JP7127266B2 - Molded article having active energy ray-polymerizable composition and its cured film - Google Patents

Description

TECHNICAL FIELD The present invention relates to an active energy ray-polymerizable composition and a molded article having a cured film thereof.

Active energy ray-polymerizable compositions have the property of being cured by polymerization in a short period of time when exposed to active energy rays such as ultraviolet rays. used for materials.

A cured film obtained from the active energy ray-polymerizable composition is mainly required to have scratch resistance and flex resistance.
Furthermore, hot stamping is often used for cosmetic containers and the like to heat and pressure-bond foil to the surface of the container.

For example, an active energy ray-polymerizable composition containing urethane acrylate and polyfunctional acrylate is known as an active energy ray-polymerizable composition that achieves both scratch resistance and flex resistance (Patent Document 1).

Further, as an active energy ray-polymerizable composition having improved scratch resistance and adhesion to a substrate, an active energy ray-polymerizable composition containing a hydroxy group-containing (meth)acrylic polymer and a polyfunctional (meth)acrylate is known (Patent Document 2).

JP 2011-241301 A JP 2015-059166 A

However, the active energy ray-polymerizable composition described in Patent Document 1 is not sufficiently satisfactory in hot stampability.
Also, the composition described in Patent Document 2 was not sufficiently satisfactory in hot stampability in addition to flex resistance.

An object of the present invention is to solve these problems and provide an active energy ray-polymerizable composition that provides a cured film having excellent scratch resistance and bending resistance and good hot stampability, and a cured film thereof. It is to provide molded products.

The above objects are achieved by the following present inventions [1] to [12].
[1] An active energy ray-polymerizable composition containing a (meth)acrylic polymer (A), a photopolymerization initiator (D) and a solvent (E), wherein the cured film of the active energy ray-polymerizable composition is An active energy ray-polymerizable composition having a glass transition temperature (Tg) of 100° C. or lower and a minimum storage elastic modulus E′ of 1×10 ⁸ Pa or higher.
[2] The active energy ray-polymerizable composition according to [1] above, wherein the (meth)acrylic polymer (A) is a hydroxy group-containing (meth)acrylic polymer (A-1).
[3] The active energy ray-polymerizable composition according to [1] or [2], wherein the hydroxyl group-containing (meth)acrylic polymer (A-1) has a hydroxyl value of 105 to 200 mg/gKOH.
[4] The above [2], wherein the hydroxy group-containing (meth)acrylic polymer (A-1) component is 10 to 50 parts by mass when the total mass of the active energy ray-polymerizable composition is 100 parts by mass. Or the active energy ray-polymerizable composition according to [3].
[5] The active energy ray-polymerizable composition according to any one of [1] to [4] above, which contains urethane (meth)acrylate (B).
[6] The active energy ray-polymerizable composition according to [5], wherein the urethane (meth)acrylate (B) has an aromatic ring.
[7] The above [5] or [6], wherein the urethane (meth)acrylate (B) is 1 to 40 parts by mass when the total mass of the active energy ray-polymerizable composition is 100 parts by mass. An active energy ray-polymerizable composition.
[8] The active energy ray according to any one of [1] to [7], wherein the active energy ray-polymerizable composition contains an alkylene oxide-modified or caprolactone-modified trifunctional or higher monomer (C). Polymerizable composition.
[9] The above [1], wherein the alkylene oxide-modified or caprolactone-modified trifunctional or higher monomer (C) is 30 to 85 parts by weight when the total weight of the active energy ray-polymerizable composition is 100 parts by weight. ] to [8], the active energy ray-polymerizable composition according to any one of [8].
[10] A molded article having a cured film of the active energy ray-polymerizable composition according to any one of [1] to [9] on the surface of the molded article.
[11] The molded article according to [10] above, which has a foil on the surface of the cured coating and has a transfer rate of the foil of 40% or more.
[12] The molded article according to the above [10] or [11], which is used as a cosmetic container.

The active energy ray-polymerizable composition of the present invention provides an active energy ray-polymerizable composition that provides a cured film having excellent scratch resistance and flex resistance and good hot stampability, and a molded article having the cured film. can provide.

As used herein, "(meth)acrylate" is a generic term for "acrylate" and "methacrylate" and means one or both of acrylate and methacrylate. "(Meth)acryloyl group" is a generic term for "acryloyl group" and "methacryloyl group", and means one or both of acryloyl group and methacryloyl group. "(Meth)acrylic acid" is a generic term for "acrylic acid" and "methacrylic acid", and means one or both of acrylic acid and methacrylic acid. "(Meth)acrylic polymer" is a generic term for "acrylic polymer" and "methacrylic polymer", and means one or both of acrylic polymer and methacrylic polymer.

The active energy ray-polymerizable composition (hereinafter referred to as the composition) of the present invention comprises a (meth)acrylic polymer (A), a photopolymerization initiator (D) and a solvent (E), and A cured film of the composition has a glass transition temperature (Tg) of 100° C. or lower and a minimum storage elastic modulus E′ of 1×10 ⁸ Pa or higher.

<(Meth) acrylic polymer (A)>
The (meth)acrylic polymer (A) (hereinafter referred to as “(A) component”) is obtained 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, 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-ethyl (Meth)acrylic acids such as hexyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, etc. Esters: hydroxy group-containing (meth)acrylic esters such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate , phenoxy (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, o-biphenyloxyethyl (meth)acrylate, and other aromatic ring-containing (meth)acrylates : glycidyl group-containing (meth)acrylic acid esters such as glycidyl (meth)acrylate: (meth)acrylic isocyanate, isocyanate group-containing (meth)acrylic acid esters such as 2-(meth)acryloyloxyethyl isocyanate: acrylic acid, (Meth) acrylic acids such as methacrylic acid: (meth) acrylic acid salts such as ammonium (meth) acrylate, sodium (meth) acrylate, potassium (meth) acrylate: (meth) acrylic monomers such as can be mentioned.

In the present invention, the (meth)acrylic polymer (A) is a hydroxy group-containing (meth)acrylic polymer (A-1) obtained by copolymerizing the hydroxy group-containing (meth)acrylic esters. is preferred.

By containing the hydroxy group-containing (meth)acrylic polymer (A-1), curability, transparency, and hot stampability are improved.

The hydroxyl value of the hydroxyl group-containing (meth)acrylic polymer (A-1) is preferably in the range of 20-200 mg/gKOH. It is more preferably in the range of 50 to 200 mg/gKOH, more preferably in the range of 105 to 200 mg/gKOH, in terms of improving hot stampability, bending resistance, adhesion to substrates, and coating workability. is more preferred.
The hydroxyl value of the hydroxyl group-containing (meth)acrylic polymer (A-1) can be measured as a potassium hydroxide equivalent value by a titration method.

The content of the hydroxy group-containing (meth)acrylic polymer (A-1) in the present composition is the hydroxy group-containing (meth)acrylic polymer (A- 1) is preferably 10 to 50 parts by mass, and more preferably 20 to 50 parts by mass from the viewpoint of improving hot stampability, bending resistance, adhesion to substrates, and coating workability.

Moreover, the monomer mixture preferably contains (meth)acrylic acids such as acrylic acid and methacrylic acid in terms of improving hot stampability.

Furthermore, the monomer mixture may contain monomer units other than (meth)acrylic monomers.

Monomers other than (meth)acrylic monomers are not particularly limited, and examples thereof include monomers having a double bond. Specifically, aromatic vinyls such as styrene and α-methylstyrene: vinyl carboxylates such as vinyl acetate and vinyl propionate; unsaturated dicarboxylic acids such as maleic anhydride, itaconic acid and fumaric acid: N-vinyl pyrrolidone, N-vinyllactams such as N-vinylcaprolactam: and the like.

From the viewpoint of good coating workability, hot stampability, flex resistance, and adhesion to the substrate, the weight average molecular weight (Mw) of component (A) is preferably in the range of 1000 to 100000, preferably 3000 to 3000. The range of 50,000 is more preferable, and the range of 5,000 to 20,000 is even more preferable.

The weight average molecular weight can be adjusted by appropriately controlling the polymerization conditions for polymerizing the component (A), such as the type and amount of polymerization initiator, the type and amount of solvent, the reaction temperature, the reaction time, and the like. It can be adjusted within the range. In the present specification, the term "mass average molecular weight" means the polystyrene-equivalent mass average molecular weight measured by Gel Permeation Chromatography.

The weight average molecular weight (hereinafter referred to as Mw) of each component can be measured under the following conditions using a GPC (Gel Permeation Chromatography) system (manufactured by Tosoh Corporation, trade name: HLC-8220GPC).

(GPC measurement conditions)
Column: "TSK-gel superHZM-M", "TSK-gel HZM-M", "TSK-gel HZ2000"
Eluent: THF
Flow rate: 0.35mL/min
Injection volume: 10 μL
Column temperature: 40°C
Detector: UV-8020

(A) Component can be polymerized according to a known method. For example, it can be synthesized by a solution polymerization method using an azo initiator, a photopolymerization method using an acylphosphine oxide initiator, or the like.

<Photoinitiator (D)>
The composition contains a photopolymerization initiator (D) (hereinafter referred to as "component (D)"). Examples of component (D) include benzoin, benzoin monomethyl ether, benzoin isopropyl ether, acetoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, benzyldimethylketal, 2,2-diethoxyacetophenone, and 1-hydroxycyclohexyl. phenyl ketone, methyl phenyl glyoxylate, ethyl phenyl glyoxylate, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2 -methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one and other carbonyl compounds: tetramethylthiuram monosulfide, tetramethylthiuram disulfide and other sulfur compounds: 2,4,6-trimethylbenzoyldiphenylphosph Fin oxide, acylphosphine oxide such as bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, and the like. These may be used individually by 1 type, and may use 2 or more types together. In particular, 1-hydroxycyclohexylphenyl ketone and 2-hydroxy-2-methyl-1-phenylpropan-1-one are preferable as the component (D) because they can impart high transmittance to the cured film of the present composition. .

The content of component (D) in the present composition is preferably 0.1 parts by mass or more and 10 parts by mass or less when the total mass of the active energy ray-polymerizable composition is 100 parts by mass. Within the above range, the larger the content of component (D), the better the scratch resistance of the cured film. Further, within the above range, the smaller the content of the component (D), the better the flex resistance and hot stampability of the cured film.

<Solvent (E)>
The composition contains a solvent (E) (hereinafter referred to as "component (E)"). Specific examples of component (E) include hydrocarbon solvents such as n-hexane, n-heptane, n-octane, cyclohexane and cyclopentane; aromatic solvents such as toluene, xylene and ethylbenzene; -Alcohol 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; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone and cyclohexanone; ethylene glycol solvents such as diethylene glycol dimethyl ether and diethylene glycol dibutyl ether; ether solvents such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane; Amide solvents such as pyrrolidone, dimethylformamide and dimethylacetamide, and carbonate solvents such as ethylene carbonate are included. The content of component (E) is preferably 30 parts by mass or less with respect to 100 parts by mass of the total amount of polymerizable components having a vinyl group. 5 parts by mass or less is more preferable from the viewpoint of improving coating workability and leveling property and reducing the amount of VOC emissions.

The cured film of the active energy ray-polymerizable composition of the present invention has a glass transition temperature (Tg) of 100° C. or less and a minimum storage elastic modulus E′ of 1×10 ⁸ Pa or more.

<Glass transition temperature (Tg)>
The glass transition temperature (Tg) of the cured film of the active energy ray-polymerizable composition of the present invention must be 100° C. or less. If the glass transition temperature (Tg) exceeds 100°C, the flex resistance and the resistance to hot stamping deteriorate. The glass transition temperature is more preferably 90° C. or lower, still more preferably 85° C. or lower, from the viewpoint of good bending resistance and hot stampability. In order to set the glass transition temperature (Tg) to 100° C. or less, for example, a urethane (meth)acrylate (B) component may be blended into the active energy ray-polymerizable composition.

The glass transition temperature Tg of the cured film of this composition is measured using a dynamic viscoelasticity measuring device (manufactured by TA Instruments, trade name: RSA II). The maximum value of tan δ under the environment of 11 Hz frequency, 5° C./min heating rate, and 30 to 200° C. is defined as glass transition temperature Tg.

<Storage elastic modulus E′>
The minimum value of the storage elastic modulus E' of the cured film of the active energy ray-polymerizable composition of the present invention is required to be 1×10 ⁸ Pa or more. If the minimum value of storage elastic modulus E' is less than 1×10 ⁸ Pa, the scratch resistance is lowered.

The storage elastic modulus E′ is more preferably 1.2×10 ⁸ Pa or more, and even more preferably 1.4×10 ⁸ Pa or more. Within the above range, the higher the storage modulus E', the better the scratch resistance tends to be. In order to make the minimum value of the storage elastic modulus E′ 1×10 ⁸ Pa or more, for example, an alkylene oxide-modified or caprolactone-modified trifunctional or higher monomer (C) component is added to the active energy ray-polymerizable composition. should be mixed.

The storage elastic modulus E' of the cured film of the composition is measured using a dynamic viscoelasticity measuring device (manufactured by TA Instruments, trade name: RSA II). The storage elastic modulus is defined as the value of E' under the environment of 11 Hz frequency, 5°C/min heating rate, and 30 to 200°C environment.

A sample for measuring the glass transition temperature Tg and the storage elastic modulus E' is prepared by the following method. That is, the active energy ray-polymerizable composition is spray-coated on glass so that the thickness of the cured film after drying is 0.02 mm, heated in an oven at 60° C. for 3 minutes to volatilize the organic solvent, and A high-pressure mercury lamp is used in air to irradiate ultraviolet rays having a wavelength of 300 nm to 400 nm and a peak illuminance of 100 mW/cm ² and an integrated light intensity of 1000 mJ/cm ² to form a cured film, and only the cured film is removed from the glass plate. Use the cut piece as a sample.

<Urethane (meth)acrylate (B)>
The composition preferably contains urethane (meth)acrylate (B) (hereinafter referred to as "(B) component").

Component (B) is synthesized from raw materials containing polyisocyanate (b1) (hereinafter referred to as "b1 raw material") and hydroxy group-containing (meth)acrylate (b3) (hereinafter referred to as "b3 raw material") described below. Urethane poly(meth)acrylate. In particular, from the viewpoint of imparting bending resistance to the resulting cured film, the b1 raw material and the polyol (b2) (hereinafter referred to as "b2 raw material") are reacted, and then the b3 raw material is reacted to obtain a urethane poly. (Meth)acrylates are preferred. Here, a hydroxy group-containing (meth)acrylate having two or more hydroxy groups is classified as a b3 raw material and not classified as a b2 raw material. As the component (B), only one kind of compound may be used, or two or more kinds may be used in combination.

Specific examples of the b1 raw material include tolylene diisocyanate, methylcyclohexane diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, dimer acid diisocyanate, trimethylhexamethylene diisocyanate, and the like. Triisocyanates such as diisocyanate and lysine triisocyanate are included. Further, polyisocyanate compounds obtained by reacting these polyisocyanate compounds with compounds having at least two active hydrogen atoms such as amino groups, hydroxyl groups, carboxyl groups, water, etc., or dimers of the above polyisocyanate compounds. Pentamers and the like can also be used. Among these, diisocyanate is preferable because the obtained component (A) has a low viscosity, the coating workability of the present composition is improved, and the cured film has good flex resistance. Among them, isophorone diisocyanate, Dicyclohexylmethane diisocyanate is more preferred.

Specific examples of b2 raw materials include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, methylpentanediol, 2,4- Diethylpentanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, neopentyl glycol hydroxypivalate, 1,4-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol , cyclohexanediol, bisphenol A, and spiroglycol; triols such as trimethylolpropane and glycerol; and tetraols such as pentaerythritol. Furthermore, polyalkylene polyols having a structure obtained by adding an alkylene oxide to the above polyols, polycaprolactone polyols obtained by adding lactones such as ε-caprolactone to the above polyols, the above polyols and alkylene carbonates, dialkyl carbonates, diaryl carbonates, etc. A polycarbonate polyol or the like obtained by transesterification reaction of a carbonate ester can be used. These can be used individually by 1 type or in combination of 2 or more types. Among these, diols are preferable from the viewpoint of imparting bending resistance to the cured film, and among them, diols into which an aromatic ring structure such as bisphenol A is introduced are more preferable.

Examples of the b3 raw material include hydroxyalkyl (meth)acrylates, caprolactone-modified and alkylene oxide-modified hydroxyalkyl (meth)acrylates, addition reaction products of monoepoxy compounds and (meth)acrylic acid, and the like. The number of carbon atoms in the hydroxyalkyl group of the hydroxyalkyl (meth)acrylate is preferably 1 to 10. Specific examples of the hydroxyalkyl (meth)acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, Hydroxyalkyl mono(meth)acrylates such as 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, glycerol acrylate methacrylate, pentaerythritol tri(meth)acrylate, dipenta and hydroxyalkyl poly(meth)acrylates such as erythritol penta(meth)acrylate. Caprolactone-modified products of hydroxyalkyl (meth)acrylates include caprolactone-modified products such as γ-caprolactone, δ-caprolactone, and ε-caprolactone. Alkylene oxide-modified products of hydroxyalkyl (meth)acrylates include alkylene oxide-modified products such as ethylene oxide, propylene oxide and butylene oxide. Examples of addition reaction products of monoepoxy compounds and (meth)acrylic acid include addition reaction products of monoepoxy compounds and (meth)acrylic acid such as butyl glycidyl ether, 2-ethylhexyl glycidyl ether, and glycidyl (meth)acrylate. mentioned. Among these, hydroxyalkyl mono(meth)acrylates having an alkyl chain of 2 to 4 carbon atoms are preferred because the viscosity of the component (B) is low and the coating workability of the present composition is improved. - hydroxyethyl (meth)acrylate is more preferred.

Regarding the method of synthesizing the component (B) from the b1 raw material and the b3 raw material, it can be synthesized according to various conventionally known methods. For example, in a mixture of the b1 raw material and a catalyst such as dibutyltin dilaurate heated to 30 to 90° C., the b3 raw material is added dropwise over 1 to 3 hours, and further reacted for 1 to 3 hours to obtain the component (B). can be synthesized.

(B) The amount of b1 raw material and b3 raw material used in the synthesis of component satisfies the condition that (total number of isocyanate groups of b1 raw material)/(total number of hydroxy groups of b3 raw material) is 0.5 or more and 1.0 or less. It is preferable to set By setting this value to 0.5 or more, it is possible to impart adhesion to the substrate to the cured film. On the other hand, by setting this value to 1.0 or less, the reaction rate of the isocyanate groups increases, and the storage stability of the present composition can be improved. A particularly preferable range of this condition is 0.9 or more and 1.0 or less.

Also, the method of synthesizing the component (B) from the b1, b2 and b3 raw materials can be carried out according to various conventionally known methods. For example, in a mixture of the b1 raw material and a catalyst such as dibutyltin dilaurate heated to 30 to 90 ° C., the b2 raw material is added dropwise over 2 to 6 hours, and further reacted for 1 to 3 hours. Component (B) can be synthesized by adding dropwise over 3 hours and further reacting for 1 to 3 hours. The amount of b1 raw material, b2 raw material and b3 raw material used for synthesis of component (B) is such that (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 or more and 1.0 or less. It is preferable to set so as to satisfy the following condition. By setting this value to 0.5 or more, it is possible to impart adhesion to the substrate to the cured film. On the other hand, by setting this value to 1.0 or less, the reaction rate of the isocyanate groups increases, and the storage stability of the present composition can be improved. A particularly preferable range of this condition is 0.9 or more and 1.0 or less.

The content of the component (B) in the present composition provides good flex resistance and wear resistance of the cured coating when the total mass of the active energy ray-polymerizable composition is 100 parts by mass. 1 part by mass or more and 40 parts by mass or less is preferable, and 10 parts by mass or more and 40 parts by mass or less is more preferable.

The mass-average molecular weight of component (B) is preferably 500 to 40,000, more preferably 2,000 to 20,000, from the viewpoint of good bending resistance and coating workability of the cured film.

<Alkylene oxide-modified or caprolactone-modified trifunctional or higher monomer (C)>
The present composition preferably contains an alkylene oxide-modified or caprolactone-modified trifunctional or higher monomer (C) (hereinafter referred to as "component (C)").

The alkylene oxide-modified or caprolactone-modified tri- or more functional (C) component is other than the (A) component and the (B) component, and is an alkylene oxide-modified or caprolactone-modified tri- or more functional (meth) Acrylate.

Specific examples of component (C) include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, polyurethane tri(meth)acrylate, polyepoxy tri(meth)acrylate, polyester tri(meth)acrylate alkylene Oxide-modified or caprolactone-modified products: ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, polyepoxytetra(meth)acrylate, polyestertetra(meth)acrylate alkylene oxide-modified or caprolactone-modified products: dipentaerythritol Penta(meth)acrylate, alkylene oxide-modified or caprolactone-modified products of tripentaerythritol penta(meth)acrylate: dipentaerythritol hexa(meth)acrylate, alkylene oxide-modified or caprolactone-modified products of tripentaerythritol hexa(meth)acrylate: tri Alkylene oxide-modified or caprolactone-modified product of pentaerythritol hepta (meth) acrylate: Alkylene oxide-modified or caprolactone-modified product of tripentaerythritol octa (meth) acrylate: Alkylene oxide-modified or caprolactone-modified trifunctional or higher polyepoxypoly(meth) ) Acrylate: alkylene oxide-modified or caprolactone-modified trifunctional or higher polyester poly(meth)acrylate, and the like. In particular, caprolactone-modified dipentaerythritol hexa(meth)acrylate is more preferable as the component (C) because it can impart high scratch resistance to the cured film of the present composition.

(C) component may use 1 type and may use 2 or more types together.

The content of the component (C) in the present composition should be less than the mass of the entire active energy ray-polymerizable composition from the viewpoint that the scratch resistance of the cured film, the flex resistance of the cured film, and the resistance to hot stamping are improved. Based on 100 parts by mass, it is preferably 30 to 85 parts by mass, more preferably 40 to 85 parts by mass.

For the purpose of improving abrasion resistance, etc., the present composition may optionally contain other polymerizable components having a vinyl group other than components (A), (B) and (C) (hereinafter referred to as “other polymerizable components”). ) may be included. As other polymerizable components, (meth)acryloyl group-containing monomers are preferred. (Meth)acryloyl group-containing monomers include monofunctional (meth)acrylates, bifunctional (meth)acrylates, trifunctional (meth)acrylates, tetrafunctional or higher (meth)acrylates, and (meth)acrylamides.

Specific examples of monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl ( meth)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 ) 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 and the like.

Specific examples of bifunctional (meth)acrylates include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate, and ethylene glycol. Di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, glycerol 1,3-di(meth)acrylate, neo Pentyl glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, neopentyl glycol hydroxypivalate di(meth)acrylate, tricyclodecanediyldimethylene di(meth)acrylate, bisphenol A di(meth)acrylate, hydrogenation Bisphenol A di(meth)acrylate, bisphenol F di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, polycarbonate di(meth)acrylate, or polyalkylene oxide adducts of these monomers, polycaprolactone Examples include adducts, polycarbonate adducts, polyepoxy di(meth)acrylates, polyester di(meth)acrylates, and the like.

Specific examples of trifunctional (meth)acrylates include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, polyepoxy tri(meth)acrylate, and polyester tri(meth)acrylate.

Specific examples of tetrafunctional or higher (meth)acrylates include ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, polyepoxytetra(meth)acrylate, polyester tetra(meth)acrylate, dipentaerythritol penta( Penta(meth)acrylates such as meth)acrylates and tripentaerythritol penta(meth)acrylates: Hexa(meth)acrylates such as dipentaerythritol hexa(meth)acrylate and tripentaerythritol hexa(meth)acrylates: tripentaerythritol Hepta (meth) acrylate such as hepta (meth) acrylate: Octa (meth) acrylate such as tripentaerythritol octa (meth) acrylate: Tetrafunctional or higher polyepoxy poly (meth) acrylate: Tetrafunctional or higher polyester poly (meth) ) acrylates and the like.

Specific examples of (meth)acrylamide include (meth)acrylamide, isobutoxymethyl(meth)acrylamide, t-octyl(meth)acrylamide, diacetone(meth)acrylamide and the like.

Other polymerizable components may be used alone or in combination of two or more.

The amount of other polymerizable components is preferably 0.1 to 10 parts by mass, more preferably 1 to 5 parts by mass, when the total mass of the active energy ray-polymerizable composition is 100 parts by mass.

The present composition may optionally contain a sensitizer, a dispersant, a wax, a light stabilizer, an antioxidant, a surface conditioner, an antifoaming agent, a heat stabilizer, an antistatic agent, an antifogging agent, fine particles, a thixotropic Other ingredients such as tropic agents, coupling agents, etc. may be included.

Specific examples of sensitizers include benzoin isopropyl ether and thioxanthone.

Specific examples of the dispersant include BYK Chemie Anti-Terra-U, Anti-Terra-203/204, Disperbyk-101, 107, 110, 111, 130, 161, 162, 163, 164, 165, 166 , 170, 400, Bykumen, BYK-P104, P105, P104S, 240S and Lactimon (all of these are trade names).

Specific examples of waxes include polyamide wax and polyethylene oxide wax.

Specific examples of light stabilizers include bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis( Hindered amines such as 1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate can be mentioned.

Specific examples of antioxidants include hindered phenol compounds, organic phosphite compounds and organic phosphonite compounds.

Specific examples of surface conditioners and antifoaming agents include non-silicone antifoaming agents such as polysiloxane, polysiloxane antifoaming agents such as fluorine-modified polysiloxane, and copolymers of alkyl methacrylate, acrylate, and acrylic acid. acrylic acid antifoaming agents, butadiene copolymer antifoaming agents and mineral oil antifoaming agents.

Specific examples of heat stabilizers include triphenylphosphite, tris(2,6-dimethylphenyl)phosphite, tris(2,4-di-t-butylphenyl)phosphite, tris(mono-nonylphenyl)phosphite, Mixtures of phyto and tris(di-nonylphenyl) phosphite, dimethylbenzene phosphonate and trimethyl phosphate are included.

Specific examples of antistatic agents include glycerol monostearate, sodium stearyl sulfonate and sodium dodecylbenzene sulfonate.

Specific examples of antifogging agents include glycerol-1-methacryloyloxyethylurethane and glycerol-1-methacryloyloxypropylurethane.

Specific examples of the polymer include (meth)acrylic polymers, (meth)acrylonitrile polymers, butadiene polymers, urethane polymers, polyester polymers, polyamide polymers, polyamideimide polymers and Phenolic polymers are mentioned.

Specific examples of fine particles include organic fillers such as acrylic beads and urethane beads, inorganic fillers such as silica and titanium, and inorganic fillers surface-organized with a silane coupling agent or the like. Examples of the method of blending these into the present composition include a method of blending in a pre-dispersed state and a method of blending the fine particles into the present composition and then dispersing them using a triple roll, a dyno mill, or the like. . Moreover, in order to improve the dispersibility, a carboxylic acid-based, polycarboxylic acid-based, or polyacrylic acid-based dispersant can be used.

Specific examples of thixotropic agents include organic thixotropic agents such as amides, polyethylene oxides, and hydrogenated castor oil; inorganic agents such as silica, bentonite, and organic silane coupling products thereof; Thixotropic agents are included.

Specific examples of coupling agents include silane coupling agents and titanium coupling agents to which functional groups such as (meth)acryloyloxy groups, vinyl groups, epoxy groups, and amino groups are added.

The composition of the present invention can be prepared by, for example, prepolymerizing the component (A) by a conventional polymerization method such as suspension polymerization or photopolymerization, and adding a photopolymerization initiator to the obtained (meth)acrylic polymer (A). It can be produced by mixing (D), solvent (E), and if necessary, component (B), component (C), and other components.

The composition can be used to coat the surface of various molded articles such as paper and polymers as substrates. Examples of polymer molded articles include sheet-shaped molded articles, film-shaped molded articles, injection-molded articles of various shapes, and the like. Materials for polymer molded articles include polymethyl methacrylate polymer, polycarbonate polymer, polyester polymer, polyester carbonate polymer, polystyrene polymer, acrylonitrile-butadiene-styrene polymer (hereinafter referred to as "ABS"), and acrylonitrile. - Styrene polymer, polyamide polymer, polyarylate polymer, polymethacrylimide polymer, polyallyldiglycol carbonate polymer and the like.

The molded article having a cured film of the active energy ray-polymerizable composition of the present invention is obtained by applying the active energy ray-polymerizable composition to the surface of the molded article and irradiating the resulting coating film with an active energy ray. A cured film can be formed by

To apply the present composition to a molded product, methods such as brush coating, spray coating, dip coating, spin coating, curtain coating, bar coating, and the like can be used. Alternatively, the composition may be heated to adjust the viscosity or diluted with a subcritical fluid before coating. The thickness of the coating film of the present composition is preferably 0.001 mm or more and 0.1 mm or less, more preferably 0.002 mm or more and 0.05 mm or less, from the viewpoints of curability and abrasion resistance of the present composition. 004 mm or more and 0.03 mm or less is more preferable.

When the coating film of the present composition is irradiated with an active energy ray, it is cured to obtain a cured coating film. The active energy rays to be used include α-rays, β-rays, γ-rays, ultraviolet rays, and the like. From the viewpoint of versatility, ultraviolet rays are preferable as active energy rays. Examples of ultraviolet light sources include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, metal halide lamps, electrodeless UV lamps using magnetrons, and LEDs.

The atmosphere for curing the coating film includes inert gases such as nitrogen and argon, and air. Air is preferable as the atmosphere from the viewpoint of practicality and economy. As a preferable curing condition when ultraviolet rays are used as the active energy ray, for example, it is preferable to irradiate with a high-pressure mercury lamp so that the integrated amount of light with a wavelength of 340 to 380 nm is 100 to 3000 mJ/cm ² .

It is preferable that the molded article of the present invention has a foil on the surface of the cured coating, and that the transfer rate of the foil is 40% or more. The active energy ray-polymerizable composition of the present invention is applied to the surface of the base material of the various molded articles described above, and the resulting coating film is irradiated with an active energy ray to form a cured film, whereby the surface of the cured film is The transfer rate of the hot stamping foil is improved to 40% or more when the hot stamping foil is pressed against. The molded product of the present invention having a foil transfer rate of 40% or more has a high print transfer rate when printing is performed on the surface of a cosmetic container by hot stamping, so the cost of printing on the surface of the cosmetic container can be minimized. can be reduced to Therefore, the molded article of the present invention can be suitably used as a cosmetic container.

The transfer rate of the foil was obtained by heating the hardened surface of the ABS plate with the hardened film to a 2 cm square rubber stamp attached to a foil stamping machine manufactured by Leather Tools Co. (trade name: 4PT) can be measured by pressing for 1 second.
Transfer rate (%) = Transferred area of hot stamp foil (cm ² ) x 100/imprinted area (4 cm ² ).

The transfer rate of the foil is preferably 40% or more, more preferably 70% or more, still more preferably 90% or more, and most preferably 100%, from the viewpoint of good hot stampability.

Hereinafter, the present invention will be described using examples. In addition, "part" means a mass part in the following description.
In addition, evaluation was performed by the following method.

(1) Evaluation sample The composition prepared at each compounding ratio was applied to a 3 mm thick ABS plate, a 0.188 mm thick 10 cm × 10 cm PET film, a 2 mm thick glass plate, and the cured film thickness after drying was 0. Each was spray-coated so as to have a thickness of 0.02 mm.
Then, the coated substrate was heated in an oven at 60° C. for 3 minutes to volatilize the organic solvent. Furthermore, using a high-pressure mercury lamp in air, ultraviolet rays having a wavelength of 300 nm to 400 nm and a peak illuminance of 100 mW/cm ² and an integrated light intensity of 1000 mJ/cm ² were irradiated, and the ABS plate 1 with the cured coating, the PET film 2, A glass plate 3 was obtained.

(2) Hot stampability The cured surface of the ABS plate 1 with the cured film obtained in (1) was heated to 150 ° C. with a 2 cm square rubber stamp attached to a foil stamping machine manufactured by Leather Tools. A second hot stamp foil (manufactured by KURZ, trade name: 4PT) was pressed to evaluate the transfer rate of the foil.
Transfer rate (%) = Transferred area of hot stamp foil (cm ² ) x 100/imprinted area (4 cm ² ).

<Evaluation Criteria for Hot Stampability>
A: Transfer rate is 40% or more F: Transfer rate is less than 40%

(3) Scratch resistance The cured surface of the ABS plate 1 with the cured coating obtained in (1) was attached to a plane friction tester manufactured by Coating Tester Co., Ltd. Steel wool # 000 manufactured by Bonstar Sales Co., Ltd. and rubbed under the conditions of a load of 250 g/cm ² and 50 reciprocations. The increase in haze due to friction was calculated from haze values before and after friction measured according to JIS-K7105 using a haze meter HM-65W manufactured by Murakami Color Research Laboratory. The obtained haze increase value was used to evaluate the scratch resistance according to the following criteria.

<Evaluation Criteria for Scratch Resistance>
A: Haze increase value of less than 2% B: Haze increase value of 2% or more and less than 4% F: Haze increase value of 4% or more

(4) Bending resistance The PET film 2 with the cured film obtained in (1) is bent so that the cured surface faces outward, and the width between the sides of the PET film 2 is 10 mm, and the cured surface Check for cracks. When there were no cracks, the gap was set to 9 mm, which was narrower by 1 mm, and the presence or absence of cracks on the hardened surface was checked.

By narrowing the gap by 1 mm by such a method, the minimum gap without cracks was evaluated.

<Evaluation Criteria for Flexibility>
A: No cracks when the gap is 8 mm or less B: No cracks when the gap is 9 mm or more and 10 mm or less F: Cracks when the gap is 10 mm

(5) Minimum value of glass transition temperature Tg and storage elastic modulus E '(1) Only the cured film is cut out from the glass plate 3 with the cured film obtained in (1), and a dynamic viscoelasticity measuring device (TA Instruments , trade name: RSA II), under the conditions of a frequency of 11 Hz and a heating rate of 5 ° C./min, the glass transition temperature Tg (maximum tan δ temperature) at 30 ° C. to 200 ° C. and the minimum storage elastic modulus E ' were measured. .

[Production Example 1] Production of hydroxy group-containing (meth)acrylic polymer (A1) 60 parts of butyl acetate (manufactured by KH Neochem Co., Ltd.) was placed in a 5-liter four-necked flask equipped with a stirrer and heated to 120°C. The temperature was raised to Then, under nitrogen bubbling, 51.75 parts of methyl methacrylate (manufactured by Mitsubishi Chemical Corporation, trade name: Acryester M), 29 parts of n-butyl methacrylate (manufactured by Mitsubishi Chemical Corporation, trade name: Acryester B). part, 2-hydroxyethyl methacrylate (manufactured by Mitsubishi Chemical Corporation, trade name: Acryester HO) 19 parts, acrylic acid (manufactured by Mitsubishi Chemical Corporation) 0.25 parts, 2'-azobis-2-methylbutyro 2.5 parts of nitrile (manufactured by Otsuka Chemical Co., Ltd., trade name: AMBN) was added dropwise over 4 hours. After holding this mixture at 120° C. for 1 hour, 0.1 part of 2′-azobis-2-methylbutyronitrile was added. After further holding this at 120°C for 1 hour, the temperature was lowered to 70°C over 1 hour, and 40 parts of ethyl acetate (manufactured by Daicel Co., Ltd.) was added to obtain a polymer (A1) having a hydroxyl group (hereinafter referred to as (A1) component). ). The Mw of the component (A1) measured under the GPC measurement conditions was 10,000.

[Production Example 2] Production of hydroxy group-containing (meth)acrylic polymer (A2) 85 parts of butyl acetate (manufactured by KH Neochem Co., Ltd.) was placed in a 5-liter four-necked flask equipped with a stirrer and heated to 120°C. The temperature was raised to Then, under nitrogen bubbling, 34.1 parts of styrene (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), 28.8 parts of methyl methacrylate (manufactured by Mitsubishi Chemical Corporation, trade name: Acryester M), t-butyl methacrylate ( Mitsubishi Chemical Corporation, trade name: Acryester TB) 5 parts, 2-hydroxyethyl methacrylate (Mitsubishi Chemical Corporation, trade name: Acryester HO) 30.9 parts, acrylic acid (Mitsubishi Chemical Co., Ltd.) 1.2 parts of azobisisobutyronitrile (manufactured by Otsuka Chemical Co., Ltd., trade name: AIBN) were added dropwise over 4 hours. After holding this mixture at 120° C. for 1 hour, 0.1 part of azobisisobutyronitrile was added. After holding this at 120° C. for 2 hours, 15 parts of butyl acetate was added to obtain a polymer (A2) having a hydroxyl group (hereinafter referred to as component (A2)). The Mw of the component (A2) measured in the same manner as in Production Example 1 was 12,000.

[Production Example 3] Production of hydroxy group-containing (meth)acrylic polymer (A3) 85 parts of butyl acetate (manufactured by KH Neochem Co., Ltd.) was placed in a 5-liter four-necked flask equipped with a stirrer and heated to 110°C. The temperature was raised to Then, under nitrogen bubbling, 48 parts of methyl methacrylate (manufactured by Mitsubishi Chemical Corporation, trade name: Acryester M), 35.4 parts of n-butyl methacrylate (manufactured by Mitsubishi Chemical Corporation, trade name: Acryester B). part, n-butyl acrylate (manufactured by Mitsubishi Chemical Corporation, trade name: butyl acrylate) 11 parts, 2-hydroxyethyl methacrylate (manufactured by Mitsubishi Chemical Corporation, trade name: Acryester HO) 5.1 parts, acrylic 0.5 parts of acid (manufactured by Mitsubishi Chemical Corporation) and 0.6 parts of azobisisobutyronitrile (manufactured by Otsuka Chemical Co., Ltd., trade name: AIBN) were added dropwise over 4 hours. After holding this mixture at 110° C. for 1 hour, 0.5 part of azobisisobutyronitrile was added. After further holding this at 110° C. for 2 hours, 15 parts of butyl acetate was added to obtain a polymer (A3) having a hydroxyl group (hereinafter referred to as component (A3)). The Mw of the component (A3) measured in the same manner as in Production Example 1 was 26,000.

[Production Example 4] Production of (meth)acrylic polymer (X1) In a 5-liter four-necked flask equipped with a stirrer, 48 parts of toluene (manufactured by Idemitsu Kosan Co., Ltd.), n-butyl alcohol (KH Neochem ( (manufactured by Co., Ltd.) was added, and the temperature was raised to 98°C. Then, under nitrogen bubbling, 79 parts of methyl methacrylate (manufactured by Mitsubishi Chemical Corporation, trade name: Acryester M), 6.5 parts of styrene (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), alkyl methacrylate (Mitsubishi Chemical Corporation ), trade name: Acryester SL) and 3 parts of t-butylperoxy-2-ethylhexanoate (manufactured by NOF Corporation, trade name: Perbutyl O) were added dropwise over 5 hours. After holding this mixture at 98° C. for 1 hour, 0.5 part of t-butylperoxy-2-ethylhexanoate was added. After further holding this at 98° C. for 1 hour, 10 parts of toluene was added to obtain a polymer (X1) having a hydroxyl group (hereinafter referred to as component (X1)). The Mw of the component (X1) measured in the same manner as in Production Example 1 was 18,000.

[Production Example 5] Production of urethane acrylate (B1) 261.6 of bisphenol A-containing diol (manufactured by ADEKA Corporation, trade name: ADEKA POLYETHER BPX-11) was added to a 5-liter four-necked flask equipped with a stirrer. part, neopentyl glycol (manufactured by Mitsubishi Gas Chemical Co., Ltd.) 19.1 parts, dibutyltin dilaurate (manufactured by ADEKA Co., Ltd., trade name: ADEKA STAB BT-11) 0.18 parts, di-t-butyl-p- 1.46 parts of cresol (manufactured by Honshu Chemical Industry Co., Ltd., trade name: H-BHT) and 224 parts of butyl acetate (manufactured by KH Neochem Co., Ltd.) were added, and the temperature was raised to 60°C. 400 parts of isophorone diisocyanate (manufactured by Sumika Bayer Urethane Co., Ltd., trade name: Desmodur 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., product 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 further held at 70°C for 5 hours to obtain urethane acrylate (B1) (hereinafter referred to as component (B1)). Moreover, the Mw of the component (B1) measured in the same manner as in Production Example 1 was 4,300.

[Production Example 6] Production of urethane acrylate (B2) Into a 5-liter four-necked flask equipped with a stirrer, 205 parts of ethoxylated bisphenol A (manufactured by Sigma-Aldrich, trade name: ethoxylated bisphenol A) and acetic acid were added. 305 parts of butyl (manufactured by KH Neochem Co., Ltd.) and 0.18 parts of dibutyltin dilaurate (manufactured by ADEKA Corporation, trade name: ADEKA STAB BT-11) were added, and the temperature was raised to 50°C. 266 parts of isophorone diisocyanate (manufactured by Sumika Bayer Urethane Co., Ltd., trade name: Desmodur I) was added dropwise over 1 hour. After heating this mixture to 70° C. over 1 hour, 139 parts of 2-hydroxyethyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name: HEA) and hydroquinone monomethyl ether (manufactured by Kawaguchi Chemical Industry Co., Ltd., Trade name: MQ) 0.3 part of the mixture was added dropwise over 1 hour. Subsequently, after holding at 70° C. for 2 hours, 305 parts of butyl acetate was added to obtain urethane acrylate (B2) (hereinafter referred to as component (B2)). The Mw of the component (B2) measured in the same manner as in Production Example 1 was 2,000.

(Examples 1 to 10 and Comparative Examples 1 to 4)
Active energy ray-polymerizable compositions were prepared according to the compositions shown in Table 1 and evaluated. Table 1 shows the evaluation results.

Abbreviations in Table 1 are as follows: A1: Synthesized in Production Example 1 (A1)
· A2: Synthesized in Production Example 2 (A2)
· A3: Synthesized in Production Example 3 (A3)
· X1: Synthesized in Production Example 4 (X1)
· B1: Synthesized in Production Example 5 (B1)
· B2: Synthesized in Production Example 6 (B2)
・ EA1: Epoxy acrylate (manufactured by MIWON, trade name: Miramar PE210)
・ DPCA-20: Caprolactone 2 mol modified dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name: DPCA-20)
・ DPCA-60: Caprolactone 6 mol modified dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name: DPCA-60)
DPEA-12: Ethylene oxide 12 mol modified dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name: DPCA-12)
・ DPHA: dipentaerythritol hexaacrylate (manufactured by MIWON, trade name: Miramar M600)
HDDA: 1,6-hexanediol diacrylate (manufactured by MIWON, trade name: Miramar M200)
・HCPK: 1-hydroxycyclohexylphenyl ketone (manufactured by BASF, trade name: Irgacure 184)
・PGM: propylene glycol monomethyl ether (manufactured by Daicel Corporation, trade name: methoxypropanol)
・Butyl cellosolve: ethylene glycol monobutyl ether (manufactured by KH Neochem Co., Ltd., trade name: BUTICEL)
Paintad Q: Silicon polyether copolymer (manufactured by Dow Corning Toray, trade name: Paintad Q)

From the evaluation results shown in Table 1, the glass transition temperature (Tg) of the cured film containing all of the hydroxyl group-containing (meth)acrylic polymer (A), the photopolymerization initiator (D) and the solvent (E) component is 100 It was found that Examples 1 to 10, in which the minimum value of storage modulus E′ was 1×10 ⁸ Pa or more at 1° C. or less, had good hot stampability, scratch resistance, and flex resistance.

On the other hand, Comparative Example 1, in which the minimum value of the storage elastic modulus E′ of the active energy ray-polymerizable composition is less than 1×10 ⁸ Pa and does not contain the A component in the composition, has a transfer rate of hot stampability. was down to 20%. Comparative Example 2, in which the active energy ray-polymerizable composition contained component A and had a glass transition temperature (Tg) exceeding 100°C, exhibited cracks at a gap of 10 mm in bending resistance. Comparative Example 3, in which the glass transition temperature (Tg) of the active energy ray-polymerizable composition exceeds 100° C., had a transfer rate of hot stampability decreased to 20%, and had cracks in the bending resistance at a gap of 10 mm. . Comparative Example 4, in which the minimum value of the storage elastic modulus E′ of the active energy ray-polymerizable composition was less than 1×10 ⁸ Pa, had a scratch-resistant haze increased to 4.8%.

INDUSTRIAL APPLICABILITY According to the present invention, the active energy ray-polymerizable composition and this composition can be widely applied as a molded article having a cured film.

Claims (10)

An active energy ray-polymerizable composition comprising a (meth)acrylic polymer (A), a photopolymerization initiator (D) and a solvent (E), wherein the (meth)acrylic polymer (A) contains a hydroxy group
It is a (meth)acrylic polymer (A-1), and the glass transition temperature (Tg) of the cured film of the active energy ray-polymerizable composition is 100° C. or less, and the minimum value of the storage elastic modulus E′ is 1×10. ^8P
a or more, and the foil transfer rate of the cured film having the active energy ray-polymerizable composition formed on the surface of the molded article is 40% or more. A linearly polymerizable composition.
(However, the storage elastic modulus E' is measured using a dynamic viscoelasticity measuring device at a frequency of 11 Hz, a heating rate of 5°C/min, and an environment of 30 to 200°C. Also, the storage elastic modulus E' is measured. For the sample, the active energy ray-polymerizable composition was spray-coated on the glass so that the thickness of the cured film after drying was 0.02 mm, and heated in an oven at 60 ° C. for 3 minutes to volatilize the organic solvent. ,
Furthermore, using a high-pressure mercury lamp in air, the peak illuminance at a wavelength of 300 nm to 400 nm is 1
A cured film is formed by irradiating ultraviolet rays of 00 mW/cm ² and an integrated light amount of 1000 mJ/cm ² , and only the cured film is cut out from the glass plate. ) The hydroxyl group-containing (meth)acrylic polymer (A-1) has a hydroxyl value of 105 to 200
The active energy ray-polymerizable composition according to claim 1 , which is mg/g KOH. The content of the hydroxy group-containing (meth)acrylic polymer (A- 1 ) component is 10 to 50 parts by mass when the total mass of the active energy ray-polymerizable composition is 100 parts by mass.
3. The active energy ray-polymerizable composition according to claim 2. The active energy ray-polymerizable composition according to any one of Claims 1 to 3 , wherein the active energy ray-polymerizable composition contains urethane (meth)acrylate (B). 5. The active energy ray-polymerizable composition according to claim 4 , wherein the urethane (meth)acrylate (B) has an aromatic ring. The urethane (
6. The active energy ray-polymerizable composition according to claim 4 , wherein the meth)acrylate (B) is 1 to 40 parts by mass. The active energy ray-polymerizable composition according to any one of claims 1 to 6 , wherein the active energy ray-polymerizable composition contains an alkylene oxide-modified or caprolactone-modified trifunctional or higher monomer (C). When the total mass of the active energy ray-polymerizable composition is 100 parts by mass, the alkylene oxide-modified or caprolactone-modified trifunctional or higher monomer (C) is 30 to 85 parts by mass.
The active energy ray-polymerizable composition according to any one of claims 1 to 7 , which is parts by mass. A molded article having a cured film of the active energy ray-polymerizable composition according to any one of claims 1 to 8 on the surface of the molded article. 10. The molded product according to claim 9 , wherein said molded product is used as a container for cosmetics.