CN114149562A

CN114149562A - Urethane (meth)acrylate, active energy ray-curable resin composition, cured product, laminate, and molded product

Info

Publication number: CN114149562A
Application number: CN202111032201.6A
Authority: CN
Inventors: 渡边有绍; 冨樫春久
Original assignee: Arakawa Chemical Industries Ltd
Current assignee: Arakawa Chemical Industries Ltd
Priority date: 2020-09-08
Filing date: 2021-09-03
Publication date: 2022-03-08
Also published as: JP2022045341A; TW202222879A

Abstract

[技术问题]本发明提供氨基甲酸酯(甲基)丙烯酸酯及包含该氨基甲酸酯(甲基)丙烯酸酯的活性能量线固化型树脂组合物，所述氨基甲酸酯(甲基)丙烯酸酯提供具有优异的耐化学品性和高延伸率的固化物。[技术手段]氨基甲酸酯(甲基)丙烯酸酯，所述氨基甲酸酯(甲基)丙烯酸酯含有具有脂环结构的二元醇(a1)、具有环状结构的二异氰酸酯(a2)和具有羟基的(甲基)丙烯酸酯(a3)作为反应成分，所述氨基甲酸酯(甲基)丙烯酸酯的重均分子量为6,000～25,000，且(甲基)丙烯酰基浓度为0.2×10^‑3～2.0×10^‑3eq/g。[Technical Problem] The present invention provides a urethane (meth)acrylate and an active energy ray-curable resin composition comprising the urethane (meth)acrylate, the urethane (meth)acrylate Acrylates provide cured products with excellent chemical resistance and high elongation. [Technical means] Urethane (meth)acrylate containing diol (a1) having an alicyclic structure and diisocyanate (a2) having a cyclic structure and a (meth)acrylate (a3) having a hydroxyl group as a reaction component, the urethane (meth)acrylate having a weight average molecular weight of 6,000 to 25,000 and a (meth)acryloyl concentration of 0.2×10 ^‑3 to 2.0×10 ^‑3 eq/g.

Description

Urethane (meth) acrylate, active energy ray-curable resin composition, cured product, laminate, and molded product

Technical Field

The present invention relates to a urethane (meth) acrylate, an active energy ray-curable resin composition, a cured product, a laminate, and a molded product.

Background

Active energy ray-curable resin compositions that are cured by ultraviolet rays or electron beams are widely used for articles such as various electric appliances and daily necessities because of their scratch resistance and chemical resistance. Among them, decoration techniques are applied to terminals of mobile phones and smart phones, housings of personal computers, interior and exterior parts of automobiles, and the like, and in addition to the above-described properties, appearance design (designability) is also demanded.

As a method of decoration, there is an in-mold decoration processing method in which a decorative film is inserted into a mold, and a molten resin is injected and integrated to decorate the surface of a plastic molded product; a method of in-mold simultaneous decoration molding in which the surface of a plastic molding is decorated at the same time as injection molding; and a vacuum pressure bonding method in which a decorative film is laminated on a molded article such as plastic, metal, or glass, or a pattern or a hard coat layer to be laminated is transferred to the decorative film. Since the decorative object and shape adaptability are wide, a hard coat agent composition for decoration is required to have a high elongation rate that can follow a complicated shape of a decorative film or a deep drawing process (deep り), and specifically, to have a performance that does not cause cracks or the like even when the decorative film is stretched by 100% or more.

As a technique for achieving these properties at the same time, for example, a photocurable resin composition for molded sheets is known in which a reactive diluent monomer and a photopolymerization initiator are blended with a bifunctional urethane (meth) acrylate obtained by reacting a (poly) alkylene glycol with an aliphatic cyclic diisocyanate and a hydroxy (meth) acrylate (patent document 1), but when cured, the crosslinking density of the hard coat layer increases, and the entire hard coat layer becomes too hard to achieve a high elongation and also has poor chemical resistance.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2019-006897

Disclosure of Invention

Technical problem to be solved by the invention

The purpose of the present invention is to provide a urethane (meth) acrylate that provides a cured product having excellent chemical resistance and high elongation, and an active energy ray-curable resin composition containing the same.

Means for solving the problems

The present inventors have focused on the composition and physical properties of urethane (meth) acrylates and have intensively studied to find that the above-mentioned problems can be solved, and have completed the present invention. That is, the present invention relates to the following urethane (meth) acrylate, active energy ray-curable resin composition, cured product, laminate, and molded product.

1. A urethane (meth) acrylate containing a diol (a1) having an alicyclic structure, a diisocyanate (a2) having a cyclic structure, and a (meth) acrylate (a3) having a hydroxyl group as reaction components,

the urethane (meth) acrylate has a weight-average molecular weight of 6,000 to 25,000 and a (meth) acryloyl group concentration of 0.2X 10^-3～2.0×10^-3eq/g。

2. The urethane (meth) acrylate according to the preceding item 1, wherein the (a1) component comprises tricyclodecanedimethanol and/or 1, 1-cyclohexanedimethanol.

3. The urethane (meth) acrylate according to item 1 or 2, wherein the component (a2) is a diisocyanate having an alicyclic structure.

4. The urethane (meth) acrylate according to any one of the preceding items 1 to 3, wherein the (a3) component comprises hydroxyalkyl (meth) acrylate and/or pentaerythritol (meth) acrylate.

5. The urethane (meth) acrylate according to any one of the preceding items 1 to 4, wherein the urethane bond concentration is 2.0X 10^-3～6.5×10^-3eq/g。

6. An active energy ray-curable resin composition containing the urethane (meth) acrylate according to any one of the preceding items 1 to 5.

7. The active energy ray-curable resin composition according to the preceding item 6, further comprising an active energy ray-polymerizable monomer (B) and/or a metal oxide (C).

8. The cured product of the active energy ray-curable resin composition according to the aforementioned item 6 or 7.

9. A laminate comprising a layer of the cured product according to the aforementioned item 8.

10. A molded article having a surface coated with the cured product according to aforementioned item 8.

Advantageous effects

The urethane (meth) acrylate according to the present invention is characterized in that a cured product of an active energy ray-curable resin composition containing the urethane (meth) acrylate has high elongation while showing excellent chemical resistance, and thus is easy to process and mold.

Detailed Description

The present invention will be described in detail below. In addition, unless otherwise specified, a cured product of the active energy ray-curable resin composition is referred to as a "cured product".

The urethane (meth) acrylate (a) (hereinafter referred to as component (a)) of the present invention contains a diol (a1) (hereinafter referred to as component (a 1)) having an alicyclic structure, a diisocyanate (a2) (hereinafter referred to as component (a 2)) having a cyclic structure, and a (meth) acrylate (a3) (hereinafter referred to as component (a 3)) having a hydroxyl group as reaction components. Since the component (a) has an alicyclic structure derived from the component (a1), the cured product thereof has excellent chemical resistance and also has high elongation.

(a1) The component (A) is a diol having one or more alicyclic structures. Examples of the component (a1) include monocyclic diols such as 1, 2-cyclopentanediol, 1, 3-cyclopentanediol, 1-cyclohexanedimethanol, 1, 2-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol, 1, 4-cyclohexanediol, 1, 2-cyclooctanediol, and 1, 5-cyclooctanediol; bicyclic diols such as 5-norbornene-2, 2-dimethanol, 5-norbornene-2, 3-dimethanol, norbornane-2, 5-dimethanol and 2, 6-decahydronaphthalene dimethanol; tricyclodiols such as 1, 3-adamantanediol, 1, 4-adamantanediol, 2, 4-adamantanediol and tricyclodecanedimethanol; hydrogenated bisphenols, and the like. These may be used alone or in combination of two or more. Among them, from the viewpoint that the cured product shows excellent chemical resistance, one or more selected from the group consisting of tricyclodecanedimethanol, 1-cyclohexanedimethanol and 1, 4-cyclohexanedimethanol are preferable, and tricyclodecanedimethanol and 1, 1-cyclohexanedimethanol are more preferable.

Further, as the reaction component of the component (a), a polyol (a1') (hereinafter, also referred to as a component (a1') other than the component (a 1)) may be used in combination. Examples of the component (a1') include alkane diols such as ethylene glycol (ethylene glycol), 1, 2-propanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 2-pentanediol, 1, 3-pentanediol, 1, 4-pentanediol and 1, 5-pentanediol; polyalkylene glycols such as diethylene glycol, dipropylene glycol, and tripropylene glycol; polyether polyols, polyester polyols, and the like. The amount of the component (a1') used is 4mol or less based on 1mol of the component (a 1).

(a2) The component (A) is a compound having a cyclic structure and two isocyanate groups. Examples of the component (a2) include:

diisocyanates having an aromatic ring such as tolylene diisocyanate (tolylene 2, 4-diisocyanate, tolylene 2, 6-diisocyanate or a mixture thereof), 2' -diphenylmethane diisocyanate, 2, 4-diphenylmethane diisocyanate, 4' -diphenylmethane diisocyanate, 3-dimethyldiphenylmethane diisocyanate, diphenyl ether 4,4' -diisocyanate, o-xylylene diisocyanate (o- キシリレンジイソシアネート), m-xylylene diisocyanate, p-xylylene diisocyanate, tetramethylxylylene diisocyanate, 1, 5-naphthalene diisocyanate;

and diisocyanates having an alicyclic structure such as hydrogenated products of the aforementioned diisocyanates having an aromatic ring, norbornene methane diisocyanate, 1, 4-cyclohexane diisocyanate, cyclohexane-1, 4-diylbis (methylene) diisocyanate, and isophorone diisocyanate.

Further, isocyanurate forms, adduct forms (アダクト forms), biuret forms, and dimers and trimers of these substances may be used. These may be used alone or in combination of two or more.

Among them, from the viewpoint of excellent chemical resistance of the cured product, a diisocyanate having an alicyclic structure is preferable, and one or more selected from the group consisting of: hydrogenated products of m-xylylene diisocyanate, hydrogenated products of 2,2 '-diphenylmethane diisocyanate, hydrogenated products of 2, 4-diphenylmethane diisocyanate, hydrogenated products of 4,4' -diphenylmethane diisocyanate, norbornene methane diisocyanate and isophorone diisocyanate.

The amount of the component (a2) used is preferably 0.7 to 1.2mol based on 1mol of the component (a 1). Within this range, the cured product can have high hardness and improved elongation. From the same viewpoint, the amount of the above-mentioned compound is preferably 0.9 to 1.0 mol.

(a3) Component (a) is a component incorporated at the end of an isocyanate group of a urethane prepolymer which is a reactant of component (a1) and component (a2), and contributes to excellent chemical resistance of a cured product. The component (a3) is not particularly limited, and examples thereof include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and 6-hydroxyhexyl (meth) acrylate; dihydroxyalkyl (meth) acrylates such as 2, 3-dihydroxypropyl (meth) acrylate, 3, 4-dihydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, and 1, 4-dihydroxyheptyl (meth) acrylate; cycloalkyl mono (meth) acrylates such as 1, 4-cyclohexanedimethanol mono (meth) acrylate and adamantyl mono (meth) acrylate; mono (meth) acrylates having a hydroxyl group and an ether bond such as 2-hydroxy-3-phenoxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, and polypropylene glycol mono (meth) acrylate; erythritol (meth) acrylates such as erythritol di (meth) acrylate and erythritol tri (meth) acrylate; pentaerythritol (meth) acrylates such as pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate, and pentaerythritol tri (meth) acrylate; dipentaerythritol (meth) acrylates such as dipentaerythritol mono (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth) acrylate; and tripentaerythritol (meth) acrylates such as tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, and tripentaerythritol hepta (meth) acrylate. These may be used alone or in combination of two or more. Among them, hydroxyalkyl (meth) acrylates and pentaerythritol (meth) acrylates are preferable from the viewpoint that the cured product has excellent chemical resistance and high elongation.

Further, a mixture containing a poly (meth) acrylate ester having no hydroxyl group may be used as the component (a 3). The poly (meth) acrylate containing no hydroxyl group is not particularly limited, and examples thereof include erythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, and the like. The content of the poly (meth) acrylate containing no hydroxyl group is 60% by weight or less based on 100% by weight of the component (a 3).

Examples of commercially available products of component (a3) include "アロニックス M305", "アロニックス M306", "アロニックス M400", "アロニックス M402", "アロニックス M403", "アロニックス M404", "アロニックス M405", "アロニックス M406", "アロニックス M933" (manufactured by Toyo Synthesis Co.), "KAYARAD DPHA" (manufactured by Nippon Chemicals), "A-9550", "A-DPH" (manufactured by Ningzhou Chemical industry), "ビスコート # 300", "ビスコート # 802" (manufactured by Osaka organic Chemical industry), "Miramer M500" (manufactured by MIWON Specialty Chemical Co., Ltd.).

The amount of the component (a3) used is not particularly limited, but is preferably 1 to 1.1mol, more preferably 1 to 1.02mol, based on 1mol of isocyanate groups in a urethane prepolymer obtained by reacting the component (a1) with the component (a2) from the viewpoint that a cured product has excellent chemical resistance and a high elongation is maintained.

The method for producing the component (a) is not particularly limited, and for example, the component (a1) and the component (a2) are reacted with each other to produce a urethane prepolymer (hereinafter referred to as the component (a ')), and then the component (a') and the component (a3) are reacted with each other. The reaction conditions are not particularly limited, but the reaction is usually carried out at a normal temperature of about 50 to 85 ℃ (preferably about 60 to 80 ℃) for about 1 to 24 hours (preferably about 5 to 10 hours).

In addition, in the production of the component (a), an organic solvent is preferably used. Examples of the organic solvent include aromatic hydrocarbons such as benzene, toluene, ethylbenzene, n-propylbenzene, t-butylbenzene, o-xylene, m-xylene, p-xylene, tetralin, decalin, and aromatic naphtha; aliphatic hydrocarbons such as n-hexane, n-heptane, n-octane, isooctane, and n-decane; alicyclic hydrocarbons such as cyclohexane; alcohols such as isopropyl alcohol, isobutyl alcohol, sec-butyl alcohol and tert-butyl alcohol; esters such as ethyl acetate, n-butyl acetate, n-pentyl acetate, 2-hydroxyethyl acetate, 2-butoxyethyl acetate, 3-methoxybutyl acetate, and methyl benzoate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone, and methyl cyclohexanone. The amount of the organic solvent used is preferably about 40 to 80% by weight based on the reaction concentration.

The weight average molecular weight of the component (A) is 6,000-25,000. When the weight average molecular weight is less than 6,000, the elongation of the cured product tends to decrease. In addition, when the weight average molecular weight is more than 25,000, the chemical resistance of the cured product tends to be lowered. For the same reason, the weight average molecular weight is preferably 9,000 to 20,000, more preferably 10,000 to 15,000. The "weight average molecular weight" herein means a value measured by a Gel Permeation Chromatography (GPC) method (in terms of polystyrene).

The concentration of (meth) acryloyl group in component (A) was 0.2X 10^-3～2.0×10^-3eq/g. The concentration is less than 0.2 × 10^-3eq/g, the chemical resistance of the cured product tends to decrease; greater than 2.0X 10^-3eq/g, the elongation of the cured product tends to decrease. From the same viewpoint, the concentration of (meth) acryloyl group in the component (A) is preferably 1.0X 10^-3～1.8×10^-3eq/g, more preferably 1.2X 10^-3～1.6×10^-3eq/g。

The (meth) acryloyl group concentration is a value obtained by dividing the (meth) acryloyl group equivalent weight by the total solid content weight of components (a1) to (a 3). For example, when 2mol of tricyclodecanedimethanol (molecular weight: 196.3) was used as the component (a1), 2mol of isophorone diisocyanate (molecular weight: 222.3) was used as the component (a2), and 1mol of hydroxyethyl acrylate (molecular weight: 116.1) was used as the component (a3), the concentration of (meth) acryloyl group was as follows.

In addition, the number of moles of the (meth) acryloyl equivalent (eq) { (a3) } component } × { (a3) component } × 1 { (meth) acryloyl equivalent (eq) } component is 1 × 1 { (meth) acryloyl equivalent

In addition, the total solid content weight (g) of the [ (a1) component to (a3) component ]

(ii) the number of moles of component (a1) } { (a1) the molecular weight of component } + { (a2) the number of moles of component } × { (a2) the molecular weight of component } + { (a3) the number of moles of component } × { (a3) the molecular weight of component }

＝2×196.3+2×222.3+1×116.1＝953.3

In addition, [ (eq/g) concentration of acryloyl group ]

(ii) total solid content weight (g) of [ (meth) acryloyl equivalent (eq) ]/[ (a1) component to (a3) component ]

＝1/953.3≒1.05×10^-3

As other physical properties of the component (A), the urethane bond concentration is preferably 2.0X 10^-3～6.5×10^- ³eq/g, more preferably 3.0X 10^-3～5.5×10^-3eq/g, more preferably 3.5X 10^-3～5.0×10^-3eq/g. When the urethane bond concentration is within this range, the cured product hasThe chemical resistance tends to be excellent.

The urethane bond concentration is a value obtained by dividing the number of moles of urethane bonds by the total solid content weight of the components (a1) to (a 3). The number of moles of urethane bonds means a smaller value of the number of isocyanate groups of the component (a2) or the total number of hydroxyl groups of the components (a1) and (a 3). For example, when 2mol of tricyclodecanedimethanol (molecular weight: 196.3) was used as the component (a1), 2mol of isophorone diisocyanate (molecular weight: 222.3) was used as the component (a2), and 1mol of hydroxyethyl acrylate (molecular weight: 116.1) was used as the component (a3), the urethane bond concentrations were as follows.

In the case of the component (a2), the number of isocyanate groups (eq) { (a2) moles } × { (a2) of isocyanate groups (2 × 2 ═ 4) }

In the meantime, the number (eq) of hydroxyl groups in the component (a1) { (a1) } mol number of hydroxyl groups in the component (a1) } 2 × 2 ═ 4

In the component (a3), the number of hydroxyl groups (eq) { (a3) in the component (a) is equal to the number of moles } × { (a3) in the component (1 × 1 ═ 1)

The total number (eq) of hydroxyl groups of the respective components (a1) and (a3)

(ii) the number of hydroxyl groups in component (a1) } + { (a3) the number of hydroxyl groups in component (4 + 1) 5 { (a1) }

In addition, [ concentration of urethane bond (eq/g) ]

(eq) }/[ (a1) total solid content weight (g) of components (a3) to (a3) ], which is the smaller of the number of isocyanate groups in component (a2) or the total number of hydroxyl groups in components (a1) and (a3)

＝4/953.3≒4.2×10^-3

The active energy ray-curable resin composition of the present invention contains the component (A).

The active energy ray-curable resin composition of the present invention may further contain an active energy ray-polymerizable monomer (B) (hereinafter referred to as component (B)) and/or a metal oxide (C) (hereinafter referred to as component (C)).

(B) The component (a) is not particularly limited as long as it is a polymerizable monomer other than the component (a), and examples thereof include:

methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, (meth) acrylates having an alkyl group such as 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, tri-n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tetradecyl (meth) acrylate, n-hexadecyl (meth) acrylate, n-octadecyl (meth) acrylate, and isostearyl (meth) acrylate;

(meth) acrylates having an alicyclic structure such as cyclohexyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, and tricyclodecane dimethylol di (meth) acrylate;

(meth) acrylates having an aromatic ring such as phenyl (meth) acrylate, benzyl (meth) acrylate, 2-phenylethyl (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate;

(meth) acrylates having an alkoxyalkyl group such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, 2-methoxyethoxyethyl (meth) acrylate, and 2-ethoxyethoxyethyl (meth) acrylate;

monoalkylene glycol (meth) acrylates such as ethylene glycol di (meth) acrylate and propylene glycol di (meth) acrylate;

polyalkylene glycol (meth) acrylates such as diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, and tripropylene glycol di (meth) acrylate;

alkoxy polyalkylene glycol (meth) acrylates such as methoxy diethylene glycol (meth) acrylate, ethoxy diethylene glycol (meth) acrylate, and methoxy dipropylene glycol (meth) acrylate;

(meth) acrylamides such as (meth) acrylamide, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, and (meth) acryloylmorpholine;

epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate;

dialkylaminoalkyl (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate and N, N-diethylaminoethyl (meth) acrylate;

pentaerythritol (meth) acrylates such as pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, or mixtures thereof;

dipentaerythritol (meth) acrylates such as dipentaerythritol mono (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, or mixtures thereof;

tripentaerythritol (meth) acrylates such as tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, or mixtures thereof;

alkylene oxide-modified bisphenol A di (meth) acrylate, alkylene oxide-modified trimethylolpropane tri (meth) acrylate, alkylene oxide-modified ditrimethylolpropane tetra (meth) acrylate, alkylene oxide-modified glycerin tri (meth) acrylate, alkylene oxide-modified polyglycerin (meth) acrylate, alkylene oxide-modified pentaerythritol di (meth) acrylate, alkylene oxide-modified pentaerythritol tri (meth) acrylate, alkylene oxide-modified pentaerythritol tetra (meth) acrylate, alkylene oxide-modified pentaerythritol tri (meth) acrylate selected from a mixture of two or more of pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate, alkylene oxide-modified dipentaerythritol poly (meth) acrylate (herein, "poly" means any of two types, three types, four types, five types, and six types, and may mean a mixture of two or more of them), alkylene oxide-modified (meth) acrylates such as alkylene oxide-modified 2-ethylhexyl (meth) acrylate, alkylene oxide-modified polyethylene glycol (meth) acrylate, and alkylene oxide-modified polypropylene glycol (meth) acrylate (examples of alkylene oxides include methane oxide, ethylene oxide, propylene oxide, and butylene oxide);

polyhydric alcohol (meth) acrylates such as trimethylolpropane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, and 1, 6-hexanediol di (meth) acrylate;

polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate other than the component (A), and the like.

These (B) components may be used alone or in combination of two or more.

When the component (B) is used as a component of the active energy ray-curable resin composition, the content thereof is usually 50% by weight or less, preferably 30% by weight or less, in terms of the weight ratio of the solid components, based on 100% by weight of the total of the components (a) and (B), from the viewpoint of showing excellent chemical resistance and high elongation of the cured product.

(C) The component (c) is not particularly limited, and examples thereof include silica, alumina, zirconia, titania, antimony oxide, tin oxide, indium oxide, zinc oxide, and the like. As the component (C), a component doped with aluminum, phosphorus, fluorine or the like can be used. These may be used alone or in combination of two or more.

Further, commercially available products include "TOL-ST", "MEK-ST-40", "MEK-ST-L", "MEK-ST-ZL", "MEK-ST-UP", "MIBK-ST", "CHO-ST-M", "EAC-ST", "PMA-ST" (manufactured by Nissan Kagaku Co., Ltd.).

In addition, as the component (C), a metal oxide having an organic functional group on the surface thereof may be used. The "organic functional group" refers to a group having at least carbon atoms, and examples thereof include a methacryloyl group, an acryloyl group, a vinyl group, an epoxy group, an isocyanate group, a urethane group, and an organosiloxane group. These may be used alone or in combination of two or more.

Examples of commercially available products of metal oxides having organic functional groups on the surface thereof include "ME K-EC-2130Y", "MEK-AC 2140Z", "MEK-AC-4130Y", "PGM-AC 2140Y", "PGM-AC 3140Y", "PGM-AC 4130Y", "MIBK-SD-L" (manufactured by Nissan chemical Co., Ltd.), "NANOBYK-3603", "NANOBYK-3650", "NANOB YK-3652" (manufactured by ビックケミー & ジャパン), "ALMIBK 30 WT% -H06", "ALMIBK 30 WT% -M114", "ALMIBK 30 WT% -M115", "SIRMIBK 15 ET% -H24", "SIRMIBK 15 ET% -H83" (manufactured by CIK ナノテック), and "EL ECOM-V # 8802", "ELECOM-V # 8803", "ELECOM-V # 4" (manufactured by daily volatilization catalyst).

The average primary particle diameter of the component (C) is not particularly limited, but is preferably about 4 to 200nm, more preferably about 7 to 50nm, from the viewpoint of transparency of the cured product. The method for measuring the average primary particle size is not particularly limited, and examples thereof include a light scattering method.

When the component (C) is used as a component of the active energy ray-curable resin composition, the content thereof is usually 30% by weight or less, preferably 20% by weight or less, in terms of the weight ratio of the solid components, based on 100% by weight of the total of the components (a) and (C) in the present invention, from the viewpoint that the cured product exhibits excellent elongation and abrasion resistance.

The active energy ray-curable resin composition of the present invention may further contain an organic solvent.

The organic solvent is not particularly limited, and examples thereof include aromatic hydrocarbons such as benzene, toluene, ethylbenzene, n-propylbenzene, t-butylbenzene, o-xylene, m-xylene, p-xylene, tetralin, decalin, and aromatic naphtha; aliphatic hydrocarbons such as n-hexane, n-heptane, n-octane, isooctane, and n-decane; alicyclic hydrocarbons such as cyclohexane; esters such as ethyl acetate, propyl acetate, n-butyl acetate, sec-butyl acetate, tert-butyl acetate, n-pentyl acetate, 2-hydroxyethyl acetate, 2-methoxyethyl acetate, 2-butoxyethyl acetate, 3-methoxybutyl acetate, 1-methoxypropyl acetate, and methyl benzoate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone, and methyl cyclohexanone; carbonates such as dimethyl carbonate, diethyl carbonate, and ethylene carbonate; acyclic ethers such as diisopropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and diethylene glycol dimethyl ether; cyclic ethers such as tetrahydrofuran, 1, 3-dioxolane, and 1, 4-dioxane; monohydroxy ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether; and alcohols such as methanol, ethanol, n-propanol, 2-propanol, n-butanol, isobutanol, sec-butanol, and tert-butanol. When an organic solvent is used as a component of the active energy ray-curable resin composition, the content thereof is preferably 0.5 to 80% by weight.

The active energy ray-curable resin composition of the present invention may further contain a photopolymerization initiator. The photopolymerization initiator may be added at the time of preparing the active energy ray-curable resin composition, or may be added immediately before coating on the substrate film.

The photopolymerization initiator is not particularly limited, and examples thereof include photopolymerization initiators such as benzoin compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene (チタノセン) compounds, thioxanthone compounds, and oxime ester compounds, and photosensitizers such as amines and quinones; more specifically, 2-dimethoxy-1, 2-diphenylethane-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl]2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- [4- [4- (2-hydroxy-2-methylpropionyl) benzyl]Phenyl radical]-2-methylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2- (dimethylamino) -2- [ (4-methylphenyl) methyl]-1- [4- (4-morpholinyl) phenyl]-1-butanone, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide, bis (. eta.⁵-2, 4-cyclopentadien-1-yl) -bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 1, 2-octanedione 1- [4- (phenylthio) -2- (o-benzoyloxime)]Ethanone 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-1- (o-acetyloxime), and the like. These may be used alone or in combination of two or more. The content of the photopolymerization initiator is preferably 0.5 to 20 parts by weight, more preferably 2 to 10 parts by weight, based on 100 parts by weight of the total of the component (A), the component (B) and the component (C) in the present invention.

The active energy ray-curable resin composition of the present invention may further contain additives such as a surface conditioner, a surfactant, an ultraviolet absorber, an antioxidant, a light stabilizer, a silane coupling agent, a defoaming agent, a wetting agent, a rust preventive, a leveling agent, and the like.

The active energy ray-curable resin composition of the present invention can be obtained by mixing the component (a), the component (B), and the component (C), a photopolymerization initiator, an organic solvent (if necessary), and the above-mentioned additives. The mixing manner and the mixing order are not particularly limited.

The cured product of the present invention is obtained by curing the active energy ray-curable resin composition.

The cured product of the present invention is not particularly limited, and can be obtained by, for example, applying the active energy ray-curable resin composition to a substrate film and irradiating the substrate film with an active energy ray.

The substrate is not particularly limited, and examples thereof include polyethylene terephthalate (PET), cycloolefin polymer (COP), polypropylene, polybutene, polybutadiene, polymethylpentene, polyolefin, polyvinyl chloride, vinyl chloride copolymer, polyethylene naphthalate, polybutylene terephthalate, polymethyl acrylate, polyurethane, ethylene vinyl acetate, ionomer resin, plastic films such AS ethylene- (meth) acrylic acid copolymers, ethylene- (meth) acrylate copolymers, acrylonitrile-styrene copolymers (AS resins), acrylonitrile-butadiene-styrene copolymers (ABS resins), epoxy resins, melamine resins, triacetyl cellulose resins, norbornene resins, fluorine resins, polystyrene, polyesters, polycarbonates, polyamides, and polyimides; metal, wood, paper, glass, slate, and the like. Further, a light release material and a heavy release material may be used as the base material, and an untreated material and a plasma-treated material may be used.

In addition, the substrate may be subjected to a peeling treatment in order to easily peel the cured product from the layer. The peeling treatment is not particularly necessary when peeling is easy, but in order to make peeling easier, a melamine resin, a silicone (シリコーン) resin, a fluororesin, a cellulose derivative, a urea resin, a polyolefin resin, or a paraffin resin may be laminated as a release layer. These resin films may be used alone, or two or more kinds may be combined.

The coating method is not particularly limited, and examples thereof include an applicator (アプリケーター), a bar coater, a roll coater, a blade coater, a gravure coater, a spray coater, a comma coater (コンマコーター), a lip coater (リップコーター), gravure printing, and screen printing. The amount of the active energy ray-curable resin composition to be applied is not particularly limited, and the coating is usually performed so that the film thickness after curing is about 1 to 10 μm.

The active energy ray is not particularly limited, and examples thereof include light rays such as ultraviolet rays, infrared rays, and visible light, electron beams, X-rays, α -rays, β -rays, γ -rays, and neutron rays. In the present invention, light is preferable, and ultraviolet rays are more preferable.

The light source of ultraviolet rays is not particularly limited, and examples thereof include xenon lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, carbon arc lamps, metal halide lamps, chemical lamps, electrodeless lamps, and LED lamps. The intensity of ultraviolet irradiation is not particularly limited, and is usually 100 to 1000mJ/cm²Left and right. After the irradiation with ultraviolet rays, heating may be performed as necessary for complete curing.

The laminate of the present invention has a layer of the cured product. The substrate and curing method used are the same as described above.

The molded article of the present invention is a product having a surface coated with the cured product, and is a product obtained by coating the surface of the molded article with the cured product by a processing method such as in-mold decoration or vacuum pressurization. Among these processing methods, there are a lamination method in which a cured product is attached to the surface of a molded product of each base material, and a transfer method in which only a cured product, other pattern ink layer, and a functional layer laminated on a plastic film are transferred to the surface of a molded product.

In the lamination method, as the structure of the decorative film, there are usually provided a layer of the cured product of the present invention, an anchor layer, a pattern ink layer, an easy-adhesion layer, a base material film, a functional layer, and an adhesion layer in this order; or a layer of the cured product of the present invention, an easy-adhesion layer, a base film, an easy-adhesion layer, a pattern ink layer, a functional layer, an adhesive layer, and the like in this order, may be laminated on the surface of the molded product via the adhesive layer.

In the above transfer method, usually, a release layer is laminated on a plastic film as necessary, and a layer of the cured product of the present invention, an anchor layer, a pattern ink layer, a functional layer, and an adhesive layer are laminated thereon in this order (transfer layer), and after the surface of the molded product is adhered via the adhesive layer, the plastic film or the release layer is peeled from the layer of the cured product, and only the transfer layer can be laminated on the surface of the molded product or coated thereon.

Examples

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Meanwhile, in each example, parts and% are all on a weight basis unless otherwise specified.

< weight average molecular weight >

The weight average molecular weight of the urethane (meth) acrylate was measured by gel permeation chromatography (GPC method) under the following conditions.

Molecular weight measuring machine (product name: "HLC-8220", manufactured by imperial ceramics ソー strain)

Column (product name: "TSKgel SuperHZ 2000", "TSKgel SuperHZM-M", manufactured by Chinese imperial ceramics ソー (strain))

Developing solvent: tetrahydrofuran (THF)

Flow rate: 0.35ml/min

Sample concentration: 0.5g/L

Standard substance: polystyrene (Standard polystyrene kit, manufactured by PStQuickA, B, C, imperial ソー strain)

Example 1

In a three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 24.4 parts (5mol) of tricyclodecanedimethanol (hereinafter referred to as "TCD"), 24.2 parts (5mol) of hydrogenated xylylene diisocyanate (H-XDI), 40.0 parts of methyl ethyl ketone and 0.01 part of tin octylate were charged. After stirring at 60 ℃ for 2 hours, 11.3 parts (1mol) of V #300 (trade name: ビスコート # 300; a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate, hydroxyl value: 122.2mgKOH/g, manufactured by Osaka organic chemical industries, Ltd.) (hereinafter referred to as PETA), 0.15 part of tin octylate, 0.03 part of hydroquinone monomethyl ether were added to the resultant reaction mixture, and the reaction was carried out until the residual isocyanate group became 0.1% or less to obtain a solution of urethane (meth) acrylate (A-1) having a solid content concentration of 60%. The physical properties of the component (A-1) are shown in Table 1 (the same applies hereinafter).

Example 2-example 8, comparative example 1-comparative example 6

According to the compositions shown in Table 1, synthesis was carried out in the same manner as in example 1 to obtain solutions of urethane (meth) acrylate (A-2) to urethane (meth) acrylate (A-8) and urethane (meth) acrylate (D-1) to urethane (meth) acrylate (D-6) each having a solid content of 60%.

[ Table 1]

The abbreviations in table 1 represent the following compounds.

< dihydric alcohol >

TCD: dicyclodecane dimethanol

1, 1-CHDM: 1, 1-cyclohexanedimethanol

1, 4-BD: 1, 4-butanediol

< diisocyanate >

H-XDI: hydrides of meta-xylylene diisocyanate

IPDI: isophorone diisocyanate

H-MDI: hydrides of 4,4' -diphenylmethane diisocyanate

HDI: hexamethylene diisocyanate

< hydroxyl group-containing (meth) acrylate >

PETA-1: trade name: "ビスコート # 300", a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate, hydroxyl number: 122.2mgKOH/g, manufactured by Osaka organic chemical industry Ltd

PETA-2: trade name: "アロニックス M-933", a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate, hydroxyl number: 280.0mgKOH/g, manufactured by Toyo Seiya Kabushiki Kaisha

PETA-3: trade name: "アロニックス M-306", a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate, hydroxyl number: 160.0mgKOH/g, manufactured by Toyo Product

HEA: 2-hydroxyethyl acrylate

Evaluation examples 1 to 8, comparative evaluation examples 1 to 6

100 parts of each urethane (meth) acrylate solution (60 parts by weight of solid content), 3.2 parts of 1-hydroxycyclohexyl phenyl ketone (photopolymerization initiator, trade name: "Omnirad 184", manufactured by IGM Resins B.V.), 0.2 part of silicone surface conditioner (additive, trade name: "BYK-378", manufactured by BYK) and 108 parts of methyl ethyl ketone were mixed and dissolved to prepare active energy ray curable resin compositions, respectively.

< preparation of test film >

The respective activation energies were applied by a bar coaterThe radiation curable resin composition was applied to the surface of a commercially available polyethylene terephthalate film (trade name: "コスモシャイン A4100", manufactured by Toyobo Co., Ltd.) so that the thickness of the cured product layer became 5 μm, and the cured product was dried at 60 ℃ for 2 minutes. Thereafter, ultraviolet rays were irradiated with a 400W high-pressure mercury lamp (1 lamp) so that the cumulative light amount reached 300mJ/cm²A test film was prepared.

< chemical resistance >

Test films were cut to 6cm by 6 cm. Sunscreen cream (trade name: "Neutrogena", manufactured by helioplex corporation) was applied in a circle having a radius of 3cm, and then placed in a dryer at a temperature of 55 ℃ for 4 hours. Cooling to room temperature, and washing the sunscreen cream with detergent and water. The surface of the test film was visually observed after wiping off water, and evaluated according to the following criteria. The results are shown in Table 2 (the same applies hereinafter).

(evaluation criteria)

Very good: no lines or blushing of the surface

O: some lines are seen on a part of the surface

X: most of the surface is whitened

< elongation >

Test pieces were prepared by cutting the test film into pieces having a width of 1.5cm and a length of 13 cm. The test piece was set in a tensile testing machine (apparatus name: "RTM-500", manufactured by オリエンテック Co.) with an inter-jig distance of 5cm, left at a temperature of 140 ℃ for 1 minute, and then stretched at a stretching speed of 5 cm/minute. The length of the test piece when the layer of the cured product was cracked was read, and the elongation was determined with 5cm as 100%. The elongation of 180% or more is preferable.

[ Table 2]

Evaluation examples 9 to 16, comparative evaluation example 7, and comparative evaluation example 8

151.6 parts of the urethane (meth) acrylate solution of example 1 to example 8 and comparative examples 1 and 2 (solid content: 85 parts), 10.7 parts of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (trade name: "NK エステル A-9550W", manufactured by Nizhongcun chemical industry Co., Ltd.), 17.8 parts of aluminum oxide having a methacryloyl group (trade name: "ALMIBK 30 WT% -H06", manufactured by CIK ナノテック (manufactured by Co., Ltd., average primary particle diameter: 15nm, solid content concentration: 30%) (solid content: 5 parts by weight), 5.4 parts of 1-hydroxycyclohexyl phenyl ketone (photopolymerization initiator, trade name: "Omnirad 184", manufactured by IGM Resins B.V.), and 0.2 part of a silicone-based surface modifier (additive, trade name: "BYK-378", BYK corporation) and 95.8 parts of methyl ethyl ketone were stirred until dissolved to prepare an active energy ray-curable resin composition, respectively.

Evaluation examples 17 to 19

The respective active energy ray-curable resin compositions were obtained by the method described in the preceding paragraph except that the compositions shown in Table 3 were changed.

Using the active energy ray-curable resin composition obtained above, a test film was produced in the same manner as described above, and chemical resistance and elongation were evaluated. The results are shown in Table 3.

[ Table 3]

The symbols shown in table 3 represent the following compounds.

A-1 to A-8, D-1, D-2: see table 1.

B-1: a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, trade name: "NK エステル A-9550W", manufactured by Newzhongcun chemical industry Co., Ltd

B-2: urethane acrylate (a reaction product of dipentaerythritol pentaacrylate and hexamethylene diisocyanate), trade name "DPHA-40H", manufactured by Nippon Kabushiki Kaisha

C-1: alumina having methacryloyl group: trade name "ALMIBK 30 WT% -H06", manufactured by CIK ナノテック (strain), average primary particle diameter: 15nm, solid content concentration: 30 percent.

Claims

1. A urethane (meth)acrylate containing a diol (a1) having an alicyclic structure, a diisocyanate (a2) having a cyclic structure, and a Hydroxy (meth)acrylate (a3) as a reaction component,

The urethane (meth)acrylate has a weight average molecular weight of 6,000 to 25,000, and a (meth)acryloyl group concentration of 0.2×10 ^-3 to 2.0×10 ^-3 eq/g.

2 . The urethane (meth)acrylate according to claim 1 , wherein the component (a1) contains tricyclodecanedimethanol and/or 1,1-cyclohexanedimethanol. 3 .

The urethane (meth)acrylate of Claim 1 or 2 whose (a2) component is a diisocyanate which has an alicyclic structure.

4. The urethane (meth)acrylate according to any one of claims 1 to 3, wherein the component (a3) contains hydroxyalkyl (meth)acrylate and/or pentaerythritol (methyl) Acrylate.

5 . The urethane (meth)acrylate according to claim 1 , wherein the urethane bond concentration is 2.0×10 ⁻³ to 6.5×10 ⁻³ eq/g. 6 .

6. An active energy ray-curable resin composition containing the urethane (meth)acrylate according to any one of claims 1 to 5.

7. The active energy ray-curable resin composition according to claim 6, wherein the active energy ray-curable resin composition further contains an active energy ray polymerizable monomer (B) and/or a metal oxide (C ).

8. The cured product of the active energy ray-curable resin composition according to claim 6 or 7.

9 . A layered body having layers of the cured product according to claim 8 .

10. A molded product whose surface is covered with the cured product according to claim 8.