JP2016172835A - Silica dispersion, and active energy ray-curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silica dispersion having excellent storage stability, and an active energy ray-curable resin composition having excellent hardness, stain resistance, adhesive tape peelability, and weather resistance.SOLUTION: A silica dispersion has a silica particle (A), a dispersant (B), and a liquid medium (C), where the dispersant (B) is an acrylic resin having a polysiloxane structure, a structure represented by the formula, and an unsaturated double bond, with a double bond equivalent of 100-3000 (Ris a C1-10 hydrocarbon group; a part of C is optionally substituted by N; * is a bond).SELECTED DRAWING: None

Description

  The present invention relates to a dispersion exhibiting excellent dispersion stability in which silica (A) is dispersed in a dispersant (B), and containing the dispersion is excellent in stain resistance and adhesive tape peelability. The present invention relates to a curable resin composition.

  In general, surface coating agents for building materials, packages, optical products, etc. are blended with silica particles in the coating agent in the sense of giving a sense of design and optical properties. On the other hand, since these coating agents become the outermost surface as a final product, a silicone resin is often added to give performances such as stain resistance and adhesive tape peelability. However, when the silica particles and the silicone resin are used together as they are, the silica particles are hydrophilic, while the silicone resin and other active energy ray-curable monomers are oleophilic, so that the familiarity is poor. Therefore, the intended stain resistance and adhesive tape peelability are less likely to be exhibited, and the performance is inferior compared to a coating agent not containing silica particles. In order to make up for this, measures such as blending a large amount of silicone resin compared with the unblended product of silica have been taken, but this is disadvantageous in terms of cost.

  On the other hand, until now, attempts have been made to impart the curability of a cured product derived from silica by adding a reactive dispersant to the silica, but the curability derived from the curable silica and the antifouling derived from the silicone. Dispersants with compatible properties have not been developed.

  In addition, in the case of silica-unblended products, when an electron beam or UV curable resin is used as the main binder, the silicone is completely oriented on the surface compared to the case where a thermoplastic resin is used as the main binder due to its immediate curing. It has a drawback that it is cured before being used and the performance such as contamination resistance and adhesive tape peelability is poor.

JP 2001-225420 A JP 2007-015232 A JP 2007-016139 A JP 2008-247016 A JP 2011-201938 A

  In the present invention, in view of the above background art, an object is to provide a silica dispersion excellent in storage stability, and an active energy ray-curable resin composition excellent in hardness, stain resistance, adhesive tape peelability, and weather resistance. And

（式中、Ｒ¹は炭素原子数１〜１０の炭化水素基であり、炭素原子の一部が窒素原子に置換されていても良い。[＊]は結合手であることを示す。） The present invention contains silica particles (A), a dispersant (B), and a liquid medium (C), and the dispersant (B) has a polysiloxane structure, a structure represented by the general formula (1), and It is related with the silica dispersion characterized by being an acrylic resin which has a saturated double bond and a double bond equivalent is 100-3000.
General formula (1)

(In the formula, R ¹ is a hydrocarbon group having 1 to 10 carbon atoms, and a part of the carbon atoms may be substituted with a nitrogen atom. [*] Indicates a bond.)

（式中、Ｒ²は炭素数１〜１０の炭化水素基であり、炭素原子の一部が窒素原子に置換されていても良い。Ｌ¹は、炭素数１〜２０の置換または無置換の直鎖、分岐、または脂環式のアルキレン基、−（Ｃ＝Ｏ）−、−（Ｃ＝Ｏ）−Ｏ−Ｘ−、または−（Ｃ＝Ｏ）−ＮＨ−Ｘ−であり、Ｘは炭素数１〜２０の置換または無置換の直鎖、分岐、または脂環式のアルキレン基であり、Ｌ²は、メルカプト基、または−ＣＨ＝ＣＨ₂、または−Ｃ（ＣＨ₃）＝ＣＨ₂である。 In the present invention, the dispersant (B) is a polymerized (meth) acrylate (a) having an epoxy group, polysiloxane mono (meth) acrylate (b), and a compound represented by the general formula (2). The silica dispersion obtained by reacting an α, β-unsaturated carboxylic acid with the copolymer.
General formula (2)

(In the formula, R ² is a hydrocarbon group having 1 to 10 carbon atoms, and part of the carbon atoms may be substituted with a nitrogen atom. L ¹ is a substituted or unsubstituted group having 1 to 20 carbon atoms. A linear, branched, or alicyclic alkylene group, — (C═O) —, — (C═O) —O—X—, or — (C═O) —NH—X—, wherein X is A substituted or unsubstituted linear, branched, or alicyclic alkylene group having 1 to 20 carbon atoms, and L ² is a mercapto group, —CH═CH ₂ , or —C (CH ₃ ) ═CH _2. It is.

（式中、Ｒ³は水素原子、または、メチル基であり、Ｒ⁴〜Ｒ⁸はそれぞれ独立に、炭素数１〜４のアルキル基であり、Ｌ³は、炭素数１〜２０の、置換または無置換の直鎖、分岐または脂環式のアルキレン基、または置換または無置換のアリーレン基が挙げられ、ｎは１０〜２００の整数である。） The present invention also relates to the silica dispersion, wherein the polysiloxane mono (meth) acrylate (b) is a polysiloxane mono (meth) acrylate represented by the general formula (1).
General formula (3)

(Wherein R ³ is a hydrogen atom or a methyl group, R ^{4 to} R ⁸ are each independently an alkyl group having 1 to 4 carbon atoms, and L ³ is a substituted group having 1 to 20 carbon atoms. Or an unsubstituted linear, branched or alicyclic alkylene group, or a substituted or unsubstituted arylene group, and n is an integer of 10 to 200.)

The present invention also relates to the silica dispersion, wherein the silica dispersion has a structure represented by the general formula (1) in one end region of the dispersant (B).

  Moreover, this invention relates to the said silica dispersion whose weight average molecular weights of a dispersing agent (B) are 5,000-100,000.

  The present invention also relates to an active energy ray-curable resin composition comprising the silica dispersion and an active energy ray-curable compound.

  Moreover, this invention relates to the decorating sheet | seat using the said active energy ray curable resin composition.

  According to the present invention, by using the dispersant (B) with respect to the silica particles (A), the silica dispersion imparted with storage stability, and the stain resistance, the adhesive tape peelability using the silica dispersion, An active energy ray-curable resin composition having excellent weather resistance can be provided.

First, each component of the present invention will be described.
The silica dispersion of the present invention contains silica particles (A) and a dispersant (B), and the dispersant (B) having the structure of the general formula (1) can be adsorbed on the surface of the silica, and is stable in storage. Can be realized.

<Silica particles (A)>
As a silica particle, the silica particle powder manufactured by the well-known method and marketed can be used. Or the colloidal silica of the state disperse | distributed with the solvent or water which can be used for the dispersion of this invention, an active energy ray curable composition, can be used.

  As a dispersion medium of colloidal silica, water, alcohols such as methanol, ethanol, isopropanol and n-butanol, polyhydric alcohols such as ethylene glycol and derivatives thereof, ketones such as methyl ethyl ketone, methyl isobutyl ketone and dimethylacetamide, Esters such as ethyl acetate and nonpolar solvents such as toluene and xylene can be used.

Silica particles include those having adsorbed organic or inorganic substances such as silane coupling agent, microcrystalline, and alumina on the surface, and untreated particles that do not have these components. The silica particles (A) are not particularly limited as long as the dispersant (B) can be adsorbed, but those having silanol groups capable of adsorbing the hydroxyl groups of the dispersant on the surface of the silica particles are preferable. For example, the untreated silica described above Particles. Untreated silica is preferable from the viewpoint of cost. Further, the untreated silica surface has a structure having pores, and the dispersant (B) enters the pores and is easily adsorbed, which is preferable.
The particle diameter of the silica particles is preferably 1 to 20 μm, but is not particularly limited because it is appropriately selected depending on the film thickness and gloss. Similarly, the shape is not particularly limited.

  Examples of the untreated silica particles (A) include nip gel BY200 (Tosoh Silica Co., Ltd.).

  In the present invention, the addition amount of silica particles is 1 to 20% by weight in the active energy ray-curable resin composition. If the silica particles are less than 1% by weight, satisfactory design feeling and optical properties cannot be obtained. If the silica particles are more than 20% by weight, the fluidity of the active energy ray-curable resin composition is lowered and the coating suitability is deteriorated. .

<Dispersant (B)>
In the present application, when “(meth) acryloyl”, “(meth) acryl”, “(meth) acrylic acid”, “(meth) acrylate”, and “(meth) acryloyloxy” are particularly expressed, Unless otherwise stated, “acryloyl and / or methacryloyl”, “acrylic and / or methacrylic”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, and “acryloyloxy and / or methacryloyloxy”, respectively. ".

  The dispersant (B) is an acrylic resin having a polysiloxane structure, a structure of the following general formula (1), an unsaturated double bond, and a double bond equivalent of 100 to 3000.

（式中、Ｒ¹は炭素原子数１〜１０の炭化水素基であり、炭素原子の一部が窒素原子に置換されていても良い。[＊]は結合手であることを示す。） General formula (1)

(In the formula, R ¹ is a hydrocarbon group having 1 to 10 carbon atoms, and a part of the carbon atoms may be substituted with a nitrogen atom. [*] Indicates a bond.)

Examples of the hydrocarbon group having 1 to 10 carbon atoms of R ¹ in the general formula (1) include a trivalent hydrocarbon group in which one hydrogen atom is further removed from an alkylene group, an alkenylene group, or an arylene group. Examples of the alkylene group include an ethylene group, a normal butylene group, an isobutylene group, a propylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a 2-ethylhexylene group, and a nonylene group.

In the above general formula (1), R ¹ is preferably a hydrocarbon group having 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms, and more preferably 2 to 5 carbon atoms. The hydroxyl groups may be bonded to the same carbon atom or may be bonded to different carbon atoms.

  The dispersant (B) includes the structure of the general formula (1), and the general formula (1) is a substituted or unsubstituted linear, branched, or alicyclic alkylene group having 1 to 20 carbon atoms,-( C═O) —, — (C═O) —O—X—, or — (C═O) —NH—X—, wherein X is a substituted or unsubstituted straight chain, branched chain having 1 to 20 carbon atoms, or It is preferably bonded to the polymer main chain of the dispersant (B) by an alicyclic alkylene group. More preferably, an alkylene group having 1 to 3 carbon atoms, — (C═O) —, — (C═O) —O—X—, or — (C═O) —NH—X— (where X is the number of carbon atoms). 1-3 alkylene groups).

  The dispersant (B) can impart antifouling properties to the surface of the coating film when the active energy ray-curable resin composition is formed by adding a polysiloxane group. Moreover, the structure of General formula (1) can coat | cover the silica vicinity because it interacts with the silanol group of the silica surface. Furthermore, a dispersing agent (B) shows curability with respect to an active energy ray. Thereby, an active energy ray-curable resin composition can be obtained by further adding an active energy ray-curable compound to the silica dispersion.

  The method for introducing an unsaturated double bond is not particularly limited, and a method in which a carboxyl group of an α, β-unsaturated carboxylic acid is reacted with an epoxy group in a copolymer using a (meth) acrylate having an epoxy group, And the reverse method, or a method of reacting a (meth) acrylate having a hydroxyl group with a (meth) acrylate having an isocyanato group. A method using (meth) acrylate having an epoxy group and an α, β-unsaturated carboxylic acid is preferred.

  Examples of the dispersant (B) include an epoxy group-containing (meth) acrylate (a), a polysiloxane mono (meth) acrylate (b), and a compound having the structure of the general formula (2) and other compounds as necessary. It can be obtained by reacting an α, β-unsaturated carboxylic acid with a copolymer obtained by polymerizing the polymerizable monomer.

（式中、Ｒ²は炭素数１〜１０の炭化水素基であり、炭素原子の一部が窒素原子に置換されていても良い。Ｌ¹は、炭素数１〜２０の置換または無置換の直鎖、分岐、または脂環式のアルキレン基、−（Ｃ＝Ｏ）−、−（Ｃ＝Ｏ）−Ｏ−Ｘ−、または−（Ｃ＝Ｏ）−ＮＨ−Ｘ−であり、Ｘは炭素数１〜２０の置換または無置換の直鎖、分岐、または脂環式のアルキレン基であり、Ｌ²は、メルカプト基、または−ＣＨ＝ＣＨ₂、または−Ｃ（ＣＨ₃）＝ＣＨ₂である。） General formula (2)

(In the formula, R ² is a hydrocarbon group having 1 to 10 carbon atoms, and part of the carbon atoms may be substituted with a nitrogen atom. L ¹ is a substituted or unsubstituted group having 1 to 20 carbon atoms. A linear, branched, or alicyclic alkylene group, — (C═O) —, — (C═O) —O—X—, or — (C═O) —NH—X—, wherein X is A substituted or unsubstituted linear, branched, or alicyclic alkylene group having 1 to 20 carbon atoms, and L ² is a mercapto group, —CH═CH ₂ , or —C (CH ₃ ) ═CH _2. .)

In this specification, the compound represented by the general formula (2) is polymerized when the compound represented by the general formula (2) constitutes a part of the polymer as a chain transfer agent (L ² is a mercapto group). Including the above).

The hydrocarbon group having 1 to 10 carbon atoms of R ² in the general formula (2) has the same meaning as the hydrocarbon group having 1 to 10 carbon atoms of R ¹ in the general formula (1).

The substituted or unsubstituted linear, branched, or alicyclic alkylene group having 1 to 20 carbon atoms of L ¹ in the general formula (2) includes a methylene group, an ethylene group, a propylene group, a butylene group, and a trimethylene group. , Tetramethylene group, hexamethylene group, octamethylene, or 1,2-cyclohexene group, 1,3-cyclohexene group, 1,4-cyclohexene group, 2-methylpropene group, and the like. Preferably, the carbon number is 1 to 3.

Examples of the substituted or unsubstituted linear, branched, or alicyclic alkylene group having 1 to 20 carbon atoms of X include the same as L ¹ .

Above, Among the compounds having the structure of general formula (2), R ² is a hydrocarbon group having 2 to 5 carbon atoms, may be substituted a part of carbon atoms to the nitrogen atom, L ¹ is, A substituted or unsubstituted linear alkylene group having 1 to 3 carbon atoms,-(C = O)-,-(C = O) -O-X-, or-(C = O) -NH-X- X is a substituted or unsubstituted linear alkylene group having 1 to 3 carbon atoms, and L ² is a mercapto group, or —CH═CH ₂ , or —C (CH ₃ ) ═CH ₂ Is preferred. Glycerin mono (meth) acrylate, diethanolacrylamide, and 1-thioglycerol are preferable from the viewpoint of availability and production cost.

  In preparing the dispersant (B), the compound having the structure of the general formula (2) is preferably contained in an amount of 0.1 to 10% by weight, more preferably, in 100% by weight of the ethylenically unsaturated monomer. Is preferably contained in an amount of 1 to 5% by weight. Within the above range, the dispersion is excellent in storage stability, which is preferable.

  Examples of the (meth) acrylate (a) having an epoxy group include glycidyl (meth) acrylate, glycidyl α-ethyl (meth) acrylate, glycidyl α-n-propyl (meth) acrylate, α-n. -Glycidyl butyl (meth) acrylate, (meth) acrylic acid-3,4-epoxybutyl, (meth) acrylic acid-4,5-epoxypentyl, (meth) acrylic acid-3,4-epoxybutyl, (meth ) Acrylic acid-6,7-epoxypentyl, α-ethyl (meth) acrylic acid-6,7-epoxypentyl, β-methylglycidyl (meth) acrylate, (meth) acrylic acid-3,4-epoxycyclohexyl, lactone Modified (meth) acrylic acid-3,4-epoxycyclohexyl, vinylcyclohexene oxide and the like can be mentioned. These may be used alone or in combination of two or more.

  Among the (meth) acrylate (a) having an epoxy group, glycidyl (meth) acrylate is preferable from the viewpoint of availability and production cost.

  In adjusting the dispersant (B), the (meth) acrylate (a) having an epoxy group is preferably contained in an amount of 25 to 90% by weight, more preferably, in 100% by weight of the ethylenically unsaturated monomer. It is preferable to contain 40 to 90 weight%, and it is especially preferable to contain 60 to 90 weight%.

  The α, β-unsaturated carboxylic acid is preferably reacted at a molar ratio of 0.95 to 1 with respect to the epoxy group in the copolymer. More preferably, it is 0.99-1.

When the said preferable range is represented by the unsaturated double bond equivalent of a dispersing agent (B), it is 100-3000, More preferably, it is 100-1000, Most preferably, it is 100-300.
It is preferable for it to be in the above range since the stain resistance of the coat layer is excellent.

  The polysiloxane mono (meth) acrylate (b) of the present invention is a compound having one (meth) acryloyl group and an organopolysiloxane unit in one molecule and represented by the following general formula (1). . The compound represented by the general formula (3) is preferable from the viewpoints of availability, production cost, and performance.

（式中、Ｒ³は水素原子、または、メチル基であり、Ｒ⁴〜Ｒ⁸はそれぞれ独立に、炭素数１〜４のアルキル基であり、Ｌ³は、炭素数１〜２０の、置換または無置換の直鎖、分岐または脂環式のアルキレン基、または置換または無置換のアリーレン基が挙げられ、ｎは１０〜２００の整数である。） General formula (3)

(Wherein R ³ is a hydrogen atom or a methyl group, R ^{4 to} R ⁸ are each independently an alkyl group having 1 to 4 carbon atoms, and L ³ is a substituted group having 1 to 20 carbon atoms. Or an unsubstituted linear, branched or alicyclic alkylene group, or a substituted or unsubstituted arylene group, and n is an integer of 10 to 200.)

Examples of the alkyl group having 1 to 4 carbon atoms of R ^{4 to} R ⁸ in the general formula (3) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a normal butyl group, and a tertiary butyl group.

L ³ in the general formula (1) is a substituted or unsubstituted linear, branched or alicyclic alkylene group having 1 to 20 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, a trimethylene group, Examples include a tetramethylene group, a hexamethylene group, an octamethylene group, a 1,2-cyclohexene group, a 1,3-cyclohexene group, a 1,4-cyclohexene group, and a 2-methylpropene group.

L ³ in the general formula (3) includes a substituted or unsubstituted arylene group such as a phenylene group, a nonylphenylene group, or a paracumylphenylene group.

  Due to the presence of the polysiloxane mono (meth) acrylate (b) component, the surface of the resulting curable resin composition is imparted with stain resistance and adhesive tape peelability, and further against silica appearing on the composition surface. By applying the surface coating, further stain resistance is imparted.

  A preferable range of n in the polysiloxane mono (meth) acrylate (b) is n = 40 to 70. Within the above range, the surface is excellent in stain resistance, and random copolymerization is easy to proceed, so that the cured film obtained is excellent in curability.

  (B) As a component, brand name "X-22-174DX" (made by Shin-Etsu Silicone) "X-22-2426" (made by Shin-Etsu Silicone) "X-22-2475" (made by Shin-Etsu Silicone), goods Name “KF-2012” (manufactured by Shin-Etsu Silicone Co., Ltd.), product name “Silaplane FM-0721” (manufactured by JNC Corporation), brand name “Silaplane FM-0711” (manufactured by JNC Corporation), etc. It can be easily obtained.

  In preparing the dispersant (B), the polysiloxane mono (meth) acrylate (b) is preferably contained in an amount of 5 to 30% by weight, more preferably 5%, in 100% by weight of the ethylenically unsaturated monomer. Although it is preferable to contain -15weight%, it is especially preferable.

  Other monomers include (meth) acrylate (a) having an epoxy group, polysiloxane mono (meth) acrylate (b), and polymerizability capable of radical polymerization with the compound represented by the general formula (2). It is not particularly limited as long as it is a monomer, and can be appropriately selected according to the use. For example,

  Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, isoamyl (meth) acrylate, Octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cetyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, Linear or branched alkyl (meth) acrylates such as isomyristyl (meth) acrylate, stearyl (meth) acrylate, or isostearyl (meth) acrylate;

  Cyclohexyl (meth) acrylate, Tertiarybutylcyclohexyl (meth) acrylate, Dicyclopentanyl (meth) acrylate, Dicyclopentanyloxyethyl (meth) acrylate, Dicyclopentenyl (meth) acrylate, Dicyclopentenyloxyethyl (meth) ) Acrylates or cyclic alkyl (meth) acrylates such as isobornyl (meth) acrylate;

Fluoroalkyl (meth) acrylates such as trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, or tetrafluoropropyl (meth) acrylate;
(Meth) acrylates having a heterocyclic ring such as tetrahydrofurfuryl (meth) acrylate or 3-methyl-3-oxetanyl (meth) acrylate;

Benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, paracumylphenoxyethyl (meth) acrylate, paracumylphenoxypolyethylene glycol (meth) acrylate, or nonylphenoxypolyethylene glycol (meth) acrylate, etc. (Meth) acrylates having the following aromatic ring;

2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 4-hydroxyvinylbenzene, 2-hydroxy-3-phenoxypropyl acrylate, or caprolactone adduct of these monomers ( (Meth) acrylates having a hydroxyl group such as 1 to 5)

Methoxy polyethylene glycol mono (meth) acrylate, octoxy polyethylene glycol polypropylene glycol mono (meth) acrylate, lauroxy polyethylene glycol mono (meth) acrylate, stearoxy polyethylene glycol mono (meth) acrylate, phenoxy polyethylene glycol mono (meth) acrylate, Phenoxy polyethylene glycol polypropylene glycol mono (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, Lauroxy polyethylene glycol mono (meth) acrylate, Nonylphenoxy polyethylene glycol mono (meth) acrylate, Nonylphenoxy polypropylene glycol mono (meth) acrylate, Nonylphenoxy polyethylene glycol polypro Lenglycol mono (meth) acrylate, phenoxypolyethyleneglycol mono (meth) acrylate, methoxypolyethyleneglycol (meth) acrylate, n-butoxyethyl (meth) acrylate, n-butoxydiethylene glycol (meth) acrylate, 2-methoxyethyl (meth) (Meth) acrylates having an ether group such as acrylate and 2-ethoxyethyl (meth) acrylate;

3- (acryloyloxymethyl) 3-methyloxetane, 3- (methacryloyloxymethyl) 3-methyloxetane, 3- (acryloyloxymethyl) 3-ethyloxetane, 3- (methacryloyloxymethyl) 3-ethyloxetane, 3- Oxetanyl groups such as (acryloyloxymethyl) 3-butyloxetane, 3- (methacryloyloxymethyl) 3-butyloxetane, 3- (acryloyloxymethyl) 3-hexyloxetane and 3- (methacryloyloxymethyl) 3-hexyloxetane (Meth) acrylates having;

  (Meth) acrylates having a primary amino group such as aminoethyl (meth) acrylate;

  (Meth) acrylates having secondary amino groups such as tertiary butylaminoethyl (meth) acrylate, methylaminoethyl (meth) acrylate, 2,2,6,6-tetramethylpiperidyl methacrylate;

  Dialkylaminoalkyl (meth) such as diethylaminomethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate (Meth) acrylates having a tertiary amino group such as attalylate, 1,2,2,6,6-pentamethylpiperidyl methacrylate;

Vinyls such as styrene, α-methylstyrene, vinyl acetate, vinyl (meth) acrylate, or allyl (meth) acrylate;
N-substituted type (meta) such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, or acryloylmorpholine ) Acrylamides;
Nitriles such as (meth) acrylonitrile;

Vinyl ethers having an ether group such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether;

(Meth) acrylates having an isocyanate group such as 2-isocyanate ethyl methacrylate, 2-isocyanate ethyl acrylate, 4-isocyanate butyl methacrylate, 4-isocyanate butyl acrylate;
Alternatively, a mixture thereof can be mentioned.

  The isocyanate group includes a blocked isocyanate group and can be preferably used. Under normal conditions, the blocked isocyanate group can protect the isocyanate group with other functional groups to suppress the reactivity of the isocyanate group, and can be deprotected by heating to regenerate the active isocyanate group. The isocyanate block body is shown.

  Examples of commercially available (meth) acrylates having such a blocked isocyanate group include 2-[(3,5-dimethylpyrazolyl) carboxyamino] ethyl methacrylate (Karenz MOI-BP, Showa Denko); methacrylic acid 2- (0- [1′methylpropylideneamino] carboxyamino) ethyl (Karenz MOI-BM, manufactured by Showa Denko) and the like can be mentioned.

  Other polymerizable monomers include (meth) acrylate (a) having an epoxy group, polysiloxane mono (meth) acrylate (b), and polymerizability with a compound having the structure of the general formula (2). And from a compatible viewpoint of monomers, a linear or branched alkyl (meth) acrylate is preferable.

  The structure of the linear or branched alkyl (meth) acrylate is not particularly limited, but methyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate Isostearyl (meth) acrylate is preferable, and methyl (meth) acrylate and butyl (meth) acrylate are particularly preferable.

  As a method for obtaining the dispersant (B), known methods such as free radical polymerization and living radical polymerization can be used.

  In the case of the free radical polymerization method, it is preferable to use a polymerization initiator. As the polymerization initiator, for example, an azo compound and an organic peroxide can be used. Examples of the azo compounds include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2 , 2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate) 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), or 2,2′-azobis [2- (2-imidazolin-2-yl ) Propane] and the like. Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxy Examples thereof include dicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide. These polymerization initiators can be used alone or in combination of two or more. The reaction temperature is preferably 40 to 150 ° C., more preferably 50 to 110 ° C., and the reaction time is preferably 3 to 30 hours, more preferably 5 to 20 hours.

Further, in the general formula (2), the compound having a thiol group in L ² functions as a chain transfer agent during radical polymerization, and the general formula (1) is added to one terminal region (one terminal region) of the acrylic resin to be generated. ) Can be introduced. The terminal region is a hydrocarbon group having 1 to 10 carbon atoms. Further, the hydroxyl groups may be bonded to the same carbon atom or may be bonded to different carbon atoms. Moreover, some carbon atoms may be substituted with nitrogen atoms.

  In the obtained dispersing agent (B), the structure represented by the general formula (1) in one end region is preferable from the viewpoint of dispersion stabilization of silica.

  In the living radical polymerization method, side reactions that occur in general radical polymerization are suppressed, and further, since the growth of polymerization occurs uniformly, it is possible to easily synthesize block polymers and resins with uniform molecular weight.

  Among them, the atom transfer radical polymerization method using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is applicable to a wide range of monomers, and has a polymerization temperature applicable to existing equipment. It is preferable in that it can be adopted. The atom transfer radical polymerization method can be carried out by the methods described in the following references 1 to 8 and the like.

(Reference 1) Fukuda et al., Prog. Polym. Sci. 2004, 29, 329 (reference 2) Matyjaszewski et al., Chem. Rev. 2001, 101, 2921
(Reference 3) Matyjaszewski et al. Am. Chem. Soc. 1995, 117, 5614
(Reference 4) Macromolecules 1995, 28, 7901, Science, 1996, 272, 866
(Reference 5) WO96 / 030421
(Reference 6) WO97 / 018247
(Reference 7) JP-A-9-208616 (Reference 8) JP-A-8-41117

  It is preferable to use an organic solvent for the polymerization. Although it does not specifically limit as an organic solvent, For example, ethyl acetate, n-butyl acetate, isobutyl acetate, acetone, methyl ethyl ketone, etc. are used. Two or more kinds of these polymerization solvents may be mixed and used.

The dispersant (B) can be obtained by reacting the epoxy group in the copolymer obtained by polymerizing the above components with an α, β-unsaturated carboxylic acid. This reaction is a reaction in which the epoxy group of the polymer is ring-opened, thereby adding α, β-unsaturated carboxylic acid.

As the α, β-unsaturated carboxylic acid, various known ones can be used without particular limitation. Specifically, for example, α, β-unsaturated monocarboxylic acid such as (meth) acrylic acid, 2-acryloyloxyethylsuccinic acid, 2-acryloyloxyethylphthalic acid, 2-acryloyloxyhexahydrophthalic acid, etc. And α, β-unsaturated dicarboxylic acid such as acid, (meth) acrylic acid dimer, maleic anhydride, maleic acid, crotonic acid, itaconic acid, fumaric acid, muconic acid, citraconic acid and the like. Among these, (meth) acrylic acid, 2-acryloyloxyethylsuccinic acid, 2-acryloyloxyethylphthalic acid, 2-acryloyl from the viewpoint of photopolymerization reactivity of the generated active energy ray-curable resin composition. Α, β-unsaturated monocarboxylic acids such as loxyhexahydrophthalic acid are preferred.

The reaction between the copolymer and the α, β-unsaturated carboxylic acid is not particularly limited, and various known methods can be employed. Usually, a copolymer and an α 1, β-unsaturated carboxylic acid are mixed, and if necessary, a solvent that does not react with each component and has good compatibility may be used. Furthermore, in the addition reaction of α 1, β-unsaturated carboxylic acid, the reaction in the temperature range of 80 to 120 ° C. suitably proceeds. Considering the temperature range of the reaction, the solvent used preferably has a solvent boiling point of 100 ° C. or higher, for example, isopropyl acetate or butyl acetate. In this addition reaction, a catalyst can be used for the purpose of shortening the reaction time. Specific examples of the catalyst include basic catalysts such as pyridine, pyrrole, triethylamine, diethylamine, amines such as dibutylamine and ammonia, phosphines such as tributylphosphine and triphenylphosphine, copper naphthenate, and naphthenic acid. Examples thereof include metal catalysts such as cobalt, zinc naphthenate, tributoxyaluminum, and tetrabutoxytrititanium, Lewis acids such as aluminum chloride, and organic tin compounds such as dibutyltin dilaurate.

  Although the molecular weight of a dispersing agent (B) is not specifically limited, It is preferable that the conversion weight average molecular weights measured by the gel permeation chromatography (GPC) are 1,000-500,000, 3,000. More preferably, it is ˜15,000.

  The addition amount of the dispersant (B) is 0.1 to 30% by weight, preferably 0.5 to 20% by weight, based on the total amount of solids in the active energy ray-curable resin composition. If it is less than 0.1% by weight, the effect of reducing the viscosity is low, and if it is 30% by weight or more, the degree of crosslinking of the film is lowered and the film properties are lowered.

<Silica dispersion>
The dispersion includes silica particles (A), a dispersant (B), and a liquid medium (C).
In the total solid content of 100% by weight of the silica particles (A) and the dispersant (B), the dispersant (B) is preferably 30 to 70% by weight.

  The liquid medium (C) is not particularly limited, and can be used as it is without removing the liquid medium contained in colloidal silica or the liquid medium used for the synthesis of the dispersant (B). Preferred examples include ethyl acetate, butyl acetate, normal propyl acetate, methyl ethyl ketone, and isopropyl alcohol.

  The method for producing the dispersion is not particularly limited, and a conventionally known apparatus can be used.

<Active energy ray-curable resin composition>
Next, the manufacturing method of an active energy ray curable resin composition is demonstrated.
Although a manufacturing method is not specifically limited, The process (1) which obtains a dispersion by processing a silica particle (A) using a dispersing agent (B), and the process of mixing an active energy ray-curable compound with the said dispersion ( It is preferable to perform 2) in order. The reason is that in step (1), the group represented by the general formula (1) is gradually adsorbed on the surface of the silica particles, and a stable dispersion of silica can be formed. Furthermore, when the silicone component of the dispersant (B) covers the silica surface, the stain resistance and the adhesive tape peelability are excellent.
In addition, the active energy ray-curable compound is preferably added and mixed in the step (2) in view of viscosity, stirrability, and silica dispersibility.

<Active energy ray-curable compound>
Preferred examples of the active energy ray-curable compound include polymerizable oligomers and polymerizable monomers. Polymerizable oligomers can impart resistance and flexibility to the surface protective layer, and those having a number average molecular weight (measured by gel permeation chromatography (GPC); hereinafter the same) 1000 or more are suitably used. .

  As the polymerizable oligomer, an oligomer having a radical polymerizable unsaturated group in the molecule, for example, epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, acrylic (meth) acrylate Etc. Of these, urethane acrylate is preferred because it is expected to provide flexibility as well as adhesion to the base.

  The epoxy (meth) acrylate oligomer can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it. Further, a carboxyl-modified epoxy (meth) acrylate oligomer obtained by partially modifying this epoxy (meth) acrylate oligomer with a dibasic carboxylic acid anhydride can also be used. The urethane (meth) acrylate oligomer can be obtained, for example, by esterifying a polyurethane oligomer obtained by reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid. Polyester (meth) acrylate oligomers include, for example, esterifying hydroxyl groups of polyester oligomers having hydroxyl groups at both ends obtained by condensation of polycarboxylic acid and polyhydric alcohol with (meth) acrylic acid, It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide to a carboxylic acid with (meth) acrylic acid. The polyether (meth) acrylate oligomer can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid.

  Furthermore, other polymerizable oligomers include polybutadiene (meth) acrylate oligomers with high hydrophobicity that have (meth) acrylate groups in the side chain of polybutadiene oligomers, and silicone (meth) acrylate oligomers that have polysiloxane bonds in the main chain. In a molecule such as an aminoplast resin (meth) acrylate oligomer modified with an aminoplast resin having many reactive groups in a small molecule, or a novolak epoxy resin, bisphenol epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc. There are oligomers having a cationic polymerizable functional group.

As the polymerizable monomer, a (meth) acrylate-based monomer having a radical polymerizable unsaturated group in the molecule is preferable, and among them, a polyfunctional (meth) acrylate is preferable. The polyfunctional (meth) acrylate is not particularly limited as long as it is a (meth) acrylate having two or more ethylenically unsaturated bonds in the molecule. Specifically, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) ) Acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified diphosphate ( (Meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylo Propane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris ( (Acryloxyethyl) isocyanurate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, Examples include ethylene oxide-modified bisphenol A diacrylate. These polyfunctional (meth) acrylates may be used singly or in combination of two or more.

In the present invention, a monofunctional (meth) acrylate can be used in combination with the polyfunctional (meth) acrylate as long as the object of the present invention is not impaired, for the purpose of lowering the viscosity. Examples of monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl ( Examples include meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and isobornyl (meth) acrylate. These monofunctional (meth) acrylates may be used alone or in combination of two or more.
Examples of the ethylene oxide-modified trimethylol acrylate include those having an ethylene oxide repeating unit number (expressed as molar modification) of 1 to 20 moles, etc., among which 3 to 9 mole modified ones are excellent in physical properties of the crosslinked film. ,preferable.

  The active energy ray-curable compound is used in an amount of 60 to 95% by weight in the active energy ray-curable resin composition. If the amount is less than 60% by weight, the physical properties of the film deteriorate, and if it exceeds 95% by weight, it is difficult to sufficiently exhibit the physical properties of the coating film such as stain resistance and peelability of the adhesive tape.

When the radically polymerizable crosslinking component is crosslinked with ultraviolet rays, examples of the photopolymerization initiator include acetophenones, benzophenones, thioxanthones, aromatic diazonium salts, and metallocenes. In addition, amines and phosphines can be used in combination as polymerization accelerators. In the case of crosslinking with an electron beam, these may not be blended.
In addition, when the cationically reactive component is cross-linked by ultraviolet rays, the cationic initiator includes Lewis acid diazonium salt, Lewis acid iodonium salt, Lewis acid sulfonium salt, Lewis acid phosphonium salt, and other halogens. Compounds, triazine-based initiators, borate-based initiators, and other photoacid generators. In the case of crosslinking with an electron beam, these may not be blended.

  The active energy ray-curable resin composition can be further blended with an organic / inorganic filler as necessary, and can impart gloss adjustment and wear properties. For example, organic fillers that have been polymerized into fine particles until resins such as epoxy resin, melamine resin, urea resin, acrylic resin, polyimide resin, Teflon resin, polyethylene resin, polyester resin, polyester resin, polyamide resin are insoluble in solvent And inorganic fillers such as alumina, talc, magnesium carbonate, calcium carbonate, natural mica, synthetic mica, aluminum hydroxide, precipitated barium sulfate, precipitated barium carbonate, barium titanate, and barium sulfate.

  The active energy ray-curable resin composition can be blended with a colorant and various additives, for example, a leveling agent, an antifoaming agent, and the like, if necessary, and is not particularly limited such as a silicone type or a polymer type.

<Decoration sheet>
The active energy ray-curable resin composition of the present invention is applied to a substrate, the liquid medium is removed, and cured by irradiating with an electron beam or ultraviolet rays to give an excellent antifouling property and adhesive tape property ( A decorative sheet) can be obtained.
Examples of the substrate include a film substrate made of polyethylene terephthalate, polypropylene, triacetyl acetate and the like, and paper substrates such as kraft paper, titanium paper, and fine paper.
Furthermore, the decorative material obtained by pasting this coated product (decorative sheet) on a substrate such as a particle board can be used for interior and exterior materials of houses and offices, furniture, and the like.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. Unless otherwise specified, “parts” means “parts by weight” and “%” means “% by weight”. Moreover, the measuring method of the weight average molecular weight (Mw) of resin is as follows.

(Resin polymerization average molecular weight (Mw))
In the present invention, the weight average relative molecular weight (RI_Mw) is an eluent using HLC-8220GPC (manufactured by Tosoh Corporation) equipped with an RI detector as an apparatus and TSKgel SUPER HZM-N (manufactured by Tosoh Corporation) as a column. Is a weight average molecular weight (RI_Mw) in terms of polystyrene measured using THF.
(Double bond equivalent)
The double bond equivalent was calculated by the following formula.
[Double bond equivalent] = [total charged monomer mass (g) + initiator mass (g)] / [amount of monomer having a double bond (mol)]

  First, the dispersant (B) used in Examples and Comparative Examples will be described.

<Method for producing dispersant (B)>
(Preparation of dispersant (B-1))
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirring device, 42.8 parts of normal propyl acetate, 70.0 parts of glycidyl methacrylate, polysiloxane methacrylate (FM-0721; JNC Corporation) 15.0 parts and 13.0 parts of n-butyl methacrylate were added, and the temperature was raised to 50 ° C. Thereafter, 2.0 parts of 1-thioglycerol was added, and the temperature was raised to 90 ° C. Thereafter, a normal propyl acetate solution of 0.1 part of 2,2′-azobis (2,4-dimethylvaleronitrile) was added and reacted over 6.5 hours. Then, after cooling to room temperature, switching to air bubbling from nitrogen substitution, adding 35.5 parts by weight of acrylic acid, 0.5 parts by weight of p-methoxyphenol, 1.4 parts by weight of dimethylbenzylamine, stirring, The temperature was raised to 105 ° C. and the reaction was held for 8 hours. Then, it cooled to room temperature. The weight average molecular weight of the obtained resin was 14000, and the double bond equivalent was 290. About 2 g of the resin solution was sampled and heated and dried at 170 ° C. for 10 minutes to measure the non-volatile content. Then, normal propyl acetate was added to the previously synthesized resin solution so that the non-volatile content was 40% by weight. B-1) was obtained.

(Preparation of dispersant (B-2))
42.8 parts of butyl acetate, 50.0 parts of glycidyl methacrylate, polysiloxane methacrylate (FM-0721; manufactured by JNC Corporation) in a reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirring device 25.0 parts and 23.0 parts of n-butyl methacrylate were charged, and the temperature was raised to 50 ° C. Thereafter, 2.0 parts of 1-thioglycerol was added, and the temperature was raised to 90 ° C. Thereafter, a butyl acetate solution of 0.1 part of 2,2′-azobis (2,4-dimethylvaleronitrile) was added and reacted over 6.5 hours. Then, after cooling to room temperature, switching to air bubbling instead of nitrogen replacement, adding 25.3 parts by weight of acrylic acid, 0.5 parts by weight of p-methoxyphenol, 1.4 parts by weight of dimethylbenzylamine, stirring, The temperature was raised to 105 ° C. and the reaction was held for 8 hours. Then, it cooled to room temperature. The obtained resin had a weight average molecular weight of 15000 and a double bond equivalent of 375. About 2 g of the resin solution was sampled and heated and dried at 170 ° C. for 10 minutes to measure the non-volatile content, and butyl acetate was added to the previously synthesized resin solution so that the non-volatile content was 40% by weight. -2) was obtained.

(Preparation of dispersant (B-3))
42.8 parts of methyl ethyl ketone, 30.0 parts of glycidyl methacrylate, polysiloxane methacrylate (FM-0721; manufactured by JNC Corporation) in a reaction vessel equipped with a separable four-necked flask, a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirring device Was charged with 10.0 parts and 58.0 parts of n-butyl methacrylate, and the temperature was raised to 50 ° C. Thereafter, 2.0 parts of 1-thioglycerol was added, and the temperature was raised to 85 ° C. Thereafter, 0.1 part of 2,2′-azobisisobutyronitrile in a methyl ethyl ketone solution was added and reacted over 6.5 hours. Then, after cooling to room temperature, switching to air bubbling instead of nitrogen substitution, adding 15.2 parts by weight of acrylic acid, 0.5 parts by weight of p-methoxyphenol, 1.4 parts by weight of dimethylbenzylamine, stirring, The temperature was raised to 105 ° C. and the reaction was held for 8 hours. Then, it cooled to room temperature. The obtained resin had a weight average molecular weight of 12,000 and a double bond equivalent of 575. About 2 g of the resin solution was sampled and heated and dried at 170 ° C. for 10 minutes to measure the non-volatile content. Then, methyl ethyl ketone was added to the previously synthesized resin solution so that the non-volatile content was 40% by weight. 3) was obtained.

(Preparation of dispersant (B-4))
42.8 parts normal propyl acetate, 70.0 parts glycidyl methacrylate, polysiloxane methacrylate (FM-0711; JNC Corporation) in a reaction vessel equipped with a separable four-necked flask equipped with a thermometer, cooling pipe, nitrogen gas introduction pipe, and stirring device Made) and 10.0 parts of n-butyl methacrylate were charged and heated to 50 ° C. Thereafter, 10.0 parts of 1-thioglycerol was added, and the temperature was raised to 90 ° C. Thereafter, 0.05 part of 2,2′-azobis (2,4-dimethylvaleronitrile) in a normal propyl acetate solution was added in portions over 6.5 hours for reaction. Then, after cooling to room temperature, switching to air bubbling from nitrogen substitution, adding 35.5 parts by weight of acrylic acid, 0.5 parts by weight of p-methoxyphenol, 1.4 parts by weight of dimethylbenzylamine, stirring, The temperature was raised to 105 ° C. and the reaction was held for 8 hours. Then, it cooled to room temperature. The weight average molecular weight of the obtained resin was 7000, and the double bond equivalent was 575. About 2 g of the resin solution was sampled and heated and dried at 170 ° C. for 10 minutes to measure the non-volatile content. Then, normal propyl acetate was added to the previously synthesized resin solution so that the non-volatile content was 40% by weight. B-4) was obtained.

(Preparation of dispersant (B-5))
42.8 parts normal propyl acetate, 70.0 parts glycidyl methacrylate, polysiloxane methacrylate (FM-0725; JNC Corporation) in a reaction vessel equipped with a separable four-necked flask equipped with a thermometer, cooling pipe, nitrogen gas introduction pipe, and stirring device 20.0 parts and n-butyl methacrylate 10.0 parts were charged, and the temperature was raised to 50 ° C. Thereafter, 5.0 parts of 1-thioglycerol was added, and the temperature was raised to 90 ° C. Thereafter, a normal propyl acetate solution of 0.1 part of 2,2′-azobis (2,4-dimethylvaleronitrile) was added and reacted over 6.5 hours. Then, after cooling to room temperature, switching from nitrogen substitution to air bubbling, adding 30.4 parts by weight of acrylic acid, 0.5 parts by weight of p-methoxyphenol, 1.4 parts by weight of dimethylbenzylamine, stirring, The temperature was raised to 105 ° C. and the reaction was held for 8 hours. Then, it cooled to room temperature. The weight average molecular weight of the obtained resin was 10,000, and the double bond equivalent was 325. About 2 g of the resin solution was sampled and heated and dried at 170 ° C. for 10 minutes to measure the non-volatile content. Then, normal propyl acetate was added to the previously synthesized resin solution so that the non-volatile content was 40% by weight. B-5) was obtained.

(Preparation of dispersant (B-6))
In a reaction vessel equipped with a separable four-necked flask, a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirring device, 42.8 parts of normal propyl acetate, 70.0 parts of glycidyl methacrylate, polysiloxane methacrylate (X-22-174DX; Shin-Etsu) 10.0 parts of Silicone Co., Ltd. and 18.0 parts of n-butyl methacrylate were charged, and the temperature was raised to 50 ° C. Thereafter, 2.0 parts of 1-thioglycerol was added, and the temperature was raised to 90 ° C. Thereafter, a normal propyl acetate solution of 0.1 part of 2,2′-azobis (2,4-dimethylvaleronitrile) was added and reacted over 6.5 hours. Then, after cooling to room temperature, switching to air bubbling from nitrogen substitution, adding 35.5 parts by weight of acrylic acid, 0.5 parts by weight of p-methoxyphenol, 1.4 parts by weight of dimethylbenzylamine, stirring, The temperature was raised to 105 ° C. and the reaction was held for 8 hours. Then, it cooled to room temperature. The obtained resin had a weight average molecular weight of 13,000 and a double bond equivalent of 276. About 2 g of the resin solution was sampled and heated and dried at 170 ° C. for 10 minutes to measure the non-volatile content. Then, normal propyl acetate was added to the previously synthesized resin solution so that the non-volatile content was 40% by weight. B-6) was obtained.

(Preparation of dispersant (B-7))
42.8 parts of methyl isobutyl ketone, 75.0 parts of glycidyl methacrylate, polysiloxane methacrylate (FM-0721; JNC Corporation) in a reaction vessel equipped with a separable four-necked flask, a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirring device Made) and 14.0 parts of n-butyl methacrylate were charged, and the temperature was raised to 50 ° C. Thereafter, 1.0 part of 1-thioglycerol was added, and the temperature was raised to 90 ° C. Thereafter, 0.1 part of 2,2′-azobis (2,4-dimethylvaleronitrile) in methyl isobutyl ketone was added in portions over 6.5 hours for reaction. Then, after cooling to room temperature, switching to air bubbling instead of nitrogen substitution, adding 38.0 parts by weight of acrylic acid, 0.5 parts by weight of p-methoxyphenol, 1.4 parts by weight of dimethylbenzylamine, stirring, The temperature was raised to 105 ° C. and the reaction was held for 8 hours. Then, it cooled to room temperature. The obtained resin had a weight average molecular weight of 23,000 and a double bond equivalent of 276. About 2 g of the resin solution was sampled and heated and dried at 170 ° C. for 10 minutes to measure the non-volatile content. Then, normal propyl acetate was added to the previously synthesized resin solution so that the non-volatile content was 40% by weight. B-7) was obtained.

(Preparation of dispersant (B-8))
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirring device was charged with 73.4 parts of butyl acetate and 80.0 parts of methyl ethyl ketone, and the temperature was raised to 90 ° C. After nitrogen substitution, 75.0 parts of glycidyl methacrylate, 10.0 parts of polysiloxane methacrylate (FM-0721; manufactured by JNC Corporation), 10.0 parts of glycerol monomethacrylate, 5.0 parts of n-butyl methacrylate from the dropping tube A mixture of 3.0 parts of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of dropping, the reaction was continued for another 3 hours. Then, after cooling to room temperature, switching to air bubbling from nitrogen substitution, adding 38.0 parts by weight of acrylic acid, 2 parts by weight of p-methoxyphenol, and 1.4 parts by weight of triphenylphosphine, stirring, 105 ° C. The reaction was continued for 8 hours and allowed to react. Then, it cooled to room temperature. The weight average molecular weight of the obtained resin was 10,000, and the double bond equivalent was 276. About 2 g of the resin solution was sampled and heated and dried at 170 ° C. for 10 minutes to measure the non-volatile content, and butyl acetate was added to the previously synthesized resin solution so that the non-volatile content was 40% by weight. -8) was obtained.

(Preparation of dispersant (B-9))
After charging 153.4 parts of normal propyl acetate into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirring device in a separable four-necked flask, the temperature was raised to 90 ° C., and the inside of the reaction vessel was purged with nitrogen. From the dropping tube, 75.0 parts of glycidyl methacrylate, 10.0 parts of polysiloxane methacrylate (FM-0721; manufactured by JNC Corporation), 5.0 parts of glycerin monomethacrylate, 10.0 parts of n-butyl methacrylate, 2, 2 ′ -A mixture of 3.0 parts of azobisisobutyronitrile was added dropwise over 2 hours. After completion of dropping, the reaction was continued for another 3 hours. Then, after cooling to room temperature, switching to air bubbling from nitrogen substitution, adding 38.0 parts by weight of acrylic acid, 2 parts by weight of p-methoxyphenol, and 1.4 parts by weight of triphenylphosphine, stirring, 105 ° C. The reaction was continued for 8 hours and allowed to react. Then, it cooled to room temperature. The obtained resin had a weight average molecular weight of 12,000 and a double bond equivalent of 276. About 2 g of the resin solution was sampled and heated and dried at 170 ° C. for 10 minutes to measure the non-volatile content, and butyl acetate was added to the previously synthesized resin solution so that the non-volatile content was 40% by weight. -9) was obtained.

(Preparation of dispersant (B-10))
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer was charged with 153.4 parts of butyl acetate, heated to 90 ° C., the inside of the reaction vessel was purged with nitrogen, and then dropped. From the tube, 70.0 parts of 3,4-epoxycyclohexylmethyl methacrylate, 10.0 parts of polysiloxane methacrylate (X-22-2475; manufactured by Shin-Etsu Silicone), 18.0 parts of n-butyl methacrylate, glycerin monomethacrylate 2 A mixture of 0.0 part and 3.0 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) was added dropwise over 2 hours. After completion of dropping, the reaction was continued for another 3 hours. Then, after cooling to room temperature, switching to air bubbling from nitrogen substitution, adding 35.5 parts 2-acryloyloxyethyl succinic acid, 2 parts by weight p-methoxyphenol, 1.4 parts by weight triphenylphosphine, and stirring While raising the temperature to 105 ° C., the reaction was carried out by maintaining for 8 hours. Then, it cooled to room temperature. The obtained resin had a weight average molecular weight of 13,500 and a double bond equivalent of 419. About 2 g of the resin solution was sampled and heated and dried at 170 ° C. for 10 minutes to measure the non-volatile content, and butyl acetate was added to the previously synthesized resin solution so that the non-volatile content was 40% by weight. -10) was obtained.

(Preparation of dispersant (B-11))
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer was charged with 153.4 parts of butyl acetate, heated to 90 ° C., the inside of the reaction vessel was purged with nitrogen, and then dropped. From the tube, 75.0 parts of 3,4-epoxycyclohexylmethyl methacrylate, 5.0 parts of polysiloxane methacrylate (FM-0721; manufactured by JNC Corporation), polysiloxane methacrylate (X-22-2426; manufactured by Shin-Etsu Silicone Corporation) A mixture of 10.0 parts, 9.0 parts of t-butyl methacrylate, 1.0 part of glycerol monomethacrylate and 3.0 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) was added dropwise over 2 hours. did. After completion of dropping, the reaction was continued for another 3 hours. Then, after cooling to room temperature, switching to air bubbling instead of nitrogen substitution, adding 19.0 parts of acrylic acid, 2 parts by weight of p-methoxyphenol and 1.4 parts by weight of triphenylphosphine, stirring to 105 ° C The temperature was raised and the reaction was held for 8 hours. Then, it cooled to room temperature. The obtained resin had a weight average molecular weight of 16000 and a double bond equivalent of 704. About 2 g of the resin solution was sampled and heated and dried at 170 ° C. for 10 minutes to measure the non-volatile content, and butyl acetate was added to the previously synthesized resin solution so that the non-volatile content was 40% by weight. -11) was obtained.

(Preparation of dispersant (B-12))
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer was charged with 153.4 parts of butyl acetate, heated to 90 ° C., the inside of the reaction vessel was purged with nitrogen, and then dropped. From the tube, 70.0 parts of glycidyl methacrylate, 15.0 parts of polysiloxane methacrylate (FM-0721; manufactured by JNC Corporation), 9.0 parts of normal butyl methacrylate, 2.0 parts of diethanolacrylamide, 2,2′-azobis A mixture of 3.5 parts of (2,4-dimethylvaleronitrile) was added dropwise over 2 hours. After completion of dropping, the reaction was continued for another 3 hours. Then, after cooling to room temperature, switching to air bubbling instead of nitrogen substitution, adding 35.5 parts of acrylic acid, 2 parts by weight of p-methoxyphenol and 1.4 parts by weight of triphenylphosphine, stirring to 105 ° C The temperature was raised and the reaction was held for 8 hours. Then, it cooled to room temperature. The weight average molecular weight of the obtained resin was 12,500, and the double bond equivalent was 290. About 2 g of the resin solution was sampled and heated and dried at 170 ° C. for 10 minutes to measure the non-volatile content, and butyl acetate was added to the previously synthesized resin solution so that the non-volatile content was 40% by weight. -11) was obtained.

(Preparation of dispersant (B-13))
After charging 153.4 parts of normal propyl acetate into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirring device in a separable four-necked flask, the temperature was raised to 90 ° C., and the inside of the reaction vessel was purged with nitrogen. From the dropping tube, 70.0 parts of glycidyl methacrylate, 5.0 parts of polysiloxane methacrylate (FM-0721; manufactured by JNC Corporation), 2.0 parts of hydroxyethyl methacrylate, 23.0 parts of n-butyl methacrylate, 2, 2 ′ -A mixture of 3.0 parts of azobisisobutyronitrile was added dropwise over 2 hours. After completion of dropping, the reaction was continued for another 3 hours. Then, after cooling to room temperature, switching to air bubbling instead of nitrogen substitution, adding 12.9 parts of acrylic acid, 2 parts by weight of p-methoxyphenol and 1.4 parts by weight of triphenylphosphine, stirring to 105 ° C The temperature was raised and the reaction was held for 8 hours. Then, it cooled to room temperature. The obtained resin had a weight average molecular weight of 15000 and a double bond equivalent of 290. About 2 g of the resin solution was sampled and heated and dried at 170 ° C. for 10 minutes to measure the non-volatile content. Then, normal propyl acetate was added to the previously synthesized resin solution so that the non-volatile content was 40% by weight. B-13) was obtained.

(Preparation of dispersant (B-14))
After charging 153.4 parts of normal propyl acetate into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirring device in a separable four-necked flask, the temperature was raised to 90 ° C., and the inside of the reaction vessel was purged with nitrogen. From the dropping tube, 70.0 parts of glycidyl methacrylate, 10.0 parts of polysiloxane methacrylate (FM-0721; manufactured by JNC Corporation), 19.0 parts of n-butyl methacrylate, 1.0 part of 4-hydroxybutyl acrylate, 2, A mixture of 3.0 parts of 2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of dropping, the reaction was continued for another 3 hours. Then, after cooling to room temperature, switching to air bubbling instead of nitrogen substitution, adding 35.5 parts of acrylic acid, 2 parts by weight of p-methoxyphenol and 1.4 parts by weight of triphenylphosphine, stirring to 105 ° C The temperature was raised and the reaction was held for 8 hours. Then, it cooled to room temperature. The obtained resin had a weight average molecular weight of 12,000 and a double bond equivalent of 290. About 2 g of the resin solution was sampled and heated and dried at 170 ° C. for 10 minutes to measure the non-volatile content, and butyl acetate was added to the previously synthesized resin solution so that the non-volatile content was 40% by weight. -14) was obtained.

(Preparation of dispersant (B-15))
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirring device, 42.8 parts of normal propyl acetate, 15.0 parts of glycidyl methacrylate, polysiloxane methacrylate (FM-0721; JNC Corporation) 15.0 parts and 67.0 parts of n-butyl methacrylate were charged, and the temperature was raised to 50 ° C. Thereafter, 2.0 parts of mercaptoethanol was added and the temperature was raised to 90 ° C. Thereafter, a normal propyl acetate solution of 0.1 part of 2,2′-azobis (2,4-dimethylvaleronitrile) was added and reacted over 6.5 hours. Then, after cooling to room temperature, switching to air bubbling from nitrogen substitution, adding 35.5 parts by weight of acrylic acid, 0.5 parts by weight of p-methoxyphenol, 1.4 parts by weight of dimethylbenzylamine, stirring, The temperature was raised to 105 ° C. and the reaction was held for 8 hours. Then, it cooled to room temperature. The weight average molecular weight of the obtained resin was 14000, and the double bond equivalent was 290. About 2 g of the resin solution was sampled and heated and dried at 170 ° C. for 10 minutes to measure the non-volatile content. Then, normal propyl acetate was added to the previously synthesized resin solution so that the non-volatile content was 40% by weight. B-15) was obtained.

(Preparation of dispersant (B-16))
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirring device, 42.8 parts of normal propyl acetate, 80.0 parts of glycidyl methacrylate, polysiloxane methacrylate (FM-0721; JNC Corporation) 10.0 parts and n-butyl methacrylate 9.0 parts were charged, and the temperature was raised to 50 ° C. Thereafter, 1.0 part of mercaptoethanol was added and the temperature was raised to 90 ° C. Thereafter, a normal propyl acetate solution of 0.1 part of 2,2′-azobis (2,4-dimethylvaleronitrile) was added and reacted over 6.5 hours. Then, after cooling to room temperature, switching to air bubbling instead of nitrogen substitution, adding 40.6 parts by weight of acrylic acid, 0.5 parts by weight of p-methoxyphenol, 1.4 parts by weight of dimethylbenzylamine, stirring, The temperature was raised to 105 ° C. and the reaction was held for 8 hours. Then, it cooled to room temperature. The obtained resin had a weight average molecular weight of 22,000 and a double bond equivalent of 263. About 2 g of the resin solution was sampled and heated and dried at 170 ° C. for 10 minutes to measure the non-volatile content. Then, normal propyl acetate was added to the previously synthesized resin solution so that the non-volatile content was 40% by weight. B-16) was obtained.

The compositions of the dispersants (B-1) to (B-16) are shown in Table 1.

<Example 1> (Preparation of active energy ray-curable resin composition 1)
Step (1): 4.8 parts of the dispersant (B) prepared by the above method as a solid content is added to a mixer having a stirring blade, and silica particles (Nipgel BY200, manufactured by Tosoh Silica Corp.) 2 with stirring. By adding 4 parts and stirring and mixing, adsorption of the dispersant (B) (B-1) to silica was promoted to obtain a silica dispersion.
Step (2): 5 parts of the dispersion obtained in Step (1), 30 parts of butyl acetate, 65 parts of urethane acrylate (purple UV-6300B, manufactured by Nippon Synthetic Chemical Co., Ltd.), photopolymerization initiator (Irgacure 184 and An active energy ray-curable resin composition was obtained by adding 5 parts of Irgacure 907 (manufactured by BASF) and stirring and mixing.

<Example 2> (Creation of active energy ray-curable resin composition 2)
Step (1): 4.8 parts of the dispersant (B) prepared by the above method as a solid content is added to a mixer having a stirring blade, and silica particles (Nipgel BY200, manufactured by Tosoh Silica Corp.) 2 with stirring. By adding 4 parts and stirring and mixing, adsorption of the dispersant (B) (B-2) to silica was promoted.
Step (2): To 5 parts of the dispersion obtained in Step (1), 30 parts of butyl acetate and 65 parts of urethane acrylate (purple UV-6300B, manufactured by Nippon Synthetic Chemical Co., Ltd.) are added and mixed by stirring. An active energy ray-curable resin composition was obtained.

(Coating material creation)
The active energy ray-curable resin composition 1 was diluted with butyl acetate / isopropyl alcohol at a ratio of 3/8, and the solid content ratio was diluted to 40%. After dilution, it was coated on a 50 μm thick corona-treated PET with a bar coater # 8, dried at 80 ° C. for 30 seconds, and then irradiated with ultraviolet rays under the following conditions to obtain a coated product.
Ultraviolet irradiation (UV): 120 W-200 mJ / cm ²
Moreover, the active energy ray-curable resin composition 2 was subjected to electron beam irradiation under the following conditions to obtain a coated product.
Electron beam irradiation (EB): 125 kV-30 kGy

<Examples 3 to 17> (Creation of active energy ray-curable resin compositions 3 to 17)
According to the preparation method of the above-mentioned active energy ray curable resin composition 1, the active energy ray curable composition was obtained using the above-mentioned dispersing agents B-2 to B-15. Furthermore, using the composition, various coated materials were obtained by the above-described coated material preparing method.
About the obtained coating material, storage stability, stain resistance, adhesive tape peelability, weather resistance, and steel wool resistance were evaluated by the following methods. The evaluation results are shown in Table 2.

(Storage stability evaluation)
In order to evaluate the storage stability of the silica dispersion-containing active energy ray-curable resin composition of the present invention, the active energy ray-curable resin compositions of Examples and Comparative Examples were left in a constant temperature room at 40 ° C. for 10 days. did. The range of change in viscosity before and after standing was evaluated according to the following criteria. The smaller the value of the viscosity change rate, the better. The results are shown in Table 2.
Evaluation criteria are: A: Viscosity change rate is less than 10%
○: Viscosity change rate is 10 to 20%
Δ: Viscosity change rate is 21 to 24%
X: Viscosity change rate is 25% or more
The practical level is Δ or more.

(Contamination resistance evaluation)
After writing with an oil-based magic on the coating surface of the active energy ray-curable resin composition coated product, wiping was performed, and the remaining conditions were compared. The smaller the remainder, the better. The evaluation was based on the following criteria.
Evaluation criteria ◎: No light left after wiping with dry wiping
○: No remaining after wiping with dry wipe
Δ: After wiping with dry wiping, there is a slight residue.
×: After wiping with dry wipe, there is a residual
The practical level is ◯ or more.

(Cero tape peelability evaluation)
Cello tape (registered trademark) (24 mm width) manufactured by Nichiban Co., Ltd. was applied to the coating surface of the active energy ray-curable resin composition coating, and the resistance to peeling was compared. The smaller the resistance, the better, and the evaluation was based on the following criteria.
Evaluation criteria A: Almost no resistance
〇: There is some resistance, but it peels off smoothly
Δ: Resistance but peeling
X: not peeled off or peeled off from substrate
Practical level is more than △

(Weather resistance evaluation)
A 196 hour accelerated weathering test was performed on the active energy ray-curable resin composition coated product with a metal weather to evaluate changes in the coating surface.
Evaluation criteria ○: No change
Δ: Some change in appearance and gloss
×: Appearance / gloss change
The practical level is more than ○.

(Steel wool resistance)
The active energy ray-curable resin composition coated product was subjected to 10 reciprocations by applying a load of 500 g to steel wool, and then the change in the coating surface was evaluated.
Evaluation criteria A: No change
○: Slight scratch and no gloss change
Δ: Slight scratch / gloss change
×: Significant scratch / gloss change
The practical level is ◯ or more.

  As described above, the active energy ray-curable resin composition containing the silica dispersion of the present invention and the active energy ray-curable compound has excellent storage stability, high hardness of the cured product, stable contamination resistance, and adhesion. It was found that the tape peelability and weather resistance were all excellent.

Claims (7)

A silica particle (A), a dispersant (B), and a liquid medium (C) are contained, and the dispersant (B) is a polysiloxane structure, a structure represented by the general formula (1), and an unsaturated double bond A silica dispersion characterized by being an acrylic resin having a double bond equivalent of 100 to 3000.
General formula (1)

(In the formula, R ¹ is a hydrocarbon group having 1 to 10 carbon atoms, and a part of the carbon atoms may be substituted with a nitrogen atom. [*] Indicates a bond.) In the copolymer in which the dispersant (B) is obtained by polymerizing the (meth) acrylate (a) having an epoxy group, the polysiloxane mono (meth) acrylate (b), and the compound represented by the general formula (2), The silica dispersion according to claim 1, wherein the silica dispersion is obtained by reacting an α, β-unsaturated carboxylic acid.
General formula (2)

(In the formula, R ² is a hydrocarbon group having 1 to 10 carbon atoms, and part of the carbon atoms may be substituted with a nitrogen atom. L ¹ is a substituted or unsubstituted group having 1 to 20 carbon atoms. A linear, branched, or alicyclic alkylene group, — (C═O) —, — (C═O) —O—X—, or — (C═O) —NH—X—, wherein X is A substituted or unsubstituted linear, branched, or alicyclic alkylene group having 1 to 20 carbon atoms, and L ² is a mercapto group, —CH═CH ₂ , or —C (CH ₃ ) ═CH _2. .) The silica dispersion according to claim 1 or 2, wherein the polysiloxane mono (meth) acrylate (b) is a polysiloxane mono (meth) acrylate represented by the general formula (3).
General formula (3)

(In the formula, R ³ is a hydrogen atom or a methyl group, R ^{4 to} R ⁸ are each independently an alkyl group having 1 to 4 carbon atoms, and L ³ is a substituted or substituted group having 1 to 20 carbon atoms. And an unsubstituted linear, branched or alicyclic alkylene group, or a substituted or unsubstituted arylene group, and n is an integer of 10 to 200.) The silica dispersion according to any one of claims 1 to 3, which has a structure represented by the general formula (1) in one end region of the dispersant (B).   The silica dispersion according to any one of claims 1 to 4, wherein the dispersant (B) has a weight average molecular weight of 5,000 to 100,000.   An active energy ray-curable resin composition comprising the silica dispersion according to claim 1 and an active energy ray-curable compound.   A decorative sheet using the active energy ray-curable resin composition according to claim 6.