KR102180159B1 - Composition for hardcoat and molded article with hardcoat layer - Google Patents

Abstract

An object of the present invention is to provide a composition for a hard coat and a molded article capable of minimizing crimp properties while exhibiting the transparency, scratch resistance, chemical resistance and anti-blocking properties of the components to be used to the maximum. (A) urethane (meth) acrylate, (B) polyfunctional (meth) acrylate, (C) a fluorine-containing (meth) acrylic resin and (D) a composition for a hard coat comprising metal oxide fine particles.

Description

A hard coat composition and a molded article in which a hard coat layer is formed {COMPOSITION FOR HARDCOAT AND MOLDED ARTICLE WITH HARDCOAT LAYER}

The present invention relates to a hard coat composition and a molded article having a hard coat layer formed thereon, and more particularly, a hard coat composition and a hard coat layer having good durability, chemical resistance, anti-blocking properties, transparency, crimp properties and adhesion, etc. It relates to a formed article.

Conventionally, various plastics have been used in various fields such as home appliances and automobile industries. Plastics have several advantages, such as light weight and inexpensiveness in addition to processability and transparency, but they are softer than materials such as glass and have drawbacks such as being easy to scratch the surface.

In order to improve these drawbacks, 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 has been used.

As such a hard coat material, for example, a thermosetting hard coat material such as a silicone-based, acrylic-based, or melamine-based resin is used. Among them, acrylic resins that can be cured by light such as ultraviolet rays are advantageous in terms of curing time and raw material cost, and are becoming mainstream.

However, acrylic resins are generally inferior in scratch resistance and abrasion resistance compared to silicone coatings.

Therefore, a method of using a polyfunctional (meth)acrylate or the like having at least two (meth)acrylic groups in the molecule has been proposed (for example, Japanese Unexamined Patent Publication No. Hei 9-48934, etc.).

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

Such a polyfunctional (meth)acrylate, etc., has a large cure shrinkage rate, and particularly has a problem that when it is molded into a thin film shape, the crimp property becomes remarkable.

In addition, when these polyfunctional (meth)acrylates are formed into a film shape, due to high static friction resistance and surface smoothness, polyfunctional (meth)acrylates such as adjacent films adhere to each other and adhere firmly. In some cases, a phenomenon that cannot be easily dropped, that is, a blocking phenomenon, occurs. As an anti-blocking agent used to prevent such a blocking phenomenon, silica powder is generally widely used. However, when the particle diameter of silica is large, the transparency is remarkably impaired, whereas when the particle diameter is small, there is a trade-off relationship that the anti-blocking effect cannot be sufficiently exhibited. Therefore, it is required to maintain high transparency while effectively preventing the occurrence of a blocking phenomenon.

The present invention has been made in order to solve the above problems, while exhibiting the hard coat performance such as scratch resistance to the maximum, at the same time, at the same time, minimizes crimp properties, and excellent anti-blocking properties and transparency resin composition and molded article for hard coat It aims to provide.

The present invention includes the following inventions.

(1) (A) urethane (meth) acrylate,

(B) a polyfunctional (meth)acrylate,

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

(D) A composition for a hard coat comprising metal oxide fine particles.

(2) The (A) urethane (meth)acrylate,

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

(2) an isocyanate compound,

(3) The composition for a hard coat according to [1], which is a polymer obtainable by reaction with a hydroxyl group-containing (meth)acrylate compound.

(3) The (A) urethane (meth)acrylate is the following formula (I)

(In formula (I), R ¹ O-is a dehydrogenated 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 dehydrogenated residue of a hydroxyl group-containing (meth)acrylate compound,

The composition for hard coats according to [1] or [2], comprising a urethane (meth)acrylate oligomer represented by m+n=1 to 50.).

(4) The isocyanate compound (2) is a polyisocyanate obtained by polycondensation of diisocyanates or diisocyanate monomers, or has a urethane structure in which an alcohol compound is added to the isocyanate group and/or a urea structure in which an amine compound is added (2) ] Or the composition for a hard coat according to [3].

[5] The composition for a hard coat according to any one of [2] to [4], wherein the (3) hydroxyl group-containing (meth)acrylate compound is hydroxyalkyl (meth)acrylates and polyol (meth)acrylates.

[6] The hard coat according to any one of [3] to [5], wherein the (1) compound having a polyether as a main chain is at least one compound selected from the group consisting of an alkylene glycol compound and an alkylene oxide addition compound. Dragon composition.

(7) The compound (1) having a polyether as a main chain is a polyalkylene glycol compound containing a single-ended hydroxyl group consisting of alkoxy polyalkylene glycols, (meth)acrylic acid added with an alkylene oxide or a mono of polyalkylene glycol. The (meth)acrylated composition for a hard coat according to [6].

(8) The (C) fluorine-containing (meth)acrylic resin,

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

(5) an alkyl (meth) acrylate monomer,

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

(10) the (6) ether group substituted alkyl (meth) acrylate monomer,

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

A represents a C ₁ to C ₂₀ alkoxy group-containing C ₁ to C ₂₀ alkyl group, a C ₁ to C ₂₀ alkyl group-containing mono and poly(C ₂ to C ₂₀ alkylene glycol) group. 9] or the composition for a hard coat according to [10].

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

[12] A molded article wherein the cured polymer of the hard coat composition according to any one of [1] to [11] is formed as 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 excellent in anti-blocking properties and transparency, while at the same time exhibiting the hard coat performance such as scratch resistance to the maximum, and at the same time minimizing crimp properties. .

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

(A) urethane (meth)acrylate,

(B) a polyfunctional (meth)acrylate,

(C) a polymer obtained by polymerizing fluorine-containing (meth)acrylate (hereinafter sometimes referred to as ``fluorine-containing (meth)acrylate-based resin''), and

(D) It contains metal oxide fine particles.

Thus, (C) fluorine-containing (meth)acrylate is effective in order to exhibit anti-blocking properties. Furthermore, by using (D) metal oxide particles together, it is possible to ensure even more favorable anti-blocking properties. Further, (A) it becomes possible to achieve a balance between low crimp and high hardness by the action of urethane (meth)acrylate.

In addition, in this specification, "(meth)acryl" represents "methacryl" and/or "acrylic", and "(meth)acrylate" represents "methacrylate" and/or "acrylate".

[(A) Urethane (meth)acrylate]

(A) Urethane (meth)acrylate may have, for example, one or more hydrophilic groups (eg, hydroxyl group, carboxyl group, ethylene glycol group, propylene glycol group, etc.). For example, a resin obtained by reaction of an isocyanate compound and a compound having a polyether as a main chain and/or a hydroxyl group-containing (meth)acrylate compound can be mentioned. Specifically,

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

(2) an isocyanate compound,

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

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

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

(2) an isocyanate compound,

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

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

(In the formula, R ¹ O-is a dehydrogenation 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 dehydrogenation residue of a hydroxyl group-containing (meth)acrylate compound, The compound represented by m+n=1-50) is mentioned.

In formula (I), m may be 0, but 1 or more is preferable. When m is 2 or more, a plurality of R ^1s may be the same or may be 2 or more. The molecular weight of the substituent constituting R ¹ is preferably about 100 to 2000, and preferably about 100 to 1000. This is because when 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. This is because when the molecular weight is too large, the hardness tends to decrease.

Although n may be 0, it is suitable that it is an integer greater than 0, that is, 1 or more. 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. This is because when the molecular weight is too large, the hardness decreases.

2 or more are preferable and, as for m+n, 3 or more, 4 or more, 5 or more, or 6 or more are more preferable. 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 and n = 1 or more.

(1) Compounds having a polyether as a main chain include compounds having an ether group, preferably a polyether group as a main chain, and having a hydroxyl group (including a product containing a hydroxyl group at one end). Here, a hydroxyl group is also included in an ether group. However, it is a compound different from the (3) hydroxyl-containing (meth)acrylate compound described later. In particular, at least one compound selected from the group consisting of an alkylene glycol compound and an alkylene oxide addition compound can be mentioned. For example, polyalkylene glycols, alkoxy polyalkylene glycols, (meth)acryloxypolyalkylene glycols, reaction products of polyalkylene and polytetramethylene glycol, epoxy compounds having oxysilane rings and (meth) (Meth)acryloyl group-containing polyethers obtained by reacting a hydroxyl group-containing (meth)acrylic acid derivative obtained by addition reaction of acrylic acid with an alkylene oxide such as ethylene oxide and propylene oxide, and a (meth)acrylate alkylene oxide addition compound, etc. Can be lifted.

Among them, polyalkylene glycols, polyalkylene glycols containing a single terminal hydroxyl group, alkoxy polyalkylene glycols, and polyethers containing (meth)acryloyl groups, and (meth)alkylene oxide addition compounds are preferred, Further, a polyalkylene glycol compound containing a single terminal hydroxyl group or an alkylene (meth)acrylate oxide addition compound is preferable.

In particular, it is preferable that the polyalkylene glycol compound containing a single terminal hydroxyl group is an alkoxy polyalkylene glycol, and the (meth)acrylic acid alkylene oxide addition compound is (meth)acrylic acid added with an alkylene oxide or polyalkyl It is preferable that the ene glycol is mono(meth)acrylated.

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

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

The alkoxy polyalkylene glycols are, for example, polyalkylene glycols containing an alkoxy group having 1 to 6 carbon atoms (the alkylene has, for example, about 1 to 6 carbon atoms), specifically, methoxy Polyethylene glycol, methoxy polypropylene glycol, and methoxy polytetramethylene glycol. Although the molecular weight of the alkoxy polyalkylene glycols can be arbitrarily selected, 100 to 2,000 are preferable.

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

The reaction product of polyalkylene and polytetramethylene glycol is, for example, a reaction product of polyethylene and polytetramethylene glycol, a reaction product of methoxy polyethylene and polytetramethylene glycol, and a reaction product of (meth)acryloxy polyethylene and polytetramethylene glycol. Can be lifted.

(Meth) acryloyl group-containing polyethers are acrylates containing an alkyl group having 1 to 6 carbon atoms in which a hydroxy group is substituted, for example, an ethylene oxide adduct of 2-hydroxyethyl acrylate (for example, The number of moles added is about 1 to 20).

The (meth)acrylic acid alkylene oxide addition compound is obtained by adding an alkylene oxide (e.g., about 2 to 6 carbon atoms) typified by ethylene oxide, propylene oxide, and butylene oxide to (meth)acrylic acid. Can be lifted.

(2) As an isocyanate compound, diisocyanates, polyisocyanates, for example, polyisocyanates polycondensed by a diisocyanate monomer, a urethane structure in which an alcohol compound is added to the isocyanate group, and/or a urea structure in which an amine compound is added What to have, etc. are mentioned. Among these, it is preferable to have polyisocyanates, urethane structures and/or urea structures.

Diisocyanates are, for example, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, (ortho, meta, para) xylenedi Isocyanate, methylenebis (cyclohexyl isocyanate), trimethylhexamethylene diisocyanate, cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1,4-dimethylene isocyanate, 1,5-naphthalene diisocyanate, norbornene indi Isocyanate etc. are mentioned.

Polyisocyanates obtained by polycondensation of polyisocyanates and/or diisocyanate monomers are, for example, polyisocyanate compounds, such as isophorone diisocyanate, hexamethylene diisocyanate, norbornene diisocyanate, tolylene diisocyanate, xylene diisocyanate, Difunctional isocyanates such as diphenylmethane diisocyanate, trimethylhexamethylene diisocyanate, hydrogenated xylene diisocyanate and hydrogenated diphenylmethane diisocyanate, and trifunctional or higher isocyanates which are biuret bodies or nurates thereof. Among them, polyisocyanate compounds having 3 or more, 4 or more, 5 or more, or 6 or more isocyanate groups in one molecule, for example, chain or cyclic alkyl or aryl groups (e.g., 6 to 12 carbon atoms Degree), and particularly, a nurate compound such as hexamethylene diisocyanate, isophorone diisocyanate, and tolylene diisocyanate is preferable.

Examples of the alcohol compound include bivalent to tetravalent alcohols having 2 to 10 carbon atoms, specifically ethylene glycol, propylene glycol, tetramethylene glycol, glycerin, trimethylolpropane, and pentaerythritol.

As an amine compound, diaminoethane, diaminopropane, and tetramethylenediamine are mentioned, for example.

When an alcohol compound or an amine compound is added, the number of functional groups per molecule of the isocyanate compound can be increased. In addition, it is preferable to use those having a small molecular weight per functional group from the viewpoint of increasing the scratch resistance of the cured polymer for these alcohol compounds and amine compounds.

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

Hydroxyalkyl (meth)acrylates are, for example, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyphenoxypropyl (meth) Acrylate is mentioned.

Polyol (meth) acrylates are, for example, di- to tetravalent polyol (meth) acrylates having 2 to 10 carbon atoms, specifically, glycerin di (meth) acrylate, trimethylol propanedi (meth) Acrylate, ditrimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate.

Examples of derivatives derived from epoxy resins and carboxylic acids include (meth)acrylic acid adducts of glycidyl (meth)acrylate.

Moreover, urethane (meth)acrylate may be used individually, and may use 2 or more types together.

In formula (1), the urethane (meth)acrylate of the present invention has a urethane structure in which an alcohol compound is added to (2) polyisocyanates as an isocyanate compound, and (1) polyether as a main chain. Polyalkylene glycols, alkoxy polyalkylene glycols and (meth)acryloyl group-containing polyethers, (meth)acrylate alkylene oxide addition compounds and/or (3) hydroxyl group-containing (meth)acrylates as compounds As the compound, a combination of hydroxyalkyl (meth)acrylates and polyol (meth)acrylates is preferable. Among them, a combination comprising all of (1), (2) and (3) described herein is more preferable.

The urethane (meth)acrylate of the present invention is suitably about 500 to 5,000 in molecular weight, for example. 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 Japanese Patent Application Laid-Open No. 2000-264936.

In (A) urethane (meth)acrylate, the molar ratio of (1) a compound having a polyether as a main chain, for example, a polyalkylene glycol compound containing a hydroxyl group at one end, is (3) a hydroxyl group-containing (meth)acrylate It is preferably less than or equal to the molar ratio of the compound. As the molecular weight of the polyether chain is larger, the hardness may decrease when crosslinking polymerization is performed. When the number of functional groups of the hydroxyl-containing (meth)acrylate compound increases, the hardness increases when crosslinked polymerization is carried out, and conversely, the smaller the number of functional groups, the lower the hardness may be. Therefore, by adjusting these, a cured polymer having an appropriate hardness can be obtained. Specifically, the weight ratio of the components (1) to (3) described above is (1): (2): (3) = 0 to 50: 10 to 70: 20 to 80, and 10 to 30:30-50:20-60 are preferable.

[(B) polyfunctional (meth)acrylate]

(B) Polyfunctional (meth)acrylate is a (meth)acrylate resin containing two or more functional groups, and refers to a thing other than (meth)acrylate having a urethane structure represented by (A). It is preferable that it is a compound which has 2 or more (meth)acryloyl groups in 1 molecule.

For example, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, dimethyloltricyclo Decane di(meth)acrylate, trimethylolpropane (ethylene oxide adduct) tri(meth)acrylate, polyester di(meth)acrylate, tetraethylene glycol di(meth)acrylate, glycerin di(meth)acrylate , (Meth)acrylate of glycerin ethylene oxide adduct, (meth)acrylate of glycerin propylene oxide adduct, ethylene glycol, diethylene glycol, triethylene glycol, tetra ethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetra Diacrylates of polyalkylene glycols such as propylene glycol, (meth)acrylates of compounds obtained by condensing polyhydric alcohols and polybasic acids, compounds obtained by reaction of the aforementioned polyisocyanates and hydroxyl group-containing (meth)acrylates, hydroxyl group-containing polymers And a compound obtained by urethanization reaction with an isocyanate containing a hydroxyl group (meth)acrylate. These compounds may be used alone or in combination of two or more.

Polyfunctional (meth)acrylate, based on 100 parts by weight of (A) urethane (meth)acrylate described above, 10 to 500 parts by weight, 10 to 200 parts by weight, 20 to 300 parts by weight, 20 to 200 parts by weight, It is preferable to use 20 to 100 parts by weight, 20 to 80 parts by weight, 20 to 50 parts by weight, and the like. When used in this range, it is possible to effectively adjust the curing shrinkage ratio in combination with other components.

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

(C) The fluorine-containing (meth)acrylic resin may include a structural unit derived from (meth)acrylate and may be a polymer containing a fluorine atom. For example,

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

(5) an alkyl (meth) acrylate monomer,

(6) A polymer obtained by reaction with an ether group-substituted alkyl (meth)acrylate monomer is mentioned.

(4) As a fluorine-substituted alkyl (meth)acrylate monomer, a (meth)acrylate monomer which has a C1-C18 fluoroalkyl group is mentioned, for example. Especially, it is preferable to have a C2-C18 fluoroalkyl group.

Specifically, perfluoro methyl acrylate, perfluoro ethyl acrylate, tetra fluoro propyl acrylate, perfluoro octyl acrylate, perfluoro methyl methacrylate, perfluoro ethyl methacrylate, tetrafluoro Low propyl methacrylate, perfluoro octyl methacrylate, and the like, perfluoro methyl methacrylate, perfluoro ethyl methacrylate, tetra fluoro propyl methacrylate, perfluoro octyl methacrylate And perfluoro octyl acrylate are preferable.

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

Specifically, n-butyl (C ₄ ), sec-butyl, tert-butyl, n-pentyl, n-hexyl, heptyl, 2-ethylhexyl, octyl, nonyl, disyl, undecyl, dodecyl (lauryl: And (meth)acrylate monomers having an alkyl group such as C ₁₂ ), tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl (stearyl: C ₁₈ ) group. Among them, (meth)acrylate monomers having n-butyl, dodecyl, octadecyl groups, and the like are preferred, and n-butyl acrylate, dodecyl methacrylate, octadecyl methacrylate, dodecyl acrylate, octa Decyl acrylate is more preferred.

(6) As an example of the ether group-substituted alkyl (meth)acrylate monomer, the monomer represented by the following formula (II) can be mentioned.

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

A represents an ether group substituted alkyl group.)

As the ether group-substituted alkyl group, specifically, (i) a C ₁ to C ₂₀ alkyl group substituted with a C ₁ to C ₂₀ alkoxy group or a C ₁ to C ₂₀ aryloxy group, (ii) C ₁ to 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 It represents a poly(C ₂ ~C ₂₀ alkylene glycol) group substituted with a group. Further, the ether group may contain a hydroxyl group.

Among them, a C ₁ to C ₂₀ alkoxy group-containing C ₁ to C ₂₀ alkyl group, a C ₁ to C ₂₀ alkyl group-containing mono and poly(C ₂ to C ₂₀ alkylene glycol) group are preferable.

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

As an aryloxy group, a phenoxy group, a benzyloxy group, etc. are mentioned.

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

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned. Among them, a chlorine atom is preferable.

Examples of the alkyl group include those described above.

Examples of the alkyl group substituted with the alkoxy group include methoxymethyl, ethoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, (2-chloroethoxy)ethyl, n-propoxyethyl, butoxyethyl, and cyclohexyloxyethyl. , (2-cyclohexylethoxy)ethyl, (2-ethylhexyloxy)ethyl, etc. are mentioned.

As an alkyl group substituted with the aryloxy group, phenoxy ethyl, benzyl oxyethyl, etc. are mentioned.

As alkylene glycol, ethylene glycol, propylene glycol, butylene glycol, etc. are mentioned.

Examples of the alkyl group substituted monoalkylene glycol group and the alkyl group substituted polyalkylene glycol) group include methoxy mono ethylene glycol, ethoxy mono ethylene glycol, methoxy diethylene glycol, methoxy triethylene glycol, methoxy nona ethylene. Glycol, methoxy polyethylene glycol, methoxy dipropylene glycol, methoxy tripropylene glycol, phenoxy diethylene glycol, phenoxy polyethylene glycol, ethoxy diethylene glycol, butoxy diethylene glycol, and the like.

(6) As an ether group-substituted alkyl (meth)acrylate monomer, for example, butoxyethyl (meth)acrylate, methoxymethyl (meth)acrylate, ethoxymethyl (meth)acrylate, 2-methoxy Ethyl acrylate, 2-ethoxyethyl (meth)acrylate, (2-chloroethoxy) ethyl (meth) acrylate, (2-ethylhexyloxy) ethyl (meth) acrylate, n-propoxyethyl ( Meth)acrylate, cyclohexyloxyethyl (meth)acrylate, (2-cyclohexylethoxy)ethyl (meth)acrylate, phenoxyethyl (meth)acrylate, benzyloxyethyl (meth)acrylate, methoxy Triethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, butoxydiethylene glycol (meth) acrylate, methoxy nonaethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, Methoxydiethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, methoxytripropylene glycol (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate Etc. are mentioned.

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

The fluorine-containing (meth)acrylic resin includes (4) a structural unit derived from a fluorine-substituted alkyl (meth)acrylate monomer, (5) an alkyl (meth)acrylate monomer, and (6) an ether group-substituted alkyl (meth)acrylate. The weight ratio of the structural unit derived from the monomer is preferably 1 to 60:40 to 99, 3 to 60:40 to 97, and 1 to 30:70 to 99, 1.5 to 30:70 to 98.5, 1 to 20:80 It is more preferable that they are -99, 1.5-20:80-98.5, and 2-20:80-98. By setting it as such a composition ratio, it is possible to obtain a uniform and stable resin while effectively giving good anti-blocking properties, giving solubility and/or compatibility of each component, and obtaining a uniform and stable resin.

It is preferable that the fluorine-containing (meth)acrylic resin has a weight average molecular weight of 1,500 to 300,000, for example. By setting it as this range, since the physical properties of the obtained composition can be maintained and the viscosity can be maintained, handling becomes easy.

The fluorine-containing (meth)acrylic resin is 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, based on 100 parts by weight of the above-described (A) urethane (meth) acrylate, It is preferable to use 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 such a range, hardness and abrasion resistance can be improved, and chemical resistance, anti-blocking property, and transparency can also be imparted.

In addition, in the hard coat composition of the present invention, it is preferable not to contain a fluorine-containing monomer or polymer other than the fluorine-containing (meth)acrylic resin described above, and in the fluorine-containing (meth)acrylic resin, (4) fluorine It is preferable not to have a fluorine-containing monomer other than a substituted alkyl (meth)acrylate.

[(D) metal oxide fine particles]

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

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, yttrium oxide, manganese oxide, holmium oxide. , Copper oxide, bismuth oxide, cobalt oxide, cobalt tetraoxide, iron tetraoxide, magnesium oxide, lanthanum oxide, praseodymium oxide, neodymium oxide, samarium oxide, europium oxide, gadolinium oxide, terbium oxide, dysprosium oxide, erbium oxide, oxide Thulium, ytterbium oxide, lutetium oxide, scandium oxide, tantalum pentoxide, niobium pentoxide, iridium oxide, rhodium oxide, ruthenium oxide, and a composite oxide obtained by combining them.

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

(In the formula,

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

Here, examples of the organic group include alkyl, alkenyl, and aryl.

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 phenyl, triyl, and xylyl groups.

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

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

As a specific compound, for example, trimethylmethoxysilane, triphenylmethoxysilane, diphenylmethylmethoxysilane, phenyldimethylmethoxysilane, vinyldimethylethoxysilane, dimethyldimethoxysilane, phenylmethyldiethoxysilane, γ -Mercaptopropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, tetraethylorthosilicate, tetramethylorthosilicate, etc. Known silicon compounds exemplified in JP 2006-70120 or partial hydrolyzate thereof It is illustrated.

In particular, a silicon compound in which R ⁹ is a methacrylic group or an acrylic group is preferable because it further increases the hardness of the film. As such a silicon compound, for example, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltri Ethoxysilane, 3-acryloxypropyltrimethoxysilane, and the like.

In addition, 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, and further 50 to 350 parts by weight in terms of solid content, based on 100 parts by weight of the above-described (A) urethane (meth)acrylate. By using in such a range, it is possible to adjust the cure shrinkage ratio together with other components.

Further, the metal oxide fine particles can be dispersed in an organic solvent and used as an organosol.

As the solvent type, examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-methoxy-2-propanol, and isopropyl alcohol.

As glycols, for example, ethylene glycol monomethyl ether acetate, ethylene glycol mono ethyl ether acetate, ethylene glycol mono propyl ether acetate, ethylene glycol mono butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol mono ethyl 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 monomethyl ether, ethylene glycol mono ethyl ether, and ethylene glycol mono butyl ether.

As alicyclic ketones, cyclohexanone, ortho, meta, paramethylcyclohexanone, etc. are mentioned, for example.

As acetate esters, ethyl acetate n-propyl acetate and n-butyl acetate are mentioned, for example.

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

Organosol can be used in the range of 5 to 100% solid content 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, for example, it is preferable to contain 0.1 to 50 parts by weight, respectively, with respect to 100 parts by weight of the entire composition. These compounds may be used alone or in combination of two or more.

The (meth)acrylic acid compound is, for example, acrylic acid amides, alkyl (meth) acrylates, amino alkyl (meth) acrylates, quaternary salts of amino alkyl (meth) acrylates, alkoxy polyalkylene glycol ( Meth)acrylates, hydroxyalkyl(meth)acrylates, acid anhydride adducts of hydroxyalkyl(meth)acrylates, polyalkylene glycol di(meth)acrylates, alkyldioldi(meth)acrylates And polyol poly(meth)acrylates, and alkylene oxide-added polyol poly(meth)acrylates. These compounds are described in Japanese Patent Application Laid-Open No. 2000-264939, for example.

Examples of the vinyl group-containing compound include vinyl acetate, N-vinyl acetamide, 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 and a lubricant imparting agent, and other additives.

The polymerization initiator is not particularly limited, but a photopolymerization initiator that generates radicals by active energy rays is preferable. For example, hydroxycyclohexylphenylketone, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-2-phenylacetphenone, benzophenone, 2-methyl[4 －(Methylthio)phenyl]-2-morpholino-1-propanone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-(4-isopropylphenyl)-2-hydro Roxy-2-methylpropane-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 4-(2-acryloyloxyethoxy)phenyl-( 2-hydroxy-2-propyl) ketone, 4-(2-methacryloyloxyethoxy)phenyl-(2-hydroxy-2-propyl) ketone, bis(2,4,6-trimethylbenzoyl)phenyl Phosphine oxide, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-hydroxy-1-{4-[4-(2-hydroxy-2-) Methylpropionyl)-benzyl]-phenyl}-2-methylpropane-1-one, oligo{2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone}, 1- [4-(4-benzoylphenylsulfonyl)phenyl]-2-methyl-2-(4-methylphenylsulfonyl)propane-1-one is mentioned.

Examples of the diluent include monoalkyl ethers of alkylene glycol, alkyl alcohols, alkylcarboxylic acid esters of alkylene glycol monoalkyl alcohols, ketones, and alkylcarboxylic acid esters of alkyl alcohols. Those described in Japanese Unexamined Patent Application Publication No. 2004-43790 are illustrated, for example.

The composition for hard coats of the present invention may contain a solvent as necessary. As the solvent, alcohols, glycols, alicyclic ketones, acetic acid esters, and others as described above can be used.

Examples of the leveling agent and the lubricant 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 with ultraviolet rays, radiation, infrared rays, X-rays, active energy rays of electron rays, or the like. 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 plastic molded articles made of general-purpose resins such as polystyrene resin, polyolefin resin, ABS resin, AS resin, AN resin, and wood, glass, metal, ceramic, paper, cement, and composites thereof. Includes those molded from various materials. Further, a molded article may be constituted by the composition of the present invention itself. Preferably, on the surface, the composition for a hard coat of the present invention is formed as a hard coat layer. In addition, as this molded article, the hard coat composition of the present invention may be in the form of a film constituting the hard coat layer, a transfer foil, or the like.

Therefore, for example, the composition for a hard coat of the present invention may be applied on a transparent substrate to form a film, and a transfer foil for a hard coat and a film for a hard coat may be used, and these transfer foils or films may be applied to the surface of a molded article. It may be applied.

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

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

Transparent substrates include polyurethane resins, polyepisulfide resins, (meth)acrylic polymers such as polymethyl methacrylate (PMMA), aryl polymers, diethylene glycol bis aryl carbonates, polycarbonates, MS resins, cyclic polyolefins, etc. Substrates made of various synthetic resins can be mentioned. The substrate may be in any shape of a flat plate shape, a curved plate shape, and a film shape.

Application can be performed by, for example, dip coating, flow coating, spray coating, gravure coating, bar coating, spin coating, roll coating, flexo printing, screen printing, brushing, etc. .

It is preferable to apply the thickness of about 0.01 to 100 µm after curing.

Light irradiation may be about 100-1,500mJ/cm ² by ultraviolet rays or the like.

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

As a primer layer, a urethane resin and an acrylic resin are mentioned, for example. 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 spray 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: Preparation of fluorine-containing (meth)acrylic resin 1

In a container equipped with a reflux condenser, a thermometer, a stirrer and a dropping tank, 150 parts by weight of Solfit (trade name manufactured by Kuraray Co., Ltd.), which is 3-methyl-3-methoxy butanol, was put, and the temperature of the liquid was kept at 120°C. In a nitrogen atmosphere, trifluoroethyl methacrylate, light ester M-3F (trade name manufactured by Kyoeisha Chemical Co., Ltd.) 5 parts by weight, methyl methacrylate 47.5 parts by weight, 2-hydroxyethyl acrylate 47.5 parts A mixed solution of 1 part by weight of parts and fabutyl D (trade name manufactured by Japan Oil Co., Ltd.) was added dropwise to the Solpit over about 1 hour. It reacted at 120 degreeC for 2 hours, and obtained the 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 in terms of polystyrene, and it was 11000.

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

150 parts by weight of Solfit (trade name manufactured by Kuraray Co., Ltd.) was put in a container equipped with a reflux condenser, a thermometer, a stirrer, and a dropping tank, and the temperature of the liquid was kept at 120°C. In a nitrogen atmosphere, 40 parts by weight of light ester M-3F (trade name manufactured by Kyoeisha Chemical Co., Ltd.), 30 parts by weight of ethyl hexyl methacrylate, 30 parts by weight of 2-hydroxyethyl acrylate, perbutyl D (Japan A mixed solution of 1 part by weight of oil and fat (manufactured by Yuji Co., Ltd.) was added dropwise to Solpit over about 1 hour. It reacted at 120 degreeC for 2 hours, and obtained the fluorine-containing (meth)acrylic copolymer liquid.

The weight average molecular weight of the obtained fluorine-containing (meth)acrylic copolymer liquid was calculated by gel permeation chromatography in terms of polystyrene, and it was 35000.

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

150 parts by weight of Solfit (trade name manufactured by Kuraray Co., Ltd.) was put in a container equipped with a reflux condenser, a thermometer, a stirrer, and a dropping tank, and the temperature of the liquid was kept at 120°C. In a nitrogen atmosphere, 15 parts by weight of light ester 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, perbutyl D (Japanese fat and oil) Co., Ltd.'s brand name) 1 part by weight of a mixed solution was added dropwise to Solpit over about 1 hour. It reacted at 120 degreeC for 2 hours, and obtained the 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 in terms of polystyrene, and it was 15,000.

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

200 parts by weight of Solfit (trade name manufactured by Kuraray Co., Ltd.) was put in a container equipped with a reflux condenser, thermometer, stirrer, and dropping tank, and the temperature of the liquid was kept at 110°C. In a nitrogen atmosphere, perfluoro octyl ethyl methacrylate, light ester FM-108 (trade name manufactured by Kyoeisha Chemical Co., Ltd.) 20 parts by weight, n-butyl acrylate 15 parts by weight, 2-hydroxyethyl acrylate A mixed solution of 65 parts by weight and 5.0 parts by weight of perbutyl O (trade name manufactured by Japan Oil Co., Ltd.) was added dropwise to Solpit over about 1 hour. It reacted at 110 degreeC for 2 hours, and obtained the fluorine-containing (meth)acrylic copolymer liquid.

The weight average molecular weight of the obtained fluorine-containing (meth)acrylic copolymer liquid was calculated by gel permeation chromatography in terms of polystyrene, and it was 5000.

Examples and Comparative Examples

(A) Urethane (meth)acrylate

(B) a polyfunctional (meth)acrylate,

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

(D) The metal oxide fine particles were kneaded at the composition ratio (parts by weight) shown in Table 1 to obtain a hard coat composition 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 Japanese Unexamined Patent Publication No. 2010-107956)

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

Resin (A) -3 　 Polyisocyanate (Colonate HK)/2-hydroxyethyl acrylate / pentaerythritol triacrylate / ethylene oxide acrylate 10 mol adduct

Resin (B) pentaerythritol triacrylate, brand name: Light acrylate PE-3A (Kyoeisha Chemical Co., Ltd. product)

Resin (C) -1 　 Fluorine-containing (meth)acrylic resin 1 prepared in Preparation Example 1

Resin (C) -2 　 Fluorine-containing (meth)acrylic resin 2 prepared in Preparation Example 2

Resin (C)-3　 Fluorine-containing (meth)acrylic resin 3 prepared in Preparation Example 3

Resin (C)-4 　 Fluorine-containing (meth)acrylic resin 4 prepared in Preparation Example 4

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

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

Organosilicarsol solution 1 Brand name: PL-2L-MEK (made by Fuso Chemical Industries, Ltd., particle diameter 10 nm, solid content 20.0%) introduced methacrylic group into fine particles (R ⁹ in formula (IV) is methacrylic Equivalent to that of flagship)

Organosilicasol solution 2 PL-2L-MEK (made by Fuso Chemical Industries, Ltd., particle diameter 10 nm, solid content 20.0%) in which an acrylic group was introduced into the microparticles (R ⁹ in formula (IV) is equivalent to that of an acrylic group) box)

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

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

Photopolymerization initiator 2 brand name: Lucirin TPO, manufactured by BASF Japan Co., Ltd.

Coating material: 100㎛ PET (untreated)

The hard coat compositions obtained in Examples and Comparative Examples were applied to the 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 irradiating ultraviolet rays twice at a position of 10 cm in height with a high pressure mercury lamp of 80 W/cm to form a coating layer having a thickness of about 5 μm containing a cured polymer.

About the obtained coating layer, the state of the coating film (transparency), pencil hardness, steel wool resistance, crimp property, anti-blocking property, adhesiveness, transmittance, and haze value were evaluated.

<Film state>

By visual observation, four steps were evaluated in which ◎ for no whitening, ○ for almost no whitening, △ for partial presence, and x for overall presence.

<pencil hardness>

The test was performed with a 500 g load of the pencil hardness tester, and the hardness of the pencil in which no scratches occurred was shown.

<Steel wool resistance>

The obtained coating layer was rubbed by reciprocating 10 times with steel wool (#0000) to which a load of about 1 kg was applied. When observed by visual observation, the evaluation was made in four stages: ⊚ that no wound was generated, ◯ that hardly wounded, △ for a little wound, and x for the wounded.

<Crimpiness>

The coated film was cut into 10 cm squares, and the average value of the floating heights of the four corners was measured. The average value of the floating height was evaluated in four steps: ◎ for 10 mm or less, ○ for 10-20 mm, △ for 20-30 mm, and x for 30 mm or more.

<Anti-blocking property>

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

<Adhesion>

A cross-cut test was conducted, and evaluated in four stages: ◎ for 100/100, ○ for 90/100 or more, △, for 50/100 or more, and x for less than 50/100.

<Total light transmittance and haze value>

The total light transmittance and haze value were measured using a haze value measuring instrument (colorimeter, ultra scan XE).

From Table 1, in Examples, satisfactory results were obtained in all evaluations by blending polyfunctional (meth)acrylate, fluorine-containing (meth)acrylic resin, and metal oxide fine particles with urethane acrylate.

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

Example 5

The composition for a hard coat obtained in Example 1 was applied to a substrate in the same manner as for evaluation of the above-described coating film state (transparency), pencil hardness, steel wool resistance, crimp property, adhesion, anti-blocking property, transmittance, and haze value, and the coating layer To prepare a hard coat film.

The obtained film was put in an injection molding mold, and an acrylic resin was injected by the simultaneous injection molding method. After cooling, a molded article having a hard coat layer was obtained.

In this way, the composition of the present invention can reduce the crimp property while exhibiting the transparency, scratch resistance, and durability of the acrylic resin to the maximum. In addition, by containing metal oxide fine particles, while obtaining good hard coat properties, in particular, it is possible to secure transmittance and/or transparency, balance with polyfunctional (meth)acrylate, and exhibit good anti-blocking performance. . In addition, chemical resistance and stain resistance can be imparted by a fluorine-containing (meth)acrylic resin.

The composition for a hard coat of the present invention can be applied to molded articles made of plastic, glass, paper, wood, etc., for these molded articles, durability such as adhesion, transparency, scratch resistance, moisture resistance, chemical resistance, and anti-blocking properties. In the case of the like, it is possible to provide a stable and excellent coating layer over a long period of time, and the crimp property of the hard coat composition, that is, the cure shrinkage rate, is also reduced, and the anti-blocking property is maintained, and a good coating layer can be obtained. Therefore, it can be used in parts and molded articles that require such properties.

Claims (12)

(A) urethane (meth)acrylate,
(B) a polyfunctional (meth)acrylate,
(C) a polymer obtained by polymerizing fluorine-containing (meth)acrylate, and
(D) contains metal oxide fine particles,
The composition for a hard coat, wherein the (C) fluorine-containing (meth)acrylate is at least 2.5 parts by weight based on 100 parts by weight of the (A) urethane (meth)acrylate. The method of claim 1,
The (A) urethane (meth)acrylate,
(1) a compound having a polyether as a main chain, and
(2) an isocyanate compound,
(3) A hard coat composition which is a polymer obtained by reaction with a hydroxyl group-containing (meth)acrylate compound. The method of claim 1,
The (A) urethane (meth)acrylate is the following formula (I)

(In formula (I), R ¹ O-is a dehydrogenation 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 dehydrogenation residue of a hydroxyl group-containing (meth)acrylate compound,
A composition for a hard coat containing a urethane (meth)acrylate oligomer represented by m+n = 1 to 50. The method of claim 2,
(2) The composition for hard coats having a urethane structure in which an alcohol compound is added to the isocyanate group and/or a urea structure in which an amine compound is added, whether the isocyanate compound is polyisocyanates obtained by polycondensing diisocyanates or diisocyanate monomers. The method of claim 2,
The composition for hard coats wherein the (3) hydroxyl group-containing (meth)acrylate compound is hydroxyalkyl (meth)acrylates and polyol (meth)acrylates. The method of claim 2,
(1) The composition for a hard coat, wherein the compound having a polyether as a main chain is at least one compound selected from the group consisting of an alkylene glycol compound and an alkylene oxide addition compound. The method of claim 6,
(1) The compound having a polyether as a main chain is a polyalkylene glycol compound containing a hydroxyl group at one end consisting of alkoxy polyalkylene glycols, (meth)acrylic acid is added with alkylene oxide or mono(meth) of polyalkylene glycol A composition for hard coat which is an acrylated compound. The method of claim 1,
The (C) fluorine-containing (meth)acrylic resin,
(4) a fluorine-substituted alkyl (meth)acrylate monomer,
(5) an alkyl (meth) acrylate monomer,
(6) A hard coat composition which is a resin obtained by reaction with an ether group-substituted alkyl (meth)acrylate monomer. The method of claim 8,
The (5) alkyl (meth) acrylate monomer has a C ₄ ~ C ₂₀ alkyl group for a hard coat composition. The method of claim 8,
The (6) ether group substituted alkyl (meth) acrylate monomer,

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