JP2021161232A - Active energy ray-polymerizable composition and article - Google Patents

Abstract

To provide an active energy ray-polymerizable composition that can provide a cured coat having excellent excoriation resistance as well as excellent hot stamp suitability and alcohol resistance, and an article having the cured coat.SOLUTION: An active energy ray-polymerizable composition includes a (meth)acrylic polymer (A) with a hydroxyl value of 20 mgKOH/g or less, a bifunctional (meth)acrylate (D) with a weight average molecular weight of 1000 or less, and a photopolymerization initiator (E). An article has a base material having a surface coated with a cured coat formed from the active energy ray-polymerizable composition.SELECTED DRAWING: None

Description

The present invention is an active energy ray-polymerizable composition used for forming a cured product such as a cured film, particularly a cured film formed on the surface of a cosmetic container or the like, and the foil is heat-pressed on the surface using a hot stamp. The present invention relates to an active energy ray-polymerizable composition capable of forming a cured film suitable for the above, and an article such as a cosmetic container coated with the cured film of the composition.

The active energy ray-polymerizable composition has a property of being polymerized and cured in a short time by irradiation with active energy rays such as ultraviolet rays. The composition is used, for example, as a material for forming a cured film for modifying the surface of a base material of home appliances such as mobile phones and cosmetic containers.

The cured film obtained from the composition is required to have an effect of improving the scratch resistance of the object to be coated, which is mainly a base material. Further, when the base material is a cosmetic container or the like, the foil may be heat-bonded to the surface of the cured film by using hot stamping. In that case, the cured film is required to have a transfer rate of foil (hot stamping property) and alcohol resistance in order to prevent corrosion by contents such as cosmetics.

For example, Patent Document 1 describes an active energy ray-polymerizable composition containing a hydroxy group-containing (meth) acrylic polymer and a polyfunctional (meth) acrylate as an active energy ray-polymerizable composition having improved scratch resistance. Has been done. Further, Patent Document 2 describes an active energy ray-polymerized composition having scratch resistance and hot stamping property.

However, the active energy ray-polymerizable composition described in Patent Document 1 did not have sufficient hot stamping properties. Further, the active energy ray-polymerizable composition described in Patent Document 2 did not have sufficient alcohol resistance.

Japanese Unexamined Patent Publication No. 2015-059166 Japanese Unexamined Patent Publication No. 2019-7008

An object of the present invention is to provide an active energy ray-polymerizable composition capable of solving the above-mentioned problems and obtaining a cured film having excellent scratch resistance and good hot stamping resistance and alcohol resistance, and a cured film thereof. To provide the goods to have.

The above problems are solved by the following inventions [1] to [12].
[1] Containing a (meth) acrylic polymer (A) having a hydroxyl value of 20 mgKOH / g or less, a bifunctional (meth) acrylate (D) having a weight average molecular weight of 1000 or less, and a photopolymerization initiator (E). Active energy ray-polymerizable composition.
[2] The active energy ray-polymerizable composition according to the above [1], wherein the (meth) acrylate (D) has a cyclic structure.
[3] The active energy ray-polymerizable composition according to the above [1] or [2], wherein the content of the (meth) acrylic polymer (A) is 10 to 50% by mass.
[4] The active energy ray-polymerizable composition according to any one of the above [1] to [3], wherein the content of the (meth) acrylate (D) is 10 to 50% by mass.
[5] The active energy ray-polymerizable composition according to any one of the above [1] to [4], further comprising a urethane (meth) acrylate (B) having a weight average molecular weight of more than 1000.
[6] The active energy ray-curable polymerization composition according to the above [5], wherein the urethane (meth) acrylate (B) has an aromatic ring.
[7] The active energy ray polymerization composition according to the above [5] or [6], wherein the content of the urethane (meth) acrylate (B) is 1 to 40% by mass.
[8] The active energy ray-polymerizable composition according to any one of the above [1] to [7], further comprising a trifunctional or higher functional (meth) acrylate (C) modified with an alkylene oxide and / or caprolactone.
[9] The active energy ray-polymerizable composition according to the above [8], wherein the content of the (meth) acrylate (C) is 30 to 85% by mass.
[10] An article in which the surface of a base material is coated with a cured film formed from the active energy ray-polymerizable composition according to any one of [1] to [9] above.
[11] The article according to the above [10], wherein the article is a cosmetic container.
[12] An article in which a foil adheres to the surface of the cured coating of the article according to the above [10] or [11].

According to the present invention, it is possible to provide an active energy ray-polymerizable composition capable of obtaining a cured film having excellent scratch resistance, hot stamping resistance and alcohol resistance, and an article having the cured film. ..

Next, the present invention will be described based on examples of embodiments. However, the present invention is not limited to the forms described below.
In the present specification, "(meth) acrylate" is a general term for "acrylate" and "methacrylate", and means one or both of them. "(Meta) acryloyl group" is a general term for "acryloyl group" and "methacryloyl group", and means one or both of them. "(Meta) acrylic acid" is a general term for "acrylic acid" and "methacrylic acid", and means one or both of them. "(Meta) acrylic polymer" is a general term for "acrylic polymer" and "methacryl polymer", and means one or both of them. "(Meta) acrylic monomer" is a general term for "acrylic monomer" and "methacrylic monomer", and means one or both of them.

[Active energy ray-polymerizable composition]
The active energy ray-polymerizable composition of the present invention (hereinafter referred to as "the present composition") is a (meth) acrylic polymer (A) having a hydroxyl value of 20 mgKOH / g or less (hereinafter referred to as "component (A)"). ), A bifunctional (meth) acrylate (D) having a weight average molecular weight of 1000 or less (hereinafter referred to as "(D) component"), and a photopolymerization initiator (E) (hereinafter referred to as "(E) component"). )including.

[(A) component]
The present composition contains a (meth) acrylic polymer (A) having a hydroxyl value of 20 mgKOH / g or less, which is a component (A). The (meth) acrylic polymer is a polymer containing a structural unit derived from a (meth) acrylic monomer. The component (A) is a component that contributes to improving the curability of the present composition and the transparency and alcohol resistance of the cured product such as the cured film of the present composition.

The component (A) can be produced by polymerizing a monomer mixture containing a (meth) acrylic monomer. Examples of the (meth) acrylic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, and n-butyl (meth) acrylate. i-butyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, i-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2 -(Meta) such as ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, etc. Acrylate: A hydroxy group-containing (meth) acrylic acid ester such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. Aromatic ring-containing (meth) acrylic acid esters such as phenoxy (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, and o-biphenyloxyethyl (meth) acrylate; Glycidyl group-containing (meth) acrylic acid ester such as glycidyl (meth) acrylate; isocyanate group-containing (meth) acrylic acid ester such as (meth) acrylic isocyanate and 2- (meth) acryloyloxyethyl isocyanate; acrylic acid, methacrylic acid, etc. (Meta) Acrylate; Examples thereof include (meth) acrylates such as ammonium (meth) acrylate, sodium (meth) acrylate, and potassium (meth) acrylate.
The component (A) preferably contains a structural unit derived from (meth) acrylic acid in that the hot stamping property is improved.

The component (A) may contain a structural unit derived from a monomer other than the (meth) acrylic monomer. Examples of the monomer other than the (meth) acrylic monomer include a monomer having a double bond. Specifically, aromatic vinyl such as styrene and α-methylstyrene; vinyl carboxylate such as vinyl acetate and vinyl propionate; unsaturated dicarboxylic acid such as maleic anhydride, itaconic acid and fumaric acid; N-vinylpyrrolidone, Examples thereof include N-vinyllactams such as N-vinylcaprolactam.
The constituent unit of the component (A) may be one kind or two or more kinds.

The component (A) can be produced by polymerizing the raw material monomer by a known method. Examples of the method for producing the component (A) include a solution polymerization method using an azo-based initiator and a photopolymerization method using an acylphosphine oxide-based initiator.

The hydroxyl value of the component (A) is preferably 0 to 10 mgKOH / g, more preferably 0 to 5 mgKOH / g. The lower the hydroxyl value, the better the hot stamping property, alcohol resistance, adhesion to the substrate, and coating workability of the cured film. The hydroxyl value of the polymer can be measured as a potassium hydroxide conversion value by a titration method.
The hydroxyl value of the component (A) can be adjusted by, for example, the copolymerization ratio of the hydroxy group-containing monomer such as the hydroxy group-containing (meth) acrylic acid ester.

The weight average molecular weight of the component (A) (hereinafter referred to as "Mw") is 1000 to 100,000 from the viewpoint of hot stamping property, alcohol resistance, adhesion to the substrate, and coating workability of the cured film. Preferably, 1000 to 90000 is more preferable, and 2000 to 80,000 is even more preferable.
Mw can be adjusted by controlling the polymerization conditions when polymerizing the component (A), for example, the type and amount of the polymerization initiator, the type and amount of the solvent, the reaction temperature, the reaction time, and the like. In addition, in this specification, the term "weight average molecular weight" means the polystyrene-equivalent weight average molecular weight measured by the Gel Permeation Chromatography method.

The component (A) in the present composition may be one kind or two or more kinds.
The content of the component (A) is preferably 10 to 50% by mass, more preferably 10 to 30% by mass, from the viewpoint of hot stamping property, alcohol resistance, adhesion to the substrate, and coating workability of the cured film. preferable.

[(D) component]
The present composition contains a bifunctional (meth) acrylate (D) having a weight average molecular weight of 1000 or less, which is a component (D). The component (D) is a component that contributes to the hot stamping property of the cured film. As the D component, for example, a compound (D1) having a cyclic skeleton between two (meth) acryloyloxy groups (hereinafter referred to as “(D1) component”) is directly between the two (meth) acryloyloxy groups. Examples thereof include compound (D2) having a chain structure (hereinafter, referred to as “(D2) component”).

Examples of the component (D1) include di (meth) acrylate having an aromatic ring skeleton such as bisphenol A di (meth) acrylate and bisphenol F di (meth) acrylate; 1,4-cyclohexanediol di (meth) acrylate, and tri. Di (meth) acrylates with an alicyclic skeleton such as cyclodecanediyl dimethylene di (meth) acrylates, hydrogenated bisphenol A di (meth) acrylates, dimethylol tricyclodecane di (meth) acrylates; or these di (meth) acrylates. Examples thereof include polyalkylene oxide adducts of acrylates, polycaprolactone adducts and polycarbonate adducts.

Examples of the component (D2) include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and triethylene. Glycoldi (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, glycerol 1,3-di (meth) acrylate, neopentyl glycol di (meth) acrylate, tripropylene glycol di (meth) Acrylate, neopentyl glycol hydroxypivalate di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polycarbonate di (meth) acrylate, or polyalkylene oxide adducts of these di (meth) acrylates, polycaprolactone. Additives and polycarbonate adducts can be mentioned.

As the component (D), the component (D1) is preferable from the viewpoint of scratch resistance of the cured film, and di (meth) acrylate having a bisphenol A skeleton and di (meth) acrylate having a tricyclodecane are more preferable, and bisphenol. A (EO) ₄ diacrylate and dimethylol tricyclodecane diacrylate are more preferred.

The component (D) in the present composition may be one kind or two or more kinds.
The content of the component (D) is preferably 1 to 70% by mass, more preferably 10 to 50% by mass. The higher the content, the better the hot stamping property of the cured film, and the lower the content, the better the alcohol resistance of the cured film.

[(E) component]
The present composition contains a photopolymerization initiator (E) which is a component (E). The component (E) is a component that polymerizes and cures the present composition by irradiation with active energy rays such as ultraviolet rays.
Examples of the component (E) include benzoin, benzoin monomethyl ether, benzoin isopropyl ether, acetoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, benzyl dimethyl ketal, 2,2-diethoxyacetophenone, and 1-hydroxycyclohexyl. Phenyl Ketone, Methylphenyl Glyoxylate, Ethylphenyl Glyoxylate, 2-Hydroxy-2-Methyl-1-phenylPropane-1-one, 2-Hydroxy-1- {4- [4- (2-Hydroxy-2) -Methyl-propionyl) -benzyl] phenyl} -2-methyl-propane-1-one and other carbonyl compounds; tetramethylthium monosulfide, tetramethylthiuram disulfide and other sulfur compounds; 2,4,6-trimethylbenzoyldiphenylphos Examples thereof include acylphosphine oxides such as finoxide and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide. As the component (D), 1-hydroxycyclohexylphenyl ketone and 2-hydroxy-2-methyl-1-phenylpropan-1-one are preferable from the viewpoint of imparting high transmittance to the cured film of the present composition.

The component (E) in the present composition may be one kind or two or more kinds.
The content of the component (E) is preferably 0.1 to 10% by mass. The higher the content, the better the scratch resistance of the cured film, and the lower the content, the better the bending resistance and hot stamping property of the cured film.

[(F) component]
The present composition may contain a solvent (F) (hereinafter, referred to as "component (F)"). Examples of the component (F) include hydrocarbon solvents such as n-hexane, n-heptane, n-octane, cyclohexane and cyclopentane; aromatic solvents such as toluene, xylene and ethylbenzene; methanol, ethanol and n-. Alcohol-based solvents such as butanol, ethylene glycol monomethyl ether and propylene glycol monomethyl ether; ester solvents such as ethyl acetate, n-butyl acetate, n-amyl acetate, ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate; acetone, methyl ethyl ketone , Methyl isobutyl ketone, methyl n-amyl ketone, cyclohexanone and other ketone solvents; diethylene glycol dimethyl ether, diethylene glycol dibutyl ether and other ethylene glycol solvents; 1,2-dimethoxyethane, tetrahydrofuran, dioxane and other ether solvents; N-methylpyrrolidone , Amido-based solvents such as dimethylformamide and dimethylacetamide; and carbonate-based solvents such as ethylene carbonate.

The component (F) in the present composition may be one kind or two or more kinds.
The content of the component (F) is 30 parts by mass with respect to 100 parts by mass of the total amount of the components having a polymerizable double bond from the viewpoint of improving the coating workability and leveling property and reducing the VOC emission amount. The following is preferable, and 5 parts by mass or less is more preferable.

[(B) component]
The present composition may contain urethane (meth) acrylate (B) (hereinafter referred to as "component (B)"). However, the component (B) is a compound other than the component (D). The component (B) is a component that contributes to the bending resistance and abrasion resistance of the cured film.
The component (B) is synthesized from, for example, a raw material containing polyisocyanate (b1) (hereinafter referred to as “b1 raw material”) and a (meth) acrylate (b3) having only one hydroxy group (hereinafter referred to as “b3 raw material”). Examples thereof include urethane poly (meth) acrylates that can be produced. The component (B) is obtained by reacting the b1 raw material with the polyol (b2) (hereinafter referred to as “b2 raw material”) and then reacting the b3 raw material from the viewpoint that the bending resistance of the cured film can be further improved. Urethane poly (meth) acrylate is preferable.

(B1 raw material)
Examples of the b1 raw material include diisocyanates such as tolylene diisocyanate, methylcyclohexane diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, dimerate diisocyanate, and trimethylhexamethylene diisocyanate. ; Triisocyanate such as lysine triisocyanate can be mentioned.
Further, as the b1 raw material, the polyisocyanate obtained by reacting the polyisocyanate such as diisocyanate and triisocyanate with a compound having two or more active hydrogen atoms such as an amino group, a hydroxyl group, a carboxyl group and water, or the above-mentioned polyisocyanate. Diisocyanates and polyisocyanates such as triisocyanates can also be used.
As the b1 raw material, diisocyanate is preferable because the viscosity of the obtained component (B) is low, the coating workability of the present composition is improved, and the bending resistance of the cured film is improved. Among them, isophorone diisocyanate is preferable. , Dicyclohexylmethane diisocyanate is more preferable.
When producing the component (B), only one kind of compound may be used as the b1 raw material, or two or more kinds may be used in combination.

(B2 raw material)
Examples of the b2 raw material include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, methylpentanediol, and 2,4-diethyl. Pentandiol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydroxypivalate neopentyl glycol ester, 1,4-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, Diols such as cyclohexanedimethanol, bisphenol A, and spiroglycol; triols such as trimethylolpropane and glycerol; polyols such as tetraol such as pentaerythritol can be mentioned.
Further, as the b2 raw material, a polyalkylene polyol obtained by adding an alkylene oxide to the polyol, a polycaprolactone polyol obtained by adding a lactone such as ε-caprolactone to the polyol, the polyol, an alkylene carbonate, and a dialkyl carbonate. , Polycaprolactone obtained by transesterification reaction with carbonic acid ester such as diaryl carbonate can also be used.
As the b2 raw material, a diol is preferable from the viewpoint of improving the bending resistance of the cured film of the present composition, and among them, a diol containing an aromatic ring such as bisphenol A is more preferable.
When producing the component (B), only one kind of compound may be used as the b2 raw material, or two or more kinds may be used in combination.

(B3 raw material)
Examples of the b3 raw material include a monohydroxyalkyl (meth) acrylate, a caprolactone-modified product or an alkylene oxide-modified product of the monohydroxyalkyl (meth) acrylate, and an addition reaction product of a monoepoxy compound and (meth) acrylic acid.
Examples of the monohydroxyalkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-. Examples thereof include monohydroxyalkyl (meth) acrylates such as hydroxyhexyl (meth) acrylates. The hydroxyalkyl group of the monohydroxyalkyl (meth) acrylate preferably has 1 to 10 carbon atoms.

Examples of the monohydroxyalkyl (meth) acrylate include monohydroxyalkyl poly (meth) acrylates such as glycerol acrylate methacrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate.
Examples of the caprolactone-modified product of monohydroxyalkyl (meth) acrylate include caprolactone-modified products such as γ-caprolactone, δ-caprolactone, and ε-caprolactone.

Examples of the alkylene oxide-modified product of the monohydroxyalkyl (meth) acrylate include alkylene oxide-modified products such as ethylene oxide, propylene oxide, and butylene oxide.
Examples of the addition reaction product of the monoepoxy compound and (meth) acrylic acid include an addition reaction product of a monoepoxy compound such as butyl glycidyl ether, 2-ethylhexyl glycidyl ether, and glycidyl (meth) acrylate and (meth) acrylic acid. And so on.
As the b3 raw material, monohydroxyalkyl mono (meth) acrylate having 2 to 4 carbon atoms of the hydroxyalkyl group is used because the viscosity of the obtained component (B) is low and the coating workability of the present composition is improved. Preferably, 2-hydroxyethyl (meth) acrylate is more preferred.

As a method for synthesizing the component (B) from the b1 raw material and the b3 raw material, for example, the b3 raw material is placed in a mixture of the b1 raw material heated to 30 to 90 ° C. and a catalyst such as dibutyl tin dilaurate over 1 to 3 hours. Examples thereof include conventionally known methods such as a method of dropping the mixture and further reacting it for 1 to 3 hours. The amount of the b1 raw material and the b3 raw material used for the synthesis of the component (B) shall be set so that (total number of isocyanate groups of the b1 raw material) / (total number of hydroxy groups of the b3 raw material) is 0.5 to 1.0. Is preferable, and 0.9 to 1.0 is more preferable. The larger the ratio, the better the adhesion of the cured film to the substrate, and the smaller the ratio, the higher the reaction rate of the isocyanate groups, so that the storage stability of the present composition tends to be improved.

Further, as a method for synthesizing the component (B) from the b1 raw material, the b2 raw material and the b3 raw material, for example, the b2 raw material is mixed in a mixture of the b1 raw material heated to 30 to 90 ° C. and a catalyst such as dibutyltin dilaurate. Conventionally known methods such as a method of dropping over 2 to 6 hours, further reacting for 1 to 3 hours, then dropping the b3 raw material over 1 to 3 hours, and further reacting for 1 to 3 hours can be mentioned. .. Regarding the amount of b1 raw material, b2 raw material and b3 raw material used for the synthesis of the component (B), (total number of isocyanate groups of b1 raw material) / (total number of hydroxy groups of b2 raw material and b3 raw material) is 0.5 to 1.0. It is preferable to set the above, and 0.9 to 1.0 is more preferable. The larger the ratio, the better the adhesion of the cured film to the substrate, and the smaller the ratio, the higher the reaction rate of the isocyanate groups, so that the storage stability of the present composition tends to be improved.

The weight average molecular weight of the component (B) is preferably 500 to 40,000, more preferably 2,000 to 20,000, from the viewpoint that the composition has a viscosity suitable for painting work and the bending resistance of the cured film is good.

The component (B) in the present composition may be one kind or two or more kinds.
The content of the component (B) is preferably 1 to 40% by mass, more preferably 10 to 40% by mass, from the viewpoint of bending resistance and wear resistance of the cured film.

[(C) component]
The composition may contain a trifunctional or higher functional (meth) acrylate (C) (hereinafter referred to as "component (C)") modified with an alkylene oxide or a caprolactone. However, the component (C) is a compound other than the component (A) and the component (B). The component (C) is a component that contributes to the scratch resistance and hot stamping property of the cured film.

As the component (C), a modified product obtained by modifying the trifunctional or higher functional (meth) acrylate exemplified below with alkylene oxide or caprolactone can be used. Examples of the trifunctional or higher functional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, polyurethane tri (meth) acrylate, polyepoxytri (meth) acrylate and polyester tri (meth). Tri (meth) acrylates such as acrylates; tetra (meth) acrylates such as ditrimethylolpropane tetra (meth) acrylates, pentaerythritol tetra (meth) acrylates, polyepoxytetra (meth) acrylates and polyester tetra (meth) acrylates; dipenta. Penta (meth) acrylates such as erythritol penta (meth) acrylate and tripenta erythritol penta (meth) acrylate; hexa (meth) acrylates such as dipentaerythritol hexa (meth) acrylate and tripenta erythritol hexa (meth) acrylate; 7-functional or higher poly (meth) acrylates such as erithitol hepta (meth) acrylate and trimethylolpropane octa (meth) acrylate; trifunctional or higher polyepoxy poly (meth) acrylates; trifunctional or higher polyester poly (meth) acrylates and the like. Can be mentioned.
The component (C) preferably contains caprolactone-modified dipentaerythritol hexa (meth) acrylate from the viewpoint of imparting high scratch resistance to the cured film of the present composition.

The component (C) in the present composition may be one kind or two or more kinds.
The content of the component (C) is preferably 30 to 85% by mass, more preferably 40 to 85% by mass, from the viewpoint of scratch resistance and hot stamping property of the cured film.

[(G) component]
The present composition has other polymerizable components (G) having a polymerizable group other than the components (A), (B), (C) and (D) for the purpose of improving abrasion resistance and the like (hereinafter, It may contain (referred to as "(G) component"). As the other polymerizable component, a (meth) acryloyl group-containing monomer is preferable. Examples of the (meth) acryloyl group-containing monomer include monofunctional (meth) acrylate, trifunctional (meth) acrylate, tetrafunctional or higher (meth) acrylate, and (meth) acrylamide.

Examples of the monofunctional (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, and heptyl (meth) acrylate. ) Acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, benzyl (meth) acrylate, Cresol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) Acrylate, 2-ethylhexyl (meth) acrylate, ethyldiethylene glycol (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, lauryl (meth) acrylate, polyepoxy mono (meth) acrylate, polyester mono (meth) ) Acrylate can be mentioned.

Examples of the trifunctional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, polyepoxytri (meth) acrylate, and polyester tri (meth) acrylate.

The tetrafunctional or higher (meth) acrylate includes, for example, a tetrafunctional (meth) acrylate such as ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyepoxytetra (meth) acrylate and polyester tetra (meth) acrylate. Meta) acrylate; pentafunctional (meth) acrylate such as dipentaerythritol penta (meth) acrylate and tripentaerythritol penta (meth) acrylate; dipentaerythritol hexa (meth) acrylate and tripentaerythritol hexa (meth) acrylate and the like. 6-functional (meth) acrylate; 7-functional or higher (meth) acrylate such as tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate and other octa (meth) acrylate; 4-functional or higher polyepoxypoly (Meta) acrylate; Examples thereof include tetrafunctional or higher functional polyester poly (meth) acrylate.

Examples of (meth) acrylamide include (meth) acrylamide, isobutoxymethyl (meth) acrylamide, t-octyl (meth) acrylamide, and diacetone (meth) acrylamide.

The component (G) in the present composition may be one kind or two or more kinds. The content of the component (G) is preferably 0.1 to 10% by mass, more preferably 1 to 5% by mass.

[Other ingredients]
The present composition may contain components other than the above-mentioned components (A) to (G) (hereinafter referred to as "other components"). Other components include, for example, sensitizers, dispersants, waxes, light stabilizers, antioxidants, surface conditioners, defoamers, heat stabilizers, antistatic agents, antifogging agents, and components other than (A). Examples include polymers, fine particles, thixotropic agents, and coupling agents.

Examples of the sensitizer include benzoin isopropyl ether and thioxanthone.
Examples of the dispersant include Anti-Terra-U, Anti-Terra-203 / 204, Disperbyk-101, 107, 110, 111, 130, 161, 162, 163, 164, 165, 166, 170 manufactured by BYK Chemie. , 400, Bykuman, BYK-P104, P105, P104S, 240S, and Lactimon (all of which are trade names).

Examples of the wax include polyamide wax and polyethylene oxide wax.
Examples of the light stabilizer include bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, and bis (1). -Hindered amines such as octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate can be mentioned.

Examples of the antioxidant include hindered phenol, organic phosphite and organic phosphonite.

Examples of the surface conditioner include silicone-based leveling agents, acrylic-based leveling agents, fluorine-based leveling agents, and vinyl-based leveling agents.

Examples of the defoaming agent include a non-silicone defoaming agent such as polysiloxane, a polysiloxane defoaming agent such as fluorine-modified polysiloxane, and an acrylic acid defoaming agent such as a copolymer of alkyl methacrylate, acrylate and acrylic acid. Examples thereof include foaming agents, butadiene copolymer-based defoaming agents and mineral oil-based defoaming agents.

Examples of the heat stabilizer include triphenylphosphine, tris (2,6-dimethylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, and tris (mono-nonylphenyl) phosphite. And a mixture of tris (di-nonylphenyl) phosphite, dimethylbenzenephosphonate and trimethylphosphate.
Examples of the antistatic agent include glycerol monostearate, sodium stearyl sulfonate and sodium dodecylbenzene sulfonate.

Examples of the anti-fog agent include glycerol-1-methacryloyloxyethyl urethane and glycerol-1-methacryloyloxypropyl urethane.
Examples of the polymer other than the component (A) include (meth) acrylic polymer, (meth) acrylonitrile-based polymer, butadiene-based polymer, urethane-based polymer, polyester-based polymer, polyamide-based polymer, and polyamide. Examples thereof include imide-based polymers and phenol-based polymers.

Examples of the fine particles include organic fillers such as acrylic beads and urethane beads, inorganic fillers such as silica and titanium, and inorganic fillers whose surface has been organically treated with a silane coupling agent or the like. Examples of the method of blending the fine particles into the composition include a method of blending the fine particles in a pre-dispersed state, and a method of blending the fine particles in the composition and then dispersing the fine particles using a three-roll roll, a dyno mill, or the like. Be done. Further, in order to improve the dispersibility, a dispersant such as a carboxylic acid type, a polycarboxylic acid type or a polyacrylic acid type can be used in combination.

Examples of the thixotropic agent include organic thixotropic agents such as amide-based, polyethylene oxide-based, and hydrogenated castor oil-based; silica, bentonite and their organic silane coupling products, and surface-treated inorganic calcium carbonate and the like. Examples include tropic agents.
Examples of the coupling agent include a silane coupling agent to which a functional group such as a (meth) acryloyloxy group, a vinyl group, an epoxy group, and an amino group is added, and a titanium coupling agent.

[Manufacturing method of this composition]
In this composition, for example, the component (D), the component (E), and the component (F) are mixed with the component (A) obtained by prepolymerization by a method such as a suspension polymerization method or a photopolymerization method. It can be produced by mixing the component B), the component (C), the component (G) and other components as necessary. The order and procedure for mixing each component are not particularly limited and can be appropriately selected.

[Article]
The present composition can be used to coat the surface of various base materials such as various molded products such as paper and polymers. In the article of the present invention, the surface of the base material is coated with a cured film formed from the present composition.
Examples of the molded product of the polymer that can be used as a base material include a sheet-shaped molded product, a film-shaped molded product, and an injection-molded product having various shapes obtained by injection molding. Examples of the type of polymer include polymethylmethacrylate polymer, polycarbonate polymer, polyester polymer, polyester carbonate polymer, polystyrene polymer, acrylonitrile-butadiene-styrene polymer (hereinafter referred to as “ABS”), and acrylonitrile-. Examples thereof include styrene polymers, polyamide polymers, polyallylate polymers, polymethacrylicimide polymers, and polyallyl diglycol carbonate polymers. Specific base materials include cosmetic containers in which foil is often heat-bonded to the surface of a cured film using hot stamping.

The article of the present invention can be produced, for example, by applying the present composition to the surface of a base material and irradiating the obtained coating film with active energy rays to form a cured film.
To apply the composition to the substrate, for example, a method such as brush coating, spray coating, dip coating, spin coating, curtain coating, bar coating and the like can be used. When applying, the viscosity may be adjusted by heating the composition or diluting it with a subcritical fluid. The thickness of the coating film of the present composition should be applied so that the thickness of the cured film is 0.001 mm or more and 0.1 mm or less from the viewpoint of the curability of the present composition and the abrasion resistance of the cured film. Preferably, it is more preferably 0.002 mm or more and 0.05 mm or less, and further preferably 0.004 mm or more and 0.03 mm or less.

Examples of the active energy rays irradiating the coating film of the present composition include α rays, β rays, γ rays and ultraviolet rays. From the viewpoint of versatility, ultraviolet rays are preferable as the active energy rays. Examples of the ultraviolet source include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a metal halide lamp, an electrodeless UV lamp using a magnetron, and an LED.

Examples of the atmosphere when irradiating the active energy rays include an inert gas such as nitrogen and argon, and air. From the viewpoint of practicality and economy, air is preferable as the atmosphere. Preferred curing conditions when ultraviolet rays are used as the active energy rays include, for example, a method of irradiating with a high-pressure mercury lamp so that the integrated light amount at a wavelength of 340 to 380 nm is 100 to 3000 mJ / cm ^2.

A preferred embodiment of the article of the present invention is an article in which a foil adheres to the surface of the cured coating of the article of the present invention. Since the cured film obtained from the present composition has a high foil transfer rate, the article of the present invention is suitable for a cosmetic container in which the surface is often printed by hot stamping. Since the printing cost can be minimized when the transfer rate of the foil is high, the transfer rate is preferably 60% or more, more preferably 80% or more, further preferably 90% or more, and most preferably 100%. The transfer rate of the foil can be determined by the method described in Examples described later.

Hereinafter, the present invention will be described with reference to Examples and Comparative Examples. In the following description, "part" means a mass part.

(1) Preparation of Evaluation Sample An ABS plate (thickness: 3 mm, size: 10 cm × 10 cm) was spray-coated with an active energy ray-polymerizable composition so that the thickness of the cured film was 0.02 mm. Next, the substrate with the coating film was heated in an oven at 60 ° C. for 3 minutes to volatilize the organic solvent. Further, using a high-pressure mercury lamp in the air, an ABS plate with a cured film used for the following evaluation is irradiated with ultraviolet rays having ^{a peak illuminance of 100 mW / cm 2} and an integrated light ^{intensity of 1000 mJ / cm 2 at a wavelength of 300 nm to 400 nm.} Made.

(2) Evaluation of hot stamping property A 2 cm square rubber stamp attached to a leather tools foil stamping machine was heated to 150 ° C. to produce a KURZ hot stamped foil (trade name: 4PT) in (1). Press against the cured film surface of the evaluation sample for 1 second, and measure the area to which the hot stamp foil is transferred. The transfer rate was calculated by the following formula.
Transfer rate (%) = Area on which the hot stamp foil was transferred (cm ² ) x 100 / Area of engraving (4 cm ² )
The hot stamping property was evaluated from the calculated transfer rate according to the following criteria.
<Evaluation criteria for hot stamping>
A: Transfer rate is 60% or more B: Transfer rate is 30% or more and less than 60% C: Transfer rate is less than 30%

(3) Evaluation of scratch resistance The cured coating surface of the evaluation sample prepared in (1) was attached to a flat friction tester made by a coating tester with steel wool # 000 manufactured by Bonstar, and the load was 250 g / cm ² . Friction was performed under the condition of 50 round trips. The haze value before and after friction was measured according to JIS-K7105 using a haze meter HM-65W manufactured by Murakami Color Technology Research Institute, and the haze increase value was obtained. The scratch resistance was evaluated based on the following criteria based on the haze increase value.
<Evaluation criteria for scratch resistance>
A: Haze increase value is less than 2% B: Haze increase value is 2% or more and less than 4% C: Haze increase value is 4% or more

(4) Evaluation of Alcohol Resistance The appearance of the cured coating surface prepared in (1) was immersed in a 50% ethanol solution at a temperature of 40 ° C. for 24 hours, then taken out and air-dried. Was visually observed. Alcohol resistance was evaluated based on the following criteria based on the area of defective parts where wrinkles, peeling, discoloration, etc. were observed.
<Evaluation criteria for alcohol resistance>
A: No defective part B: Defective part is more than 0% of the whole cured film and 20% or less C: Defective part is more than 20% of the whole cured film

(5) Measurement of Weight Average Molecular Weight The weight average molecular weight (Mw) was measured under the following conditions using a GPC (Gel Permeation Chromatography) system (manufactured by Tosoh Corporation, trade name: HLC-8220 GPC).
<GPC measurement conditions>
Columns: "TSK-gel superHZM-M", "TSK-gel HZM-M", "TSK-gel HZ2000"
Eluent: THF
Flow rate: 0.35 mL / min
Injection volume: 10 μL
Column temperature: 40 ° C
Detector: UV-8020

[Production Example 1] Production of Polymer (A1) 75 parts of toluene was placed in a 5-liter four-necked flask equipped with a stirrer, and the temperature was raised to 90 ° C. Then, under nitrogen bubbling, 55.4 parts of methyl methacrylate (manufactured by Mitsubishi Chemical, trade name: Acryester M), 22.3 parts of i-butyl methacrylate (manufactured by Mitsubishi Chemical, trade name: Acryester B), dicyclo 22.3 parts of pentanyl methacrylate (manufactured by Hitachi Chemical Co., Ltd., trade name: FA-513M) and 0.3 part of azobisisobutyronitrile (manufactured by Otsuka Chemical Co., Ltd., trade name: AIBN) were added dropwise over 4 hours. Then, every 45 minutes, 0.05 parts, 0.1 parts, 0.1 parts, and 0.2 parts of azobisisobutyronitrile were added. After raising the temperature of this mixture to 98 ° C. and holding it for 2 hours, toluene and xylene are added to prepare a (meth) acrylic polymer (A1) (hereinafter referred to as “polymer (A1)”) solution having a non-volatile content of 40% by mass. Obtained. The hydroxyl value calculated from the charged composition of the raw material of the polymer (A1) was 0 mgKOH / g, and Mw was 59000.

[Production Example 2] Production of Comparative Polymer (X1) 60 parts of butyl acetate (manufactured by KH Neochem) was placed in a 5-liter four-necked flask equipped with a stirrer, and the temperature was raised to 120 ° C. Then, under nitrogen bubbling, 51.75 parts of methyl methacrylate (manufactured by Mitsubishi Chemical, trade name: acrylic ester M), 29 parts of n-butyl methacrylate (manufactured by Mitsubishi Chemical, trade name: acrylic ester B), 2-hydroxyethyl. Methacrylate (manufactured by Mitsubishi Chemical, trade name: Acryester HO) 19 parts, acrylic acid (manufactured by Mitsubishi Chemical) 0.25 parts, 2'-azobis-2-methylbutyronitrile (manufactured by Otsuka Chemical, trade name: AMBN) 2 .5 parts were added dropwise over 4 hours. After holding the mixture at 120 ° C. for 1 hour, 0.1 part of 2'-azobis-2-methylbutyronitrile was added. After holding this at 120 ° C. for 1 hour, the temperature was lowered to 70 ° C. in 1 hour, 40 parts of ethyl acetate (manufactured by Daicel) was added, and a (meth) acrylic polymer (X1) having a hydroxyl group having a non-volatile content of 50% by mass was added. A solution (hereinafter referred to as "polymer (X1)") was obtained. The hydroxyl value calculated from the charged composition of the raw material of the polymer (X1) was 82 mgKOH / g, and Mw was 10,000.

[Production Example 3] Production of Comparative Polymer (X2) 85 parts of butyl acetate (manufactured by KH Neochem) was placed in a 5-liter four-necked flask equipped with a stirrer, and the temperature was raised to 110 ° C. Then, under nitrogen bubbling, 48 parts of methyl methacrylate (manufactured by Mitsubishi Chemical, trade name: acrylic ester M), 35.4 parts of n-butyl methacrylate (manufactured by Mitsubishi Chemical, trade name: acrylic ester B), n-butyl acrylate. (Mitsubishi Chemical, trade name: butyl acrylate) 11 parts, 2-hydroxyethyl methacrylate (Mitsubishi Chemical, trade name: Acryester HO) 5.1 parts, acrylic acid (Mitsubishi Chemical) 0.5 parts, azo 0.6 part of bisisobutyronitrile (manufactured by Otsuka Chemical Co., Ltd., trade name: AIBN) was added dropwise over 4 hours. After holding this mixture at 110 ° C. for 1 hour, 0.5 part of azobisisobutyronitrile was added. After holding this at 110 ° C. for 2 hours, 15 parts of butyl acetate was added to obtain a (meth) acrylic polymer (hereinafter referred to as “polymer (X2)”) solution having a hydroxyl group having a non-volatile content of 50% by mass. .. The hydroxyl value calculated from the charged composition of the raw material of the polymer (X2) was 22 mgKOH / g, and Mw was 26000.

[Production Example 4] Production of urethane acrylate (B1) 261.6 parts of bisphenol A-containing diol (manufactured by ADEKA, trade name: ADEKApolyether BPX-11) in a 5-liter four-mouth flask equipped with a stirrer, neo Pentyl glycol (manufactured by Mitsubishi Gas Chemicals) 19.1 parts, dibutyltin dilaurate (manufactured by ADEKA, trade name: ADEKA STAB BT-11) 0.18 parts, di-t-butyl-p-cresol (manufactured by Honshu Chemical Industry, trade name) : 1.46 parts of H-BHT) and 224 parts of butyl acetate (manufactured by KH Neochem) were added, and the temperature was raised to 60 ° C. 400 parts of isophorone diisocyanate (manufactured by Sumika Bayer Urethane, trade name: Death Module I) was added dropwise over 4 hours. After holding this mixture at 60 ° C. for 1 hour, 217 parts of 2-hydroxyethyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name: HEA) was added dropwise while raising the temperature to 70 ° C. over 2 hours. Subsequently, after holding at 70 ° C. for 1 hour, 0.1 part of dibutyltin dilaurate was added, and the mixture was further held at 70 ° C. for 5 hours to obtain urethane acrylate (B1). The Mw of urethane acrylate (B1) was 4300.

[Examples 1 to 3 and Comparative Examples 1 to 4]
An active energy ray-polymerizable composition was prepared according to the formulation shown in Table 1, and various evaluations were performed. The evaluation results are shown in Table 1.

The abbreviations in Table 1 are as follows.
-A1: Polymer (A1) solution produced in Production Example 1-X1: Polymer (X1) solution produced in Production Example 2-X2: Polymer (X2) solution produced in Production Example 3-B1: Production example Urethane acrylate (B1) produced in 4.
-DPCA-20: Caprolactone 2 mol-modified dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku, trade name: DPCA-20)
-DPCA-60: Caprolactone 6 mol-modified dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku, trade name: DPCA-60)
-A-BPE-4: Bisphenol A (EO) ₄ diacrylate (manufactured by MIWON, trade name: Miramar M240)
-DCPA: Dimethylol tricyclodecanediacrylate (manufactured by Kyoei Kagaku, trade name: light acrylate DCP-A)
-M216: Neopentyl glycol (PO) ₂ diacrylate (manufactured by MIWON, trade name: Miramar M216)
-HCPK: 1-Hydroxycyclohexylphenyl ketone (manufactured by IGM, trade name: Omnirad 184)
-PGM: Propylene glycol monomethyl ether (manufactured by Daicel, trade name: methoxypropanol)
-DIBK: Diisobutyl ketone (manufactured by KH Neochem, product name: DIBK)
-Paintad M: Silicon polyether copolymer (manufactured by Toray Dow Corning, trade name, Paintad M)

From Table 1, it was found that the cured coatings of the active energy ray-polymerizable compositions prepared in Examples 1 to 3 had good hot stamping resistance, scratch resistance and alcohol resistance.
On the other hand, since the active energy ray-polymerizable composition prepared in Comparative Example 1 did not contain the component (A), the alcohol resistance of the cured film was low. Since the active energy ray-polymerizable compositions of Comparative Examples 2 and 3 did not contain the component (D), the cured film had low hot stamping resistance and alcohol resistance. Since the active energy ray-polymerizable composition of Comparative Example 4 did not contain the components (A) and (D), the cured film had low hot stamping resistance and alcohol resistance.

Since the active energy ray-polymerizable composition of the present invention can form a cured film having excellent scratch resistance and good hot stamping resistance and alcohol resistance, the foil is heated on the surface of the cured film using hot stamping. It can be suitably used for applications such as cosmetic containers to be crimped.

Claims (12)

An active energy ray containing a (meth) acrylic polymer (A) having a hydroxyl value of 20 mgKOH / g or less, a bifunctional (meth) acrylate (D) having a weight average molecular weight of 1000 or less, and a photopolymerization initiator (E). Polymerizable composition. The active energy ray-polymerizable composition according to claim 1, wherein the (meth) acrylate (D) has a cyclic structure. The active energy ray-polymerizable composition according to claim 1 or 2, wherein the content of the (meth) acrylic polymer (A) is 10 to 50% by mass. The active energy ray-polymerizable composition according to any one of claims 1 to 3, wherein the content of the (meth) acrylate (D) is 10 to 50% by mass. The active energy ray-polymerizable composition according to any one of claims 1 to 4, further comprising a urethane (meth) acrylate (B) having a weight average molecular weight of more than 1000. The active energy ray-curable polymerization composition according to claim 5, wherein the urethane (meth) acrylate (B) has an aromatic ring. The active energy ray-polymerized composition according to claim 5 or 6, wherein the content of the urethane (meth) acrylate (B) is 1 to 40% by mass. The active energy ray-polymerizable composition according to any one of claims 1 to 7, further comprising a trifunctional or higher functional (meth) acrylate (C) modified with an alkylene oxide and / or caprolactone. The active energy ray-polymerizable composition according to claim 8, wherein the content of the (meth) acrylate (C) is 30 to 85% by mass. An article in which the surface of a base material is coated with a cured film formed from the active energy ray-polymerizable composition according to any one of claims 1 to 9. The article according to claim 10, wherein the article is a cosmetic container. An article in which a foil adheres to the surface of the cured coating of the article according to claim 10 or 11.