JP3362322B2 - Radiation curable resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a radiation curable resin composition having excellent curability, good adhesion to various plastic substrates, and excellent stain resistance, flexibility, abrasion resistance, scratch resistance and the like. Regarding More specifically, the present invention relates to a radiation curable resin composition suitable for modifying the surface characteristics of a printed plastic film used for a decorative wood material in which a plastic film is laminated on the surface of the wood material.

[0002]

2. Description of the Related Art There is known a method for producing a decorative plywood by wrapping a film such as polyvinyl chloride (PVC) printed with a design pattern such as a wood grain pattern on synthetic wood such as particle board or MDF (a kind of recycled wood). Has been. P
Since the VC film has low hardness and poor surface properties as it is, the surface of the VC film is coated with a two-component thermosetting urethane. However, the two-part thermosetting urethane not only takes a long time to cure the resin and has low productivity, but also the surface characteristics are not sufficiently modified, and its improvement is required.

As a countermeasure, for example, it has been attempted to coat the surface of a PVC film with an ultraviolet or electron beam curable coating agent. The following characteristics are required for the ultraviolet ray or electron beam curable coating agent for coating various films such as PVC film. (1) It is liquid at room temperature and has high workability. (2) Curing by ultraviolet rays or electron beams is fast and productivity is good. (3) Sufficient adhesion to the substrate. (4) It is tough, has flexibility, and has good moldability. (5) Excellent stain resistance. (6) It has sufficient hardness and is excellent in abrasion resistance, scratch resistance and the like. (7) Excellent weather resistance. (8) It has excellent heat resistance and hydrolysis resistance. (9) Excellent water resistance, oil resistance, solvent resistance, etc. (10) Excellent chemical resistance. (11) Gloss can be controlled by the compounding ratio.

As described above, the coating agent is required to have various characteristics, and in particular, the method of processing the decorative plywood includes bending, V-cutting, vacuum pressing, etc., and in any case, it is the same as PVC. High stretching performance is required.

[0005]

DISCLOSURE OF THE INVENTION The object of the present invention is that it is highly curable by radiation, satisfies the above-mentioned characteristics, has good adhesion to a substrate, and is suitable for modifying the surface characteristics of a printed plastic film coating. Another object of the present invention is to provide a radiation curable resin composition.

[0006]

The present invention provides the following components (A), (B) and (C): (A) (a) polycarbonate diol, (b) diisocyanate compound, and (c) hydroxyalkyl ( Urethane (meth) acrylate obtained by reacting (meth) acrylate, (B) (d) polyol compound having 3 or more hydroxyl groups in one molecule, (b) diisocyanate compound, and (c) hydroxyalkyl (meth) Urethane (meth) acrylate obtained by reacting acrylate, (C) carboxyl group-containing (meth) acrylate compound
The present invention provides a radiation-curable resin composition containing a reactive diluent containing

The preferred embodiments of the invention are described below. 1) A radiation curable resin composition in which the polycarbonate diol (a) is a compound represented by the following formula. H- (OR ² -O-CO) _m -OR ¹ -O- (COO-R ² -O) _n -H (In the formula, R ¹ and R ² each represent an alkylene group having 1 to 12 carbon atoms, m and n are numbers of 1 or more and 49 or less, and show numbers of m + n = 2 to 50).

[0008]

3) (a) Polycarbonate diol is a compound represented by the following formula: H- (OR ² -O-CO) _m -OR ¹ -O- (COO-R ² -O) _n -H ( In the formula, R ¹ and R ² each represent an alkylene group having 1 to 12 carbon atoms, m and n are numbers of 1 or more and 49 or less, and m + n = 2 to 50) The component (C) Radiation curable resin in which the reactive diluent is two kinds of a carboxyl group-containing (meth) acrylate compound and another (meth) acrylate compound (however, excluding the (meth) acrylate of the components (A) and (B)) Composition.

The present invention will be described in detail below. The bifunctional polycarbonate urethane (meth) acrylate of the component (A) used in the present invention includes (a) a polycarbonate diol, (b) a diisocyanate compound and (c).
It is produced by reacting a hydroxyalkyl (meth) acrylate. Further, the trifunctional or higher functional urethane (meth) acrylate of the component (B) is (d) a polyol compound having three or more hydroxyl groups in one molecule, (b) a diisocyanate compound and (c) a hydroxyalkyl (meth) acrylate. It is manufactured by reacting.

Examples of the diisocyanate compound (b) commonly used for the production of the components (A) and (B) include, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate and 1,3-xylylene. Diisocyanate, 1,4-xylene diisocyanate, 1,5-
Naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3 '
-Dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate,
3,3'-dimethylphenylene diisocyanate, 4,
4'-biphenylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate,
2,2,4-trimethylhexamethylene diisocyanate, bis (2-isocyanatoethyl) fumarate, 6
-Isopropyl-1,3-phenyl diisocyanate,
4-diphenylpropane diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, tetramethyl xylylene diisocyanate and the like can be mentioned. Of these, hydrogenated xylylene diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate and the like are particularly preferable. These diisocyanate compounds can be used alone or in combination of two or more.

Similarly, as the (c) hydroxyalkyl (meth) acrylate commonly used in the production of the components (A) and (B), one hydroxyl group and one (meth) acryloxy group in one molecule. Those having a group are preferable, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2
-Hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 2-hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl ( (Meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, the following formula:

[0013]

[Chemical 1]

[Wherein R ³ represents a hydrogen atom or a methyl group, and p represents a number of 1 to 15] (meta)
Acrylate etc. are mentioned. Further, a compound obtained by an addition reaction of a glycidyl group-containing compound such as alkyl glycidyl ether, aryl glycidyl ether, glycidyl (meth) acrylate and (meth) acrylic acid can also be used. Among these hydroxyalkyl (meth) acrylates, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate are particularly preferable.

Examples of the (a) polycarbonate diol used for the production of the component (A) include, for example, the following formula (1): H- (OR ² -O-CO) _m -OR ¹ -O- (COO-R ² -O) _n -H (1) (In the formula, R ¹ and R ² are the same or different and each represents an alkylene group having 1 to 12 carbon atoms, and m and n are 1 or more and 4
It is a number less than or equal to 9 and indicates a number such that m + n = 2 to 50).
The compound represented by Specifically, 1,6
-Polycarbonate diol of hexanediol, 3-
Examples include polycarbonate diol of methyl-1,5-pentamethylene diol, polycarbonate diol of 2-methyl-1,8-octamethylene diol, polycarbonate diol of 1,9-nonamethylene diol, and the like. Commercially available products include N- 980, 981, 982, 9
83 (above, Nippon Polyurethane Company), PC-8000
(Made by PPG, USA), PNOC1000, 2000, P
MC-100, 2000 (above, manufactured by Kuraray Co., Ltd.) or the like can be used.

Examples of the (d) polyol compound having three or more hydroxyl groups in one molecule used in the production of the component (B) include glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol and dipenta. Examples thereof include erythritol, polyols obtained by adding alkylene oxides such as ethylene oxide and propylene oxide, and compounds obtained by adding 3 moles or more of alkylene oxides such as ethylene oxide and propylene oxide to 1 mole of ethylenediamine. Moreover, as a commercially available product, for example, TMP30,
PNT4Glycol, EDA P4, EDA P8
(Above, manufactured by Nippon Emulsifier Co., Ltd.), quadrol, EDP-4
50, EDP-1100 (all manufactured by Asahi Denka Co., Ltd.) and the like. Of these, the 3 mol adduct of ethylene oxide with glycerin and the 3 mol adduct of ethylene oxide with trimethylolpropane are particularly preferable.

In the production of component (B), (d),
In addition to (b) and (c), it is preferable to use a diol compound as necessary. Examples of such a diol compound include a polyether diol and a polyester diol in addition to the polycarbonate diol used in the production of the component (A). , Polycaprolactone diol and the like.

Examples of the above polyether diols include aliphatic, aromatic or alicyclic polyether diols. Among these, examples of the aliphatic polyether diol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and polyether diol obtained by ring-opening copolymerization of two or more kinds of ion-polymerizable cyclic compounds. Here, as the ionically polymerizable cyclic compound, ethylene oxide, propylene oxide, butene-1-oxide, isobutene oxide, 3,3-bischloromethyloxetane, tetrahydrofuran, dioxane, trioxane, tetraoxane, cyclohexene oxide, styrene oxide, epichlorohydrin, glycidyl. Methacrylate, allyl glycidyl ether, allyl glycidyl carbonate, butanediene monoxide, isoprene monoxide, vinyl oxetane, vinyl tetrahydrofuran, vinyl cyclohexene oxide, phenyl glycidyl ether,
Examples thereof include cyclic ethers such as butyl glycidyl ether and benzoic acid glycidyl ester.

As the aromatic polyether diol, alkylene oxide addition diol of bisphenol A,
Examples thereof include an alkylene oxide addition diol of bisphenol F, an alkylene oxide addition diol of hydroquinone, and an alkylene oxide addition diol of naphthoquinone. Examples of the alicyclic polyether diol include hydrogenated bisphenol A alkylene oxide addition diol and hydrogenated bisphenol F alkylene oxide addition diol.

Commercial products of these polyether diols include aliphatic polyether diols such as Unisafe DC1100, Unisafe DC1800, Unisafe DCB1100, Unisafe DCB1800,
(Above, manufactured by NOF CORPORATION); PPTG4000, PPTG
2000, PPTG1000, PTG2000, PTG
3000, PTG650, PTGL2000, PTGL
1000 (above, Hodogaya Chemical Co., Ltd.); EXENOL4
020, EXENOL3020, EXENOL202
0, EXENOL 1020 (above, Asahi Glass Co., Ltd.); PB
G3000, PBG2000, PBG1000, Z30
01 (above, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and the like, and as the aromatic polyether diol, for example, Uniol DA4
00, DA700, DA1000, DB400 (above,
Manufactured by Nippon Oil & Fats Co., Ltd., etc.

Examples of the polyester diol include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,6-hexanediol, neopentyl glycol and 1,4-cyclohexanediene. Methanol, 3-
Polyhydric alcohols such as methyl-1,5-pentanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol and phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, Examples thereof include polyester diols obtained by reacting with a polybasic acid such as sebacic acid. These commercial products include
Curapol P-2010, PMIPA, PKA-A, P
KA-A2, PNA-2000 (above, manufactured by Kuraray Co., Ltd.) and the like can be used.

Further, as the polycaprolactone diol, ε-caprolactone may be used, for example, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,2-polybutylene glycol, 1, Examples thereof include polycaprolactone diol obtained by addition reaction with a divalent diol such as 6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol and 1,4-butanediol. These commercially available products include Praxel 20
5, 205AL, 212, 212AL, 220, 220
AL (above, manufactured by Daicel) and the like can be obtained.

Further, many diols other than those mentioned above can be used, for example, poly β-methyl-δ-valerolactone diol, hydroxy-terminated polybutadiene, hydroxy-terminated hydrogenated polybutadiene, castor oil-modified diol, polydimethylsiloxane-terminated diol compound, poly Examples thereof include dimethyl siloxane carbitol-modified diol. Among these diol compounds, polyether diol and polycarbonate diol are particularly preferable.

In the production of components (A) and (B), copper naphthenate, cobalt naphthenate, zinc naphthenate, di-n-butyltin laurate, triethylamine, 1,4-diazabicyclo [2,2,2] are usually used. ] Octane, 1,4-diaza-2-methylbicyclo [2,2,2]
2] The total amount of the reaction products is 10
The reaction is preferably carried out using 0.01 to 1 part by weight with respect to 0 part by weight. The reaction temperature in this reaction is usually 1
It is preferably carried out at 0 to 90 ° C, particularly 30 to 80 ° C.

In the production of the components (A) and (B), even if these are separately synthesized and then mixed,
You may synthesize simultaneously.

The method of synthesizing the component (A) is not particularly limited, but it is carried out, for example, according to the following methods (i) to (iii). (I) A method in which a diisocyanate compound (b) and a hydroxyalkyl (meth) acrylate (c) are reacted, and then (a) a polycarbonate diol is reacted in that order. (Ii) A method in which (a) a polycarbonate diol, (b) a diisocyanate compound, and (c) a hydroxyalkyl (meth) acrylate are charged all at once and reacted. (Iii) (a) polycarbonate diol and (b)
A method of reacting a diisocyanate compound and then reacting with (c) a hydroxyalkyl (meth) acrylate. Of these, the method (i) is preferable.

The use ratio of each raw material is not particularly limited as long as the component (A) can be obtained. For example, (b) a diisocyanate compound (1 to 3 mol) and (c) a hydroxyalkyl to 1 mol of (a) a polycarbonate diol. 1 to 3 mol of (meth) acrylate is used.

The method of synthesizing the component (B) is not particularly limited, but for example, the method of synthesizing the above component (A) (i) to (ii).
In i), the method is carried out by changing the polycarbonate diol (a) to the polyol compound (d). Among these, the method modified as described above in the synthesis method (i) of the component (A) is preferable.

The ratio of each raw material to be used is not particularly limited as long as the component (B) can be obtained. For example, when the number of hydroxyl groups of the (d) polyol compound is n, 1 mol of the (d) polyol compound is used. (B) diisocyanate compound n
-1 to n + 1 (mol), and (c) hydroxyalkyl (meth) acrylate n-1 to n + 1 (mol) are used.

The method for simultaneously synthesizing the component (A) and the component (B) is not particularly limited. For example, in the synthesis methods (i) to (iii) of the above component (A), the polycarbonate diol (a) (a) ) In addition to the method in which the polycarbonate diol and the polyol compound (d) are changed, the following method (iv) is performed. (Iv) A method in which (b) a diisocyanate compound and (c) a hydroxyalkyl (meth) acrylate are reacted, (a) a polycarbonate diol is reacted, and then (d) a polyol compound is reacted. Of these, the method (iv) is preferable.

The ratio of each raw material to be used is not particularly limited as long as component (A) and component (B) can be obtained. For example, (a) polycarbonate diol x mol and polyol compound y mol (provided that the number of hydroxyl groups is z. (B) diisocyanate compound 2x + zy-1 to
2x + zy + 1 (mol), and (c) hydroxyalkyl (meth) acrylate 2x + zy-1 to 2x + zy.
Use +1 (mol).

The bifunctional polycarbonate urethane (meth) acrylate of the component (A) includes the component (A) and the component (B).
It is preferable to add 2 to 40 parts by weight, particularly 5 to 25 parts by weight, relative to 100 parts by weight of a composition (hereinafter, referred to as "composition (I)") containing the component (C) and the component (C). If it is less than 2 parts by weight, the adhesion to the substrate may be impaired, and if it exceeds 40 parts by weight, stain resistance and abrasion resistance may be impaired.

The trifunctional or higher functional urethane (meth) acrylate as the component (B) is preferably blended in an amount of 5 to 50 parts by weight, particularly 7 to 40 parts by weight, per 100 parts by weight of the composition (I). If it is less than 5 parts by weight, stain resistance and scratch resistance may be impaired, and if it exceeds 50 parts by weight, flexibility and adhesion to the substrate may be impaired.

As the reactive diluent of the component (C) used in the present invention, a carboxyl group-containing (meth) acrylate compound and, if necessary, other (meth) acrylate compound (provided that the components (A) and ( (Excluding (meth) acrylate of B), acrylamides, N-vinyl compounds, and other monofunctional reactive compounds can be used.

Examples of the carboxyl group-containing (meth) acrylate compound include a monomer having a carboxyl group and a (meth) acryloxy group, and an oligomer of the monomer. The above carboxyl group and (meth)
The monomer containing an acryloxy group is represented by the following formula: CH ₂ = CR ⁴ -COO-X-COOH (wherein R ⁴ represents a hydrogen atom or a methyl group, and X represents a divalent organic group). Those that can be used are preferred. Here, the divalent organic group represented by X includes an alkylene group, an arylene group, a cycloalkylene group, an alkenylene group, a cycloalkenylene group, an -A ^1- (OOC-A ² ) _q -group (A ¹ and A ² represents an alkylene group, a cycloalkylene group, an alkenylene group, a cycloalkenylene group, an arylene group or the like, and q represents an integer of 1 or more) and the like. Specific examples of such a compound include the following compounds.

CH ₂ = CR ⁵ -COO- (C ₅ H ₁₀ COO) _r -H, CH ₂ = CR ⁵ -COOCH ₂ CH ₂ OOC-C ₆ H ₄ -COOH, CH ₂ = CR ⁵ -COOCH ₂ CH ₂ OOCCH ₂ CH ₂ COOH, CH ₂ = CR ⁵ -COO- (CH ₂ CH ₂ COO) _r H, CH ₂ = CR ⁵ -COOCH ₂ CH ₂ OOC-C ₆ H ₁₀ -COOH, CH ₂ = CR ^5- COOCH ₂ CH (CH ₃ ) OOC-C ₆ H ₄ -COOH, CH ₂ = CR ⁵ -COOCH ₂ CH (CH ₃ ) OOC-C ₆ H ₁₀ -COOH

(In the formula, R^FiveIs a hydrogen atom or a methyl group
, R is a number from 1 to 10, and -C₆H _Four-Is phenylene
Group, -C₆H_Ten-Represents a cyclohexylene group)

Further, the above-mentioned carboxyl group and (meth)
As the oligomer of the monomer containing an acryloxy group, 2 to 20 mer of the monomer is preferable.

Commercial products of the (meth) acrylate compound containing a carboxyl group include, for example, Aronix.
M-5300, M-5400, M-5500, M-56
00 (above, Toa Gosei Chemical Co., Ltd.), NK ester S
A, A-SA (above, Shin Nakamura Chemical Co., Ltd.), Viscoat #
2000, # 2100, # 2150, # 2180 (above, manufactured by Osaka Organic Chemical Co., Ltd.) and the like.

Examples of the other (meth) acrylate compounds described above include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl ( (Meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl ( (Meth) acrylate,
Hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth)
Acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) ) Acrylate, ethoxydiethylene glycol (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxyethylene glycol ( (Meth) acrylate, ethoxyethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate Methoxy polypropylene glycol (meth) acrylate, dicyclopentadiene (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, tricyclodecanyl (meth) acrylate, isobornyl (meth) acrylate, bornyl ( (Meth) acrylate, dimethylaminoethyl (meth) acrylate,
Diethylaminoethyl (meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate,
Examples thereof include (meth) acryloylmorpholine and compounds represented by the following formula.

CH ₂ = CR ⁹ -COO- (C ₅ H ₁₀ COO) _t -CH ₂ -R ¹⁰ (wherein R ⁹ represents a hydrogen atom or a methyl group, and R ¹⁰ represents
-C ₄ H ₇ O, t is a number from 1 to 10)

[0042]

[Chemical 2]

(In the formula, R ¹¹ represents a hydrogen atom or a methyl group, and u represents a number of 1 to 10)

Examples of the acrylamides include diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, t-octyl (meth) acrylamide, N,
Examples thereof include N-diethyl (meth) acrylamide and N, N'-dimethylaminopropyl (meth) acrylamide. Examples of the N-vinyl compound include N-vinylpyrrolidone and N-vinylcaprolactam. Further, other compounds represented by the following formulas can be given.

CH ₂ = CR ⁶ -O (R ⁷ O) _s -C ₆ H ₄ -R ⁸ (In the formula, R ⁶ represents a hydrogen atom or a methyl group, and R ⁷ has 2 to 6 carbon atoms, preferably 2 to 4 alkylene groups, R ⁸ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, preferably 1 to 9 carbon atoms, and s represents a number of 0 to 12, preferably 1 to 8).

As a commercially available product, Aronix M
101, M102, M111, M113, M114, M
117 (above, manufactured by Toagosei Kagaku), KAYARAD
TC110S, R629, R644 (all manufactured by Nippon Kayaku Co., Ltd.), Viscoat LA, STA, IBXA, DMA,
# 158, # 190, # 192, # 3700 (above, manufactured by Osaka Organic Chemical Co., Ltd.), light acrylate L-A, S-
A, BO-A, EC-A, DPM-A, light ester PA (above, Kyoeisha Yushi-Kagaku Kogyo Co., Ltd.) etc. are mentioned.

Of these, isobornyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, acryloylmorpholine, N-vinylcaprolactam, N-vinylpyrrolidone and the like are particularly preferable.

Further, a polyfunctional reactive compound may be used as the reactive diluent, for example, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di ( (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) ) Acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate,
Tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxypivalic acid neopentyl glycol diacrylate,
Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane trioxy Ethyl (meth) acrylate, trimethylolpropane trioxypropyl (meth) acrylate, trimethylolpropane polyoxyethyl (meth) acrylate, trimethylolpropane polyoxypropyl (meth) acrylate, tris (2
-Hydroxyethyl) isocyanurate tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, ethylene oxide-added bisphenol A di (meth) acrylate, ethylene oxide-added bilphenol F di (meth) acrylate, Propylene oxide-added bisphenol A di (meth) acrylate, propylene oxide-added bisphenol F di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, bisphenol A epoxy (meth) acrylate, bisphenol F
Epoxy (meth) acrylate etc. are mentioned.

Further, commercially available products include Uupimer UV S
A1002, SA2007 (above, manufactured by Mitsubishi Petrochemical Co., Ltd.), Viscoat # 195, # 215, # 230, # 260,
# 295, # 300, # 310, # 312, # 360,
# 400, # 700, GPT (above, manufactured by Osaka Organic Chemical Co., Ltd.), KAYARAD MANDA, DPHA, R-6
04, DPCA20, -30, -60, -120, HX
-620, D-310, D-330 (above, Nippon Kayaku Co., Ltd.), Aronix M-210, M-215, M-22.
0, M-270, M-310, M-315, M-32
5, M-350, M-360, M-400, M-45
0, M-6100, M-6500, M-7100, M-
8030, M-8530 (above, Toa Gosei Chemical Co., Ltd.),
SR-355 (manufactured by Sartomer) and the like can be mentioned.

Among these polyfunctional reactive compounds, especially human loxypivalic acid neopentyl glycol diacrylate (MANDA), trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meta). ) Acrylate, dimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, ethylene oxide-added bisphenol A di (meth) acrylate (biscoat # 700) and the like are preferable. .

The reaction diluent of the component (C) may be one kind or two kinds.
One or more species can be used in combination, and the composition (I) 1
10 to 93 parts by weight, especially 35 to 88, relative to 00 parts by weight
It is preferred to blend in parts by weight. If it is less than 10 parts by weight, sufficient hardness and flexibility cannot be obtained, and if it exceeds 93 parts by weight, stain resistance, toughness and curability may be impaired. In addition, when a monomer containing 5 to 30 parts by weight of a carboxyl group and a (meth) acryloxy group is used as the component (C) with respect to 100 parts by weight of the composition of the present invention, the stain resistance can be further improved. it can.

When the composition of the present invention is cured with visible light, ultraviolet rays, etc., a photopolymerization initiator is added to the composition,
Further, it is preferable to add a photosensitizer if necessary.

As the photopolymerization initiator used here,
For example, benzophenone, benzoin ethyl ether, benzoin propyl ether, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4 ′ -Diaminobenzophenone, Michler's ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-dodecylphenyl) -2-
Hydroxy-2-methylpropan-1-one, 4- (2
-Hydroxyethoxy) phenyl- (2-hydroxy-
2-propyl) ketone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl]
-2-morpholino-propan-1-one, 2,4,6-
Trimethylbenzoyldiphenylphosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, methylbenzoylformate, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, Carbazole, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone] and the like can be mentioned.

Commercially available products are IRGACURE
184, 261, 369, 500, 651, 907 (above, manufactured by Ciba Geigy), Lucirin LR872
8 (manufactured by BASF), Darocur 953, 111
6, 1173, 1664, 2959, ZL1 3331
(Above, manufactured by Merck), Yubekuriru P36 (manufactured by UCB), VICURE55 (manufactured by Akzo), ESACUR
E KIP100F (made by LAMBERTI) etc. can be mentioned.

Among these photopolymerization initiators, benzophenone, IRGACURE 184, VICURE 55, E
SACURE KIP100F and the like are preferable.

Examples of the photosensitizer include triethylamine, diethylamine, N-methyldiethanolamine,
Ethanolamine, 4-dimethylaminobenzoic acid, 4-
Methyl dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, Ubecryl P102, 103, 104 manufactured by UCB.
105 and the like.

These photopolymerization initiators and photosensitizers are 1
It is possible to use one kind or a combination of two or more kinds. The photopolymerization initiator is preferably added to the composition of the present invention in the range of 0.1 to 10 parts by weight. The photosensitizer can be blended in the range of 0 to 5 parts by weight with respect to 100 parts by weight of the composition (I). Further, when the composition of the present invention is radiation-cured, the above photopolymerization initiator may not be used.

In the composition of the present invention, as other additives, epoxy resin, polyamide, polyamideimide, polyurethane, polybutadiene, chloroprene, polyether, polyester, pentadiene derivative, SB.
Polymers such as S (styrene / butadiene / styrene block copolymer), hydrogenated SBS, SIS (styrene / isoprene / styrene block copolymer), petroleum resin, xylene resin, ketone resin, fluorine-based oligomer, silicone A system oligomer, a polysulfide system oligomer, etc. can be blended. These polymers or oligomers are used in an amount of 2 based on 100 parts by weight of the composition (I).
It can be added in an amount of 0 parts by weight or less.

Further, various coating additives other than the above, for example, antioxidants, ultraviolet absorbers, light stabilizers, silane coupling agents, foam control defoaming agents, leveling agents, matting agents, surfactants, storage stabilizers. A thermal polymerization inhibitor, a plasticizer, a lubricant, a solvent, a filler, a colorant, a wettability improver, a coating surface improver and the like can also be added as necessary.

For example, as an antioxidant, Irgan
ox1010, 1035, 1076, 1222 (above,
Ciba Geigy) and the like, and the composition (I) 100.
1 part by weight or less can be blended with respect to parts by weight. UV absorbers include TINUVIN P, 213, 234, 32
0, 326, 327, 328, 329 (all manufactured by Ciba Geigy), SEESORB 102, 103, 202,
501, 712 (above, manufactured by Cypro Kasei Co., Ltd.) and the like, and 5 parts by weight or less can be added to 100 parts by weight of the composition (I).

As the light stabilizer, Tinuvin 14
4,292,622LD (above, manufactured by Ciba-Geigy) Sanol LS440, LS770 (above, manufactured by Sankyo), S
umisorb TM-061 (manufactured by Sumitomo Chemical Co., Ltd.) and the like can be included, and 5 parts by weight or less can be mixed with 100 parts by weight of the composition (I). As the silane coupling agent, γ
-Aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane and the like, and as commercial products, SH6062, 6030 (above, Toray Silicone Co., Ltd.), KBE403, 603, 903 (above, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like, and 5 parts by weight or less can be added to 100 parts by weight of the composition (I).

As the foam stabilizer and the leveling agent, DC is used.
11PA, SH28PA, SH190, SH200 (above, Toray Silicone Co., Ltd.), Floren AC-114
0, AC-1190, Polyflow No. 7, No. 7
5, Granol 400 (above, manufactured by Kyoeisha Yushi Co., Ltd.) and the like, and 5 parts by weight or less can be blended with 100 parts by weight of the composition (I). Examples of the matting agent include wet or dry silica, TS-100 (manufactured by Degussa Japan),
Aerosil 200, T600 (above, manufactured by Nippon Aerosil Co., Ltd.), Nipseal E200, SS50 (above manufactured by Nippon Silica Co., Ltd.), X-80 (above manufactured by Tokuyama Soda Co., Ltd.), magnesium carbonate and the like, and other polymer-based matting agents. Agents can also be used. These matting agents can be incorporated in an amount of 20 parts by weight or less based on 100 parts by weight of the composition (I).

The composition of the present invention is produced by mixing the components, and has a viscosity of 10 to 10,000 cp / 20.
C., especially 100 to 3000 cp / 20.degree. C. is preferable. When adjusting the viscosity according to the coating method,
It is also possible to dilute with a solvent. Preferred solvents include toluene, xylene, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, cyclohexanone, cyclohexane, etc., and 200 parts by weight or less can be added to 100 parts by weight of the composition (I).

The composition of the present invention is cured by radiation. Here, radiation means infrared rays, visible rays, ultraviolet rays, X
Rays, electron rays, α rays, β rays, γ rays and the like.

The irradiation dose of radiation is 50 in the case of ultraviolet rays.
It is preferably about 1000 mJ / cm ² . Further, for example, when the composition is cured by irradiation with an electron beam, it is not necessary to add a photopolymerization initiator, and the irradiation amount is 1 to 5 Mrad.
Is preferred. The composition of the present invention is used by coating on the surface of a substrate and irradiating with radiation to cure the composition. The thickness of the base material at this time is usually 0.1.
Preferably, the coating layer has a thickness of ˜5 mm and the coating layer has a thickness of 3 to 100 μm.

[0066]

The present invention will be further described below with reference to examples, but the present invention is not limited to these examples.
In the following, "parts" means "parts by weight" unless otherwise specified.

Synthesis Example 1 A reaction vessel equipped with a stirrer was charged with 236 g (1.25 mol) of hydrogenated xylylene diisocyanate, and 0.26 of 2,6-di-t-butyl-4-methylphenol as a polymerization inhibitor.
g and 0.8 g of dibutyltin dilaurate as a catalyst were charged. Cool it to 10 ° C in an ice-water bath and add 2
-145 g (1.25 mol) of hydroxyethyl acrylate were added while controlling the temperature below 20 ° C. After the addition, the mixture was further stirred at 10 to 20 ° C for 1 hour, and then 625 g (0.625 mol) of a polycarbonate diol having a number average molecular weight of 1000 (N981 manufactured by Nippon Polyurethane Industry Co., Ltd.) was added while keeping the temperature at 50 ° C or lower. . Then, the reaction is terminated by stirring at 50 to 60 ° C. for 5 hours, and the bifunctional polycarbonate urethane acrylate (A
-1) was obtained.

Synthesis Example 2 In a reaction vessel equipped with a stirrer, 485 g (2.58 mol) of hydrogenated xylylene diisocyanate and 0.2 of 2,6-di-t-butyl-4-methylphenol as a polymerization inhibitor were added.
g and 0.8 g of dibutyltin dilaurate as a catalyst were charged. Cool it to 10 ° C in an ice-water bath and add 2
300 g (2.58 mol) of hydroxyethyl acrylate were added while controlling the temperature below 20 ° C. After the addition, the mixture was further stirred at 10 to 20 ° C. for 1 hour, and then trimethylolpropane ethylene oxide-added triol having a molecular weight of 271 (TMP-30, manufactured by Nippon Emulsifier Co., Ltd.) 2
33 g (0.86 mol) was added keeping the temperature below 50 ° C. Then, the reaction is terminated by stirring at 50 to 60 ° C. for 5 hours, and the trifunctional urethane acrylate (B-
1) was obtained.

Synthetic Example 3 In a reaction vessel equipped with a stirrer, 408 g (2.17 mol) of hydrogenated xylylene diisocyanate, 0.2 of 2,6-di-t-butyl-4-methylphenol as a polymerization inhibitor was added.
4 g and 0.8 g of dibutyltin dilaurate as catalyst
Was charged. This was cooled to 10 ° C. in an ice-water bath, and 330 g (2.84 g) of 2-hydroxyethyl acrylate was added thereto.
Mol) was added while controlling the temperature below 20 ° C.
After the addition, after continuing stirring for 1 hour at 10 to 20 ° C.,
179 g (0.18 mol) of a polycarbonate diol having a number average molecular weight of 1000 (PNOC1000 manufactured by Kuraray Co., Ltd.) was added while maintaining the temperature at 50 ° C. or lower. Next, trimethylolpropane ethylene oxide-added triol having a molecular weight of 271 (manufactured by Nippon Emulsifier Co., Ltd., TMP-30) 1
03 g (0.38 mol) was added keeping the temperature below 50 ° C. After the addition was completed, the temperature was stirred at 50 to 60 ° C. for 5 hours and then the reaction was terminated to obtain urethane acrylate (B-2). The urethane acrylate (B-2) is a mixture of the components (A) and (B) of the present invention and a urethane acrylate (S) obtained by adding 2 mol of hydroxyethyl acrylate to hydrogenated xylylene diisocyanate. The weight ratio of (A) :( B) :( S) is 2
It was 3:37:20.

Example 1 A reaction vessel equipped with a stirrer was charged with urethane acrylate (A
-1) 17 parts, urethane acrylate (B-1) 23
Part, carboxyl group-containing (meth) acrylate compound (Aronix M5500, manufactured by Toagosei Kagaku) 15
Parts and monofunctional reactive compound isobornyl acrylate (IBXA, made by Osaka Organic Co., Ltd.) 20 parts, ditrimethylolpropane tetraacrylate (SR355, made by Sartomer Co.) 15 parts, hydroxypivalic acid neopentyl diacrylate (MANDA, (Nippon Kayaku Co., Ltd.) 10
Parts, 3 parts of benzophenone as a photopolymerization initiator, 1 part of 1-hydroxycyclohexyl-phenylketone and 10 parts of methylbenzoylformate, 45 parts of toluene, 45 parts of ethyl acetate, and 35 parts of methylethylketone were added, and T. K. A homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.) was used and stirred and mixed at 3000 rpm for 15 minutes to obtain a composition solution.

Example 2 A reaction vessel equipped with a stirrer was charged with urethane acrylate (B
-2) 45 parts, 2-acryloyloxypropyl hydrogen phthalate (biscoat # 2100, manufactured by Osaka Organic Co.) 15 parts, acryloylmorpholine 10 parts, 2,2-
20 parts of bis [4- (acryloxydiethoxy) phenyl] propane, 10 parts of dipentaerythritol hexaacrylate, and ESACURE as a photopolymerization initiator
5 parts of KIP100F (manufactured by LAMBERTI) and 1 part of methylbenzoyl formate were added and mixed with stirring to obtain a composition. To this, 30 parts of a polycarbonate resin powder (X-2331, manufactured by Gifu Shellac Co., Ltd.) as a polymer matting agent, 30 parts of toluene, 30 parts of ethyl acetate and 22 parts of methyl ethyl ketone were added, and T.I. K. Using a homodisper, the mixture was stirred and mixed at 3000 rpm for 15 minutes to obtain a composition solution.

Example 3 A reaction vessel equipped with a stirrer was charged with urethane acrylate (A
-1) 20 parts, urethane acrylate (B-1) 25
Part, carboxy group-containing (meth) acrylate compound (Aronix M5400, manufactured by Toagosei Co., Ltd.) 25 parts,
10 parts of phenoxyethyl acrylate, 20 parts of hydroxypivalic acid neopentyl diacrylate, 3 parts of benzophenone as a photoinitiator, 1 part of 1-hydroxycyclohexyl-phenylketone and 1 part of methylbenzoylformate, and γ-methacryl as a silane coupling agent. Add 1 part of Roxypropyltrimethoxysilane,
The composition was obtained by mixing with stirring. To this, 10 parts of silicon dioxide (finely powdered silica) (TS-100, manufactured by Degussa Japan) as a matting agent, 45 parts of toluene, 45 parts of ethyl acetate and 35 parts of methyl ethyl ketone were further added, and T.I.
K. Using a homodisper, the mixture was stirred and mixed at 3000 rpm for 15 minutes to obtain a composition solution.

Comparative Example 1 A composition was obtained in the same manner as in Example 1 except that 17 parts of urethane acrylate (A-1) and 23 parts of urethane acrylate (B-1) were replaced with 40 parts of urethane acrylate (A-1). A product solution was obtained.

Comparative Example 2 A composition was prepared in the same manner as in Example 1 except that 17 parts of urethane acrylate (A-1) and 23 parts of urethane acrylate (B-1) were replaced with 40 parts of urethane acrylate (B-1). A product solution was obtained.

Test Example 1 The composition solutions prepared in Examples 1 to 3 and Comparative Examples 1 to 2 were applied to the surface of a PVC film having a thickness of 0.2 mm using a bar coater, and the solvent was air-dried to obtain a thick film. A 20 μm thick coating film was obtained. After that, it is irradiated with ultraviolet rays (irradiation dose 500 mJ / c
m ² ), and the composition was cured. The resulting coating P
The VC film was evaluated for gloss, adhesion, stain resistance, scratch resistance and bending resistance according to the following methods.
The results are shown in Table 1.

(Evaluation Method) (1) Gloss: According to JIS K7105, the 60-degree specular gloss of the coated surface of the coated PVC film was measured by GLOSS CHECKER IG-320.
(Manufactured by Horiba).

(2) Adhesion: In accordance with JIS K5400, a 100-cut cross-cut was made on the coated surface of the coated PVC film using a cutter guide with a gap of 1 mm, and a coating layer was formed by the cross-cut tape method. The adhesion of the PVC film was evaluated. The evaluation result was 100 when the coating layer was not peeled at all and 0 when all the coating layers were peeled off.

(3) Stain resistance: coated PV
The coated surface of the C film was colored with red and black magic ink and shoe ink, left at 23 ° C. for 24 hours, wiped with petroleum benzine, and the color difference was measured using a colorimeter with regard to the colored state. And evaluated.

(4) Scratch resistance: coated PV
The coated surface of the C film was strongly rubbed with a nail, and the state change of the rubbed portion was observed. When the coating layer was destroyed, it was marked as [X]. When the coating layer was not destroyed, the gloss of the rubbed portion changed and the rubbed mark could be identified [○]. Those that could not be identified were marked as [◎].

(5) Bend resistance: coated P
Bend the VC film, pinch the part with your fingers, and do 3
It was bent at 60 degrees and it was checked whether the film was broken. The case where there was no crack was designated as [○], and the case where it was cracked was designated as [x].

[0081]

[Table 1]

[0082]

The radiation-curable resin composition of the present invention is highly curable by radiation and has various characteristics required for coating agents for various films, such as adhesion to substrates, flexibility, stain resistance, It has excellent scratch resistance and the like. The radiation-curable resin composition of the present invention is suitable for coating plastics, particularly films, but is also suitable for coating a wide range of materials such as wood materials and inorganic materials.

Front page continuation (72) Inventor Etsuko Ono 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (72) Takashi Ukaji 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic rubber (56) References JP-A-6-256444 (JP, A) JP-A-59-204624 (JP, A) JP-A-6-145276 (JP, A) JP-A-61-283670 (JP, A) (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08F 290/00-290/14 C08F 299/00-299/08 C08F 18/67 C09D 1/00-201/10

Claims (5)

(57) [Claims] 1. The following components (A), (B) and (C) (A) (a) polycarbonate diol, (b) diisocyanate compound, and (c) hydroxyalkyl (meth) acrylate obtained by reacting Urethane (meth) acrylate, (B) (d) Polyol compound having three or more hydroxyl groups in one molecule, (b) Diisocyanate compound, and (c) Urethane obtained by reacting hydroxyalkyl (meth) acrylate ( (Meth) acrylate,
And (C) carboxyl group-containing (meth) acrylate compound
A radiation-curable resin composition , comprising a reactive diluent containing 2. The polycarbonate diol (a) in the component (A) has the following formula H- (OR ² -O-CO) _m -OR ¹ -O- (COO-R ² -O) _n -H (wherein , R ¹ and R ² each represent an alkylene group having 1 to 12 carbon atoms, m and n are numbers from 1 to 49, and m + n = 2 to 50). The radiation curable resin composition according to claim 1. 3. Urethane (meth) acrylate (A)
Is (a) 1 mol of polycarbonate diol,
(B) 1 to 3 mol of diisocyanate compound, and (c) 1 to 3 of hydroxyalkyl (meth) acrylate
The radiation-curable resin composition according to claim 1 or 2, which is obtained by using moles. 4. Urethane (meth) acrylate (B)
Where n is the number of hydroxyl groups of the (d) polyol compound, (b) is added to 1 mol of the (d) polyol compound.
Diisocyanate compounds n-1 to n + 1 (mol), and (c) hydroxyalkyl (meth) acrylate n-
The radiation curable resin composition according to claim 1, which is obtained by using 1 to n + 1 (mol). 5. Radiation according to any one of claims 1 to 4.
A coating film obtained by curing a linear curable resin composition .