer liquid.

The weight average molecular weight of the resulting fluorine-containing (meth) acrylic copolymer liquid was determined by gel permeation chromatography to be 15,000 in terms of polystyrene.

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

In a container equipped with a reflux condenser, a thermometer, a stirrer and a dropping funnel, 200 parts by weight of Solfit (trade name, manufactured by Kuraray Co., Ltd.) was added and the liquid temperature was kept at 110 占 폚. 20 parts by weight of LIGHTEST FM-108 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) which is perfluorooctylethyl methacrylate, 15 parts by weight of n-butyl acrylate, 2 parts by weight of 2-hydroxyethyl acrylate 65 parts by weight and 5.0 parts by weight of perbutyl O (trade name, manufactured by Nippon Oil & Fats Co., Ltd.) was added dropwise to the sole pit over a period of about 1 hour. The reaction was carried out at 110 DEG C for 2 hours to obtain a fluorine-containing (meth) acrylic copolymer liquid.

The weight average molecular weight of the obtained fluorine-containing (meth) acrylic copolymer liquid was determined by gel permeation chromatography, which was found to be 5000 in terms of polystyrene.

Examples and Comparative Examples

(A) urethane (meth) acrylate

(B) a polyfunctional (meth) acrylate,

(C) a fluorine-containing (meth) acrylic resin,

(D) metal oxide fine particles were kneaded at a composition ratio (parts by weight) shown in Table 1 to obtain a composition for a hard coat containing about 30% by weight of a resin component.

The components in Table 1 are as follows.

Resin (A) -1 Polyisocyanate (Colonate HK) / 2-hydroxyethyl acrylate / pentaerythritol triacrylate (prepared according to Synthesis Example 1 of JP-A-2010-107956)

Resin (A) -2 Product name: UA-306H (pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer made by Kyoeisha Chemical Co., Ltd.)

Resin (A) -3 Polyisocyanate (Colonate HK) / 2-hydroxyethyl acrylate / pentaerythritol triacrylate / 10 molar addition of acrylic acid ethylene oxide

(B) pentaerythritol triacrylate, trade name: Light Acrylate PE-3A (manufactured by Kyoeisha Chemical Co., Ltd.)

Resin (C) -1 The fluorine-containing (meth) acrylic resin 1 prepared in Production Example 1

Resin (C) -2 The fluorine-containing (meth) acrylic resin 2 produced in Production Example 2

Resin (C) -3 The fluorine-containing (meth) acrylic resin 3 produced in Production Example 3

Resin (C) -4 The fluorine-containing (meth) acrylic resin 4 produced in Production Example 4

(C) -5 alkyl-based copolymer, trade name: Polyflow 99C (manufactured by Kyoeisha Chemical Co., Ltd.)

Resin (C) -6 silicone copolymer, trade name: Polyflow KL-401 (manufactured by Kyoeisha Chemical Co., Ltd.)

Organosilica sol solution 1 A product obtained by introducing a methacryl group into the fine particles of PL-2L-MEK (manufactured by Fuso Kagaku Kogyo K.K., particle size of 10 nm, solid content 20.0%) (R ⁹ in formula (IV) Equivalent to that of the former)

(R ⁹ in the formula (IV) is equivalent to that of an acrylic group) in which the acrylic group is introduced into the fine particles of the organosilica sol solution 2 PL-2L-MEK (manufactured by Fuso Chemical Co., Ltd., particle size of 10 nm, solid content 20.0% box)

Anti-blocking filler Product name: PL-20 (manufactured by Fuso Chemical Co., Ltd., particle diameter: 220 nm)

Photopolymerization initiator 1 Product name: Irgacure 184, manufactured by BASF Japan Co., Ltd.

Photopolymerization initiator 2 Product name: Lucirin TPO, manufactured by BASF Japan KK

Applied substrate: 100 mu m PET (untreated)

The compositions for hard coatings obtained in Examples and Comparative Examples were applied to a substrate, and the solvent was dried. This was loaded on a conveyor at a speed of 6 m / min and subjected to crosslinking polymerization by irradiation of ultraviolet rays twice at a height of 10 cm by a high pressure mercury lamp of 80 W / cm to form a coating layer having a thickness of about 5 탆 including a cured polymer.

The coating layer thus obtained was evaluated for the coating film state (transparency), pencil hardness, resistance to hardening of steel, winding property, anti-blocking property, adhesion property, transmittance and haze value.

≪ Film state &

In the observation by the moxibustion, it was evaluated in four stages that there was no whitening at all, ∘ was little, △ was partial, and x was wholly.

<Pencil hardness>

Pencil Hardness Tester The test was carried out under a load of 500 g, and the hardness of the pencil which did not cause scratches was shown.

<My Steel Steel>

The obtained coating layer was rubbed and rubbed back and forth 10 times with a steel wool (# 0000) having a load of about 1 kg. When observed by the naked eye, it was rated as ⊚, no scarring was observed, scarcely scarred scarcely scarred scarcely scarred scarcely, and wound scarred scarred scarcely.

<Kwon Sung-sung>

The coated film was cut in 10 cm square, and the average value of the floating heights of the four corners was measured. The average value of the floating height was 10 mm or less; the case of 10 to 20 mm; the case of 20 to 30 mm; the case of 30 mm or more.

<Anti-blocking property>

The coating film was allowed to stand for 1 day under a load of 1 kg in a state in which the back side (non-coated side) or the coated side was adhered, and it was confirmed that the opposite sides were not in close contact with each other.

&Lt; Adhesion >

A cross-cut test was conducted. The results were rated as?, 100/100?, 90/100 or more?, 50/100 or more?, And 50/100 or less.

&Lt; Total light transmittance and haze value >

The total light transmittance and the haze value were measured using a haze value measuring device (colorimetry colorimeter, Ultra Scan XE).

It can be seen from Table 1 that in the examples, by mixing polyfunctional (meth) acrylate, fluorine-containing (meth) acrylic resin and metal oxide fine particles with urethane acrylate, results satisfactory in all evaluations were obtained.

On the other hand, in the comparative example, it was found that the anti-blocking effect was in particular deteriorated.

Example 5

The composition for a hard coat obtained in Example 1 was applied to a substrate in the same manner as in the evaluation of the coating film state (transparency), pencil hardness, resistance to stiffness, curling resistance, adhesion, antilocking property, transmittance and haze value, To prepare a hard coat film.

The resulting film was sandwiched between injection molding dies and an acrylic resin was injected by simultaneous injection molding. After cooling, a molded article having a hard coat layer was obtained.

As described above, the composition of the present invention can exhibit the transparency, scratch resistance and durability of the acrylic resin to the maximum, while reducing the winding property. In addition, by containing the metal oxide fine particles, it is possible to obtain a good hard coat property, in particular, to secure transparency and / or transparency, balance with polyfunctional (meth) acrylate, and exhibit good anti-blocking performance . The fluorine-containing (meth) acrylic resin can impart the chemical resistance and the antifouling property.

The composition for a hard coat of the present invention can be applied to a molded article made of plastic, glass, paper, wood or the like, and is excellent in durability such as adhesion, transparency, scratch resistance and moisture resistance, chemical resistance and anti- A stable and excellent coating layer can be imparted over a long period of time, and the winding property of the composition for a hard coat, that is, the hardening shrinkage ratio, is also reduced, and an anti-blocking property can be maintained and a good coating layer can be obtained. Therefore, a part requiring such properties can be used in a molded article.

Claims (12)

(A) a urethane (meth) acrylate,
(B) a polyfunctional (meth) acrylate,
(C) a polymer obtained by polymerizing a fluorine-containing (meth) acrylate,
(D) a metal oxide fine particle. The method according to claim 1,
Wherein the (A) urethane (meth)
(1) a compound having a polyether as a main chain,
(2) an isocyanate compound,
(3) a polymer obtained by a reaction with a hydroxyl group-containing (meth) acrylate compound. 3. The method according to claim 1 or 2,
Wherein the (A) urethane (meth) acrylate is represented by the following formula (I)

(In the formula (I), R ¹ O- represents a dehydroxyl residue of a compound having a polyether as a main chain,
-R ² - is a deisocyanate group residue of the isocyanate compound,
R ³ O- is a dehydroxyl residue of a hydroxyl group-containing (meth) acrylate compound,
and m + n = an integer of 1 to 50). The method according to claim 2 or 3,
Wherein the isocyanate compound (2) is a polyisocyanate obtained by polycondensation of a diisocyanate or a diisocyanate monomer, or a urethane structure in which an alcohol compound is added to an isocyanate group and / or a urea structure in which an amine compound is added. 5. The method according to any one of claims 2 to 4,
Wherein the hydroxyl group-containing (meth) acrylate compound (3) is a hydroxyalkyl (meth) acrylate or a polyol (meth) acrylate. 6. The method according to any one of claims 3 to 5,
Wherein the compound (1) is at least one compound selected from the group consisting of an alkylene glycol compound and an alkylene oxide addition compound. The method according to claim 6,
(1) the polyether having a main chain is a polyalkylene glycol compound having an alkoxypolyalkylene glycol at one end and a (meth) acrylic acid with an alkylene oxide or a mono (meth) acrylate of a polyalkylene glycol; Acrylate compound. &Lt; / RTI &gt; 8. The method according to any one of claims 1 to 7,
The fluorine-containing (meth) acrylic resin (C)
(4) a fluorine-substituted alkyl (meth) acrylate monomer,
(5) an alkyl (meth) acrylate monomer,
(6) an ether group-substituted alkyl (meth) acrylate monomer. 9. The method of claim 8,
(5) The composition for a hard coat, wherein the alkyl (meth) acrylate monomer has a C ₄ -C ₂₀ alkyl group. 10. The method according to claim 8 or 9,
The above-mentioned (6) ether group-substituted alkyl (meth)

(In the formula (II), R ²¹ represents a hydrogen atom or a methyl group
A represents a mono and poly (C ₂ - C ₂₀ alkylene glycol) group containing a C ₁ - C ₂₀ alkyl group having a C ₁ - C ₂₀ alkoxy group and an C ₁ - C ₂₀ alkyl group containing a C ₁ - C ₂₀ alkyl group) / RTI &gt; 11. The method according to any one of claims 1 to 10,
Wherein the (B) polyfunctional (meth) acrylate is a compound having at least two (meth) acryloyl groups in one molecule. A molded article, characterized in that the cured polymer of the composition for hard coating according to any one of claims 1 to 11 is formed from a hard coat layer.