JP2017002245A - Active energy ray curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active energy ray curable composition easy to manufacture a composition and providing a cured film excellent in soft feeling property and adhesion, further excellent in scratch resistance so that it is not damaged even by scratching with nails.SOLUTION: There is provided an active energy ray curable composition containing (A) a compound having an ethylenically unsaturated group containing polyether di(meth)acrylate (A1) as an essential component and (B) a fine particulate polymer filler having glass transition temperature of -100°C to 30°C.SELECTED DRAWING: None

Description

The present invention relates to an active energy ray-curable composition, and the cured film has a moist feeling especially called “soft feel” and is excellent in adhesion to a substrate and scratch resistance, and is therefore preferable for coating applications such as paints. Can be used and belongs to these technical fields.
In the present specification, acrylate or / and methacrylate are represented as (meth) acrylate, acrylic acid or / and methacrylic acid (meth) acrylic acid, and acryloyl group or / and methacryloyl group are referred to as (meth) acryloyl group. Represent.

  Conventionally, for various substrates such as metal, glass and plastic, a protective film is formed on the substrate using a coating composition for the purpose of protecting the substrate surface or imparting aesthetics or design. The forming method is used. In particular, the plastic substrate is lightweight and excellent in impact resistance, easy moldability, and the like. However, since the surface is easily damaged and has low hardness, there is a drawback that the appearance is remarkably impaired when used as it is. For this reason, it is required that the surface of the plastic substrate is coated with a coating composition and is subjected to a so-called hard coat treatment to impart scratch resistance and improve surface hardness.

Conventionally, as a method for improving the surface hardness of a plastic substrate, an active energy ray curable composition comprising a (meth) acrylate having an alicyclic skeleton excellent in hardness of a cured film is known (Patent Documents 1 and 2). ). (Meth) acrylates having an alicyclic skeleton have a high glass transition point (Tg) and good hardness in many cases, but there is a tendency that adhesion to a substrate is difficult to obtain due to a large stress during active energy ray curing. is there. In Patent Documents 1 and 2, adhesion to a plastic substrate is not disclosed in Examples.
In the method of Patent Document 2, a reactive polymer is produced in advance using a thermal polymerization initiator. If the thermal polymerization initiator used at this time remains, the active energy ray-curable composition is being stored. However, it cannot be said to have sufficient stability.

On the other hand, an active energy ray-curable coating agent that has low stress during curing and good adhesion and curl resistance is known that utilizes photocationic polymerization of cyclic ether (Patent Document 3). It is disclosed in the Examples that this method has better adhesion and curl resistance than a coating agent using photoradical polymerization of (meth) acrylate.
However, in cationic polymerization, it is known that the humidity in the working atmosphere greatly affects the curability. In particular, since hard coating is often applied as a thin film, the influence of humidity is likely to occur, and the desired curability and performance as a coating may not be obtained in the rainy season or summer.

  As an active energy ray-curable coating agent that is not easily affected by humidity and has good adhesion, there is known a method of combining 4- (meth) acryloylmorpholine and a trifunctional or higher functional (meth) acrylate having one or more hydroxyl groups. (Patent Document 4). Although good adhesion is obtained by using 4- (meth) acryloylmorpholine, this method has a large shrinkage at the time of curing and cannot have good curl resistance.

  Recently, not only a “hard coating” but also a cured film not only has a sufficient scratch resistance, but also has a high-grade appearance and a soft feeling. Especially in cosmetic containers and mobile phones, when touching these articles with a coating film, there is not a hard and glossy tactile feeling but a moist soft feeling, and a coating film that moderately suppresses gloss gives a high-class feeling. Therefore, a coating material having characteristics different from those of conventional hard coats has been demanded.

As a method for forming such a “soft feel” cured film, an undercoating paint containing a solvent having a boiling point of 120 to 180 ° C., a polyisocyanate and a polyol is applied, and the solvent is evaporated at room temperature. A method is known in which after a layer is foamed, a top coating containing an organic bead layer is applied and cured by heating (Patent Document 5).
However, this method requires two-layer coating of undercoating and topcoating, so the process is complicated, and the topcoating paint takes time for heat curing, so it cannot be said that it has sufficient productivity. .

An active energy ray-curable composition comprising urethane (meth) acrylate and a synthetic resin filler is disclosed as a composition with improved productivity (Patent Document 6).
According to the composition, the obtained cured film can have a moist and soft touch feeling by a simple method of irradiating and curing an active energy ray.
However, in applications where the model change cycle is fast and durability over a long period of time is not required, such as cosmetic containers and mobile phones, paints that can be handled more easily are preferred, and lower-cost compositions are required.

JP 2003-268263 A JP 2013-49802 A JP 2007-284613 A JP 2012-111943 A JP 2009-131821 A JP 2014-122338 A

According to the study results of the present inventors, in a composition containing urethane (meth) acrylate and a synthetic resin filler as in Patent Document 6, when trying to mix these, urethane (meth) acrylate has a high viscosity, It is difficult to uniformly disperse the synthetic resin filler, the synthetic resin filler tends to agglomerate, and the appearance of the cured film is impaired due to the occurrence of locally high and low synthetic resin filler concentrations, resulting in a high-class feeling. It had the problem that it was hard to be formed.
Although this problem can be solved by diluting the composition with an organic solvent or the like, a large amount of the organic solvent is required to lower the viscosity, so the drying time for removing the organic solvent becomes longer and the process becomes longer. For this reason, there is a problem that the economical efficiency is deteriorated, the plastic base material which is weak to heating is deformed, and the film thickness is inevitably lowered due to the volatilization of the solvent, and the high-quality feeling of the cured film is impaired.
The inventors of the present invention have an active energy that is easy to produce a composition, and the resulting cured film has excellent soft feel and adhesion, and also has excellent scratch resistance such that it is not scratched by scratching with a nail. In order to find a wire curable composition, intensive studies were conducted.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that an active energy ray-curable composition containing polyether di (meth) acrylate and a fine polymer filler has soft feel, substrate adhesion material, and nail. The scratches are not easily damaged by scratching, and since the amount of the organic solvent to be used is small, the drying time may be short, and the cured film having a high-class feeling can be easily obtained because the film thickness does not decrease. As a result, the present invention has been completed.
Hereinafter, the present invention will be described in detail.

  According to the composition of the present invention, the polyether di (meth) acrylate as the main component has a low viscosity, so that it has excellent dispersibility with the fine polymer filler and good handling properties, and the amount of the organic solvent. Therefore, the drying time may be short, the film thickness does not decrease, and the resulting cured film is excellent in soft feel, adhesion and scratch resistance.

The present invention relates to a compound having an ethylenically unsaturated group (hereinafter referred to as “component (A)”) containing polyether di (meth) acrylate (A1) [hereinafter referred to as “component (A1)”] as an essential component, and glass transition. The present invention relates to an active energy ray-curable composition containing a particulate polymer filler (hereinafter referred to as “component (B)”) having a temperature of −100 ° C. to 30 ° C.
Hereinafter, the essential components (A), (B), other components, usage methods, and the like will be described.

1. (A) component (A) A component is a compound which has an ethylenically unsaturated group, and is a compound which hardens | cures by irradiating an active energy ray. And (A) component contains polyether di (meth) acrylate which is (A1) component as an essential component.
The component (A) contains the component (A1) as an essential component, but if necessary, polyester (meth) acrylate (hereinafter referred to as “component (A2)”) and components (A1) and (A2) Other than the above, a compound having one or more ethylenically unsaturated groups [hereinafter referred to as “component (A3)”] may be contained.

The viscosity of the component (A) is preferably low because, when mixed with the component (B), it is difficult to disperse if there is high viscosity and further stringing or the like.
Specifically, the viscosity of the component (A) is preferably 5 to 5,000 mPa · s, more preferably 10 to 2,000 mPa · s, as the viscosity at room temperature (25 ° C.). By setting the viscosity of the component (A) within a preferable range, the viscosity is several orders of magnitude lower than that of general urethane (meth) acrylate, and the handling is excellent, and the dispersion of the component (B) is facilitated.
The viscosity in the present invention means a value measured with an E-type viscometer at 25 ° C.
Hereinafter, the components (A1), (A2) and (A3) will be described.

1) Component (A1)
The component (A1) is polyether di (meth) acrylate.
The ether structure in the component (A1) is a compound having an alkylene oxide unit. As the alkylene oxide unit, ethylene oxide, propylene oxide and tetramethylene oxide are preferable, and among these, ethylene oxide is more preferable because of excellent curability of the component (A).
The repetition of the alkylene oxide unit in the component (A1) is preferably 3 to 15 and more preferably 4 to 12 because it has a low viscosity and the cured product of the composition has a good soft feel. By setting the number of repeating alkylene oxide units to 3 or more, it is possible to prevent the resulting cured film from becoming too hard and to obtain good soft feel. Further, by setting the number of repetitions to 15 or less, it is possible to achieve excellent scratch resistance against scratching with a nail while maintaining soft feel.

The viscosity of the component (A1) is preferably low because, when mixed with the component (B), it is difficult to disperse if there is a high viscosity and further stringing or the like.
Specifically, the viscosity of the component (A1) is preferably 5 to 100 mPa · s, more preferably 10 to 80 mPa · s. By setting the viscosity of the component (A1) within a preferable range, the viscosity is several orders of magnitude lower than that of a general urethane (meth) acrylate, the handling is excellent, and the dispersion of the component (B) is facilitated.

The component (A) has the component (A1) as an essential component, but the proportion of the component (A1) when the component (A2) or / and the component (A3) is blended is as follows: When the total number of parts is 100 parts by weight, it is preferably 50 to 98 parts by weight, more preferably 60 to 95 parts by weight.
By setting the component (A1) to 50 parts by weight or more, it is possible to impart a good soft feel to the cured film, and by setting it to 98 parts by weight or less, the cured film is prevented from becoming too soft and resistant. It can be excellent in scratch resistance.

2) Component (A2)
The component (A2) is polyester (meth) acrylate.
As the component (A2), a reaction product of a polyhydric alcohol, a divalent carboxylic acid or an anhydride thereof (hereinafter simply referred to as “divalent carboxylic acid (anhydride)”) and (meth) acrylic acid And (A2-1) component ”], and a reaction product of polyester polyol and (meth) acrylic acid (hereinafter referred to as (A2-2) component), with component (A2-1) being preferred.
Hereinafter, the component (A2-1) and the component (A2-2) will be described.

(1) Component (A2-1)
The component (A2-1) is a reaction product of a polyhydric alcohol, a divalent carboxylic acid (anhydride), and (meth) acrylic acid.
Hereinafter, a raw material compound and a manufacturing method are demonstrated.
(A) Polyhydric alcohol As the polyhydric alcohol, various compounds can be used as long as they are dihydric or higher alcohols.
Examples of the divalent alcohol include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 2-methyl-1,3-propanediol, and 1,3-butanediol. Aliphatic diols such as neopentyl glycol, 1,4-butanediol, 1,6-hexanediol; hydrogenated bisphenol A, 1,2-cyclohexane glycol, 1,3-cyclohexane glycol, 1,4-cyclohexane glycol, 1,4-cyclohexanedimethanol, bicyclohexyl-4,4′-diol, alicyclic diols such as 2,6-decalin glycol and 2,7-decalin glycol, etc .; paraxylene glycol Aromatic diols and the like.
Examples of the trivalent or higher alcohol include glycerin, trimethylolpropane, trimethylolethane, tris (2-hydroxyethyl) isocyanurate, pentaerythritol, ditrimethylolpropane, and dipentaerythritol.
As the polyhydric alcohol, an alkylene oxide adduct of these compounds can be used. Preferable specific examples of alkylene oxide include ethylene oxide, propylene oxide, butylene oxide and the like.

  In the present invention, when a polyhydric alcohol having an alkylene oxide is used, the amount of alkylene oxide added per hydroxyl group equivalent of the polyhydric alcohol is preferably 20 mol or less, and the total amount of alkylene oxide added per mol of the polyhydric alcohol. Is preferably 40 mol or less. By setting the added mole number of alkylene oxide to 20 mol or less per equivalent of hydroxyl group of polyhydric alcohol or 40 mol or less per mol of polyhydric alcohol, the viscosity increase of the (meth) acrylate obtained is suppressed, and the cured product It is possible to have excellent water resistance.

  Among the above-mentioned compounds, the polyhydric alcohol is preferably alkylene glycol, dialkylene glycol, trimethylolpropane, pentaerythritol, and tris (2-hydroxyalkyl) isocyanurate.

(B) Divalent carboxylic acid (anhydride)
The divalent carboxylic acid (anhydride) may be an organic acid having two carboxyl groups per molecule or an acid anhydride thereof.
Specific compounds include, for example, succinic acid, and specific compounds include, for example, succinic acid, adipic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydro Examples thereof include phthalic acid, hymic acid and endohetic acid, and anhydrides of these compounds.
As the divalent carboxylic acid (anhydride), divalent carboxylic acid anhydride is preferable, and phthalic acid anhydride, tetrahydrophthalic acid anhydride and hexahydrophthalic acid anhydride are more preferable.

(C) Reaction ratio
The reaction ratio of the polyhydric alcohol, divalent carboxylic acid (anhydride) and (meth) acrylic acid in the component (A2-1) may be appropriately set according to the purpose.
As the component (A2-1), various compounds ranging from a low molecular weight substance to a high molecular weight substance can be used, but it is preferable to use a low molecular weight substance.
In the case of producing a low molecular weight product, it is preferable that the following reaction [1] is satisfied.
1.1 ≦ A / B and 0.5 ≦ C / (TA-2B) [1]
However, the symbol in Formula [1] means the following.
A: Number of moles of polyhydric alcohol, B: Number of moles of divalent carboxylic acid (anhydride), C: Number of moles of (meth) acrylic acid, T: Number of moles of polyhydric alcohol

By setting the molar ratio A / B to 1.1 or more, it is possible to prevent the molecular weight of the reaction product from becoming too large and to obtain a (meth) acrylate having a low viscosity. The upper limit of the molar ratio A / B is preferably 5 or less, whereby the proportion of the reaction product composed of two components of polyhydric alcohol and (meth) acrylic acid can be reduced, and a three-component reactant can be used. Excellent cured product characteristics resulting from a certain (meth) acrylate can be maintained. The molar ratio A / B is more preferably 4 or less.
The molar ratio A / B is preferably 1.1 to 2.2, and more preferably 1.5 to 2.0.
By setting the equivalent ratio C / (TA-2B) to 0.5 or more, the curability obtained from the resulting (meth) acrylate-containing composition can be made excellent. The upper limit of the equivalent ratio C / (TA-2B) is preferably 2 or less, whereby unreacted (meth) acrylic acid can be reduced in the reaction product, which is economical and economical. It is possible to prevent adverse effects on the properties, curing characteristics, physical properties of the resulting cured product, and the like.
The equivalent ratio C / (TA-2B) is preferably 0.9 to 1.5, and more preferably 1.0 to 1.5.

If the ratio of each raw material is reacted under the above condition [1], the component (A2) which is a low-viscosity low-molecular weight substance can be easily obtained, and those having a number average molecular weight of 500 to 3,000 are preferred. .
Furthermore, as the component (A2), a compound having 1 to 50 repetitions of polyhydric alcohol and divalent carboxylic acid (anhydride) is preferable.
The repetition is calculated from each elution time of a peak showing a molecular weight distribution obtained by gel permeation chromatography (hereinafter abbreviated as “GPC”). By assigning the molecular weight corresponding to each elution time converted from the calibration curve by the molecular weight of the constituent components, polyhydric alcohol, divalent carboxylic acid (anhydride) and (meth) acrylic acid added to the terminal, it is repeated. It can be determined by measuring the number.

(D) Manufacturing method There is no restriction | limiting in particular about the order which reacts said each raw material, For example, after making polyhydric alcohol and dihydric carboxylic acid (anhydride) react, (meth) acrylic acid is made to react, or polyvalent There is a two-stage reaction in which an alcohol and (meth) acrylic acid are reacted and then a divalent carboxylic acid (anhydride) is reacted, or a method in which each raw material is reacted in one stage at a time.

  The two-stage reaction is preferable in that the molecular weight distribution is narrow and a low-viscosity (A2) component can be obtained in a high yield. On the other hand, the one-stage reaction has a small number of steps, and the target product can be obtained at low cost. Is preferable. Of the two-stage reactions, since reaction control is easy, a method of reacting a polyhydric alcohol and a divalent carboxylic acid (anhydride) and then reacting with (meth) acrylic acid is most preferable.

In the production of the component (A2-1), the above-described conditions relating to the molar ratio and equivalent ratio of each raw material used in the present invention may be satisfied, and the reaction temperature and reaction time are not particularly limited.
The esterification reaction between the polyhydric alcohol and the divalent carboxylic acid (anhydride) is preferably performed at a temperature of 50 to 300 ° C., particularly preferably 70 to 250 ° C. When (meth) acrylic acid is reacted, In order to suppress the polymerization of (meth) acrylic acid, it is preferably carried out at a temperature slightly lower than that of the esterification reaction, generally at a temperature of about 50 to 130 ° C., particularly preferably about 65 to 110 ° C. . A preferable reaction temperature in the case of the one-stage reaction is a temperature at which (meth) acrylic acid is reacted. The progress of the esterification reaction can be determined by the amount of water distilled from the reaction system. If a predetermined amount of water is distilled, the reaction may be terminated.

An acid catalyst is used in the esterification reaction.
Examples of the acid catalyst include inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid and fluorinated boric acid, organic sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid and trifluoromethanesulfonic acid, and strongly acidic cation ion exchange resins. Is mentioned.
The ratio of the acid catalyst is preferably 0.1 to 20 mol%, particularly preferably 1 to 7 mol%, based on the acid component of the divalent carboxylic acid (anhydride) and / or (meth) acrylic acid. Make it exist.

The esterification reaction is preferably carried out in the presence of a polymerization inhibitor in order to suppress polymerization of the raw material (meth) acrylic acid or the obtained (meth) acrylate.
Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, p-benzoquinone, t-butylcatechol, phenothiazine, N-nitrosodiphenylamine, and a copper salt.
As another effective method for suppressing polymerization, there are a method of reacting in an atmosphere of an oxygen-containing gas or a method of reacting while introducing an oxygen-containing gas into a reaction solution.

In the esterification reaction, it is preferable to use an organic solvent for the purpose of azeotropic dehydration of the generated water.
Preferred organic solvents include, for example, aromatic hydrocarbon compounds such as toluene, benzene and xylene, aliphatic hydrocarbon compounds such as hexane and heptane, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, and chlorine-based compounds such as trichloroethylene and tetrachloroethylene. Examples include hydrocarbon compounds and ketones such as methyl ethyl ketone.
The amount of the organic solvent used is a ratio of 10 to 75% by weight, more preferably 15 to 55% by weight, based on the total amount of polyol, divalent carboxylic acid (anhydride) and (meth) acrylic acid. preferable.

(2) Component (A2-2)
Component (A2-2) is a reaction product of polyester polyol and (meth) acrylic acid.
In component (A2-1), polyhydric alcohol, divalent carboxylic acid (anhydride) and (meth) acrylic acid are reacted simultaneously, whereas component (A2-2) is already manufactured as a raw material. The difference is that a high molecular weight polyester polyol is used.
(A2-2) The component component polyester polyol is produced from a polyhydric alcohol and a polyhydric carboxylic acid or anhydride thereof.
Examples of the polyhydric alcohol include the same compounds as those described above.
The polyvalent carboxylic acid or anhydride thereof is preferably a divalent carboxylic acid (anhydride), and examples thereof include the same compounds as described above.
The component (A2-2) is a compound obtained by the reaction of polyester polyol and (meth) acrylic acid, and can be produced according to the same production method as described above.

(3) Content ratio
The content ratio of the component (A2) is preferably 2 to 50% by weight, more preferably 3 to 40% by weight in 100 parts by weight of the total amount of the component (A).
By setting the content ratio of the component (A2) to 2% by weight or more, the cured film can be excellent in surface hardness and scratch resistance. By setting it as 50 weight part or less, it can prevent that a cured film becomes hard too much and can give a moist feeling.
Component (A2) not only improves the scratch resistance of the cured film by a crosslinking reaction in the curing process, but also has a surface curing rate compared to other acrylic oligomers such as urethane (meth) acrylate and epoxy (meth) acrylate. Since the hardness of the outermost surface of the cured film is slightly lower than the internal hardness, there is an effect of improving the soft feel of the cured film.

3) Component (A3)
The component (A3) is a compound having one or more ethylenically unsaturated groups in one molecule other than the components (A1) and (A2).
As the component (A3), various compounds can be used as long as they are compounds other than the components (A1) and (A2) and have one or more ethylenically unsaturated groups in one molecule.
Specifically, a compound having one ethylenically unsaturated group (hereinafter referred to as “monofunctional unsaturated compound”) and a compound having two or more ethylenically unsaturated groups (hereinafter referred to as “polyfunctional unsaturated group”). Compound ”).

(1) Monofunctional unsaturated compound Examples of the monofunctional unsaturated compound include (meth) acrylate having one (meth) acryloyl group (hereinafter referred to as “monofunctional (meth) acrylate”), and one And (meth) acrylamide compounds having a (meth) acryloyl group (hereinafter referred to as “monofunctional (meth) acrylamide”).

As a specific example of monofunctional (meth) acrylate,
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, lauryl ( Alkyl (meth) acrylates such as (meth) acrylate and stearyl (meth) acrylate;
Cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, etc. A monofunctional (meth) acrylate having an alicyclic group of
Glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, cyclohexanespiro-2- (1,3-dioxolane Monofunctional (meth) acrylates having cyclic ether groups such as -4-yl) methyl (meth) acrylate and 3-ethyl-3-oxetanylmethyl (meth) acrylate;
Aromatic monofunctional (meth) acrylates such as benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, o-phenylphenoxy (meth) acrylate and p-cumylphenolethylene (meth) acrylate;
A monofunctional (meth) acrylate having a maleimide group such as (meth) acryloyloxyethyl hexahydrophthalimide;
(Meth) acryloylmorpholine;
Monofunctional (meth) acrylates having alkoxyalkyl groups such as ethyl carbitol (meth) acrylate and alkyl carbitol (meth) acrylate such as 2-ethylhexyl carbitol (meth) acrylate;
Such as 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane and 3- (meth) acryloxypropylmethyldiethoxysilane and 3- (meth) acryloxypropyltriethoxysilane Examples include alkoxysilyl group-containing monofunctional (meth) acrylates.

Specific examples of monofunctional (meth) acrylamides include N-methyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn-butyl (meth) acrylamide, N-alkyl- (meth) acrylamides such as N-sec-butyl (meth) acrylamide, Nt-butyl (meth) acrylamide, Nn-hexyl (meth) acrylamide; N such as N-hydroxyethyl (meth) acrylamide -Hydroxyalkyl (meth) acrylamide; and N, N-dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meta) ) Acrylamide, N, N-di-n-propi N, N-dialkyl (meth) acrylamide of (meth) acrylamide, N, N-diisopropyl (meth) acrylamide, N, N-di-n-butyl (meth) acrylamide and N, N-dihexyl (meth) acrylamide Can be mentioned.

(2) Polyfunctional unsaturated compound As an example of a polyfunctional unsaturated compound, (meth) acrylate having two (meth) acryloyl groups (hereinafter referred to as “bifunctional (meth) acrylate”), and two or more (Meth) acrylate having a (meth) acryloyl group (hereinafter referred to as “trifunctional or higher (meth) acrylate”) and the like.
Specific examples of the bifunctional (meth) acrylate include di (meth) acrylate of an alkylene oxide adduct of bisphenol A, di (meth) acrylate of an alkylene oxide adduct of bisphenol F, butanediol di (meth) acrylate, Diol di (meth) acrylates such as hexanediol di (meth) acrylate and nonanediol di (meth) acrylate;
Di (meth) acrylates of polyols such as di (meth) acrylate of glycerin, di (meth) acrylate of pentaerythritol, di (meth) acrylate of ditrimethylolpropane, di (meth) acrylate of dipentaerythritol;
Di (meth) acrylates of these polyol alkylene oxide adducts, di (meth) acrylates of isocyanuric acid; and di (meth) acrylates of isocyanuric acid alkylene oxide adducts. In this case, examples of the alkylene oxide in the alkylene oxide adduct include ethylene oxide, propylene oxide, and tetramethylene oxide.
In addition, an epoxy (meth) acrylate having a bisphenol skeleton, a polyether skeleton, or a polyalkylene skeleton can also be used.

Specific examples of tri- or higher functional (meth) acrylates include glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri or tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, and ditrile. Poly (meth) acrylates of polyols such as tri- or tetra (meth) acrylate of methylolpropane, dipentaerythritol tri, tetra, penta or hexapenta (meth) acrylate;
Di (meth) acrylates of these polyol alkylene oxide adducts;
Examples include tris (2- (meth) acryloyloxyethyl) isocyanurate; and tri (meth) acrylates of isocyanuric acid alkylene oxide adducts. In this case, examples of the alkylene oxide in the alkylene oxide adduct include ethylene oxide, propylene oxide, and tetramethylene oxide.
In addition, a polyfunctional epoxy (meth) acrylate having a novolak skeleton may be used.

As the component (A3), a compound having a hydrophilic group is preferred in order to further improve the adhesion to the substrate.
In the case of a compound having a hydroxyl group as a hydrophilic group, a hydroxyl group-containing monofunctional (meth) acrylate and a hydroxyl group-containing (meth) acrylamide are preferred.
Examples of the hydroxyl group-containing monofunctional (meth) acrylate include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate.
Examples of the hydroxyl group-containing (meth) acrylamide include N-hydroxyethyl (meth) acrylamide.
Examples of the compound having an acidic group as a hydrophilic group include carboxyl groups such as (meth) acrylic acid, ω-carboxy-polycaprolactone mono (meth) acrylate and monohydroxyethyl (meth) acrylate phthalate and ( And (meth) acryloyl group-containing compounds and phosphoric acid group-containing (meth) acrylates such as esterified products of phosphoric acid and (meth) acrylic acid.
(A3) As a ratio in case a component is a compound which has an acidic group as a hydrophilic group, 0.0001-20 weight% is preferable in a sclerosing | hardenable component total amount, More preferably, it is 0.001-5 weight%. It is.

As the component (A3), a polyfunctional (meth) acrylate having an alkylene oxide unit is preferable because it can further improve the scratch resistance without impairing the moist feeling.
Examples of the alkylene oxide unit include ethylene oxide, diethylene oxide, triethylene oxide, polyethylene oxide, propylene oxide, dipropylene oxide, tripropylene oxide having a longer repetition, and polypropylene oxide, tetramethylene oxide, poly (tetramethylene oxide) having a longer repetition. ) And the like.
Specific examples of the compound are as described above, and among them, poly (meth) acrylate of a pentaerythritol alkylene oxide adduct, poly (meth) acrylate of a trimethylolpropane alkylene oxide adduct, and dipentaries. Poly (meth) acrylates of lithol alkylene oxide adducts are preferred.

The content ratio of the component (A3) is preferably 0 to 30% by weight, more preferably 2 to 15% by weight, in 100 parts by weight of the total amount of the component (A).
By setting it as this ratio, the adhesiveness to a base material can be improved.

2. Component (B) The component (B) is a fine polymer filler having a glass transition temperature (hereinafter referred to as “Tg”) of −100 ° C. to 30 ° C.
(B) A component can provide a moist feeling to a cured film by mix | blending with a composition. A soft so-called soft cured film can be obtained with only the component (A), but a moist feeling cannot be obtained because of low resistance when touched with a finger. By using the component (B) in combination, a soft and moist feel can be obtained.

In order to obtain an excellent tactile sensation in the cured film, the Tg of the component (B) needs to be −100 ° C. to 30 ° C. Those having a temperature lower than −100 ° C. are difficult to obtain in general, and there is almost no resistance when touched with a finger. On the other hand, when the Tg exceeds 30 ° C., the cured film cannot obtain a sufficient soft feeling, resulting in a hard touch.
In the present invention, Tg means a value measured using a differential scanning calorimeter (DSC) at a heating rate of 10 ° C./min.

As the polymer in the component (B), various materials such as polyurethane, poly (meth) acrylate, polyamide, polyurea, nylon, polystyrene, polyethylene, and polypropylene can be used.
Among these polymers, polyurethane and poly (meth) acrylate are preferable because those having the above Tg range can be easily obtained, and polyurethane is more preferable because the cured film is more moist.

The component (B) is fine particles, and the average particle size thereof is preferably 1 to 15 μm, more preferably 4 to 12 μm. By setting the average particle size to 1 μm or more, the cured film can be prevented from becoming a hard and smooth tactile sensation, and a moist feeling can be imparted to the cured film. On the other hand, by setting the thickness to 15 μm or less, it is possible to prevent the cured film from having a rough feel, or from becoming scratched due to the increase in resistance when scratched by a nail. .
The average particle diameter in the present invention means a value measured by a laser diffraction method at a wavelength of 680 nm.

(B) A commercial item can be used for a component.
In the component (B), as the polyurethane polymer filler, Art Pearl P series, Art Pearl JB series, Art Pearl C series, Art Pearl U series, Art Pearl AK series, Art Pearl CE series, Art manufactured by Negami Kogyo Co., Ltd. Pearl HI series and the like can be mentioned. Among these, C-800, C-600, P-600T, P-800T, JB-600T, JB-800T, AK-800TR, MM-120T, etc. are mentioned.

  As a ratio of (B) component, it is preferable that (B) component is 10-200 weight part with respect to 100 weight part of total parts of (A) component, More preferably, it is 25-100 weight part. (B) By making the ratio of a component 10 parts by weight or more, the cured film can be given a moist feeling, the gloss of the cured film is prevented from becoming too high, and the appearance has a high-class feeling. can do. On the other hand, by setting it to 200 parts by weight or less, it is possible to prevent the surface of the cured film from becoming too rough and to have excellent scratch resistance.

3. Active energy ray-curable composition As a method for producing the composition of the present invention, the components (A) and (B) may be stirred and mixed, and after mixing the component (A) and other components described later, the The method of stirring and mixing after adding the component (B) to the mixture is preferable because the component (B) can be dispersed throughout the composition.
What is necessary is just to set the viscosity of a composition suitably according to the objective, and 100-20,000 mPa * s is preferable.

The composition of the present invention essentially comprises the components (A) and (B), but various components can be blended as necessary.
Preferred other components include a photopolymerization initiator (hereinafter referred to as “component (C)”) and an organic solvent (hereinafter referred to as “component (D)”).
Hereinafter, the components (C) and (D) will be described.

1) Component (C) The composition of the present invention is an active energy ray-curable composition, which is cured by irradiation with active energy rays such as ultraviolet rays, visible rays, and electron beams.
When used as an electron beam curable composition, it can be cured by an electron beam without containing the component (C) (photopolymerization initiator).
It is preferable that the composition of this invention further contains (C) component from a viewpoint of the ease of hardening or cost.
As the component (C) in the present invention, various known photopolymerization initiators can be used.
The component (C) is preferably a radical photopolymerization initiator.

Specific examples of the component (C) include 2,2-dimethoxy-1,2-diphenylethane-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-methyl-1- [4- (methylthio) phenyl] -2-morpholinopro Pan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, diethoxyacetophenone, oligo {2-hydroxy-2-methyl-1- [4- ( 1-methylvinyl) phenyl] propanone} and 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl Acetophenone compounds such as 2-methylpropan-1-one;
Benzophenone compounds such as benzophenone, 4-phenylbenzophenone, 2,4,6-trimethylbenzophenone and 4-benzoyl-4′-methyldiphenylsulfide;
Α-ketoester compounds such as methylbenzoylformate, 2- (2-oxo-2-phenylacetoxyethoxy) ethyl ester of oxyphenylacetic acid and 2- (2-hydroxyethoxy) ethyl ester of oxyphenylacetic acid;
2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide Phosphine oxide compounds such as
Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; titanocene compounds; 1- [4- (4-benzoylphenylsulfanyl) phenyl] -2-methyl-2- (4 An acetophenone / benzophenone hybrid photoinitiator such as -methylphenylsulfinyl) propan-1-one;
Examples include oxime ester photopolymerization initiators such as 2- (O-benzoyloxime) -1- [4- (phenylthio)]-1,2-octanedione; and camphorquinone.

  Among these, acetophenone compounds, benzophenone compounds, and phosphine oxide compounds are preferable, and acetophenone compounds are particularly preferable.

As the component (C), only one type may be used, or two or more types may be used in combination.
The content ratio of the component (C) is preferably 0.01 to 10 parts by weight, more preferably 0.5 to 7 parts by weight with respect to 100 parts by weight of the total amount of the component (A). 1 to 5 parts by weight is particularly preferable. Within the above range, the composition has excellent curability and the resulting cured film has excellent scratch resistance.

2) (D) component The composition of this invention can further contain the organic solvent which is (D) component from a viewpoint of the applicability | paintability and handleability of a composition.
The component (A), which is a curable component of the present invention, has a relatively low viscosity and good handling properties, so that it can often be easily mixed with the component (B) without adding the component (D). It is preferable to further use the component (D) when the component (B) is used in a large number.
Various known organic solvents can be used as the organic solvent in the present invention.
As the component (D), a component that dissolves the component (A) is preferable. When the component (D) is contained, a component that dissolves the component (A) and the component (C) is more preferable.

Specific examples of preferred component (D) include alcohol compounds such as methanol, ethanol, isopropanol and butanol; alkylene glycol monoether compounds such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether; acetone alcohols such as diacetone alcohol; benzene, Aromatic compounds such as toluene and xylene; ester compounds such as propylene glycol monomethyl ether acetate, ethyl acetate and butyl acetate; ketone compounds such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ether compounds such as dibutyl ether; and N-methylpyrrolidone Is mentioned.
Among these, alkylene glycol monoether compounds and ketone compounds are preferable, and alkylene glycol monoether compounds are more preferable.

As the component (D), only one type may be used, or two or more types may be used in combination.
The content ratio of the component (D) is preferably 10 to 1,000 parts by weight, more preferably 50 to 500 parts by weight, with respect to 100 parts by weight of the total amount of the component (A). More preferably, it is 300 parts by weight. Within the above range, the composition can have a viscosity suitable for coating, and the composition can be easily applied by a known application method described later.

3) Other components The composition of the present invention may further contain other components other than the components (C) and (D) described above.
As other components, known additives can be used. For example, ultraviolet absorbers, light stabilizers, acidic substances, inorganic particles, antioxidants, silane coupling agents, surface modifiers, polymers, acids Examples include generators, pigments, dyes, tackifiers, polymerization inhibitors, and the like.
Other components described later may be used alone or in combination of two or more.

<Ultraviolet absorber>
Specific examples of the ultraviolet absorber include 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl)- 1,3,5-triazine, 2- [4-[(2-hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2- [4-[(2-hydroxy-3- (2-ethylhexyloxy) propyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-butyroxyphenyl) -6- (2,4-bisbutyroxyphenyl) -1,3,5-triazine, 2- ( 2-hydroxy-4- 1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine and other triazine ultraviolet absorbers; 2- (2H-benzotriazol-2-yl)- 4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, 2- [2-hydroxy-5- (2- ( Benzotriazole ultraviolet absorbers such as (meth) acryloyloxyethyl) phenyl] -2H-benzotriazole; benzophenone ultraviolet absorbers such as 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone, ethyl-2-cyano -3,3-diphenyl acrylate, octyl-2-cyano-3,3-diphenyl Cyanoacrylate ultraviolet absorbers such as acrylate, titanium oxide particles, zinc oxide particles, and inorganic particles, and the like to absorb the ultraviolet rays or the like tin oxide particles.

Among the compounds, benzotriazole ultraviolet absorbers are particularly preferable.
The content of the ultraviolet absorber is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the total amount of the component (A). More preferably, it is 1-2 parts by weight.

<Light stabilizer>
As the light stabilizer, a known light stabilizer can be used. Among them, a hindered amine light stabilizer (HALS) is preferably exemplified.
Specific examples of the hindered amine light stabilizer include bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate and methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate. 2,4-bis [N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) amino] -6- (2-hydroxyethylamine) -1,3 , 5-triazine, decanedioic acid bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester, and the like.
Examples of commercially available hindered amine light stabilizers include BASIN, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, and TINUVIN 5100.

  The content of the ultraviolet absorber is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 2 parts by weight with respect to 100 parts by weight of the total amount of the component (A). More preferably, it is 1-1 weight part.

<Acid substance>
Although the composition of this invention is excellent in the adhesive material to base materials, such as a plastics, adhesiveness can be improved further by adding an acidic substance.
Examples of the acidic substance include a photoacid generator that generates an acid upon irradiation with active energy rays, sulfuric acid, nitric acid, hydrochloric acid, p-toluenesulfonic acid, methanesulfonic acid, phosphoric acid, and the like.
Among these, an inorganic acid or an organic acid is preferable, an organic sulfonic acid compound is more preferable, an aromatic sulfonic acid compound is further preferable, and p-toluenesulfonic acid is particularly preferable.
The content ratio of the acidic substance is preferably 0.0001 to 5 parts by weight, more preferably 0.0001 to 1 part by weight with respect to 100 parts by weight of the total amount of the component (A). More preferably, the amount is 0005 to 0.5 parts by weight. Within the above range, the adhesion to the substrate is excellent, and problems such as corrosion of the substrate and decomposition of other components can be prevented.

<Antioxidant>
The composition of the present invention may further contain an antioxidant for the purpose of improving the heat resistance and weather resistance of the cured film.
Examples of the antioxidant used in the present invention include phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants.
As a phenolic antioxidant, hindered phenols, such as di-t-butylhydroxytoluene, can be mentioned preferably, for example. As what is marketed, Ade-20 Co., Ltd. AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, AO-80 etc. are mentioned.
Preferable examples of the phosphorus antioxidant include phosphines such as trialkylphosphine and triarylphosphine, trialkyl phosphite, triaryl phosphite, and the like. Examples of commercially available products of these derivatives include Adeka Co., Ltd., ADK STAB PEP-4C, PEP-8, PEP-24G, PEP-36, HP-10, 260, 522A, 329K, 1178, 1500, 135A, 3010. Etc.
Examples of sulfur-based antioxidants include thioether compounds, and examples of commercially available products include AO-23, AO-412S, and AO-503A manufactured by Adeka Corporation.

  The content ratio of the antioxidant is preferably 0.01 to 5 parts by weight, and more preferably 0.1 to 1 part by weight with respect to 100 parts by weight of the total amount of the component (A). In the above embodiment, the composition is excellent in stability, and curability and adhesive strength are good.

<Silane coupling agent>
The composition of the present invention may further contain a silane coupling agent for the purpose of improving the adhesion to the substrate.
The silane coupling agent used in the present invention is not particularly limited, and a known silane coupling agent can be used.
Preferable specific examples of the silane coupling agent include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycol. Sidoxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl)- 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, N-phenyl-3- Aminopropyltrimethoxysilane, 3-mercaptopropyl Chill dimethoxysilane, 3-mercaptopropyl trimethoxy silane and the like.
Moreover, the compound which has the ethylenically unsaturated group and alkoxysilyl group which were mentioned above can also be used.

  The content ratio of the silane coupling agent is preferably 0.1 to 10 parts by weight, and more preferably 1 to 5 parts by weight with respect to 100 parts by weight of the total amount of the component (A). It is excellent in adhesiveness with a base material as it is the said range.

<Surface modifier>
In the composition of the present invention, a surface modifier may be added for the purpose of increasing the leveling property at the time of coating, the purpose of increasing the slipping property of the cured film and improving the scratch resistance, and the like.
Examples of the surface modifier include a surface conditioner, a surfactant, a leveling agent, an antifoaming agent, a slipperiness imparting agent, and an antifouling imparting agent, and these known surface modifiers can be used. .
Of these, silicone-based surface modifiers and fluorine-based surface modifiers are preferred. Specific examples include silicone polymers and oligomers having a silicone chain and a polyalkylene oxide chain, silicone polymers and oligomers having a silicone chain and a polyester chain, and fluorine polymers having a perfluoroalkyl group and a polyalkylene oxide chain. And a fluorine-based polymer and an oligomer having a perfluoroalkyl ether chain and a polyalkylene oxide chain.
In addition, for the purpose of increasing the slidability, a surface modifier having an ethylenically unsaturated group, preferably a (meth) acryloyl group, in the molecule may be used.

  It is preferable that the content rate of a surface modifier is 0.01-1.0 weight part with respect to 100 weight part of total amounts of (A) component. It is excellent in the surface smoothness of a coating film as it is the said range.

<Polymer>
The composition of the present invention may further contain a polymer other than the component (B) for the purpose of further improving the curl resistance of the resulting cured film.
Suitable polymers include (meth) acrylic polymers, and suitable constituent monomers include methyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid, glycidyl (meth) acrylate, N- ( 2- (meth) acryloxyethyl) tetrahydrophthalimide and the like. In the case of a polymer copolymerized with (meth) acrylic acid, glycidyl (meth) acrylate may be added to introduce a (meth) acryloyl group into the polymer chain.
It is preferable that the content rate of a polymer is 0.01-10 weight part with respect to 100 weight part of total amounts of (A) component. It is excellent in the curl resistance of the cured film obtained as it is the said range.

4). Method of Use As a method of using the composition of the present invention, a conventional method may be followed.
For example, after apply | coating a composition to the base material applied by a normal coating method, the method of irradiating an active energy ray and hardening is mentioned. The active energy ray irradiation method may be a general method known as a conventional curing method.
Also, a method of improving the adhesion to the substrate by using the component (D) (photopolymerization initiator) in combination with the composition, irradiating it with active energy rays, and then heat-curing it can be employed. .

The substrate to which the composition of the present invention can be applied is applicable to various materials, and examples thereof include plastic, wood, metal, inorganic material, and paper.
Specific examples of plastics include polyolefins such as polyethylene and polypropylene, ABS resins, cellulose acetate resins such as polyvinyl alcohol, triacetyl cellulose and diacetyl cellulose, acrylic resins, polyethylene terephthalate, polycarbonate, polyarylate, polyethersulfone, norbornene, etc. And cyclic polyolefin resin having a cyclic olefin as a monomer, polyvinyl chloride, epoxy resin and polyurethane resin.
Examples of the wood include natural wood and synthetic wood.
Examples of the metal include steel plates, metals such as aluminum and chromium, and metal oxides such as zinc oxide (ZnO) and indium tin oxide (ITO).
Examples of inorganic materials include glass, mortar, concrete, and stone.
Among these, a plastic substrate is particularly preferable.

  The method of applying the composition of the present invention to the substrate may be appropriately set according to the purpose, and is a bar coater, applicator, doctor blade, dip coater, roll coater, spin coater, flow coater, knife coater, comma. Examples of the coating method include a coater, a reverse roll coater, a die coater, a lip coater, a spray coater, a gravure coater, and a micro gravure coater.

  What is necessary is just to set the film thickness of the composition cured film with respect to a base material suitably according to the objective. The thickness of the cured film may be selected according to the use of the base material to be used or the base material having the manufactured cured film, but is preferably 1 to 100 μm, more preferably 5 to 40 μm. .

When the composition contains the component (D) (organic solvent), it is preferable to heat and dry the organic solvent after coating on the substrate.
The drying temperature is not particularly limited as long as the applied substrate is at a temperature that does not cause a problem such as deformation. A preferable heating temperature is 40 to 100 ° C. What is necessary is just to set drying time suitably with the base material to apply and heating temperature, Preferably it is 0.5 to 3 minutes.

Examples of the active energy rays for curing the composition of the present invention include electron beams, ultraviolet rays and visible rays, but ultraviolet rays or visible rays are preferable, and ultraviolet rays are particularly preferable. Examples of the ultraviolet irradiation device include a high pressure mercury lamp, a metal halide lamp, an ultraviolet (UV) electrodeless lamp, and a light emitting diode (LED).
The irradiation energy should be appropriately set according to the type and composition of the active energy ray. As an example, when a high-pressure mercury lamp is used, the irradiation energy in the UV-A region is 100 to 5,000 mJ / cm ² is preferable, and 200 to 2,000 mJ / cm ² is more preferable.

5. Applications The composition of the present invention can be used for various applications and can be preferably used as a coating agent.
Specific examples of the coating agent include plastic hard coats, wood paints, top coat paints such as mortar and slate, and waterproof paints for printed circuit boards constituting electronic circuits.
Specific usage forms of the coating agent include cosmetic containers such as lipstick containers, coating of mobile phone bodies, coating of automobile interior members, and the like.
The cured film of the composition of the present invention is preferably used as a coating agent for cosmetic containers, mobile phones and the like because it has excellent soft feel and can be used in applications where design and aesthetics are required.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In addition, this invention is not limited by these Examples.
In the following, unless otherwise specified, “part” means part by weight and “%” means percent by weight.

1. Production example
1) Production Example 1 [Production of component (A2)]
In a 3 L side-tube four-necked flask equipped with a reflux tube, 164 parts of hexahydrophthalic anhydride, 235 parts of trimethylolpropane, 250 parts of acrylic acid, 20 parts of p-toluenesulfonic acid, 0.2 part of 4-methoxyphenol, 780 g of toluene was charged, and the mixture was heated and stirred at a reaction liquid temperature of 82 to 97 ° C. while oxygen-containing gas (oxygen 5 vol%, nitrogen 95 vol%) was blown into the flask. With the progress of the reaction, the dehydrated esterification reaction was carried out for 5 hours while taking out the generated water out of the system with a Dean-Stark tube.
After completion of the reaction, 1000 g of toluene was added for dilution. After adding 600 g of 20% aqueous sodium hydroxide solution with stirring, the mixture was sufficiently stirred and allowed to stand, and then the lower phase was removed. Next, under stirring, 250 g of distilled water was added to the organic phase and stirred, and after standing, the lower layer was removed. The upper organic phase was heated under reduced pressure to distill off toluene.
The obtained acrylate was 630 g (yield 96%), and the viscosity was 35000 mPa · s (50 ° C.). Hereinafter, it is referred to as “PEA1”.
Using PEA1, each elution time of a peak showing the molecular weight distribution obtained by using GPC (column: Styragel HR 4ETHF and Styragel HR 1THF, eluent: THF, manufactured by Waters) was measured.
As a result of calculating the number of repetitions by assigning the molecular weight corresponding to each elution time converted from the calibration curve by the molecular weight of the constituent components trimethylolpropane, hexahydrophthalic anhydride and acrylic acid added to the terminal, 1 to It was a mixture of 48 repeats.

2. Examples 1 to 5 and Comparative Examples 1 to 4 (Preparation of compositions)
About (A) component shown to postscript Table 1 and Table 2, the viscosity in 25 degreeC was measured with the E-type viscosity meter. The results are shown in Tables 1 and 2.
Regarding each component shown in Table 1 and Table 2 below, the components other than the component (B) are stirred and mixed at room temperature, and then the component (B) is further added and mixed to further the active energy ray-curable composition. I got a thing.
In Comparative Example 2, 50 parts of the component (D) (organic solvent) was blended in the same manner as in the example, and then the component (B) was mixed. However, the viscosity was high and the component (B) was agglomerated. ) 100 parts of the component had to be blended.
About the obtained composition, the viscosity in 25 degreeC was measured. The results are shown in Tables 1 and 2.

3. Evaluation Method Using a doctor blade, the obtained composition was applied to acrylic resin plate Acrylite L # 001 manufactured by Mitsubishi Rayon Co., Ltd. so that the film thickness after drying would be 20 μm, and 3 times with a 90 ° C. dryer. Dried for minutes.
In the case of the composition of Comparative Example 2, since the drying was insufficient, the composition was dried for a total of 5 minutes.
After drying, ultraviolet rays were irradiated at a UV-A illuminance of 80 W / cm and an irradiation energy of 800 mJ / cm ² using a high-pressure mercury lamp equipped with a conveyor (H06-L 41 manufactured by Eye Graphics Co., Ltd.).
The obtained cured film was used and evaluated according to the following method. The results are shown in Table 3.

1) Finger touch (soft feel)
About the obtained cured film, the touch when the surface of the coating film was rubbed with a finger was evaluated and judged according to the following three levels.
(Double-circle): There exists moderate resistance and elasticity on the coating-film surface, and a moist soft feeling is felt.
○: Slightly smooth with little resistance on the surface of the coating film, and a sufficient soft feeling is felt.
X: A soft feeling is not felt at all.

2) Adhesiveness The obtained cured film was cut with 1 mm vertical and horizontal intervals with a cutter knife to form 100 squares of 1 mm × 1 mm size, and Nichiban Co., Ltd. # 405 made by Nichiban Co., Ltd. After cellophane tape was applied, it was peeled off strongly. The following three levels were evaluated based on the number of remaining films after peeling.
◎: Number of remaining film cells is 90 or more, ○: Number of remaining film cells is 80 to 89, ×: Number of remaining film cells is 79 or less

3) Scratch resistance With respect to the obtained cured film, the surface of the cured film after rubbing with a nail was visually observed to confirm the presence or absence of scratches or dents, and evaluated according to the following three levels.
○: No scratch or dent, △: No scratch, but a slight dent remains in the coating film, ×: Clearly scratch

4) Workability Since the viscosity of the composition of the present invention increases significantly when component (B) is blended, the lower viscosity of component (A) is easier to handle, and no organic solvent is required when mixing component (B). Even if an organic solvent is added, the number of added parts can be reduced.
When the viscosity of the component (A) is 10,000 mPa · s or less at room temperature, the one having a workability of 10,000 mPa · s was determined to be workability x.

Abbreviations in Table 1 and Table 2 mean the following. The brackets in Tables 1 and 2 mean the number of parts of each component.
◆ (A1) component M-245: Polyethylene glycol diacrylate (repeating number of ethylene glycol: 9), Aronix M-245 manufactured by Toagosei Co., Ltd., viscosity (25 ° C.): 54 mPa · s
M-270: Polypropylene glycol diacrylate (repetition number of propylene glycol: 12), Aronix M-270 manufactured by Toagosei Co., Ltd., viscosity (25 ° C.): 71 mPa · s
M-240: polyethylene glycol diacrylate (ethylene glycol repeat number: 4), Aronix M-240 manufactured by Toagosei Co., Ltd., viscosity (25 ° C.): 19 mPa · s
◆ (A3) component EO-PETA: Pentaerythritol ethylene oxide modified (added mole number of ethylene oxide: 4) tetraacrylate, MT-3533 manufactured by Toagosei Co., Ltd.
M-1200: Polyester urethane acrylate, Aronix M-1200 manufactured by Toagosei Co., Ltd.
◆ (B) component · JB-800T: Polyurethane beads, JB-800T manufactured by Negami Kogyo Co., Ltd. (Tg: -52 ° C, average particle size: 6 µm)
C-600: Polyurethane beads, C-600 manufactured by Negami Kogyo Co., Ltd. (Tg: −13 ° C., average particle size: 10 μm)
◆ Component (B ′) SE-006T: Polymethylmethacrylate-based crosslinked beads, SE-006T manufactured by Negami Kogyo Co., Ltd. (Tg:> 100 ° C., average particle size: 6 μm)
SE-1: Silica beads, Excelica SE-1 manufactured by Tokuyama Corporation (average particle diameter: 1 μm)
◆ (C) component · HCPK: 1-hydroxycyclohexyl phenyl ketone, IRGACURE184 manufactured by BASF
TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide, DAROCURPO manufactured by BASF
◆ Other components・ CER929: Micronized wax additive CERAFLOUR 929 made by BYK

4). Evaluation Results As is clear from the results of Examples 1 to 5, the composition of the present invention is excellent in all of the soft feel of the cured film, adhesion to the substrate, scratch resistance and workability. there were.
On the other hand, since the composition of Comparative Example 1 did not contain the component (A1), the soft film of the cured film was insufficient and the adhesion was not obtained. The composition of Comparative Example 2 uses a polymer filler having a Tg much higher than the upper limit of 30 ° C. of the present invention instead of the component (B). Although the composition of Comparative Example 2 is excellent in workability, the cured film does not have soft feel, and the polymer filler is hard, so that the resistance feeling when scratched with a nail is large, so that the cured film is scratch resistant. The nature has greatly deteriorated. The composition of Comparative Example 3 does not contain (A1), and the main component is urethane acrylate. The composition of Comparative Example 3 can impart soft feel, adhesion, and scratch resistance, and sufficient performance as a cured film can be obtained, but the viscosity of the curable component becomes too high, so that it is described above. If the amount of the component (D) (organic solvent) is not blended twice as much as in the examples, the component (B) cannot be dispersed, and the workability is poor because drying takes time. The composition of Comparative Example 4 uses an inorganic filler instead of the component (B). Although the composition of Comparative Example 4 is excellent in workability, the cured film does not have soft feel due to the use of hard inorganic particles, and furthermore, the surface becomes rough and the surface is rubbed with a nail. Resistance was high and scratch resistance was poor.

  The active energy ray rigid composition of the present invention can be suitably used as a coating agent, and the resulting cured film has excellent soft feel, adhesion, and scratch resistance, and is a cosmetic container, smartphone, tablet terminal. It can be preferably used as a coating material for casings and the like.

Claims (12)

Activity containing a compound (A) having an ethylenically unsaturated group containing polyether di (meth) acrylate (A1) as an essential component and a fine polymer filler (B) having a glass transition temperature of −100 ° C. to 30 ° C. Energy ray curable composition. 2. The curable composition according to claim 1, wherein the component (A1) is a compound containing any one of ethylene oxide, propylene oxide, and tetramethylene oxide as an alkylene oxide unit, wherein the number of repeating alkylene oxide units is 3 to 15. 3. object. The active energy ray-curable composition according to claim 1 or 2, wherein the component (B) has an average particle size of 1 to 15 µm. The active energy ray-curable composition according to any one of claims 1 to 3, wherein the polymer of the component (B) is polyurethane. The active energy ray-curable resin composition according to any one of claims 1 to 4, wherein the component (A) further contains a polyester (meth) acrylate (A2). The activity according to any one of claims 1 to 5, wherein the component (A2) is a reaction product of a polyhydric alcohol, a divalent carboxylic acid or anhydride thereof, and (meth) acrylic acid. Energy ray curable resin composition. The component (A) further contains a compound (A3) having one or more ethylenically unsaturated groups in one molecule other than the components (A1) and (A2). The active energy ray-curable composition according to Item. The active energy ray hardening-type composition of any one of Claims 1-7 which contain (B) component in the ratio of 10-200 weight part with respect to a total of 100 weight part of (A) component. Furthermore, the active energy ray hardening-type resin composition of any one of Claims 1-8 containing a photoinitiator (C). Furthermore, the active energy ray hardening-type composition of any one of Claims 1-9 containing an organic solvent (D). The active energy ray hardening-type coating agent composition which consists of a composition of any one of Claims 1-10. The active energy ray hardening-type coating agent composition for plastics which consists of a composition of any one of Claims 1-10.