TW202222879A - Urethane (meth)acrylate, active energy ray-curable resin composition, cured product, laminate, and molded product capable of providing a cured product with excellent chemical resistance and high elongation - Google Patents

Abstract

The present invention provides a urethane (meth)acrylate and an active energy ray-curable resin composition containing the urethane (meth)acrylate, and the urethane (meth)acrylate provides a cured product with excellent chemical resistance and high elongation. The urethane (meth)acrylate of the present invention is used as a reactive component containing a diol (a1) having an alicyclic structure, a diisocyanate (a2) having a cyclic structure, and a (meth)acrylate (a3) having a hydroxyl group, in which the weight average molecular weight is 6,000 to 25,000, and the (meth)acryloyl group concentration is 0.2 * 10 <SP>-3</SP> to 2.0 * 10 <SP>-3</SP> eq/g.

Description

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

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.

Active energy ray-curable resin compositions cured by ultraviolet rays, electron beams, or the like are widely used for various electrical appliances, daily necessities, and other articles because they impart scratch resistance and chemical resistance. Among them, decoration technology is applied to terminals of mobile phones and smart phones, casings of personal computers, and interior and exterior parts of automobiles. In addition to the above-mentioned performance, design properties (designability) are also pursued.

The method of decoration includes: inserting the decorative film into the mold, injecting molten resin and integrating it to decorate the surface of the plastic molded object; the in-mold decoration method of decorating the surface of the plastic molded object at the same time of injection molding; Molding method; lamination of decorative film on plastic, metal or glass molded products, or vacuum lamination method to transfer laminated pattern or hard coating on decorative film, etc. Due to the wide adaptability of decorative objects and shapes, high elongation ratios that can follow complex shapes or deep drawing processes (deep drawing) for decorative films are being sought for hard coating compositions for decorative films. Specifically, In other words, even if the decorative film is stretched to 100% or more, the performance such as cracks will not occur.

As a technique for making these properties simultaneously established, for example, although a difunctional urethane (methyl) obtained by reacting a (poly)alkylene glycol and an aliphatic cyclic diisocyanate with a hydroxy (meth)acrylate is used A photocurable resin composition for forming sheets in which a reactive diluting monomer and a photopolymerization initiator are blended with acrylic acid ester is known (Patent Document 1). The increased density makes the bulk too stiff, high elongation is not attained, and chemical resistance is poor. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Laid-Open No. 2019-006897

[Technical problem to be solved by the invention]

An object of the present invention is to provide a urethane (meth)acrylate and an active energy ray-curable resin composition containing the urethane (meth)acrylate, wherein the urethane ( Meth)acrylates provide hardened products with excellent chemical resistance and high elongation. [Technical means]

The inventors of the present invention have focused on the composition and physical properties of urethane (meth)acrylate, and through intensive research, have found that the aforementioned technical problems can be solved, thereby completing the present invention. That is, the present invention relates to the following urethane (meth)acrylates, active energy ray-curable resin compositions, cured products, laminates, and molded products.

1. A urethane (meth)acrylate, characterized by containing a dihydric alcohol (a1) having an alicyclic structure, a diisocyanate (a2) having a cyclic structure and (meth)acrylic acid having a hydroxyl group The ester (a3) is used as a reaction component; and the weight average molecular weight is 6,000 to 25,000, and the (meth)acryloyl group concentration is 0.2×10 ^-3 to 2.0×10 ^-3 eq/g.

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

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

4. The urethane (meth)acrylate described in any one of the preceding paragraphs 1 to 3, wherein the component (a3) contains a hydroxyalkyl (meth)acrylate and/or neotaerythritol ( meth)acrylate.

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

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

7. The active energy ray-curable resin composition according to the above item 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. A cured product, characterized in that it is a cured product of the active energy ray-curable resin composition described in 6 or 7 above.

9. A layered body characterized by having a layer of the cured product as described in the preceding item 8.

10. A molded article, characterized in that the surface is covered by the hardened article as described in the preceding item 8. [Effect of invention]

The urethane (meth)acrylate of the present invention exhibits excellent chemical resistance due to the cured product of the active energy ray-curable resin composition containing the urethane (meth)acrylate. At the same time, it also has high elongation, so it has the characteristics of easy processing and molding.

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

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

The component (a1) is a dihydric alcohol having one or more alicyclic structures. (a1) Component, for example, 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,1-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 1,3 - Cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,2-cyclooctanediol, 1,5-cyclooctanediol and other monocyclic Diols; 5-Norbornene-2,2-Dimethanol, 5-Norbornene-2,3-Dimethanol, Norbornane-2,3-Dimethanol, Norbornane-2,5-Dimethanol Bicyclic diols such as methanol, 2,6-decahydronaphthalene dimethanol; 1,3-adamantanediol, 1,4-adamantanediol, 2,4-adamantanediol, tricyclodecanediol Tricyclic dihydric alcohols such as methanol; hydrogenated bisphenols, etc. These may be used alone or in combination of two or more. Among them, from the viewpoint that the cured product exhibits excellent chemical resistance, it is desirable to be selected from the group consisting of tricyclodecanedimethanol, 1,1-cyclohexanedimethanol, and 1,4-cyclohexanedimethanol One or more of them are more preferably tricyclodecane dimethanol and 1,1-cyclohexane dimethanol.

Moreover, the reaction component of (A) component can also use together the polyol (a1') (henceforth (a1') component) other than (a1) component. (a1') Component, for example, 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, 1,5-pentanediol and other alkane diols; diethylene glycol, dipropylene glycol, tripropylene glycol such as polyalkylene glycols; polyether polyols, polyester polyols, etc. The usage-amount of (a1') component is 4 mol or less with respect to 1 mol of (a1) component.

The component (a2) is a compound having a cyclic structure and two isocyanate groups. (a2) Component, for example: Toluene diisocyanate (toluene-2,4-diisocyanate, toluene-2,6-diisocyanate or mixtures thereof), 2,2'-diphenylmethane diisocyanate, 2,4-diphenylmethane diisocyanate , 4,4'-diphenylmethane diisocyanate, 3,3-dimethyldiphenylmethane diisocyanate, diphenyl ether-4,4'-diisocyanate, o-xylylene diisocyanate, m-phenylene Diisocyanates with aromatic rings such as dimethyl diisocyanate, p-xylylene diisocyanate, tetramethylxylylene diisocyanate, 1,5-naphthalene diisocyanate; The hydrides of the aforementioned diisocyanates having an aromatic ring, norbornene methane diisocyanate, 1,4-cyclohexanediisocyanate, cyclohexane-1,4-diylbis(methylene)diisocyanate, isophor Diisocyanates etc. which have an alicyclic structure, such as a ketone diisocyanate. Moreover, these isocyanurate bodies, adducts, and biuret bodies may be used, and dimers and trimers may also be used. These may be used alone or in combination of two or more. Among them, from the viewpoint that the cured product exhibits excellent chemical resistance, a diisocyanate having an alicyclic structure is preferable, and a hydrogenated product of m-xylylene diisocyanate, 2,2'-diphenylene is more preferable. Hydrogenated methane diisocyanate, hydride of 2,4-diphenylmethane diisocyanate, hydride of 4,4'-diphenylmethane diisocyanate, norbornylmethane diisocyanate and isophorone diisocyanate More than one of the groups.

The amount of the component (a2) to be used is preferably 0.7 to 1.2 mol relative to 1 mol of the component (a1). By being within this range, the hardened product can increase the elongation while having high hardness. From the same viewpoint, the above-mentioned usage amount is more preferably 0.9 to 1.0 mol.

The component (a3) is a component bonded to the isocyanate group terminal of the urethane prepolymer which is a reactant of the components (a1) and (a2), and contributes to the excellent chemical resistance of the cured product. The component (a3) is not particularly limited, and examples thereof include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and (meth)acrylic acid. 3-Hydroxybutyl acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate and other hydroxyalkyl (meth)acrylates; 2,3-dihydroxypropyl (meth)acrylate , 3,4-dihydroxybutyl (meth)acrylate, (meth)acrylate monoglyceride, (meth)acrylate 1,4-dihydroxyheptyl and other (meth)acrylate dihydroxyalkyl esters; (meth)acrylate (meth)acrylic acid cycloalkyl monoester; (meth)acrylic acid 2-hydroxy-3-phenoxy Mono(meth)acrylates with hydroxyl and ether bonds, such as propyl propyl ester, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, etc.; erythritol di(meth)acrylic acid Erythritol (meth)acrylates such as esters, erythritol tri(meth)acrylate; neotaerythritol mono(meth)acrylate, neotaerythritol di(meth)acrylate, Neotaerythritol (meth)acrylates, such as neotaerythritol tri(meth)acrylate; Dipiveaerythritol (meth)acrylates such as Dipiveaerythritol tri(meth)acrylate, Dipiveaerythritol tetra(meth)acrylate, Dipovaerythritol penta(meth)acrylate, etc. Classes; Trinepentaerythritol tetra(meth)acrylate, Trinepentaerythritol penta(meth)acrylate, Trinepentaerythritol hexa(meth)acrylate, Trinepentaerythritol hepta(meth)acrylate ) Trinetaerythritol (meth)acrylates such as acrylates and the like. These may be used alone or in combination of two or more. Among them, hydroxyalkyl (meth)acrylates and neotaerythritol (meth)acrylates are preferable from the viewpoints that the cured product exhibits excellent chemical resistance and high elongation.

Moreover, the said (a3) component can also use the mixture containing the poly (meth)acrylate which does not contain a hydroxyl group. The poly(meth)acrylate that does not contain a hydroxyl group is not particularly limited, and examples thereof include erythritol tetra(meth)acrylate, neopentaerythritol tetra(meth)acrylate, dipeoerythritol hexa(meth)acrylate Meth)acrylate, Trinetaerythritol octa(meth)acrylate, etc. The content of the hydroxyl-free poly(meth)acrylate is 60 wt % or less with respect to 100 wt % of the (a3) component.

(a3) Commercial products of the component include, for example, "ARONIX M305", "ARONIX M306", "ARONIX M400", "ARONIX M402", "ARONIX M403", "ARONIX M404", "ARONIX M405", "ARONIX M405", "ARONIX M402" M406", "ARONIX M933" (manufactured by Toagosei Co., Ltd.), "KAYARAD DPHA" (manufactured by Nippon Kayaku Co., Ltd.), "A-9550", "A-DPH" (manufactured by Shin-Nakamura Chemical Industry Co., Ltd. ), "Viscoat #300", "Viscoat #802" (manufactured by Osaka Organic Chemical Industry Co., Ltd.), "Miramer M500" (manufactured by MIWON Specialty Chemical Co., Ltd.), etc.

The amount of the component (a3) to be used is not particularly limited, but from the viewpoint that the cured product exhibits excellent chemical resistance and maintains high elongation, the amount of the amine group obtained by reacting the component (a1) and the component (a2) is relatively high. The isocyanate group in the formate prepolymer is preferably 1 to 1.1 mol, more preferably 1 to 1.02 mol, per mol of the isocyanate group.

The manufacturing method of (A) component is not specifically limited, For example, (a1) component and (a2) component are reacted to manufacture a urethane prepolymer (hereinafter referred to as (A') component), followed by (A') component. ') component reacts with (a3) component. The reaction conditions are not particularly limited, but usually the temperature is about 50 to 85°C (preferably about 60 to 80°C), and the time is about 1 to 24 hours (preferably about 5 to 10 hours).

Moreover, in manufacture of (A) component, it is preferable to use an organic solvent. Examples of organic solvents include aromatics such as benzene, toluene, ethylbenzene, n-propylbenzene, tertiary butylbenzene, ortho-xylene, meta-xylene, para-xylene, tetralin, decalin, and aromatic naphtha. Aliphatic hydrocarbons; n-hexane, n-heptane, n-octane, isooctane, n-decane and other aliphatic hydrocarbons; cyclohexane and other alicyclic hydrocarbons; isopropanol, isobutanol, secondary butanol, tertiary Alcohols such as butanol; ethyl acetate, n-butyl acetate, n-amyl acetate, 2-hydroxyethyl acetate, 2-butoxyethyl acetate, 3-methoxybutyl acetate, methyl benzoate and other esters ; Acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone, methyl cyclohexanone and other ketones. In addition, the usage-amount of an organic solvent is about 40 to 80 weight% as a reaction density|concentration ideally.

The weight average molecular weight of the obtained (A) component is 6,000-25,000. When the weight average molecular weight is less than 6,000, the elongation of the hardened product tends to decrease. In addition, when the weight average molecular weight is more than 25,000, the chemical resistance of the hardened product tends to decrease. Further, for the same reason, the weight average molecular weight is preferably 9,000 to 20,000, and more preferably 10,000 to 15,000. In addition, the "weight average molecular weight" here means the measurement value by gel permeation chromatography (GPC) method (polystyrene conversion).

In addition, the (meth)acryloyl group concentration of the component (A) is 0.2×10 ^-3 to 2.0×10 ^-3 eq/g. When the concentration is less than 0.2×10 ^-3 eq/g, the chemical resistance of the cured product tends to decrease, and when the concentration exceeds 2.0 x 10 ^-3 eq/g, the elongation of the cured product tends to decrease. Further, from the same viewpoint, the (meth)acryloyl group concentration of the component (A) is preferably 1.0×10 ^-3 to 1.8×10 ^-3 eq/g, more preferably 1.2×10 ^-3 to 1.6× 10 ^-3 eq/g.

The aforementioned (meth)acryloyl group concentration is a value obtained by dividing the (meth)acryloyl group equivalent by the total solid weight of the components (a1) to (a3). For example, when 2 moles of tricyclodecane dimethanol (molecular weight: 196.3) is used as the component (a1), 2 moles of isophorone diisocyanate (molecular weight: 222.3) is used as the (a2) component, and 1 mole of acrylic acid is used as the component (a2). When hydroxyethyl ester (molecular weight: 116.1) is used as the component (a3), the (meth)acryloyl group concentration is as follows.

※[(Meth)acryloyl equivalent (eq)]={Molar number of (a3)component}×{(a3)component of acryl group}=1×1=1 ※[(a1)component～ (a3) Total solid content weight of component (g)] = {(a1) component molar} × {(a1) component molecular weight} + {(a2) component molar} × {(a2) component Molecular weight of {{(a3) component molar}×{(a3) component molecular weight}=2×196.3+2×222.3+1×116.1=953.3 ※[(meth)acryloyl group concentration (eq/ g)] = [(meth)acryloyl equivalent (eq)]/[(a1)-(a3) component total solid content weight (g)] = 1/953.3≒1.05×10 ^-3

(A) other physical properties of the component, the urethane bond concentration is ideally 2.0×10 ^-3 to 6.5×10 ^-3 eq/g, more preferably 3.0×10 ^-3 to 5.5×10 ^-3 eq/g, More preferably, it is 3.5×10 ^-3 to 5.0×10 ^-3 eq/g. With the urethane bond concentration within this range, the hardened product tends to have excellent chemical resistance.

The aforementioned urethane bond concentration is a value obtained by dividing the molar number of the urethane bond by the total solid weight of the components (a1) to (a3). The molar number of the urethane bond means the smaller value of the number of isocyanate groups of the component (a2) or the total number of hydroxyl groups of the component (a1) and (a3). For example, when 2 moles of tricyclodecane dimethanol (molecular weight: 196.3) is used as the component (a1), 2 moles of isophorone diisocyanate (molecular weight: 222.3) is used as the (a2) component, and 1 mole of acrylic acid is used as the component (a2). When hydroxyethyl ester (molecular weight: 116.1) is used as the component (a3), the urethane bond concentration is as follows.

※(a2) The number of isocyanate groups in the component (eq) = {(a2) The number of moles of the component}×{(a2) The number of isocyanate groups in the component}=2×2=4 ※(a1) The number of hydroxyl groups in the component (eq ) = {(a1) The number of moles of component}×{(a1) The number of hydroxyl groups of the component}=2×2=4 ※(a3) The number of hydroxyl groups of the component (eq)={(a3) The number of moles of the component }×{(a3) The number of hydroxyl groups of the component}=1×1=1 ※{The total number of hydroxyl groups of the (a1) component and the (a3) component} = {(a1) The number of hydroxyl groups of the component}+{(a3) component The number of hydroxyl groups of the Smaller value (eq)}/[(a1)-(a3) component total solid content weight (g)] = 4/953.3≒4.2×10 ^-3

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

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 (B) component) and/or metal oxide (C) (hereinafter referred to as (C) Element).

The component (B) 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, tertiary (meth)acrylate Butyl, isobutyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, (meth)acrylate ) 2-ethylhexyl acrylate, n-nonyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, tri-n-decyl (meth)acrylate, (meth)acrylate N-lauryl acrylate, n-myristyl (meth)acrylate, n-palmityl (meth)acrylate, n-stearyl (meth)acrylate, isostearyl (meth)acrylate, etc. base) acrylate; Cyclohexyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxy (meth)acrylate (Meth)acrylic acid with alicyclic structure such as ethyl ester, dicyclopentyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, etc. ester; (meth) phenyl acrylate, benzyl (meth) acrylate, 2-phenylethyl (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, etc. (methyl) having an aromatic ring base) acrylate; Methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, 2-methoxyethoxyethyl (meth)acrylate, ( (meth)acrylates with alkoxyalkyl groups such as 2-ethoxyethoxyethyl meth)acrylate; Monoalkylene glycol (meth)acrylates such as ethylene glycol di(meth)acrylate and propylene glycol di(meth)acrylate; Diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipropylene glycol Polyalkylene glycol (meth)acrylates such as di(meth)acrylate and tripropylene glycol di(meth)acrylate; Methoxydiethylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, etc. )Acrylate; (Meth) acrylamides such as (meth) acrylamide, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, (meth) acryl morpholine; (Meth)acrylates having epoxy groups such as glycidyl (meth)acrylate; (Meth) Dialkylaminoalkyl acrylates such as N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, etc.; neotaerythritol mono(meth)acrylate, neotaerythritol di(meth)acrylate, neotaerythritol tri(meth)acrylate, neotaerythritol tetra(meth)acrylate or the like The mixture of neotaerythritol (meth)acrylates; Dipiveaerythritol mono(meth)acrylate, Dipiveaerythritol di(meth)acrylate, Dipiveaerythritol tri(meth)acrylate, Dipiveaerythritol tetra(meth)acrylic acid esters, dipeotaerythritol penta(meth)acrylates, dipeotaerythritol hexa(meth)acrylates or dipeotaerythritol (meth)acrylates of mixtures of these; Tripiotaerythritol tetra(meth)acrylate, Tripiotaerythritol penta(meth)acrylate, Tripiotaerythritol hexa(meth)acrylate, Tripiotaerythritol hepta(meth)acrylate esters, trinepentaerythritol octa(meth)acrylates or mixtures of these; Alkylene oxide modified bisphenol A di(meth)acrylate, alkylene oxide modified trimethylolpropane tri(meth)acrylate, alkylene oxide modified bis(trimethylolpropane) tetra(methyl) Acrylate, alkylene oxide modified glycerol tri(meth)acrylate, alkylene oxide modified polyglycerol (meth)acrylate, alkylene oxide modified neotaerythritol di(meth)acrylate, epoxy Alkane-modified neotaerythritol tri(meth)acrylate, alkylene oxide-modified neotaerythritol tetra(meth)acrylate, selected from neotaerythritol di(meth)acrylate and neotaerythritol Alkylene oxide modified product of mixture of two or more of tri(meth)acrylate and neopentaerythritol tetra(meth)acrylate group, and alkylene oxide modified dipivalerythritol poly(methyl) base) acrylate (here, "poly" means any one of two types, three types, four types, five types, six types, and can also mean a mixture of two or more of these), alkylene oxide modified Alkylene oxide modified (meth)acrylate such as 2-ethylhexyl (meth)acrylate, alkylene oxide modified polyethylene glycol (meth)acrylate, alkylene oxide modified polypropylene glycol (meth)acrylate, etc. base) acrylates (oxyalkylene, for example: methyl oxide, ethylene oxide, propylene oxide, butylene oxide, etc.); Trimethylolpropane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate polyol (meth)acrylates such as base) acrylates; Polyester (meth)acrylate, polyether (meth)acrylate, urethane (meth)acrylate other than (A) component, etc.

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, from the viewpoint of exhibiting excellent chemical resistance and high elongation of the cured product, the content thereof is based on the solid content weight ratio: In 100 weight% of the total of (A) component and (B) component, it is 50 weight% or less normally, Preferably it is 30 weight% or less.

The component (C) is not particularly limited, and examples thereof include silicon dioxide, aluminum oxide, zirconium oxide, titanium oxide, antimony oxide, tin oxide, indium oxide, and zinc oxide. Moreover, (C) component doped with aluminum, phosphorus, fluorine, etc. can also be used. These may be used alone or in combination of two or more.

In addition, as commercially available products, "TOL-ST", "MEK-ST-40", "MEK-ST-L", "MEK-ST-ZL", "MEK-ST-UP", "MIBK" can be mentioned. -ST", "CHO-ST-M", "EAC-ST", "PMA-ST" (the above are manufactured by Nissan Chemical Co., Ltd.), etc.

Moreover, (C)component can also use the metal oxide which has an organic functional group on the surface. "Organofunctional group" refers to a group having at least carbon atoms, for example: methacryloyl group, acryl group, vinyl group, epoxy group, isocyanate group, urethane group, organosiloxane Base et al. These may be used alone or in combination of two or more.

Examples of commercially available metal oxides having organic functional groups on the surface include "MEK-EC-2130Y", "MEK-AC2140Z", "MEK-AC-4130Y", "PGM-AC2140Y", "PGM- "AC3140Y", "PGM-AC4130Y", "MIBK-SD", "MIBK-SD-L" (manufactured by Nissan Chemical Co., Ltd.); "NANOBYK-3603", "NANOBYK-3650", "NANOBYK-3652" (Japan BYK Chemicals Co., Ltd.); "ALMIBK30WT%-H06", "ALMIBK30WT%-M114", "ALMIBK30WT%-M115", "SIRMIBK15ET%-H24", "SIRMIBK15ET%-H83" (manufactured by CIK NanoTek Co., Ltd. ); "ELECOM-V#8802", "ELECOM-V#8803", "ELECOM-V#8804" (manufactured by Nippon Chemical Co., Ltd.), etc.

The average primary particle size of the component (C) is not particularly limited, but from the viewpoint of transparency of the cured product, it is preferably about 4 to 200 nm, and more preferably about 7 to 50 nm. Moreover, the measuring method of an average primary particle diameter is not specifically limited, For example, a light scattering method etc. are mentioned.

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

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 benzene, toluene, ethylbenzene, n-propylbenzene, tertiary butylbenzene, ortho-xylene, meta-xylene, para-xylene, tetralin, decalin, and aromatic naphtha. Aromatic hydrocarbons such as oil; aliphatic hydrocarbons such as n-hexane, n-heptane, n-octane, isooctane, n-decane; alicyclic hydrocarbons such as cyclohexane; ethyl acetate, propyl acetate, n-butyl acetate , secondary butyl acetate, tertiary butyl acetate, n-amyl acetate, 2-hydroxyethyl acetate, 2-methoxyethyl acetate, 2-butoxyethyl acetate, 3-methoxybutyl acetate Ester, 1-methoxypropyl acetate, methyl benzoate and other esters; acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone, methyl cyclohexanone and other ketones; Dimethyl carbonate, diethyl carbonate, ethylene carbonate and other carbonates; diisopropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether and other acyclic ethers; tetrahydrofuran , 1,3-dioxolane, 1,4-dioxane and other cyclic ethers; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether and other monohydroxy ethers; methanol, ethanol, n-propanol, 2-propanol, n-butanol, isobutanol, secondary butanol, tertiary butanol Alcohol etc. Moreover, when using an organic solvent as a component of an active energy ray-curable resin composition, the content is desirably 0.5 to 80 weight% or less.

The active energy ray-curable resin composition of the present invention further contains a photopolymerization initiator. In addition, the photopolymerization initiator may be blended at the time of preparing the active energy ray-curable resin composition, or may be blended immediately before coating on the base film.

The photopolymerization initiator is not particularly limited, and examples thereof include photopolymerization initiators such as benzoin compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, thioxanthone compounds, and oxime ester compounds, amines, quinones, etc. etc.; more specifically, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexyl phenyl ketone, 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]-2-methylpropan-1-one, 2-methyl-1-(4- Methylthiophenyl)-2-morpholinoprop-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4 -Morpholinyl)phenyl]-1-butanone, 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzyl)- Phenylphosphine oxide, bis(n 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-benzyl oxime)], ethyl ketone 1-[9-ethyl-6-(2-methylbenzyl) base)-9H-carbazol-3-yl]-1-(o-acetyloxime) and the like. These may be used alone or in combination of two or more. In addition, the content of the photopolymerization initiator is preferably 0.5 to 20 parts by weight, more preferably 2 to 10 parts by weight with respect to 100 parts by weight of the total of (A) component, (B) component, and (C) component of the present invention .

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

The active energy ray-curable resin composition of the present invention can be obtained by mixing (A) component, (B) component, and (C) component, a photopolymerization initiator, an organic solvent as required, and the aforementioned additives. The mixing means and mixing order are not particularly limited.

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

The hardened|cured material of this invention is not specifically limited, For example, it can be obtained by apply|coating the said active energy ray hardening-type resin composition on a base film, and irradiating an active energy ray.

The base material is not particularly limited, and examples thereof include polyethylene terephthalate (PET), cycloolefin polymer (COP), polypropylene, polybutene, polybutadiene, polymethylpentene, poly Olefin, polyvinyl chloride, vinyl chloride copolymer, polyethylene naphthalate, polybutylene terephthalate, polymethyl acrylate, polyurethane, ethylene vinyl acetate, ionomer resin, ethylene-( Meth)acrylic acid copolymer, ethylene-(meth)acrylate copolymer, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), epoxy resin, Melamine resin, cellulose triacetate resin, norbornene resin, fluororesin, polystyrene, polyester, polycarbonate, polyamide, polyimide and other plastic films; metal, wood, paper, glass, slate, etc. . In addition, a light peeling material and a heavy peeling material can be used for the base material, and an untreated material or a plasma-treated material can also be used.

Moreover, in order to peel easily from the layer of hardened|cured material, you may perform peeling process to the said base material. The peeling treatment is not particularly necessary in the case of easy peeling, but for easier peeling, melamine resin, silicone resin, fluororesin, cellulose derivative, urea resin, polyolefin resin, paraffin resin can be laminated as a release layer. . These resin films may be used alone or in combination of two or more.

The coating method is not particularly limited, and examples thereof include an applicator, a bar coater, a roll coater, a knife coater, a gravure coater, a spray coater, a comma coater, and a lip coater. Machine (lip coater), gravure printing, screen printing, etc. The coating amount of the active energy ray-curable resin composition is also not particularly limited, but is usually applied so that the film thickness after curing is about 1 to 10 μm.

The active energy rays are not particularly limited, and examples thereof include light rays such as ultraviolet rays, infrared rays, and visible rays; electron beams, X rays, alpha rays, beta rays, gamma rays, and neutron beams. In the present invention, light rays are desirable, and ultraviolet rays are more desirable.

The light source of ultraviolet rays is not particularly limited, and examples thereof include xenon lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, chemical lamps, electrodeless lamps, and LED lamps. In addition, the irradiation intensity of ultraviolet rays is not particularly limited, either, but is usually about 100 to 1000 mJ/cm 2 . Moreover, after irradiating an ultraviolet-ray, you may heat as needed for the purpose of complete hardening.

The lamination system of the present invention has the layer of the aforementioned cured product. The used base material, hardening method, etc. are the same as described above.

The molded product of the present invention is obtained by coating the surface of the above-mentioned hardened product, and is obtained by coating the surface of the molded product with the hardened product by using the in-mold simultaneous decoration method and the vacuum pressing method. Among these methods, there are the lamination method in which the cured product is attached to the surface of the molded product of each base material, and the cured product layered on the plastic film or other pattern ink layers and functional layers are transferred to the molded product. surface transfer method.

In the lamination method, as the composition of the decorative film, it generally has the order of the layer of the cured product of the present invention, the anchor layer, the pattern ink layer, the easy-bonding layer, the base film, the functional layer, and the adhesive layer; The layer of the cured product of the present invention, the easily bonding layer, the base film, the easily bonding layer, the pattern ink layer, the functional layer, the sequence of the bonding layer, etc., can be laminated on the surface of the molded product via the bonding layer.

In the above-mentioned transfer method, a peeling layer can generally be layered on the plastic film as required, 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 layered sequentially on top of it. (transfer layer), after the surface of the molded object is attached via the adhesive layer, the plastic film or the release layer and the layer of the cured product are peeled off, and only the transfer layer is laminated and covered on the surface of the molded object. [Example]

The following examples are given and described in detail, but the present invention is not limited to these examples. In addition, unless otherwise indicated, in each Example, "part" and "%" are based on weight.

<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 analyzer (product name: "HLC-8220", manufactured by Tosoh Corporation) . Column (product name: "TSKgel superHZ2000", "TSKgel superHZM-M", manufactured by Tosoh Corporation) . Developing solvent: tetrahydrofuran . Flow rate: 0.35ml/min . Sample concentration: 0.5g/L . Standard material: Polystyrene (Standard polystyrene kit, PStQuickA, B, C, manufactured by Tosoh Corporation)

Example 1 In a three-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, 24.4 parts (5 moles) of tricyclodecane dimethanol (hereinafter referred to as "TCD") and 24.2 parts of hydrogenated xylene diisocyanate (H-XDI) were added. parts (5 moles), 40.0 parts of methyl ethyl ketone, and 0.01 part of tin octoate. After stirring at 60°C for 2 hours, V#300 (trade name: "Viscoat#300", a mixture of neotaerythritol triacrylate and neotaerythritol tetraacrylate, hydroxyl value: 122.2 mgKOH/g, manufactured by Osaka Organic Chemical Industry Co., Ltd. (hereinafter referred to as PETA) 11.3 parts (1 mole), 0.15 parts of tin octoate, 0.03 parts of hydroquinone monomethyl ether, and reacted until the residual isocyanate group was 0.1% Until then, a solution of urethane (meth)acrylate (A-1) having a solid content concentration of 60% was obtained. The physical properties of the component (A-1) are shown in Table 1 (the same applies hereinafter).

Examples 2 to 8, Comparative Examples 1 to 6 According to the composition shown in Table 1, the synthesis was carried out in the same manner as in Example 1 to obtain urethane (meth)acrylates (A-2) to (A-8), ( D-1) to (D-6) solutions.

[Table 1]

The abbreviations in Table 1 represent the following compounds. ＜Diol＞ . TCD: Tricyclodecane dimethanol . 1,1-CHDM: 1,1-cyclohexanedimethanol . 1,4-BD: 1,4-Butanediol <Diisocyanate> . H-XDI: Hydride of m-xylylene diisocyanate . IPDI: isophorone diisocyanate . H-MDI: hydride of 4,4'-diphenylmethane diisocyanate . HDI: hexamethylene diisocyanate <(Meth)acrylate having hydroxyl group> . PETA-1: Trade name: "Viscoat#300", a mixture of neotaerythritol triacrylate and neotaerythritol tetraacrylate, hydroxyl value: 122.2 mgKOH/g, manufactured by Osaka Organic Chemical Industry Co., Ltd. . PETA-2: Trade name: "ARONIX M-933", mixture of neotaerythritol triacrylate and neotaerythritol tetraacrylate, hydroxyl value: 280.0 mgKOH/g, manufactured by Toagosei Co., Ltd. . PETA-3: Trade name: "ARONIX M-306", mixture of neotaerythritol triacrylate and neotaerythritol tetraacrylate, hydroxyl value: 160.0 mgKOH/g, manufactured by Toagosei Co., Ltd. . HEA: 2-hydroxyethyl acrylate

Evaluation Examples 1 to 8, Comparative Evaluation Examples 1 to 6 100 parts of each urethane (meth)acrylate solution (solid content weight: 60 parts), 1-hydroxycyclohexyl phenyl ketone (photopolymerization initiator, trade name: "Omnirad 184", IGM Resins B.V. Co., Ltd.) 3.2 parts, a silicone-based surface conditioner (additive, trade name: "BYK-378", BYK Co., Ltd.) 0.2 parts, and 108 parts of methyl ethyl ketone were mixed, stirred until dissolved, and prepared active Energy ray curable resin composition.

<Preparation of test film> Each active energy ray-curable resin composition was coated on a commercially available polyethylene terephthalate film (trade name: "COSMOSHINE A4100", manufactured by Toyobo Co., Ltd.) by a bar coater. The surface of the cured product was made to have a thickness of 5 μm, and was dried at a temperature of 60° C. for 2 minutes. Then, ultraviolet rays were irradiated using a 400W high-pressure mercury lamp (one lamp) so that the accumulated light amount became 300 mJ/cm ² , and a test film was produced.

＜Chemical resistance＞ The test films were cut into 6 cm x 6 cm. A sunscreen (trade name: "Neutrogena", manufactured by Helioplex Co., Ltd.) was applied in a circle with a radius of 3 cm, and then left in a dryer at a temperature of 55°C for 4 hours. Cool to room temperature and rinse sunscreen with lotion and water. The water was wiped off, and the surface of the test film was visually observed and evaluated according to the following criteria. The results are shown in Table 2 (the same applies hereinafter). (Evaluation Criteria) ◎: No streaks or whitening are seen on the surface at all ○: Some streaks are seen in part of the surface ×: Most of the surface is whitened

<Elongation> The test film was prepared to be cut into test pieces of 1.5 cm in width and 13 cm in length. The test piece was set in a tensile tester (device name: "RTM-500", manufactured by Orientec Co., Ltd.) so that the distance between the clamps was 5 cm, and after being left at a temperature of 140° C. for 1 minute, the test piece was pulled out. The stretching speed was 5cm/min. The length of the test piece at the time when cracks appeared in the layer of the cured product was read, and the elongation was obtained by taking 5 cm as 100%. The case where the elongation rate is 180% or more is favorable.

[Table 2]

Evaluation Examples 9 to 16, Comparative Evaluation Examples 7 and 8 151.6 parts (solid content weight: 85 parts) of solutions of urethane (meth)acrylates of Examples 1 to 8 and Comparative Examples 1 and 2, dipivoerythritol pentaacrylate, and dipivaltetracycline Mixture of alcohol hexaacrylate (trade name: "NKesterA-9550W", manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 10.7 parts, methacryloyl group-containing alumina (trade name: "ALMIBK30WT%-H06", CIK NanoTek Co., Ltd., average primary particle size: 15 nm, solid content concentration: 30%) 17.8 parts (solid content weight: 5 parts), 1-hydroxycyclohexyl phenyl ketone (photopolymerization initiator, trade name: "Omnirad 184 ”, manufactured by IGM Resins B.V.) 5.4 parts, a silicone-based surface conditioner (additive, trade name: “BYK-378”, manufactured by BYK Corporation) 0.2 parts, and 95.8 parts of methyl ethyl ketone were mixed and stirred until dissolved , respectively, to prepare active energy ray-curable resin compositions.

Evaluation Examples 17 to 19 Except having changed to the composition shown in Table 3, it carried out in accordance with the method described in the preceding paragraph, and obtained the active energy ray-curable resin composition, respectively.

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

［表3］

[table 3]

The symbols described in Table 3 represent the following compounds. . A-1 to A-8, D-1, D-2: Refer to Table 1. . B-1: Mixture of Dipiveaerythritol Pentaacrylate and Dipiotaerythritol Hexacrylate, trade name: "NKester A-9550W", manufactured by Shin-Nakamura Chemical Industry Co., Ltd. . B-2: Urethane acrylate (reaction product of dipivalerythritol pentaacrylate and hexamethylene diisocyanate), trade name "DPHA-40H", manufactured by Nippon Kayaku Co., Ltd. . C-1: Alumina having a methacryloyl group: trade name "ALMIBK30WT%-H06", manufactured by CIK NanoTek Co., Ltd., average primary particle size: 15 nm, solid content concentration: 30%

Claims (10)

A urethane (meth)acrylate characterized by containing a dihydric alcohol (a1) having an alicyclic structure, a diisocyanate (a2) having a cyclic structure, and a (meth)acrylate (meth)acrylate having a hydroxyl group ( a3) as a reaction component; and the weight average molecular weight is 6,000 to 25,000, and the (meth)acryloyl group concentration is 0.2×10 ^-3 to 2.0×10 ^-3 eq/g. The urethane (meth)acrylate according to claim 1, wherein the component (a1) contains tricyclodecanedimethanol and/or 1,1-cyclohexanedimethanol. The urethane (meth)acrylate according to claim 1 or 2, wherein the component (a2) is a diisocyanate having an alicyclic structure. The urethane (meth)acrylate according to any one of claims 1 to 3, wherein the component (a3) contains a hydroxyalkyl (meth)acrylate and/or neotaerythritol (methyl) base) acrylate. The urethane (meth)acrylate according to any one of claims 1 to 4, wherein the urethane bond concentration is 2.0×10 ^-3 to 6.5×10 ^-3 eq/g. An active energy ray-curable resin composition characterized by containing the urethane (meth)acrylate according to any one of claims 1 to 5. 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). A hardened product, characterized in that it is a hardened product of the active energy ray-curable resin composition according to claim 6 or 7. A laminated body characterized by having a layer of the cured product according to claim 8. A molded product characterized in that the surface is covered with the hardened product as claimed in claim 8.