JP2003192751A - Photo-curing (meth)acrylate resin composition having excellent soil removal, its film and base material for the film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photo-curing (meth)acrylate resin composition capable of forming a film having excellent soil removal, where such soil on a film surface covering a wooden floor created by blue ink, a felt pen or the like can be easily wiped out, and also to provide its film and a base material for the film. <P>SOLUTION: The photo-curing (meth)acrylate resin composition comprises a photo-curing (meth)acrylate resin, a photo-curing polysiloxane urethane (meth) acrylate resin, a photo-curing silicone block (meth)acrylate resin, a photo-polymerization initiator and a photo-curing (meth)acrylate resin composition. The film is prepared from the above composition. The base material is covered with the film prepared. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photocurable (meth) acrylate resin composition having excellent stain removability, a coating film and a coating substrate therefor, and more specifically, wood materials, paper materials,
The present invention relates to a photocurable (meth) acrylate resin composition for topcoat, which is used for non-combustible building materials and plastics and which can form a film excellent in stain removability, its film, and a coated substrate coated with the film.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Base materials such as wood materials, paper materials, non-combustible building materials, plastics, etc. having a film formed from a conventional photocurable composition (paint) for top coating on the surface, such as wood floors, are If the surface is contaminated, it will not be removed by wiping with a dry cloth. Further, there is a problem that the stain does not come off with the blue ink of the JAS (Japanese Agricultural Standards) contamination test.

Therefore, conventionally, even when the surface of a substrate is contaminated with blue ink, magic or the like, a photocurable composition excellent in decontamination capable of forming a film capable of easily removing the stain, The advent of coatings and coated substrates coated with the coatings is desired.

[0004]

It is an object of the present invention to solve the problems associated with the prior art as described above, and even if the surface of the base material is contaminated with blue ink, magic or the like, the stain can be easily removed. It is an object of the present invention to provide a photocurable (meth) acrylate resin composition having excellent stain removability capable of forming a coating film capable of forming the coating film, the coating film thereof, and a coated substrate coated with the coating film.

[0005]

SUMMARY OF THE INVENTION A photocurable (meth) acrylate resin composition having excellent stain removability according to the present invention comprises (A) a photocurable (meth) acrylate resin and (B) a photocurable polysiloxane resin. Urethane (meth) acrylate resin, (C)
It is characterized by containing a photocurable silicone block (meth) acrylate resin and (D) a photopolymerization initiator.

In this composition, the above-mentioned component (A),
In addition to (B), (C) and (D), if necessary,
A (meth) acrylate-based monomer can be included. The coating film according to the present invention is characterized by being formed from the photocurable (meth) acrylate resin composition excellent in stain removability according to the present invention. The coated substrate according to the present invention is characterized in that it is coated with a film formed from the photocurable (meth) acrylate resin composition excellent in stain removability according to the present invention.

[0007]

DETAILED DESCRIPTION OF THE INVENTION The photocurable (meth) acrylate resin composition excellent in stain removability, the coating film and the coated substrate according to the present invention will be specifically described below. The photocurable (meth) acrylate resin composition according to the present invention is (A) a photocurable (meth) acrylate resin,
(B) photocurable polysiloxane urethane (meth) acrylate resin, (C) photocurable silicone block (meth) acrylate resin, (D) photopolymerization initiator, and, if necessary, (E) (meth) It contains an acrylate monomer.

Photocurable (meth) acrylate resin
(A) As the photocurable (meth) acrylate-based resin used in the present invention, a conventionally known photocurable (meth) acrylate-based resin can be used, and any of aliphatic and aromatic (meth) ) A resin composed of an acrylate compound may be used. The photocurable (meth) acrylate resin (A) used in the present invention has two or more acryloyl groups (CH ₂ ═CH—CO—) or methacryloyl groups (C) in one molecule.
_{H 2 = C (CH 3)} -CO-) is a resin having.

Specific examples of such a photocurable (meth) acrylate resin (A) include epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, and polyether (meth) acrylate. A resin obtained by polymerizing a photocurable (meth) acrylate-based monomer can be mentioned. These photocurable (meth) acrylate resins (A) can be used alone or in combination of two or more.

Photocurable (meth) acrylate resin (A)
The epoxy (meth) acrylate constituting the is synthesized by reacting a compound having a glycidyl group with (meth) acrylic acid. Examples of the compound having a glycidyl group include bisphenol-type glycidyl ether which is a reaction product of bisphenol such as bisphenol A, bisphenol S, and bisphenol F with epichlorohydrin,
It is a reaction product of novolac type glycidyl ether which is a reaction product of phenol novolac and epichlorohydrin, or a reaction product of polyether glycol such as bisphenol A to which polyethylene glycol, polypropylene glycol, ethylene oxide (EO) or propylene oxide (PO) is added, and epichlorohydrin. Examples thereof include glycol type glycidyl ether.

Photocurable (meth) acrylate resin (A)
The urethane (meth) acrylate constituting the compound is obtained, for example, by reacting isocyanates, polyols and hydroxyalkyl (meth) acrylates, and has an acryloyl group (CH ₂ =
CHCO-) or methacryloyl group (CH ₂ = C (C
And H ₃₎ -CO-), a urethane bond (-NH · COO
-) And.

Specific examples of the isocyanates used for the synthesis of urethane (meth) acrylate include hexamethylene diisocyanate [HDI], isophorone diisocyanate [IPDI], methylenebis (4-cyclohexylisocyanate) [H ₁₂ MDI] and trimethyl. Diisocyanates such as hexamethylene diisocyanate [TMHMDI], tolylene diisocyanate [TDI], 4,4-diphenylmethane diisocyanate [MDI] and xylylene diisocyanate [XDI] can be mentioned. Furthermore, polyisocyanates such as an adduct obtained by modifying diisocyanate with trimethylolpropane, a trimer of diisocyanate (isocyanurate), and a buret obtained by the reaction of diisocyanate with water can be given.

Polyols used for the synthesis of urethane (meth) acrylate are classified into (1) polyether polyol, (2) polyester polyol and (3) alkylene polyol. (1) As the polyether polyol, specifically,
Examples thereof include polypropylene glycol (diol, triol, etc.), polyethylene glycol, polytetramethylene glycol and the like.

(2) As the polyester polyol,
Specifically, a condensation produced by a dehydration condensation reaction between a dibasic acid such as adipic acid and phthalic anhydride and an alcohol such as ethylene glycol, 1,4-butanediol, 1,6-hexanediol, and trimethylolpropane. Examples thereof include polyester polyester polyols and lactone polyester polyols obtained by ring-opening polymerization of δ-caprolactone.

Specific examples of the alkylene polyol (3) include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, and trimethylolpropane. These polyols may be used alone or in combination of two or more. The alkylene polyol is used in combination with the polyether polyol or the polyester polyol.

Specific examples of hydroxyalkyl (meth) acrylates used in the synthesis of urethane (meth) acrylate include 2-hydroxyethyl acrylate [HEA] and 2-hydroxyethyl methacrylate [HE].
MA], 2-hydroxypropyl acrylate [HP
A], 2-hydroxypropyl methacrylate [HPM
A], 4-hydroxybutyl acrylate [4-HBA],
Pentaerythritol triacrylate [PETA] and the like can be mentioned.

Photocurable (meth) acrylate resin (A)
The polyester (meth) acrylate that constitutes is a dibasic acid such as phthalic anhydride, isophthalic acid, adipic acid, and maleic anhydride, and ethylene glycol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane,
It is synthesized by reacting a polyester obtained by a dehydration condensation reaction with an alcohol such as glycerin or pentaerythritol, and (meth) acrylic acid.

Photocurable (meth) acrylate resin (A)
The polyether (meth) acrylate constituting the compound reacts with ethylene oxide or propylene oxide in the presence of a basic or acidic catalyst (BF ₃ , NaOH) using a polyol such as propylene glycol, ethylene glycol or glycerin as an initiator. And then
It is synthesized by reacting the obtained polyether with (meth) acrylic acid.

The photocurable (meth) acrylate resin (A) as described above is 15 to 75 parts by weight, preferably 20 to 100 parts by weight based on 100 parts by weight of the entire photocurable (meth) acrylate resin composition. 65 parts by weight, more preferably 2
It is used in a proportion of 5 to 55 parts by weight. Photocurable polysiloxane urethane (meth) acrylate
Resin (B) The photocurable polysiloxane urethane (meth) acrylate resin (B) used in the present invention is a polydialkylsiloxane urethane (meth) acrylate, preferably polydimethylsiloxane urethane (meth) acrylate. , For example, by reacting isocyanates with silicone polyols and hydroxyalkyl (meth) acrylates, and acryloyl group (CH ₂ ═CH—CO—) or methacryloyl group (CH ₂ ═C) as a functional group in the molecule. (CH ₃₎ -CO-) having a urethane bond (and -NH-COO-), poly dialkyl siloxane bond, preferably polydimethyl siloxane bonds _{(- (- Si (CH 3} ) 2 -O-) n - ) Has.

Specific examples of the isocyanates used for synthesizing the polydialkylsiloxane urethane (meth) acrylate include hexamethylene diisocyanate [HDI] and isophorone diisocyanate [IPD].
I], methylenebis (4-cyclohexylisocyanate) [H ₁₂ MDI], trimethylhexamethylenediisocyanate [TMHMDI], tolylene diisocyanate [TDI], 4,4-diphenylmethane diisocyanate [MDI], xylylene diisocyanate [XDI] and other diisocyanates. And further, an adduct of an aliphatic polyhydric alcohol (i) having 3 or more valences and a diisocyanate (ii), and a trimer of a diisocyanate,
Examples thereof include a ring-containing isocyanurate structure (nurate structure) represented by the following formula [I], and a buret body formed by a reaction of diisocyanate and water.

[0021]

[Chemical 1]

Specific examples of the trihydric or higher aliphatic polyhydric alcohol (i) used as a constituent component of the adduct include glycerin and trimethylolpropane (TM).
P), 1,2,6-hexanetriol, trimethylolethane, 2,4-dihydroxy-3-hydroxymethylpentane,
1,1,1-tris (bishydroxymethyl) propane, 2,2-
Trihydric alcohols such as bis (hydroxymethyl) butanol-3; tetrahydric alcohols such as pentaerythritol and diglycerol; pentahydric alcohols (pentit) such as arabit, ribitol, xylitol; sorbit, mannitol, galactitol, alodulcit Hexahydric alcohol (hexite) etc. are mentioned. Of these, trimethylolpropane is particularly preferable.

Further, as the isocyanates (ii) used as a constituent component of the adduct, all the above-mentioned isocyanates can be mentioned, and among them, hexamethylene diisocyanate (HDI) is preferable. The adduct used in the present invention is obtained by addition-polymerizing the above-mentioned trivalent or higher polyhydric aliphatic alcohol (i) and isocyanates (ii).

The adducts preferably used in the present invention include, for example, compounds represented by the following formula.

[0025]

[Chemical 2]

The isocyanurate structure (nurate structure) used as the isocyanates in the present invention has one or more rings represented by the above general formula [I] in the molecule. The isocyanurate structure used in the present invention can be obtained, for example, by performing the above-mentioned trimerization reaction of hexamethylene diisocyanate (HDI).

The burette used in the present invention is synthesized by the reaction of diisocyanate and water, and the burette preferably used is, for example, a compound represented by the following formula.

[0028]

[Chemical 3]

As the silicone diols used for synthesizing the polydialkylsiloxane urethane (meth) acrylate, for example, diols represented by the following general formula are used.

[0030]

[Chemical 4]

(In the formula, each R ¹ independently represents -C _{3
H 6 OC 2 H 4 OH,} -C 3 H 6 OCH 2 -C (CH 2 OH) 2
—CH ₂ CH ₃ or an alkyl group, R ² and R ³ are each independently an alkyl group, a cycloalkyl group or a phenyl group, and n is 10 to 400, preferably 20 to 200. ) The alkyl group represented by R ¹ , R ² and R ³ has 1 to 4 carbon atoms, preferably 1
To alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and t-butyl group.

The cycloalkyl group of R ² and R ^{3 is} a cycloalkyl group having 5 to 12 carbon atoms, preferably 6 to 10 carbon atoms, for example, cyclopentyl group, cyclohexyl group, methylcyclohexyl group, cyclohebutyl group, cyclooctyl group, Examples thereof include a cyclononyl group, a cyclodecyl group, and a cyclododecyl group. Examples of R ² and R ³ include a phenyl group.

Specific examples of the above silicone diols include polysiloxane polyols having a hydroxyl group in polysiloxanes such as polydimethylsiloxane, polydiethylsiloxane, and polymethylphenylsiloxane, and preferably polydimethyl having a hydroxyl group. Siloxane polyols are good. Examples of the polydimethylsiloxane polyol having a hydroxyl group include polydimethylsiloxane monool having one hydroxyl group at one end, polydimethylsiloxanediol having two hydroxyl groups at one end, and polydimethyl having one hydroxyl group at both ends. Examples include siloxane diol.

Specifically, as a polydimethylsiloxane monool having one hydroxyl group at one end, X-22
-4015 (trade name; manufactured by Shin-Etsu Chemical Co., Ltd.), Silaplane FM-0411, FM-0412, FM-04
Examples of the polydimethylsiloxane diol having two hydroxyl groups at one end, such as 25 (trade name; manufactured by Chisso Co., Ltd.) include Silaplane FM-DA11, FM-DA12,
As the polydimethylsiloxane diol having one hydroxyl group at each end, such as FM-DA25 (trade name; manufactured by Chisso Corporation), X-22-160AS, KF-600.
1, KF-6002, KF-6003 (trade name; manufactured by Shin-Etsu Chemical Co., Ltd.), Silaplane FM-4411, F
M-4512, FM-4425 (trade name; Chisso Corporation)
Manufactured by Toagosei Co., Ltd.) and macromonomer HK-20 (trade name; manufactured by Toagosei Co., Ltd.).

Specific examples of hydroxyalkyl (meth) acrylates used in the synthesis of polydialkylsiloxane-based (meth) acrylates include 2-hydroxyethyl acrylate [HEA], 2-hydroxyethyl methacrylate [HEMA], 2 -Hydroxypropyl acrylate [HPA], 2-Hydroxypropyl methacrylate [HPMA], 4-Hydroxybutyl acrylate [4-HBA], Pentaerythritol triacrylate [PETA], HEA-added ε-caprolactone hydroxyacrylate [Plaxel FA1DT , F
A2D, FA3, FA4DT, FA-5 (trade name; manufactured by Daicel Chemical Industries, Ltd.) and the like, hydroxy methacrylate in which ε-caprolactone is added to HEMA [Placcel FA1D, FM2D, FM3, FM4, FM-5].
(Trade name; manufactured by Daicel Chemical Industries Ltd.) and the like] and the like.

The photocurable polysiloxane urethane (meth) acrylate resin (B) was added in an amount of 0.1% by weight based on 100 parts by weight of the entire photocurable (meth) acrylate resin composition.
It is used in a proportion of 5 to 20 parts by weight, preferably 1 to 10 parts by weight, more preferably 1 to 5 parts by weight. In the present invention, when the photocurable polysiloxane urethane (meth) acrylate resin (B) is used in the above ratio, stain removability can be imparted.

Photocurable silicone block (meth) ac
Relate-based resin (C) The photocurable silicone block (meth) acrylate-based resin (C) used in the present invention is a mercapto-modified polydimethylsiloxane, an epoxy group-containing ester of an unsaturated carboxylic acid, or any of the above components. Obtained by copolymerizing "another monomer" which is copolymerizable with the above, and then subjecting the obtained epoxy group-containing silicone block acrylic copolymer to an addition reaction with an unsaturated carboxylic acid, which is a mercapto-modified polydimethylsiloxane. An alkylene thioether group-containing polydimethylsiloxane-based component unit derived from, and an unsaturated group-containing (meth) acrylic acid ester-based component derived from an addition reaction between an epoxy group-containing ester of an unsaturated carboxylic acid and an unsaturated carboxylic acid Unit and the above mercapto-modified polydimethylsiloxane and And a component unit derived from with any copolymerizable monomer of the epoxy group-containing ester of a saturated carboxylic acid.

The photocurable silicone block (meth) acrylate resin (C) is composed of (A-1) an alkylenethioether group-containing polydimethylsiloxane component unit derived from a mercapto-modified polydimethylsiloxane, and (A)
-2) an unsaturated group-containing (meth) acrylic acid ester-based component unit derived from an addition reaction product of an unsaturated carboxylic acid epoxy group-containing ester with an unsaturated carboxylic acid, and (A-
3) The above mercapto-modified polydimethylsiloxane, and
And a component unit derived from another monomer copolymerizable with any of the epoxy group-containing esters of unsaturated carboxylic acids.

In the present invention, the above-mentioned alkylene thioether group-containing polydimethylsiloxane component unit (A-
As 1), as shown in the following formula (A-1b), “—RS— (R: a divalent hydrocarbon group which may have a substituent having 1 to 10 carbon atoms) is included in the side chain of polydimethylsiloxane. Having an alkylene thioether group (hydrocarbon group-containing thioether group) represented by the following formula (A-1
As shown in c), it is desirable that the polydimethylsiloxane has the above-mentioned alkylene thioether groups at both ends of the main chain. Furthermore, from the viewpoint of compatibility, the following formula (A-1) is used.
c) is desirable.

Formula (A-1b):

[0041]

[Chemical 5]

In the above formula (A-1b), m represents an integer of 10 to 400, n represents an integer of 1 to 100, R ¹ may have a substituent and has 1 to 10 carbon atoms. , Preferably 1
5 divalent hydrocarbon radical, especially an alkylene group of number of carbon atoms, e.g., propylene group (-CH ₂ CH ₂ CH
₂ −) and the like. Formula (A-1c):

[0043]

[Chemical 6]

In the above formula (A-1c), R ¹ may have a substituent, and is a divalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, particularly an alkylene group having the above carbon number. , For example,
A propylene group is shown and p shows the integer of 10-400.
As the macromonomer capable of deriving such a preferable alkylenethioether group-containing polydimethylsiloxane-based component unit (A-1), "KP-358" manufactured by Shin-Etsu Chemical Co., Ltd., which is a compound capable of deriving the formula (A-1b), "KF-200
1 "," KF-2004 ";" X-22-167B "manufactured by Shin-Etsu Chemical, which is a compound capable of inducing formula (A-1c), and the like.

In the photocurable silicone block (meth) acrylate resin (C) of the present invention, either one of such component units (A-1b) and (A-1c) is present. Although both may be present, the component unit (A-1b) is particularly preferable because it is excellent in stain removability of the resulting coating film. Further, as the unsaturated group-containing (meth) acrylic acid ester-based component unit (A-2),
Those represented by the following formula (A-2a) are preferable. (A-2a):

[0046]

[Chemical 7]

In the formula (A-2a), a plurality of R ^{3's, which} may be the same or different, each represents H or CH ₃ ,
⁴ has 1 to 10 carbon atoms which may have an ether bond.
Is an alkylene group. Particularly when R ⁴ is an alkylene group, it has 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms. When R ⁴ is an alkylene group having an ether bond, the total number of carbon atoms thereof is 2 to 10, preferably 2 to 5.

The above alkylene group R^FourAs a linear,
It may be alicyclic or branched, and specifically, for example,
-CH₂-,-(CH₂)₂-,-(CH₂)₃-, -CH (C
H₃) -CH₂-,-(CH₂)_Four-,-(CH₂)_Five-And so on
The above alkylene group having 1 to 4 carbon atoms is preferable,
On-CH₂-Is preferred. Alkyle having ether bond
Group R^FourMeans that some of the carbon atoms in the alkylene group are oxygen
Substituted with a child, for example, the formula "-R^a-OR^b
-"(However, R ^a, R^bAre each branched with 1 to 10 carbon atoms
R is an alkylene group which may have^aAnd R^bCharcoal
The sum of prime numbers is 1 to 10, preferably 2 to 5,
Is preferably R^aAnd R^bThe total carbon number of
And R^bBut-CH₂− Is desirable. )
To be done.

Specific examples of the ether bond-containing alkylene group include, for example, —CH ₂ —O—CH ₂ —, —
_{CH 2 -O- (CH 2) 2} -, - CH 2 -O- (CH 2) 3 -, - CH
_{(CH 3) -O-CH 2} -, - (CH 2) 4 -O-CH 2 - and the like, in particular _{- (CH 2) 4 -O-} CH 2 - is preferred. W is

[0050]

[Chemical 8]

(In the formula, a plurality of R ^{5 s} may be the same or different from each other, and R ⁵ is H or an alkyl group having 1 to 5 carbon atoms, preferably H or an alkyl group having 1 to 3 carbon atoms. R ⁵ bonded to adjacent carbon atoms may bond to each other together with other carbon atoms to form a ring structure such as a cyclohexyl ring, particularly an alicyclic structure).

The above-mentioned alkyl group is a straight-chain or alicyclic group.
It may be either branched or branched, and specifically, for example, -C
H₃, -C₂H_Five, -CH (CH₃)₂,-(CH₂)₂-CH₃,
-(CH ₂)₃-CH₃,-(CH₂)_Four-CH₃Etc.,
The above alkyl group having 1 to 3 carbon atoms is preferable, and especially -C
H₃Is preferred. T is a single bond or

[0053]

[Chemical 9]

One of the above groups is shown. ) Is mentioned. In the present invention, it is preferable that T is a single bond, that is, a monovalent direct bond not via another group or atom. The "other component unit" (A-3) is a component unit derived from an unsaturated carboxylic acid anhydride such as maleic anhydride or phthalic anhydride, or a unit represented by the following formula (A-3a). And the like, and those represented by the following formula (A-3a) are preferable.

[0055]

[Chemical 10]

In the formula (A-3a), R⁷Is H or CH₃To
Where X is R⁸OCO- {however, R ⁸Has 1 to 1 carbon atoms
8, preferably 1 to 8 alkyl groups, cyclohexyl
Group, benzyl group, isobornyl group:

[0057]

[Chemical 11]

^{_{[0058], R 9 OC 2 H 4 -}} (R 9: -CH 3, -C 2 H
Indicates either of ₅ ). _{}, C 6 H 5 -,} R 10 COO- (R
¹⁰ : H or an alkyl group having 1 to 5 carbon atoms), and these groups may have a substituent. Among these X, R ⁸ OCO- {R ⁸ is the same as above. ) Is desirable. Such other component units (A-
As 3), specifically, for example,

[0059]

[Chemical 12]

And the like, and one or more of these may be present. Among these, the other component units (A-3) include (e), (f), (la), that is,

[0061]

[Chemical 13]

Is particularly preferred. In the photocurable silicone block (meth) acrylate resin (C) of the present invention, these component units (A-1b) and / or (A-
1c), (A-2a) and (A-3a) may be present alone or in combination of two or more. In particular, when the component unit (A-1) constituting the photocurable silicone block (meth) acrylate resin (C) is a component unit (A-1b) having one "-R ¹ S-" In the copolymer, the copolymerization unit so that both ends of a long chain composed of the component unit (A-2) and the component unit (A-3) bound to each other in a block or random manner are blocked. It is considered that there is one component unit (A-1b) at each end of the united body, and the total amount of each component unit is as follows. Also, for example, this photocurable silicone block (meta)
Component unit (A-1) that constitutes the acrylate resin (C)
Is a component unit (A-1c) having one "-R ¹ S-" at both ends, in the copolymer,
One or more component units (A-1c) are present at one or more arbitrary positions in the long chain formed by the component units (A-2) and the component units (A-3) linked in a block or random manner. It is considered that the total amount of each component unit is present as follows by interposing the individual pieces.

In such a photocurable silicone block (meth) acrylate resin (C), the total of each component unit (A-1), (A-2) and (A-3) is 100% by weight.
The alkylenethioether group-containing polydimethylsiloxane-based component unit (A-1) is usually 1 to 8
The amount of the unsaturated group-containing (meth) acrylic acid ester-based component unit (A-2) is usually 1 to 80% by weight, preferably 0 to 50% by weight, particularly preferably 5 to 60% by weight. , Preferably 5 to 60% by weight, particularly preferably 10 to
It is desirable that the other component unit (A-3) is contained in the balance of 50% by weight.

When the amount of the alkylene thioether group-containing polydimethylsiloxane component unit (A-1) is within the above range, contaminants generated on the surface of the coating film can be easily and completely removed, and the hardness and abrasion of the coating film can be improved. The physical properties such as properties tend to be excellent, and if it is less than 1% by weight, the stain removability, that is, the property of easily and completely removing the contaminants generated on the surface of the coating film obtained tends to deteriorate. If it exceeds, physical properties such as hardness and abrasion resistance of the coating film may deteriorate. Further, when the amount of the unsaturated group-containing (meth) acrylic acid ester-based component unit (A-2) is within the above range, the crosslink density is high, and the solvent resistance and stain removability tend to be excellent, and the amount is less than 1% by weight. In that case, the cross-linking density is low, the solvent resistance and the stain removability tend to be lowered, and the copolymer exceeding 80% by weight tends to have a high viscosity and be difficult to synthesize.

The viscosity of such a photocurable silicone block (meth) acrylate resin (C) at 25 ° C. varies depending on the use of the copolymer used and is not unconditionally determined. Considering the viewpoint of preventing sagging when the obtained composition is diluted with a solvent, usually 10 cps to 100,000 (100,000) c
ps, preferably 100-30,000 (30,000) cps
Is desirable.

The acid value of the photocurable silicone block (meth) acrylate resin (C) is usually 0 to 1
0, preferably 0-5, and the number average molecular weight (Mn) by gel permeation chromatography (GPC) is usually 500-5,000, preferably 1,000-3,000. Weight average molecular weight (M
w) is usually 1,000 to 20,000 (20,000), preferably 2,000 to 10,000 (10,000), and the dispersion ratio (Mn / Mw) is usually 1.0 to 5 0.0, preferably 1.5 to 3.0.

<Photocurable Silicone Block (Meth)
Production of acrylate-based resin (C)> To produce such a photocurable silicone block (meth) acrylate-based resin (C), (a-1) mercapto-modified polydimethylsiloxane (macromonomer) and (a-1) -2) Copolymerizing an epoxy group-containing ester of an unsaturated carboxylic acid with (a-3) "another monomer" copolymerizable with any of the above components (a-1) and (a-2) Then, the obtained epoxy group-containing silicone block acrylic copolymer [A] and the unsaturated carboxylic acid [C] may be subjected to an addition reaction.

First, the above monomers (a-1) and (a-2)
The copolymerization reaction with (a-3) will be described in detail, and then the epoxy group-containing silicone block acrylic copolymer [A]
And the addition reaction with unsaturated carboxylic acid [C] will be described in detail. [Copolymerization Reaction of Monomers (a-1), (a-2) and (a-3)] That is, in the present invention, first, a mercapto-modified polydimethylsiloxane (a-1) and an unsaturated carboxylic acid The epoxy group-containing ester (a-2) and the "other monomer" (a-3) are copolymerized.

Such a copolymerization reaction is preferably carried out in the presence of a radical polymerization initiator, a solvent, an inert gas and the like, for example, by a solution polymerization method. In addition, these monomers (a
-1), (a-2) and (a-3) can be reacted at once or by adding and mixing in any order, in a preferred embodiment, with the monomer (a-1) (a-2) and (a-3) are added at the same time and reacted, or the monomer (a-1)
And a part of the monomer (a-2) and a part of the monomer (a-3) are reacted together, and the rest of the monomer (a-
It is preferable to add 2) and the monomer (a-3) and further carry out a copolymerization reaction. Thus, the monomer (a-1), the monomer (a-2) and the monomer (a-3) are added at the same time, or the total amount of the monomer (a-1) and a part of the monomer (a-2) and (a -3) is partially mixed with the rest of the monomers (a-2) and (a-3).
Monomer (a-2) and monomer (a-3), such as by adding and mixing
When the reaction with the monomer (a
-1) is added and reacted, unreacted monomer (a-1), that is, unreacted mercapto-modified polydimethylsiloxane (a-
The residual amount of 1) becomes small, and for example, the obtained coating film tends to have less cloudiness and excellent transparency.

Hereinafter, the raw material monomer for copolymerization, the catalyst for copolymerization, the solvent, which is used when the photocurable silicone block (meth) acrylate resin (C) of the present invention is produced,
The catalyst for addition reaction and the like will be described in detail. As the mercapto-modified polydimethylsiloxane (a-1), one represented by the following formula (A-1bb) or the following formula (A-1cc), particularly the following formula (A-1bb) can be obtained. It is preferable because it is excellent in removability and is well balanced in transparency and contact angle.

Formula (A-1bb):

[0072]

[Chemical 14]

In the formula (A-1bb), m represents an integer of 10 to 400, n represents an integer of 1 to 100, R ¹ may be substituted, and has 1 to 10 carbon atoms, preferably 1 carbon atom. A divalent hydrocarbon group of 5 to 5, especially an alkylene group having such a carbon number,
For example, a propylene group - shows the _{(-CH 2 CH 2 CH 2)} . Formula (A-1cc):

[0074]

[Chemical 15]

In the formula (A-1cc), R ¹ has 1 to 10 carbon atoms,
It is preferably a divalent hydrocarbon group having 1 to 5, especially an alkylene group having such a carbon number, for example, a propylene group (-CH ₂
CH ₂ CH ₂ -) indicates, p is an integer of 10 to 400. Examples of such a mercapto-modified polydimethylsiloxane (macromonomer) include "KP-358" and "KF-200" represented by the above formula (A-1bb) manufactured by Shin-Etsu Chemical.
1 "," KF-2004 ";" X-22-167B "manufactured by Shin-Etsu Chemical Co., Ltd. represented by the above formula (A-1cc) and the like.

In the present invention, these mercapto-modified polydimethylsiloxanes (macromonomers) (A-1b
Any one of b) or (A-1cc) may be used alone or two types may be used in combination.
It is also preferable that Examples of the epoxy group-containing ester (a-2) of the unsaturated carboxylic acid include those represented by the following formula (A-2a
a):

[0077]

[Chemical 16]

[In the formula (A-2aa), R ³ is H or CH ₃
R ⁴ represents an alkylene group having 1 to 10 carbon atoms which may have an ether bond, and W ¹ represents

[0079]

[Chemical 17]

(In the formula, plural R ^{5 s} may be the same or different from each other and represent H or an alkyl group having 1 to 5 carbon atoms, and R ^{5 s} bonded to adjacent carbon atoms are different from each other. , For example, may be bonded to each other together with carbon atoms constituting an epoxy group to form a ring structure such as a cyclohexyl ring, particularly an alicyclic structure. ] What is represented by these is preferable.

More specifically, as the epoxy group-containing ester (a-2) of the unsaturated carboxylic acid, more specifically, the following formula (A-2aa-1) or formula (A-2aa-2):

[0082]

[Chemical 18]

[In the formula (A-2aa-1), R ^4a represents the above alkylene group which may have an ether bond, and R ³
R ⁵ is the same as above. In the formula (A-2aa-2), R
^4b represents the above alkylene group having no ether bond, and R ³ is the same as above. ] Is desirable. As such epoxy group-containing ester of unsaturated carboxylic acid (a-2), more specifically,

[0084]

[Chemical 19]

And the like, methacrylic acid glycidyl ester is preferred. As the other monomer (a-3),
Examples thereof include unsaturated carboxylic acid anhydrides such as maleic anhydride and fumaric anhydride, and those represented by the following formula (A-3aa).

[0086]

[Chemical 20]

In the formula (A-3aa), R ⁷ represents H or CH ₃ . X is R ⁸ OCO- {wherein R ⁸ is an alkyl group having 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms similar to the above, a cyclohexyl group, a benzyl group, an isobornyl group, R ⁹ OC ₂ Any one of H ₄ — (R ⁹ : —CH ₃ , —C ₂ H ₅ ) is shown. }, A phenyl group _{(C 6 H 5 -),} R 10 COO
-(R ¹⁰ : H or an alkyl group having 1 to 5 carbon atoms similar to the above), a hydrogen atom, a halogen atom, and 1 to 1 carbon atoms
0 alkyl group, epoxy group-containing group, C 1-10 alkoxy group, C 2-10 double bond-containing group, naphthyl group, pyridyl group, aldehyde group (-CHO), nitrile group (-CN) , trimethoxysilylpropyl group _{[-OC 3 H 6 -Si (OCH} 3) 3], triethoxysilyl group _{[-Si (OC 2 H 5)} 3],

[0088]

[Chemical 21]

And the like. These groups have substituents
You may have. “Other models” represented by this formula (A-3aa)
In Nomar, X is R⁸OCO- {however, R⁸Is
The number of carbon atoms is 1 to 18, preferably 1 to 8
Similar alkyl groups, cyclohexyl groups, benzyl groups,
Sobornyl group, R⁹OC₂H_Four-(R⁹: -CH₃, -C₂H
_Five). }, A phenyl group (C₆H_Five-), R
^TenCOO- (R^Ten: H or same as above with 1 to 5 carbon atoms
Preferred alkyl groups) are preferred. In addition, these
Some of the hydrogen atoms (H) in the groups of are other groups or atoms.
It may be substituted. Such a substitutable group or
Is an atom, for example, hydroxyl group (OH-), halogen
An atom etc. are mentioned. In the present invention, among these X
Is the above R⁸OCO- (R⁸Is the same as above. ) Is especially desirable
Good

As the other monomer (a-3) represented by the formula (A-3aa), more specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate,
Propyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acrylic acid 2-ethoxyethyl, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth)
Tertiary acrylate, methyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, styrene, vinyltoluene, vinyl acetate, vinyl fluoride, vinyl chloride , Ethylene, propylene, dienes (eg butadiene, etc.), acrolein (acrylaldehyde), acrylonitrile, N-vinylpyrrolidone, N-vinylcaprolactam, vinyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, etc. Can be mentioned.

Among these other monomers (a-3),
Methyl (meth) acrylate and isobornyl (meth) acrylate are preferably used. These other monomers (a
-3) can be used alone or in combination of two or more. In the present invention, during such a copolymerization reaction,
The total amount of the monomers (a-1), (a-2) and (a-3) is 100% by weight, and the mercapto-modified polydimethylsiloxane (a
-1) is usually 1 to 80% by weight, preferably 5 to 60% by weight, particularly preferably 10 to 50% by weight, and the epoxy group-containing ester of unsaturated carboxylic acid (a-2) is usually ,
The amount of the other monomer (a-) is 1 to 80% by weight, preferably 5 to 60% by weight, particularly preferably 10 to 50% by weight.
3) is used in the balance.

When the amount of the mercapto-modified polydimethylsiloxane (a-1) is within the above range, contaminants generated on the surface of the obtained coating film can be easily and completely removed, and the hardness and abrasion resistance of the coating film can be improved. It is preferable because physical properties such as tend to be excellent. In addition, epoxy group-containing ester of unsaturated carboxylic acid
When the amount of (a-2) is within the above range, the crosslinking density tends to be high, and the solvent resistance and stain removability tend to be excellent.

Further, in such a copolymerization reaction (radical polymerization reaction), a conventionally known method can be used,
A catalyst or a solvent may or may not be used, and examples thereof include a radiation irradiation method and a method using a radical polymerization initiator (copolymerization catalyst). Among these, polymerization operability and ease of molecular weight adjustment are included. Considering the above, a method using a radical polymerization initiator is preferable. Examples of the method using this radical polymerization initiator include a solution polymerization method using a solvent, a bulk polymerization method, and an emulsion polymerization method.

Thus, the copolymerization reaction can be carried out in the absence of a catalyst or solvent, but is preferably carried out in the presence of a copolymerization catalyst and / or solvent, and in a preferred embodiment thereof, it is unsaturated. At a reaction temperature at which polymerization of the carboxylic acid does not occur, preferably at a temperature of 40 to 160 ° C., under normal pressure or under pressure (eg 10 to 300 kgf / cm ² ), 3
It is desirable to proceed by holding it for about 0 minutes to 20 hours.

The copolymerization catalyst used at this time is
2,2'-azobis (2-methylbutyronitrile),
2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis-isobutyronitrile, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, t-butylperoxy Examples thereof include benzoate. Such a copolymerization catalyst is, for example, 0.01 to 15 parts by weight, preferably 0 to 100 parts by weight of the raw material monomers (a-1), (a-2) and (a-3). 0.1 to 8 parts by weight. Such a catalyst may be added at once, or may be added in a plurality of times, but it is preferable to add the catalyst in a plurality of times in terms of adjustment of molecular weight, reaction efficiency, and conversion rate.

As the solvent, the above-mentioned monomer for copolymerization (a-
1), (a-2), (a-3) is inert without reacting with, and is not particularly limited as long as these monomers can be dissolved, for example, aromatic hydrocarbons such as toluene, xylene Solvents; Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone; Ester solvents such as ethyl acetate, propyl acetate, isobutyl acetate, butyl acetate; Methanol, isopropyl alcohol, ethanol, n
-Alcohol solvents such as butanol and isobutanol; and the like, and butyl acetate is preferable. These solvents are used in an amount of, for example, 1 to 500 parts by weight, preferably 10 to 300 parts by weight, based on 100 parts by weight of the total amount of the monomers for copolymerization.

[Addition Reaction of Epoxy Group-Containing Silicon Block Acrylic Copolymer with Unsaturated Carboxylic Acid] In the present invention, the epoxy group-containing silicone block acrylic copolymer [A] obtained after the above copolymerization reaction , An unsaturated carboxylic acid [C] is subjected to an addition reaction.

Thus, the epoxy group-containing silicone block acrylic copolymer [A] and the unsaturated carboxylic acid [C]
When an addition reaction is performed with, for example, as shown in the following formula <P> or the following formula <Q>, the epoxy group of the epoxy group-containing silicone block acrylic copolymer [A] and the carboxyl group of the unsaturated carboxylic acid React to form an unsaturated group-containing (meth) acrylic acid ester-based component unit (A-2), preferably represented by formula (A-2a-1) or formula (A-2a-2). Then, the photocurable silicone block (meth) acrylate resin (C) of the present invention is obtained.
(Note that the abbreviations in the following formulas have the same meanings as described above.) <Formula P>

[0099]

[Chemical formula 22]

<Q>

[0101]

[Chemical formula 23]

In the present invention, such an addition reaction can be carried out in the absence of a catalyst or a solvent, but is preferably a catalyst for addition reaction and / or a solvent similar to that used in the above-mentioned copolymerization reaction. And the like, and in a preferred embodiment thereof, at a reaction temperature at which polymerization of the unsaturated carboxylic acid does not occur, preferably at a temperature of 40 to 130 ° C., under normal pressure or under pressure (eg: 10 to 300 kgf / c).
m ² ) for about 30 minutes to 20 hours,
The photocurable silicone block (meth) acrylate resin (C) of the present invention can be obtained by advancing the addition reaction.

Examples of the addition reaction catalyst used at this time include N, N-dimethylbenzialamine, N, N-dimethylphenylamine, triethylamine, triphenylphosphine, tributylphosphine, trimethylbenzylammonium chloride, triethylbenzylammonium chloride and the like. Is mentioned. Such an addition reaction catalyst is, for example, 0.01 to 10 parts by weight, preferably 0 to 100 parts by weight of the raw material monomers (a-1), (a-2) and (a-3). 0.1 to 5 parts by weight.

As the solvent, the same inert solvent as that used in the above copolymerization reaction is used. In the present invention, in the addition reaction, in addition to the solvent used in the copolymerization reaction, an organic solvent similar to this, for example, butyl acetate may be additionally used. By such addition reaction, the photocurable silicone block (meth) acrylate resin (C) as described above is obtained, and its viscosity, acid value, gel permeation chromatography (GPC) is obtained.
Number average molecular weight (Mn), weight average molecular weight (M
w), dispersion ratio (Mn / Mw), etc. are as described above.

The unsaturated carboxylic acid used in the addition reaction is, for example, as follows:

[0106]

[Chemical formula 24]

In addition to the above, it has a hydroxyl group (meth)
Examples thereof include reaction products of an acrylate and a dibasic acid anhydride (eg, succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, etc.). Of these, acrylic acid is particularly preferable in view of its excellent reaction rate.

These unsaturated carboxylic acids are theoretically equivalent to the epoxy groups in the obtained epoxy group-containing silicone block acrylic copolymer [A], in other words, the copolymer [A]. A] Epoxy group-containing ester of unsaturated carboxylic acid used at the time of synthesis (a-2) For example, glycidyl (meth) acrylate and the like may be used in equimolar amounts, but usually epoxy group-containing ester of unsaturated carboxylic acid
The unsaturated carboxylic acid is used in an amount of 10 to 500 parts by weight, preferably 30 to 300 parts by weight, based on 100 parts by weight of (a-2).

In addition, the unsaturated carboxylic acid (eg acrylic acid) used in the addition reaction under heating.
The polymerization reaction at the double bond site of is likely to proceed under heating, and a polymerization inhibitor may be added in order to promote the above addition reaction while suppressing / blocking this radical polymerization reaction. As such a polymerization inhibitor, for example, p-methoxyphenol, hydroquinone, pt-butylcatechol, phenothiazine and the like are used.

The photocurable silicone block (meth) acrylate resin (C) is 5 to 60 parts by weight, preferably 10 to 55 parts by weight, based on 100 parts by weight of the entire photocurable (meth) acrylate resin composition. Parts, more preferably 15 to 50 parts by weight. The photocurable (meth) acrylate-based resin composition according to the present invention has poor compatibility between the photocurable (meth) acrylate-based resin (A) and the (meth) acrylate-based monomer (E) and these components. Photocuring compatible with any of the components (A), (E) and (B) as an intermediate for satisfactorily mixing with the photocurable polysiloxane urethane (meth) acrylate resin (B) Since the silicone block (meth) acrylate resin (C) is used in the above proportion, it is possible to form a film excellent in stain removability.

Photopolymerization Initiator (D) Specific examples of the photopolymerization initiator (D) used in the present invention include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether. -Based photopolymerization initiators; benzyl dimethyl ketal (also known as 2,2-dimethoxy-2-phenylacetophenone), diethoxyacetophenone, 4-phenoxydichloroacetophenone,
4-t-butyl-dichloroacetophenone, 4-t-butyl-trichloroacetophenone, 2-hydroxy-2-methyl-1-
Phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-
(4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone, 2- Acetophenone-based photopolymerization initiators such as methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone , 4-benzoyl-4'-methyldiphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone and other benzophenone-based photopolymerization initiators; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4 -Dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-die Examples thereof include thioxanthone photopolymerization initiators such as tylthioxanthone and 2,4-diisopropylthioxanthone. Among them, benzyl dimethyl ketal and 1-hydroxycyclohexyl phenyl ketone are preferably used.

The photopolymerization initiator (D) as described above is used as the photocurable (meth) acrylate resin composition composition as a whole.
0 to 10 parts by weight, preferably 2 to 8 parts by weight
It is used in an amount of 3 parts by weight, more preferably 3 to 6 parts by weight. (Meth) acrylate-based monomer (E) Specific examples of the (meth) acrylate-based monomer used in the present invention include alkylene polyols and polyether polyols having a low polymerization rate, and (meth) acrylic acid. 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, 2 (2-ethoxyethoxy) ethyl acrylate, tetrahydrofurfuryl acrylate, 2-phenoxyethyl acrylate, diethylene glycol Diacrylate, tetraethylene glycol diacrylate, 1,3-butylene glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, hydroxy Such as pivalic acid neopentyl glycol diacrylate.

The above-mentioned (meth) acrylate-based monomer (E) can be used as a reactive diluent alone or in combination of two or more. The (meth) acrylate-based monomer (E) is, if necessary, usually 5 to 40 parts by weight, preferably 10 to 30 parts by weight, based on 100 parts by weight of the entire photocurable (meth) acrylate-based resin composition. More preferably, it is used in a proportion of 15 to 25 parts by weight.

Other Components The photocurable (meth) acrylate resin (A) and the photocurable polysiloxane urethane are added to the photocurable (meth) acrylate resin composition having excellent stain removability according to the present invention. In addition to the (meth) acrylate resin (B), the photocurable silicone block (meth) acrylate resin (C), the photopolymerization initiator (D) and the (meth) acrylate monomer (E), if necessary, Polymerization inhibitor, non-reactive diluent, matting agent, defoaming agent, anti-settling agent, leveling agent,
A dispersant, a heat stabilizer, an ultraviolet absorber and the like can be added within a range that does not impair the object of the present invention.

Preparation of Composition The photocurable (meth) acrylate resin composition according to the present invention contains the above-mentioned components in a conventionally known mixer, disperser,
It can be obtained by mixing and stirring using a device such as a stirrer. Examples of such an apparatus include a mixing / dispersion mill, a mortar mixer, a roll, a paint shaker,
A homogenizer etc. are mentioned.

The photocurable (meth) acrylate resin composition according to the present invention can be applied to the surface of various base materials as an overcoat by any conventionally known method. Examples of the coating method include a spraying method, an airless spray method, an air spray method, a brush coating, a roller coating, a trowel coating, a dipping method, a pulling method, a nozzle method, a winding method, a sinking method, a coating method and a patching method. , May be automated or may be painted manually.

Specific examples of the base material include wood-based substrates such as plywood, hard boards, and particle boards, flexible boards, calcium silicate boards, gypsum boards, asbestos slate boards, and other non-combustible building materials, paper-based materials, and plastics. , Metals such as iron, and the like. Examples of the wooden substrate include a wooden floor base material, a wooden furniture material, a wooden wall material, a wooden ceiling material, a counter table, and a wooden stair material.

When a photocurable (meth) acrylate resin composition according to the present invention is applied, when a porous base material such as wood material, non-combustible building material or paper material is used as the base material, the base material is used. It is desirable to form a sealing coating film and / or a colored undercoat coating film by a sealing treatment and / or undercoating in advance. Particularly, in the case of an alkaline inorganic porous substrate, an alkali on the substrate surface is It is desirable to previously apply a sealer treatment for the purpose of preventing exudation. Further, before coating the photocurable (meth) acrylate resin composition, for example, printing may be performed for patterning on the colored undercoat coating film.

The coating of the photocurable (meth) acrylate resin composition is carried out by using a coating machine such as a rubber or sponge roll coater, a spray coater and a vacuum coater. These coating machines can be used alone or in combination of two or more. The coating amount of the photocurable (meth) acrylate resin composition varies depending on the type of base material used and the application, but in the case of a wood floor base material, it is usually 5 to 200 g / m ² , preferably 10 in a wet state. -10
Is preferably a 0 g / m ^2, also in the case of inorganic porous substrate, typically 5 to 200 g / m ² in the wet state,
It is preferably 10 to 100 g / m ² .

The number of times the photocurable (meth) acrylate resin composition is applied is not particularly limited and may be once or twice or more. By applying an electron beam or light, preferably light to the coating surface of the photocurable (meth) acrylate resin composition coated on the substrate surface as described above to cure the wet coating film. A cured coating film (coating) having excellent stain removability can be obtained.

This electron beam irradiation can be performed by a conventionally known irradiation method. For example, 200 kV, 3-1
The coating film is cured by electron beam irradiation under the condition of 0 Mrad.
The light for light irradiation is ultraviolet light or visible light, and light irradiation can be performed by a conventionally known irradiation method. For example, a high pressure mercury lamp is 80 to 120 W / cm.
The belt speed is 5 to 20 m / min with one light, and the belt speed can be increased by increasing the number of lights. Further, the belt speed can be increased by increasing the W / cm capacity.

The coating film according to the present invention is a coating film (coating film) formed from the above-mentioned photocurable (meth) acrylate resin composition according to the present invention by the method as described above.
The coated substrate according to the present invention is a substrate whose surface is coated with this coating.

[0123]

The photo-curable (meth) acrylate resin composition according to the present invention is excellent in stain removability, and the surface of a substrate such as a wood material or a non-combustible building material is contaminated with blue ink, magic or the like. Even if it is applied, it is possible to form a film capable of easily removing the dirt.

Further, since the coating film of the present invention is formed from the photocurable (meth) acrylic resin composition of the present invention having the above effects, it is excellent in stain removability. Since the surface of the coated substrate according to the present invention is coated with the above coating, the coated surface is excellent in stain removability.

[0125]

The present invention will be described below with reference to examples.
The present invention is not limited to these examples. The finish appearance, the adhesion of the coating film and the stain removability in Examples and Comparative Examples were evaluated according to the following methods. (1) Finished Appearance The coating film formed on the surface of the wooden floor material was visually observed, and cissing and transparency of the coating film were evaluated in three levels.

<Three-stage evaluation> 3 ... The coating film is transparent without cissing. (Pass) 2 ... Slight cissing and cloudiness of the coating film. (Failure) 1 ... There is slight cissing and turbidity of the coating film. (Failure) (2) Adhesion of coating film Adhesion of coating film is based on JIS K 5400 and is a cross-cut test (cross-cut test of 2 mm width, cellophane tape (R) peeling test).
Was carried out, and the number of remaining squares of the coating film was evaluated.

<3-level evaluation> 3 ... Remaining squares 98 to 100 (pass) 2 ... Remaining squares 90 to 97 (fail) 1 ... Remaining squares 89 or less (Failure) (3) Contamination removability (A) The surface of the coating film formed on the surface of the wooden floor material is stained with black magic, red magic, red crayon, blue ink, and 4 hours later, with water or JAS lacquer thinner. The surface was wiped off, and the surface was visually observed, and the stain removability was evaluated in three levels.

<3-level evaluation> 3 ... No stain. (Pass) 2 ... Slight stain. (Pass) 1 ... There is dirt. (Failure) (4) Contamination removability (B) The surface of the coating film formed on the surface of the wooden floor material is stained with black magic, and after 5 seconds, wiped dry with a waste cloth. This operation was repeated at the same location, and the stain removal property was evaluated on a scale of 5 by the number of times until a black magic mark remained.

<5-level evaluation> 5 ... Black magic can be wiped off 30 times or more. (Pass) 4 ... A black magic mark remains between 10 and 29 times. (Pass) 3 ... Black magic marks remain between 5 and 9 times. (Failure) 2 ... A black magic mark remains between 2 and 4 times. (Failure) 1 ... A black magic mark remains in one shot. (failure)

[0130]

[Synthesis example of polydimethylsiloxane urethane acrylate resin] KF6003 [trade name; in a reaction vessel of 1 liter capacity equipped with a stirrer, a thermometer and a reflux condenser]
Shin-Etsu Chemical Co., Ltd., reactive silicone oil] 44
8 parts by weight, Coronate HX [trade name; manufactured by Nippon Polyurethane, isocyanurate type of HDI] 94.6 parts by weight, Praxel FA2D [trade name; manufactured by Daicel Chemical Industries, Ltd., monomer obtained by adding ε-caprolactone to HEA] 112.9 parts by weight, p-methoxyphenol (polymerization inhibitor) 0.046 parts by weight, dibutyltin dilaurate 0.131 parts by weight, and butyl acetate 163.8 parts by weight are charged and heated to 80 ° C. for 1 hour. After the temperature was maintained, 0.393 parts by weight of dibutyltin dilaurate was added and the temperature was further maintained at 80 ° C. for 3 hours. The obtained resin solution was analyzed by an infrared spectrophotometer (IR), and as a result, the NCO absorption peak had disappeared.

The obtained resin solution had a nonvolatile content of 80.4
% By weight, a viscosity measured by an E-type viscometer manufactured by Tokyo Keiki Co., Ltd. is a cloudy solution having a viscosity of 13,930 cps / 25 ° C.
Gel Permeation Chromatography (GP
The number average molecular weight (Mn) according to C) is 2,210,
The weight average molecular weight (Mw) is 11,740, and
The dispersion ratio (Mw / Mn) was 5.32. Hereinafter, this resin solution is abbreviated as resin A.

The resin A is presumed to have the following structural formula.

[0133]

[Chemical 25]

(In the formula, X is-(CH ₂ ) in each of two nitrogen atoms of the three nitrogen atoms forming the ring of the isocyanurate structure represented by the above general formula [I]. _{6 -NH-CO - [- O} (CH 2) 5 CO-] 2 -O-C 2 H 4
O-CO-CH = CH ₂ represents a group attached, R _{represents, -C 3 H 6 OC 2 H} 4 -
Represents a group. )

[0135]

[Synthesis example of photo-curable silicone block acrylate resin] 100 parts by weight of butyl acetate was charged into a 300 ml reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas introduction tube and a reflux cooling tube, and the temperature was 100 ° C in a nitrogen gas atmosphere. The temperature was raised to. 50 parts by weight of methyl methacrylate (MMA), 30 parts by weight of glycyl methacrylate (GMA) and ABN-
E [trade name; 2,2'-azobis (2-methylbutyronitrile) manufactured by Nippon Hydrazine Co., Ltd.]
2-167B [trade name; manufactured by Shin-Etsu Chemical Co., Ltd., mercapto-modified polydimethylsiloxane] (20 parts by weight) was simultaneously added dropwise at 100 ° C. The mixture was added dropwise over 2 hours, and X22-167B was added dropwise over 1 hour. While maintaining the same temperature, ABN-E was added every 30 minutes after completion of the dropping.
After adding 0.2 parts by weight twice, the mixture was kept warm for 6 hours.

Further, 15.52 parts by weight of 98% acrylic acid, 15.52 parts by weight of butyl acetate, 0.0078 parts by weight of p-methoxyphenol, dimethylbenzylamine 1.
65 parts by weight was added, and the mixture was reacted at 110 ° C. for 5 hours. Thus, a photocurable silicone block acrylic resin B was obtained. The resin B thus obtained was a translucent solution having a nonvolatile content of 49.8%, a viscosity of 8240 cps / 25 ° C., and an acid value of 4.0, and the number was measured by gel permeation chromatography (GPC). Average molecular weight (Mn) is 1680
The weight average molecular weight (Mw) was 3640, and the dispersion ratio Mn / Mw was 2.17.

[0137] The resin B, an acrylic _{backbone, -SR (-Si (CH 3)} 2 -O-) n -Si (CH 3) 2 -R
S- (R in the formula, C ₃ H ₆₎ has, on side _{chain, -COO-CH 2 CH (OH} ) -CH 2 -OCO-CH = C
It is presumed to have a structural formula with H ₂ .

[0138]

Example 1 [Preparation of coating composition] 1 part by weight of resin A (polydimethylsiloxane urethane acrylate resin) obtained in the above synthesis example was dissolved in 1 part by weight of toluene, and further obtained in the above synthesis example. It was mixed with 25 parts by weight of Resin B (photocurable silicone block acrylate resin).

Next, as a photocurable (meth) acrylate resin, UV-72 [trade name; urethane acrylate resin manufactured by Otakena Shinkagaku Co., Ltd.] 19 parts by weight, Hitaloid 85
1 (20TP) [Product name: Epoxy acrylate resin manufactured by Hitachi Chemical Co., Ltd.] 19 parts by weight, Irgacure 184 as a photopolymerization initiator [Product name: Ciba Specialty Chemicals] 4 parts by weight, diluting solvent Then, 31 parts by weight of butyl acetate was added and stirred to prepare a photocurable coating composition. [Preparation of wood flooring coating product] First, a colored stain [manufactured by China Paint Co., Ltd., trade name Stain W EXL] is applied to the wood flooring material with a roll coater and dried at 80 ° C for 1 minute, and then Undercoat UV paint on top [Product name: Aulex No., manufactured by China Paint Co., Ltd.] 822F-2) was applied with a roll coater and UV cured.

Next, on the obtained cured coating film, an intermediate coating UV paint [China Paint Co., Ltd., trade name Aurex N]
o. 674B] was similarly applied and UV-cured, and the photocurable coating composition obtained as above as an overcoat paint was applied by a roll coater and UV-cured to prepare a wood flooring coating product. With respect to the coated product of the wooden flooring material obtained as described above, the finished appearance, the adhesion of the coating film, and the stain removability (A) and (B) were evaluated according to the methods described above. The results are shown in Table 1.

[0141]

[Example 2] [Preparation of coating composition] In Example 1,
31 parts by weight of butyl acetate is used as an acrylic monomer GX
-8301S [trade name; manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.] 20 parts by weight, TRPGDA [trade name; manufactured by Daicel UCB] 7
A photocurable coating composition was prepared in the same manner as in Example 1 except that 4 parts by weight of New Frontier PET-3 [trade name; manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.] was used. [Preparation of wood floor material coated product] A wood floor material coated product was prepared in the same manner as in Example 1.

With respect to the coated wood flooring material obtained as described above, the finished appearance, the adhesion of the coating film, and the stain removability (A) and (B) were evaluated according to the methods described above. The results are shown in Table 1.

[0143]

[Example 3] [Preparation of coating composition] In Example 2,
Resin A content is changed from 1 part by weight to 2 parts by weight, and GX-83
A photocurable coating composition was prepared in the same manner as in Example 2 except that the blending amount of 01S was changed from 20 parts by weight to 18 parts by weight. [Preparation of wood floor material coated product] A wood floor material coated product was prepared in the same manner as in Example 1.

With respect to the coated wood flooring material obtained as described above, the finished appearance, the adhesion of the coating film, and the stain removability (A) and (B) were evaluated according to the methods described above. The results are shown in Table 1.

[0145]

[Example 4] [Preparation of coating composition] In Example 2,
Except that the amount of resin A was changed from 1 part by weight to 4 parts by weight, the amount of toluene was changed from 1 part by weight to 4 parts by weight, and the amount of GX-8301S was changed from 20 parts by weight to 14 parts by weight.
A photocurable coating composition was prepared in the same manner as in Example 2. [Preparation of wood floor material coated product] A wood floor material coated product was prepared in the same manner as in Example 1.

With respect to the coated wood flooring material obtained as described above, the finished appearance, the adhesion of the coating film, and the stain removability (A) and (B) were evaluated according to the methods described above. The results are shown in Table 1.

[0147]

[Example 5] [Preparation of coating composition] In Example 2,
A photocurable coating composition was obtained in the same manner as in Example 2 except that the amount of the resin B was changed from 25 parts by weight to 40 parts by weight and the amount of Hitaloid 851 (20TP) was changed from 19 parts by weight to 4 parts by weight. The thing was prepared. [Preparation of wood floor material coated product] A wood floor material coated product was prepared in the same manner as in Example 1.

With respect to the coated wood flooring material obtained as described above, the finished appearance, the adhesion of the coating film, and the stain removability (A) and (B) were evaluated according to the methods described above. The results are shown in Table 1.

[0149]

[Example 6] [Preparation of coating composition] In Example 2,
The resin A content was changed from 1 to 4 parts by weight, the toluene content was changed from 1 to 4 parts by weight, and the resin B content was changed to 2 parts.
Example 2 was repeated except that the amount of GX-8301S was changed from 20 parts by weight to 0 part by weight, and the amount of TRPGDA was changed from 7 parts by weight to 6 parts by weight. A photocurable coating composition was prepared. [Preparation of wood floor material coated product] A wood floor material coated product was prepared in the same manner as in Example 1.

With respect to the coated wood flooring material obtained as described above, the finished appearance, the adhesion of the coating film, and the stain removability (A) and (B) were evaluated according to the methods described above. The results are shown in Table 1.

[0151]

[Example 7] [Preparation of coating composition] In Example 2,
The compounding amount of GX-8301S was changed from 20 parts by weight to 14 parts by weight, and Mizuka Seal P-80 was used as a matting agent.
A photocurable coating composition was prepared in the same manner as in Example 2 except that 6 parts by weight of 2Y [trade name; manufactured by Mizusawa Chemical Co., Ltd.] was used. [Preparation of wood floor material coated product] A wood floor material coated product was prepared in the same manner as in Example 1.

With respect to the coated wood flooring material obtained as described above, the finished appearance, the adhesion of the coating film, and the stain removability (A) and (B) were evaluated according to the methods described above. The results are shown in Table 1.

[0153]

Comparative Example 1 [Preparation of coating composition] In Example 1,
UV-72, Hitaloid 7851 (20TP), Resin A, Toluene, Resin B, Butyl acetate content was changed to 30 parts by weight, 30 parts by weight, 0 parts by weight, 0 parts by weight, 0 parts by weight, 36 parts by weight, respectively. A photocurable coating composition was prepared in the same manner as in Example 1 except for the above. [Preparation of wood floor material coated product] A wood floor material coated product was prepared in the same manner as in Example 1.

With respect to the coated wood flooring material obtained as described above, the finished appearance, the adhesion of the coating film, and the stain removability (A) and (B) were evaluated according to the methods described above. The results are shown in Table 1.

[0155]

[Comparative Example 2] [Preparation of coating composition] In Example 1,
UV-72 content from 19 to 20 parts by weight, Hitaroid 7851 (20TP) content from 19 to 20 parts by weight, Resin A content from 1 to 0 parts by weight, toluene A photocurable coating composition was prepared in the same manner as in Example 1 except that the compounding amount was changed from 1 part by weight to 0 part by weight. [Preparation of wood floor material coated product] A wood floor material coated product was prepared in the same manner as in Example 1.

With respect to the coated wood flooring material obtained as described above, the finished appearance, the adhesion of the coating film, and the stain removability (A) and (B) were evaluated according to the methods described above. The results are shown in Table 1.

[0157]

[Comparative Example 3] [Preparation of coating composition] In Example 1,
The amount of UV-72 was changed from 19 parts by weight to 32 parts by weight, the amount of Hitaloid 7851 (20TP) was changed from 19 parts by weight to 31 parts by weight, and the amount of resin B was changed from 25 parts by weight to 0 parts by weight. A photocurable coating composition was prepared in the same manner as in Example 1 except for the above. [Preparation of wood floor material coated product] A wood floor material coated product was prepared in the same manner as in Example 1.

With respect to the coated wood flooring material obtained as described above, the finished appearance, the adhesion of the coating film, and the stain removability (A) and (B) were evaluated according to the methods described above. The results are shown in Table 1.

[0159]

[Comparative Example 4] [Preparation of coating composition] In Example 2,
UV-72 content from 19 to 20 parts by weight, Hitaroid 7851 (20TP) content from 19 to 20 parts by weight, Resin A content from 1 to 0 parts by weight, toluene A photocurable coating composition was prepared in the same manner as in Example 2 except that the blending amount was changed from 1 part by weight to 0 part by weight. [Preparation of wood floor material coated product] A wood floor material coated product was prepared in the same manner as in Example 1.

With respect to the coated wood flooring material obtained as described above, the finished appearance, the adhesion of the coating film, and the stain removability (A) and (B) were evaluated according to the methods described above. The results are shown in Table 1.

[0161]

[Comparative Example 5] [Preparation of coating composition] In Example 2,
Resin B content is changed from 25 parts by weight to 0 parts by weight, GX-8
Change the blending amount of 301S from 20 parts by weight to 30 parts by weight, TR
Change the amount of PGDA compounded from 7 to 17 parts by weight,
A photocurable coating composition was prepared in the same manner as in Example 2 except that 5 parts by weight of Mizuka Seal P-802Y [trade name; manufactured by Mizusawa Chemical Co., Ltd.] was used as a matting agent. [Preparation of wood floor material coated product] A wood floor material coated product was prepared in the same manner as in Example 1.

With respect to the coated wood flooring material obtained as described above, the finished appearance, the adhesion of the coating film, and the stain removability (A) and (B) were evaluated according to the methods described above. The results are shown in Table 1.

[0163]

[Table 1]

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09D 175/14 C09D 175/14 183/10 183/10 183/14 183/14 201/02 201/02 F term (reference) 4F100 AK25A AK25J AK51A AK51J AK52A AK52J AL01A AT00B BA02 BA07 BA10A CA30A CA30H GB08 JB14A JL06 4J027 AB01 AB02 AB06 AB15 AB18 AB23 AB24 AC01 AE01 AE02 AE03 AF01 AG01 AG12 AG23 AG24 AG25 AG34 AH03 AJ09 4J038 FA111 FA112 FA241 FA242 FA251 FA252 FA261 FA262 FA271 FA272 FA281 FA282 GA13 JA24 JA33 JC18 KA03 NA05 PA17

Claims (6)

[Claims] 1. A photocurable (meth) acrylate resin (A) and a photocurable polysiloxane urethane (meth) (B).
A photocurable (meth) acrylate-based resin having excellent stain removability, which comprises an acrylate resin, (C) a photocurable silicone block (meth) acrylate-based resin, and (D) a photopolymerization initiator. Resin composition. 2. A (meth) acrylate monomer (E) in addition to the components (A), (B), (C) and (D).
The photocurable (meth) acrylate-based resin composition according to claim 1, which comprises: 3. A photocurable (meth) acrylate resin (A) and a photocurable polysiloxane urethane (meth) (B).
It is characterized by being formed from a photocurable (meth) acrylate resin composition containing an acrylate resin, (C) a photocurable silicone block (meth) acrylate resin, and (D) a photopolymerization initiator. Coating. 4. The composition comprises the components (A), (B),
4. A (meth) acrylate-based monomer (E) is contained in addition to (C) and (D).
The coating described in. 5. A photocurable (meth) acrylate resin (A) and a photocurable polysiloxane urethane (meth) (B).
It is covered with a film formed from a photocurable (meth) acrylate resin composition containing an acrylate resin, (C) a photocurable silicone block (meth) acrylate resin, and (D) a photopolymerization initiator. A coated substrate characterized by the above. 6. The composition comprises the components (A), (B),
The (meth) acrylate-based monomer (E) is contained in addition to (C) and (D).
The coated substrate according to.