JP6057741B2 - Polysiloxane structure-containing urethane (meth) acrylate-based compound, active energy ray-curable resin composition, and coating agent using the same - Google Patents

Description

  The present invention relates to a polysiloxane structure-containing urethane (meth) acrylate-based compound. More specifically, the present invention has a well-balanced antifouling performance (stain removal property) and chemical resistance (alkali resistance), and the appearance of a coating film. And a urethane (meth) acrylate compound for forming a cured coating film having excellent scratch resistance, an active energy ray-curable resin composition, and a coating agent using the same.

  Conventionally, urethane (meth) acrylate has the property of being cured by irradiation with active energy rays, and after curing, a coating film with high hardness can be obtained. Therefore, it is widely used as a coating agent for hard coat applications. ing.

  In recent years, the surface of base materials such as wood materials, paper materials, and plastics cannot be removed by wiping with a waste cloth when contaminated with oil-based pens. In order to improve antifouling performance such as anti-adhesion property and dirt removal property, a method of overcoating a coating agent has been studied.

  In the method of overcoating a coating agent for improving the soil removability, urethane (meth) acrylate containing a polysiloxane structure is used among urethane (meth) acrylates widely used as a coating agent.

  For example, in the technique disclosed in Patent Document 1, a coating using a photocurable (meth) acrylate resin, a photocurable polysiloxane urethane (meth) acrylate resin, and a photocurable silicone block (meth) acrylate resin in combination. In the technique disclosed in Patent Document 2, urethane obtained mainly by reacting isocyanurates with polydimethylsiloxane diol having one hydroxyl group at both ends and hydroxyalkyl (meth) acrylates is disclosed. A photocurable resin composition using (meth) acrylate is described.

JP 2003-192751 A Japanese Patent Laid-Open No. 06-136078

  However, even in the technique disclosed in Patent Document 1, since the coating film has a polysiloxane structure, a certain degree of antifouling performance is exhibited, but since there are few ethylenically unsaturated double bonds, dirt is removed. In addition, there are problems that antifouling performance is lowered when chemicals such as alkalis are used or when wiping is continued repeatedly, and that the hardness of the coating film is insufficient and the film is easily damaged.

  Further, in the technique disclosed in Patent Document 2, although polydimethylsiloxane urethane (meth) acrylate has a certain degree of antifouling property, polydimethylsiloxane has a low molecular weight and sufficient antifouling performance and chemical resistance. Therefore, further improvement in antifouling performance has been demanded.

  Therefore, in the present invention, a cured coating film having excellent balance of antifouling performance (stain removal properties) and chemical resistance (alkali resistance), and excellent coating film appearance and scratch resistance is formed in this background. It is an object of the present invention to provide a urethane (meth) acrylate-based compound, an active energy ray-curable resin composition, and a coating agent using the same.

  However, as a result of intensive studies in view of such circumstances, the present inventor, in a urethane (meth) acrylate compound using a polysiloxane compound containing two or more hydroxyl groups, has a higher molecular weight than conventional polysiloxanes. Chemical resistance (alkali resistance) is improved by using a compound, antibacterial performance (dirt removal) and chemical resistance (alkali resistance) are well balanced, and the coating film appearance and scratch resistance are also excellent. It discovered that a cured coating film was obtained and came to complete this invention.

  That is, the gist of the present invention is obtained by reacting a polysiloxane compound (a1) having two or more hydroxyl groups, a polyvalent isocyanate compound (a2), and a hydroxyl group-containing (meth) acrylate compound (a3). The polysiloxane structure-containing urethane (meth) acrylate compound (A), wherein the polysiloxane compound (a1) having two or more hydroxyl groups has a weight average molecular weight of 2,000 or more, and is ethylenically unsaturated. The present invention relates to a polysiloxane structure-containing urethane (meth) acrylate compound characterized by containing 10 or more double bonds.

  Moreover, in this invention, the active energy ray-curable resin composition containing the said urethane (meth) acrylate type compound and the coating agent using the same are also provided.

  The urethane (meth) acrylate compound of the present invention has a well-balanced antifouling performance (stain removal property) and chemical resistance (alkali resistance) when it is used as a cured coating film, and the appearance and scratch resistance of the coating film. And is particularly useful as a coating agent.

The present invention is described in detail below.
In the present invention, (meth) acryl means acryl or methacryl, (meth) acryloyl means acryloyl or methacryloyl, and (meth) acrylate means acrylate or methacrylate.

  First, the polysiloxane structure-containing urethane (meth) acrylate compound (A) (hereinafter sometimes referred to as “urethane (meth) acrylate compound (A)”) will be described.

  The polysiloxane structure-containing urethane (meth) acrylate compound (A) is a polysiloxane compound (a1) having two or more hydroxyl groups (hereinafter sometimes referred to as “polysiloxane compound (a1)”). And a polyisocyanate compound (a2), a hydroxyl group-containing (meth) acrylate compound (a3), and a polyol compound (a4) as necessary.

  As the polysiloxane compound (a1) having two or more hydroxyl groups of the present invention, a known general polysiloxane compound may be used as long as it is a polysiloxane compound containing two or more hydroxyl groups. It is a polysiloxane compound in which two or more hydroxyl groups are bonded to different silicon atoms, and particularly preferably at both ends represented by the following general formula (1) in that the reaction control with the polyvalent isocyanate compound (a2) is excellent. It is a polysiloxane compound having a hydroxyl group.

〔式中、Ｒ^１、Ｒ^３は炭化水素基又はヘテロ原子を含む有機基を示し、Ｒ^２はそれぞれ独立にアルキル基、シクロアルキル基又はフェニル基を示し、ａは１０以上の整数であり、ｂ、ｃは１〜３の整数である。〕

[Wherein R ¹ and R ³ represent a hydrocarbon group or an organic group containing a hetero atom, R ² independently represents an alkyl group, a cycloalkyl group or a phenyl group, and a is an integer of 10 or more, b and c are integers of 1 to 3. ]

Regarding the polysiloxane compound having hydroxyl groups at both ends represented by the following general formula (1), R ¹ and R ³ in the general formula (1) are hydrocarbon groups or organic groups containing a hetero atom.
As a hydrocarbon group, it is C1-C100 normally, Preferably it is C1-C25, Most preferably, it is 1-5, and a bivalent or a trivalent hydrocarbon group is mentioned.
Examples of the divalent hydrocarbon group include an alkylene group. The alkylene group preferably has 1 to 10 carbon atoms, particularly preferably 1 to 4 carbon atoms, and examples thereof include an ethylene group, a propylene group, and a tetramethylene group.
Examples of the organic group containing a hetero atom include an oxyalkylene group, a polyoxyalkylene group, a polycaprolactone group, and an amino group.

R ² in the general formula (1) is each independently an alkyl group, a cycloalkyl group, or a phenyl group.
The alkyl group preferably has a relatively short carbon number. Specifically, the number of carbon atoms is usually 1 to 15, preferably 1 to 10, and particularly preferably 1 to 5. For example, a methyl group, an ethyl group, a propyl group, a butyl group, and the like are preferable, and a methyl group is particularly preferable. is there.
As carbon number of a cycloalkyl group, it is C3-C10 normally, Preferably it is 5-8, for example, a cyclopentyl group, a cyclohexyl group, norbornyl group etc. are mentioned.

The alkyl group, cycloalkyl group, and phenyl group may have a substituent. Examples of the substituent usually include a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a mercapto group, a sulfanyl group, a vinyl group, an acryloxy group, a methacryloxy group, an aryl group, and a heteroaryl group. In the case where the substituent has a carbon atom, said carbon atom shall not included in the number of carbon atoms is specified in the description of the R ^2.

  A in the general formula (1) is an integer of 10 or more, preferably 30 to 200, particularly preferably an integer of 40 to 120. b and c are each independently an integer of 1 to 3, preferably 1.

The weight average molecular weight of the polysiloxane compound (a1) is important to be 2,000 or more, particularly preferably 2,000 to 150,000, more preferably 2,000 to 10,000, Preferably it is 3,000-5,000.
If the weight average molecular weight is too low, the antifouling performance and chemical resistance are poor. In addition, when a weight average molecular weight is too high, compatibility will fall, there exists a tendency for a coating agent to become cloudy or the haze of a cured coating film to become high.

In addition, said weight average molecular weight is a weight average molecular weight by standard polystyrene molecular weight conversion, and is a high performance liquid chromatography (Nippon Waters Co., Ltd., "Waters 2695 (main body)" and "Waters 2414 (detector)"). Column: Shodex GPC KF-806L (exclusion limit molecular weight: 2 × 10 ⁷ , separation range: 100 to 2 × 10 ⁷ , theoretical plate number: 10,000 plates / pack, packing material: styrene-divinylbenzene copolymer, packing It is measured by using three series of agent particle size: 10 μm).
Hereinafter, the measurement of the weight average molecular weight of the urethane (meth) acrylate compound described later is measured according to the above method.

  As a specific example of the polysiloxane compound (a1) having two or more hydroxyl groups, as the polysiloxane compound having hydroxyl groups at both ends represented by the general formula (1), for example, “KF manufactured by Shin-Etsu Chemical Co., Ltd.” -6001 "," KF-6002 "," KF-6003 "," Silaplane FM-4421 "," Silaplane FM-4425 "manufactured by JNC," IM15 "," IM22 "manufactured by Asahi Kasei Wacker Silicone, “CT5000M”, “CT6000M”, “XF42-B0970” manufactured by Momentive Performance Materials Japan, “BY 16-004” manufactured by Toray Dow Corning, “SF 8427”, “manufactured by Toagosei” Macromonomer HK-20 "," DMS-C21 "," DMS-C23 "," GELEST " Products such as “DBL-C31” and “DMS-CA21” are listed. Examples of polysiloxane compounds having two or more hydroxyl groups other than these include “X-22-4039” manufactured by Shin-Etsu Chemical Co., Ltd. “X-22-4015”, “X-22-176DX”, “X-22-176GX-A”, “SF 8428” manufactured by Toray Dow Corning, “DMS-S15”, “DMS” manufactured by GELEST -S21 "," DMS-S27 "," DMS-S31 "," DMS-S32 "," DMS-S33 "," DMS-S35 "," DMS-S42 "," DMS-S45 "," DMS-S51 " ”,“ PDS-0338 ”,“ CMS-626 ”,“ CMS-222 ”and the like.

Examples of the polyvalent isocyanate compound (a2) include aromatics such as tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate. Aliphatic polyisocyanates such as polyisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis (Isocyanatomethyl) Alicyclic polyisocyanates such as hexane, trimer compounds or multimeric compounds of these polyisocyanates, allophanate type polyisocyanates, burette type polyisocyanates, adduct type polyisocyanates, water-dispersed polyisocyanates (for example, Nippon Polyurethane Industry) ("Aquanate 100", "Aquanate 110", "Aquanate 200", "Aquanate 210", etc.) manufactured by Co., Ltd.). These can be used alone or in combination of two or more.
Among these, an isocyanate compound having three or more isocyanate groups in one molecule is preferable, and a polyisocyanate trimer or multimer is particularly preferable in terms of coating film hardness, scratch resistance, and chemical resistance. A compound, more preferably an isocyanurate structure-containing polyvalent isocyanate compound.

Examples of the hydroxyl group-containing (meth) acrylate compound (a3) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth). Acrylate, hydroxyalkyl (meth) acrylate such as 6-hydroxyhexyl (meth) acrylate, 2-hydroxyethylacryloyl phosphate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, caprolactone-modified 2-hydroxyethyl (meth) ) Acrylate, dipropylene glycol (meth) acrylate, fatty acid-modified glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) Acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, glycerin di (meth) acrylate, 2-hydroxy-3-acryloyl-oxypropyl methacrylate, pentaerythritol tri (meth) acrylate, caprolactone-modified penta Erythritol tri (meth) acrylate, ethylene oxide modified pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, ethylene oxide modified dipentaerythritol penta (meth) acrylate, etc. Is mentioned. These can be used alone or in combination of two or more.
Among these, those having a large number of ethylenically unsaturated double bonds are preferable in that they are sufficiently easy to cure, particularly 3 or more ethylenically unsaturated double bonds, preferably 5 or more, particularly pentaerythritol. Tri (meth) acrylate and dipentaerythritol penta (meth) acrylate are preferable, and dipentaerythritol penta (meth) acrylate is more preferable.

  Furthermore, a polyol compound (a4) may be used as long as the effects of the present invention are not impaired. For example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,2-butanediol, 1 , 3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octane Diol, 1,9-nonanediol, 2,2-dimethylolheptane, hydrogenated bisphenol A, hydroxyalkylated bisphenol A, 1,4-cyclohexanedimethanol, 2,2,4-trimethyl-1,3-pentanediol N, N-bis- (2-hydroxyethyl) dimethylhydanto Low molecular weight polyols such as ethylene, glycerin, sorbitol, trimethylolethane, trimethylolpropane, trimethylolbutane, hexanetriol, pentaerythritol, dipentaerythritol, tris- (hydroxyethyl) isocyanurate, polyether-based polyol, polyester-based polyol , Polycarbonate polyol, polyolefin polyol, polybutadiene polyol, (meth) acrylic polyol, polycaprolactone polyol, polyurethane polyol and the like.

  Examples of polyether polyols include polyether polyols containing alkylene structures such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene glycol, and polyhexamethylene glycol, and random or block copolymers of these polyalkylene glycols. Is mentioned.

Examples of the polyester-based polyol include a condensation polymer of a polyhydric alcohol and a polycarboxylic acid; a ring-opening polymer of a cyclic ester (lactone); a polyhydric alcohol, a polycarboxylic acid, and a cyclic ester. And reactants.
Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylene diol, 1,3-tetramethylene diol, 2-methyl-1,3-trimethyl. Methylene diol, 1,5-pentamethylene diol, neopentyl glycol, 1,6-hexamethylene diol, 3-methyl-1,5-pentamethylene diol, 2,4-diethyl-1,5-pentamethylene diol, glycerin , Trimethylolpropane, trimethylolethane, cyclohexanediols (such as 1,4-cyclohexanediol), bisphenols (such as bisphenol A), and sugar alcohols (such as xylitol and sorbitol).
Examples of the polyvalent carboxylic acid include aliphatic dicarboxylic acids such as malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid; -Cycloaliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, paraphenylene dicarboxylic acid, trimellitic acid, and the like.
Examples of the cyclic ester include propiolactone, β-methyl-δ-valerolactone, and ε-caprolactone.

  As a weight average molecular weight of a polyol type compound (a4), 50-8,000 are preferable, Especially preferably, it is 50-5,000, More preferably, it is 600-3,000. If the weight average molecular weight of the polyol (a4) is too large, mechanical properties such as coating film hardness tend to decrease during curing, and if it is too small, the viscosity tends to increase during production and stability tends to decrease.

  The urethane (meth) acrylate compound (A) of the present invention needs to contain 10 or more ethylenically unsaturated double bonds, preferably 15 or more, and particularly preferably 20 or more. Moreover, the upper limit of the ethylenically unsaturated group which a urethane (meth) acrylate type compound (A) contains is 60 normally, Preferably it is 40 or less.

As a manufacturing method of a urethane (meth) acrylate type compound (A), it is not specifically limited, for example,
(I): Polysiloxane compound (a1), polyvalent isocyanate compound (a2) (if necessary, polyisocyanate compound (a2) previously reacted with polyol compound (a4)), hydroxyl group-containing A method in which the (meth) acrylate compound (a3) is charged all at once and reacted;
(B): A polysiloxane compound (a1) and a polyvalent isocyanate compound (a2) (if necessary, a polyisocyanate compound (a2) previously reacted with a polyol compound (a4)) are reacted. And then reacting the hydroxyl group-containing (meth) acrylate compound (a3),
(C): Polyvalent isocyanate compound (a2) (Polyisocyanate compound (a2) previously reacted with polyol compound (a4) if necessary) and hydroxyl group-containing (meth) acrylate compound (a3 ) And then reacting the polysiloxane compound (a1),
(D): Polyvalent isocyanate compound (a2) (Polyisocyanate compound (a2) previously reacted with polyol compound (a4) if necessary) and hydroxyl group-containing (meth) acrylate compound (a3 ), After reacting a part of the polysiloxane compound (a1), and further reacting the remaining hydroxyl group-containing (meth) acrylate compound (a3),
Among these, the method (b) or (d) is preferred, and the method (b) is particularly preferred from the viewpoint of stability of reaction control and compatibility.

  In addition, what is necessary is just to follow the manufacture example of a well-known general urethane type polyol, for example, when making a polyol type compound (a4) and a polyvalent isocyanate type compound (a2) react in advance.

  In the method (b), after reacting the hydroxyl group of the polysiloxane compound (a1) with the isocyanate group of the polyvalent isocyanate compound (a2) under the condition that the isocyanate group remains, the polyvalent isocyanate compound is then reacted. The residual isocyanate group of the compound (a2) is reacted with the hydroxyl group of the hydroxyl group-containing (meth) acrylate compound (a3).

  The reaction molar ratio between the polysiloxane compound (a1) and the polyvalent isocyanate compound (a2) is, for example, that the polysiloxane compound (a1) has two hydroxyl groups and the polyisocyanate compound (a2) has an isocyanate group. Is polysiloxane compound (a1): polyvalent isocyanate compound (a2) 1: about 1.1 to 2.2, and polysiloxane compound (a1) has two hydroxyl groups. When the polyisocyanate compound (a2) has three isocyanate groups, the polysiloxane compound (a1): polyisocyanate compound (a2) may be about 0.5 to 2.2. .

  In the addition reaction between the reaction product and the hydroxyl group-containing (meth) acrylate compound (a3), the reaction is terminated when the residual isocyanate group in the reaction system is 0.5% by weight or less. ) An acrylate compound (A) is obtained.

  The weight of the structural portion derived from the polysiloxane compound (a1) contained in 100 parts by weight of the urethane (meth) acrylate compound (A) is preferably 0.1 to 80 parts by weight.

  In such a reaction, it is also preferable to use a catalyst for the purpose of accelerating the reaction. As such a catalyst, a known so-called urethanization catalyst can be used. For example, a tin-based catalyst such as dibutyltin dilaurate or dioctyltin dilaurate, tetramethoxy Titanium catalysts such as titanium, tetraethoxy titanium, tetraisopropoxy titanium and tetrabutoxy titanium, zirconium catalysts such as tetramethoxy zirconium, tetraethoxy zirconium, tetraisopropoxy zirconium and tetrabutoxy zirconium, triethylenediamine, triethylamine, diazabicyclo Examples thereof include organic amine catalysts such as undecene and diazabicyclononene, and salts thereof.

  In this reaction, an organic solvent having no functional group that reacts with an isocyanate group, for example, esters such as methyl acetate, ethyl acetate, butyl acetate, 2-ethoxyethyl acetate, 2-methoxy-1-methylethyl acetate, etc. Organic solvents such as ketones such as methyl ethyl ketone and methyl isobutyl ketone, and aromatics such as toluene and xylene can be used.

  The reaction temperature of such a reaction is usually 30 to 100 ° C., preferably 40 to 90 ° C., and the reaction time is usually 2 to 10 hours, preferably 3 to 8 hours.

  The weight average molecular weight of the urethane (meth) acrylate compound (A) thus obtained is preferably 3,000 to 200,000, particularly preferably 4,000 to 50,000, and more preferably 5,000. ~ 20,000. If the weight average molecular weight is too small, the antifouling property and chemical resistance tend to decrease, and if too large, the coating property tends to decrease.

The viscosity of the urethane (meth) acrylate compound (A) at 60 ° C. is preferably 500 to 150,000 mPa · s, particularly 1,000 to 100,000 mPa · s, more preferably 2,000 to 50, 000 mPa · s is preferable. When the viscosity is out of the above range, the coatability tends to be lowered.
The viscosity is measured with an E-type viscometer.

  The said urethane (meth) acrylate type compound (A) may be used individually by 1 type, and may use 2 or more types together.

  Thus, the polysiloxane structure-containing urethane (meth) acrylate compound (A) of the present invention is obtained. Such a urethane (meth) acrylate compound (A) is preferably used as an active energy ray-curable resin composition.

  In the active energy ray-curable resin composition, in addition to the urethane (meth) acrylate compound (A), an ethylenically unsaturated compound (B) [excluding (A)] (hereinafter referred to as “ethylene”) It may be described as “a photo-unsaturated compound (B)”) in view of excellent coating film hardness and scratch resistance.

The content of the ethylenically unsaturated compound (B) is preferably 0 to 10,000 parts by weight, particularly preferably 10 to 5, based on 100 parts by weight of the urethane (meth) acrylate compound (A). 000 parts by weight, more preferably 100 to 2,000 parts by weight.
When the content of the ethylenically unsaturated compound (B) is too large, there is a tendency that sufficient antifouling performance cannot be obtained.

  As an ethylenically unsaturated compound (B), it is preferable that they are a urethane (meth) acrylate type compound (B1) and / or an ethylenically unsaturated monomer (B2), for example.

  The urethane (meth) acrylate compound (B1) is also required to be a urethane (meth) acrylate compound (B1-1) represented by the following general formula (2) when used for various purposes. It is preferable in that it is easy to impart physical properties.

〔式中、Ｒ^１は多価イソシアネート系化合物のウレタン結合残基、Ｒ^２は水酸基含有（メタ）アクリレート系化合物のウレタン結合残基、ａは２〜５０の整数である。〕

[Wherein, R ¹ is a urethane bond residue of a polyvalent isocyanate compound, R ² is a urethane bond residue of a hydroxyl group-containing (meth) acrylate compound, and a is an integer of 2 to 50. ]

  The urethane (meth) acrylate (B1-1) represented by the general formula (2) (hereinafter sometimes abbreviated as “urethane (meth) acrylate compound (B1-1)”) is a polyvalent isocyanate compound. And a hydroxyl group-containing (meth) acrylate compound.

  In the general formula (2), a may be an integer of 2 to 50, preferably 2 to 10, particularly preferably 2 to 3.

  Examples of the polyvalent isocyanate compound are the same as those exemplified as the polyvalent isocyanate compound (a2) in the description of the urethane (meth) acrylate (A), or the polyvalent isocyanate compound. What reacted (a2) and the polyol type compound (a4) is mentioned.

  Examples of the hydroxyl group-containing (meth) acrylate compound include those exemplified as the hydroxyl group-containing (meth) acrylate compound (a3) in the description of the urethane (meth) acrylate (A). It is done.

  What is necessary is just to manufacture the manufacturing method of a urethane (meth) acrylate type compound (B1-1) according to the manufacturing method of a well-known general urethane (meth) acrylate type compound. For example, the polyvalent isocyanate compound (a2) and the hydroxyl group-containing (meth) acrylate compound (a3) may be charged or reacted together in a reactor.

The reaction molar ratio between the polyvalent isocyanate compound and the hydroxyl group-containing (meth) acrylate compound is, for example, that the polyisocyanate compound has two isocyanate groups and the hydroxyl group-containing (meth) acrylate compound has one hydroxyl group. In the case of individual, the polyvalent isocyanate compound: hydroxyl group-containing (meth) acrylate compound is about 1: 2 to 3, the polyisocyanate compound has three isocyanate groups, and the hydroxyl group-containing (meth) acrylate compound. When the compound has one hydroxyl group, the ratio of polyisocyanate compound: hydroxyl group-containing (meth) acrylate compound is about 1: 3-4.
In the addition reaction between the polyvalent isocyanate compound and the hydroxyl group-containing (meth) acrylate compound, the reaction is terminated when the residual isocyanate group content in the reaction system is 0.5% by weight or less. A (meth) acrylate compound (B1-1) is obtained.

The number of ethylenically unsaturated groups contained in the urethane (meth) acrylate compound (B1-1) obtained above is preferably 2 to 100, particularly preferably 3 to 20, and more preferably 6 ~ 15.
If the number of ethylenically unsaturated groups is too small, there is a tendency that the hardness and scratch resistance of the coating film cannot be obtained. If the number is too large, the curing shrinkage of the coating film increases and the adhesion to the substrate decreases, or the coating film becomes brittle. There is a tendency to become.

  The weight average molecular weight of the urethane (meth) acrylate compound (B1) is preferably 300 to 50,000, more preferably 1,000 to 30,000, and particularly preferably 2,000 to 10,000. preferable. If the weight average molecular weight is too small, it tends to be difficult to maintain a balance between the coating film hardness and the shrinkage resistance, or the wettability to the substrate tends to decrease, and the weight average molecular weight is too large. , It tends to be difficult to maintain scratch resistance and hardness.

The viscosity at 60 ° C. of the urethane (meth) acrylate compound (B1) is preferably 200 to 150,000 mPa · s, particularly 100 to 50,000 mPa · s, more preferably 2,000 to 20,000 mPa · s. It is preferable that it is s. When the viscosity is out of the above range, the coatability tends to be lowered.
The viscosity is measured with an E-type viscometer.

  As said ethylenically unsaturated monomer (B2), if it is an ethylenically unsaturated monomer (however, urethane (meth) acrylate type compound (except B1)) which has 1 or more ethylenically unsaturated groups in 1 molecule. For example, a monofunctional monomer, a bifunctional monomer, a trifunctional or higher monomer can be used.

  The monofunctional monomer may be any monomer containing one ethylenically unsaturated group, such as styrene, vinyltoluene, chlorostyrene, α-methylstyrene, methyl (meth) acrylate, ethyl (meth) acrylate, acrylonitrile. , Vinyl acetate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate 2-hydroxy-3-phenoxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, glycidyl (meth) acrylate, lauryl (meth) acrylate , Cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) Acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, n-stearyl (meth) acrylate, benzyl (meth) acrylate, phenol ethylene oxide modified Phthalic acid derivatives such as (meth) acrylate, nonylphenol propylene oxide modified (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate Fester (meth) acrylate, furfuryl (meth) acrylate, carbitol (meth) acrylate, benzyl (meth) acrylate, butoxyethyl (meth) acrylate, allyl (meth) acrylate, acryloylmorpholine, 2-hydroxyethylacrylamide, N- Examples include methylol (meth) acrylamide, N-vinylpyrrolidone, 2-vinylpyridine, 2- (meth) acryloyloxyethyl acid phosphate monoester and the like.

  In addition to the monofunctional monomer, there may be mentioned a Michael adduct of acrylic acid or 2-acryloyloxyethyldicarboxylic acid monoester. Examples of the acrylic acid Michael adduct include acrylic acid dimer, methacrylic acid dimer, and acrylic acid trimer. Methacrylic acid trimer, acrylic acid tetramer, methacrylic acid tetramer and the like. Examples of 2-acryloyloxyethyl dicarboxylic acid monoester which is a carboxylic acid having a specific substituent include 2-acryloyloxyethyl succinic acid monoester, 2-methacryloyloxyethyl succinic acid monoester, and 2-acryloyloxyethyl. Examples include phthalic acid monoester, 2-methacryloyloxyethyl phthalic acid monoester, 2-acryloyloxyethyl hexahydrophthalic acid monoester, and 2-methacryloyloxyethyl hexahydrophthalic acid monoester. Furthermore, oligoester acrylate is also mentioned.

  The bifunctional monomer may be any monomer containing two ethylenically unsaturated groups. For example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol Di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide Modified bisphenol A type di (meth) acrylate, propylene oxide modified bisphenol A type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate 1,6-hexanediol ethylene oxide modified di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) Examples include acrylate, diglycidyl phthalate di (meth) acrylate, hydroxypivalic acid-modified neopentyl glycol di (meth) acrylate, isocyanuric acid ethylene oxide-modified diacrylate, and 2- (meth) acryloyloxyethyl acid phosphate diester.

  The tri- or higher functional monomer may be any monomer containing three or more ethylenically unsaturated groups. For example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (meth) acryloyloxyethoxytrimethylolpropane, glycerin polyglycidyl ether poly (meth) acrylate, isocyanuric acid ethylene oxide modified triacrylate, ethylene Oxide-modified dipentaerythritol penta (meth) acrylate, ethylene oxide-modified dipentaerythritol hexa (meth) acrylate, ethylene Side modified pentaerythritol tri (meth) acrylate, ethylene oxide modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, caprolactone modified pentaerythritol tri (meth) ) Acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, succinic acid-modified pentaerythritol tri (meth) acrylate, and the like.

  These ethylenically unsaturated monomers (B2) may be used alone or in combination of two or more.

The ethylenically unsaturated monomer (B2) is preferably a monomer containing one or more ethylenically unsaturated groups, particularly preferably a monomer containing two or more ethylenically unsaturated groups and having a high hardness. In view of obtaining a coating film, the monomer is more preferably a monomer containing three or more ethylenically unsaturated groups.
Specifically, a pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, or dipentaerythritol hexa (meth) acrylate is required to obtain a coating film having high hardness. Is preferred.

  As the ethylenically unsaturated compound (B), the content ratio (weight ratio) of (B1) and (B2) when the urethane (meth) acrylate compound (B1) and the ethylenically unsaturated monomer (B2) are used in combination. , (B1) :( B2) = 5: 95 to 95: 5, particularly preferably (B1) :( B2) = 20: 80 to 80:20.

In the present invention, a photopolymerization initiator (C) can further be contained.
Examples of the photopolymerization initiator (C) include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2 -Hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4- Acetophenones such as morpholinophenyl) butanone and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomer; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl Ben such as ether Ins; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethananium bromide, (4-benzoylbenzyl) trimethylammonium Benzophenones such as chloride; 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy -3 Thioxanthones such as 4-dimethyl-9H-thioxanthone-9-one mesochloride; 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl- And acyl phosphine oxides such as pentylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; In addition, these photoinitiators (C) may be used individually by 1 type, and may use 2 or more types together.

  These auxiliary agents include triethanolamine, triisopropanolamine, 4,4′-dimethylaminobenzophenone (Michler ketone), 4,4′-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, 4-dimethylaminobenzoic acid. Ethyl, 4-dimethylaminobenzoic acid (n-butoxy) ethyl, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone Etc. can be used in combination.

  The compounding quantity of a photoinitiator (C) is 0. 0 with respect to a total of 100 weight part of a urethane (meth) acrylate type compound (A) and the ethylenically unsaturated compound (B) used as needed. The amount is preferably 1 to 10 parts by weight, more preferably 1 to 8 parts by weight, and particularly preferably 1 to 5 parts by weight. If the amount is too small, the curing rate in the case of ultraviolet curing tends to be extremely slow, and if too large, the curability is not improved and is inefficient.

  In the present invention, in addition to the components (A) to (C), fillers, electrolyte salts, dyes and pigments, oils, plasticizers, waxes, desiccants, dispersants, wetting agents, emulsifiers, gelling agents. , Stabilizer, antifoaming agent, leveling agent, surface conditioner, thixotropy imparting agent, antioxidant, flame retardant, filler, reinforcing agent, matting agent, crosslinking agent, UV absorber, weathering agent, light stabilizer , Thickeners, rust inhibitors, adhesion improvers, film-forming aids, and the like can also be blended.

  In addition to these, unsaturated polyester resins, vinyl urethane resins, vinyl ester urethane resins, polyisocyanates, polyepoxides, acrylic resins, alkyd resins, urea resins, melamine resins for the purpose of suppressing the curing shrinkage of the coating film Polymers such as polyvinyl acetate, vinyl acetate copolymers, polydiene elastomers, saturated polyesters, saturated polyethers, and cellulose derivatives such as nitrocellulose and cellulose acetate butyrate may be blended.

  Thus, an active energy ray-curable resin composition containing the polysiloxane structure-containing urethane (meth) acrylate compound (A) of the present invention, preferably further containing an ethylenically unsaturated compound (B) is obtained.

Such a resin composition can be used by blending an organic solvent and adjusting the viscosity, if necessary, and is usually diluted to 10 to 80% by weight, preferably 20 to 60% by weight. Can be applied.
Examples of the organic solvent include alcohols such as methanol, ethanol, propanol, n-butanol and i-butanol, ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone and cyclohexanone, and cellosolve such as ethyl cellosolve, butyl cellosolve and cellosolve acetate. , Aromatics such as toluene and xylene, glycol ethers such as propylene glycol monomethyl ether, acetates such as ethyl acetate, butyl acetate and 2-methoxy-1-methylethyl acetate, and diacetone alcohol. These organic solvents may be used alone or in combination of two or more.

In addition, in manufacturing the active energy ray-curable resin composition of the present invention, a polysiloxane structure-containing urethane (meth) acrylate compound (A), an ethylenically unsaturated compound (B), and a photoinitiator (C) are blended. The method is not particularly limited, and the separately produced components (A) to (C) may be blended in various orders. First, (A) and (B) are produced in the same reaction system. (C) may then be blended. When an organic solvent such as ethyl acetate or methyl isobutyl ketone is used, the organic solvent may be added to the above mixture, or the respective compositions may be dissolved in the organic solvent and then mixed.
Among these, the method of adding (C) at the end after blending (A) and (B) is preferably used.

  The active energy ray-curable resin composition of the present invention is useful as a coating agent composition, and is effectively used as a curable resin composition for coating film formation, such as a top coat agent and an anchor coat agent for various substrates. After the active energy ray-curable resin composition is applied to the substrate (if the composition diluted with an organic solvent is applied, it is further dried) and then irradiated with active energy rays. Can be cured. The coating method is not particularly limited, and examples thereof include wet coating methods such as spray, shower, dipping, roll, spin, screen printing, and the like.

  The coating film thickness (film thickness after curing) is usually preferably 1 to 50 μm, particularly preferably 3 to 30 μm.

  Examples of the base material to be coated include polyolefin resin, polyester resin, polycarbonate resin, acrylic resin, acrylonitrile butadiene styrene copolymer (ABS), polystyrene resin, cellulose resin, and the like. Examples include molded products (films, sheets, cups, etc.), metals, glass, wood materials, paper materials, and the like.

  As such active energy rays, for example, rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, electromagnetic waves such as X-rays and γ rays, electron beams, proton rays, neutron rays and the like can be used. Curing by ultraviolet irradiation is advantageous because of the availability of the irradiation device and the price. In addition, when performing electron beam irradiation, it can harden | cure even without using a photoinitiator (C).

As a method of curing by ultraviolet irradiation, a high-pressure mercury lamp that emits light in a wavelength range of 150 to 450 nm, an ultra-high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrodeless lamp, an LED, etc. What is necessary is just to irradiate about 3000 mJ / cm < ² >.
After the ultraviolet irradiation, heating can be performed as necessary to complete the curing.
Thus, a cured coating film obtained by irradiating the coating composition of the present invention with active energy rays is obtained.

  Polysiloxane structure-containing urethane obtained by reacting a polysiloxane compound (a1) having two or more hydroxyl groups, a polyvalent isocyanate compound (a2), and a hydroxyl group-containing (meth) acrylate compound (a3) according to the present invention. It is a (meth) acrylate compound, wherein the polysiloxane compound (a1) having two or more hydroxyl groups has a weight average molecular weight of 2,000 or more and contains 10 or more ethylenically unsaturated double bonds. The polysiloxane structure-containing urethane (meth) acrylate-based compound is characterized by having a well-balanced antifouling performance (stain removal property) and chemical resistance (alkali resistance) when used as a cured coating film, and It has an excellent effect on coating film appearance and scratch resistance, and is particularly useful as a coating agent, especially as a coating agent for the outermost surface. It is.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to a following example, unless the summary is exceeded.
In the examples, “%” and “parts” are based on weight unless otherwise specified.

  As the polysiloxane structure-containing urethane (meth) acrylate compound (A), the polysiloxane group-containing urethane (meth) acrylate compound [A-1] to [A-3], [A′-1], [A′− 2] was prepared according to the following method.

・ <Production of polysiloxane group-containing urethane (meth) acrylate-based compound [A-1]>
In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas blowing port, hexamethylene diisocyanate trimer (a2) (isocyanate group content 23.4%) 72.4 g, general formula (1 polysiloxane compound represented ^{_{by) (a1) (R 1 =}} -C 2 H 4 OC 3 H 6 -, R 2 = ^{_{methyl, R 3 = -C 3 H 6}} OC 2 H 4 -, a = average 37 , B = 1, c = 1, weight average molecular weight 3,000) 125.8 g, dibutyltin dilaurate 0.1 g, and methyl ethyl ketone 500 g were reacted at 60 ° C. for 3 hours, resulting in a residual isocyanate group of 1.6%. At that time, dipentaerythritol pentaacrylate (a3) [dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate 301.8 g of the mixture (hydroxyl value 50 mg KOH / g)] and 1 g of 2,6-di-tert-butylcresol were added dropwise over about 1 hour, the reaction was continued as it was, and the reaction was terminated when the isocyanate group disappeared. , Polysiloxane group-containing urethane (meth) acrylate compound [A-1] (68% with respect to the total amount of (A) and (B)) and dipentaerythritol hexaacrylate [B-3] ((A) and In (B), a mixture solution of 32% with respect to the total amount was obtained (solid content concentration 50%).
In addition, the said polysiloxane group containing urethane (meth) acrylate type compound [A-1] corresponds to the urethane (meth) acrylate type compound (A) in the text, and contains ethylenically unsaturated double bonds. The number is 20.

・ <Production of polysiloxane group-containing urethane (meth) acrylate-based compound [A-2]>
In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas blowing port, isophorone diisocyanate trimer (a2) (isocyanate group content 17.3%) 111.8 g, general formula (1) Polysiloxane compound (a1) (R ¹ = —C ₂ H ₄ OC ₃ H ₆ —, R ² = methyl group, R ³ = —C ₃ H ₆ OC ₂ H ₄ —, a = average 64, b = 1, c = 1, weight average molecular weight 5,000) 245.2 g, dioctyltin dilaurate 0.10 g and methyl ethyl ketone 500 g were charged and reacted at 60 ° C. for 3 hours, resulting in a residual isocyanate group of 1.5%. At that time, pentaerythritol triacrylate (a3) [a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate ( Hydroxyl value 120 mgKOH / g)] 143.0 g and methylhydroquinone 0.5 g were added dropwise over about 1 hour, the reaction was continued as it was, and when the isocyanate group disappeared, the reaction was terminated. ) Acrylate compound [A-2] (90% based on the total amount in (A) and (B)) and pentaerythritol tetraacrylate [B-4] (based on the total amount in (A) and (B)) 10%) mixture solution was obtained (solid content concentration 50%).
The polysiloxane group-containing urethane (meth) acrylate compound [A-2] corresponds to the urethane (meth) acrylate compound (A) in the text, and contains an ethylenically unsaturated double bond. The number is twelve.

・ <Production of polysiloxane group-containing urethane (meth) acrylate-based compound [A-3]>
In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser and a nitrogen gas inlet, hexamethylene diisocyanate trimer (a2) (isocyanate group content 23.4%) 52.7 g, hexamethylene diisocyanate ( a2) 3.5 g, 1,3-butanediol (a4) 1.9 g, dibutyltin dilaurate 0.1 g were charged and reacted at 60 ° C. for 5 hours. When the remaining isocyanate group reached 21.3%, Polysiloxane compound (a1) represented by formula (1) (R ¹ = —OC ₃ H ₆ —, R ² = methyl group, R ³ = —C ₃ H ₆ O—, a = average 65, b = 1 , C = 1, weight average molecular weight 5,000) 17.9 g, dibutyltin dilaurate 0.1 g, and methyl ethyl ketone 500 g were reacted at 60 ° C. for 3 hours. When the cyanate group became 2.0%, dipentaerythritol pentaacrylate (a3) [mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (hydroxyl value 50 mg KOH / g)] 424.1 g, 2 , 6-di-tert-butylcresol 1 g was added dropwise over about 1 hour, the reaction was continued as it was, and the reaction was terminated when the isocyanate group disappeared, and the polysiloxane group-containing urethane (meth) acrylate compound [A -3] (6% by weight based on the total amount in (A) and (B)), urethane (meth) acrylate compound [B-1] (34% based on the total amount in (A) and (B)) ) And dipentaerythritol hexaacrylate [B-3] (60% of the total amount in (A) and (B)) Obtained (solid concentration 50%).
In addition, the said polysiloxane group containing urethane (meth) acrylate type compound [A-3] corresponds to the urethane (meth) acrylate type compound (A) in the text, and contains an ethylenically unsaturated double bond. The number is 20.

-<Production of polysiloxane group-containing urethane (meth) acrylate-based compound [A'-1]>
In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas blowing port, hexamethylene diisocyanate trimer (a2) (isocyanate group content 23.4%) 81.1 g, general formula (1 ) Polysiloxane compound (a1) (R ¹ = —C ₂ H ₄ OC ₃ H ₆ —, R ² = methyl group, R ³ = —C ₃ H ₆ OC ₂ H ₄ —, a = average 118 , B = 1, c = 1, weight average molecular weight 9000) 383.9 g, dibutyltin dilaurate 0.1 g, and methyl ethyl ketone 500 g were reacted at 60 ° C. for 3 hours, and when the residual isocyanate group became 1.3%. Furthermore, 35.0 g of hydroxyethyl acrylate (a3) and 1 g of methylhydroquinone were added dropwise over about 1 hour, and the reaction was continued as it was. At the time of disappearance, the reaction was terminated to obtain a polysiloxane group-containing urethane (meth) acrylate-based compound [A′-1] solution (solid content concentration 50%).
The polysiloxane group-containing urethane (meth) acrylate compound [A′-1] contains 4 ethylenically unsaturated double bonds.

-<Production of polysiloxane group-containing urethane (meth) acrylate-based compound [A'-2]>
In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser and a nitrogen gas inlet, 138.7 g of hexamethylene diisocyanate trimer (a2) (isocyanate group content 23.4%), general formula (1 polysiloxane compound represented ^{_{by) (a1) (R 1 =}} -C 2 H 4 OC 3 H 6 -, R 2 = ^{_{methyl, R 3 = -C 3 H 6}} OC 2 H 4 -, a = average 10 , B = 1, c = 1, weight average molecular weight 1,000) 120.4 g, dibutyltin dilaurate 0.1 g, and methyl ethyl ketone 500 g were allowed to react at 60 ° C. for 3 hours, resulting in a residual isocyanate group of 2.9%. At that time, pentaerythritol triacrylate (a3) [a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate ( Hydroxyl value 120 mg KOH / g)] 240.8 g, 2,6-di-tert-butylcresol 1 g was added dropwise over about 1 hour, the reaction was continued as it was, and the reaction was terminated when the isocyanate group disappeared. Siloxane group-containing urethane (meth) acrylate compound [A′-2] (83% based on the total amount of [A′-2] and [B-4]) and pentaerythritol tetraacrylate [B-4] ([ 17% of the total amount of A′-2] and [B-4] was obtained (solid content concentration 50%).
In addition, the content number of the ethylenically unsaturated double bond of the said polysiloxane group containing urethane (meth) acrylate type compound [A'-2] is 12.

  As the ethylenically unsaturated compound (B), ethylenically unsaturated compounds [B-1] and [B-2] were produced according to the following method.

-<Production of ethylenically unsaturated compound [B-1]>
In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser and nitrogen gas inlet, 76.1 g of hexamethylene diisocyanate trimer (isocyanate group content 21.0%), 0.1 g of dibutyltin dilaurate, methyl ethyl ketone 500 g was charged, and dipentaerythritol pentaacrylate [mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (hydroxyl value 50 mg KOH / g)] 423.9 g and methyl hydroquinone 1 g were added dropwise in about 1 hour at 60 ° C. or less. The reaction was continued at 60 ° C., and the reaction was terminated when the isocyanate group disappeared. 55% of the total amount of the ethylenically unsaturated compound [B-1] ([B-1] and [B-3]) ) And dipentaerythritol hexaacrylate [B- ] To obtain a mixture solution of ([45% of the total amount of B-1] and [B-3]) (solid concentration 50%).
The ethylenically unsaturated compound [B-1] corresponds to the urethane (meth) acrylate compound (B1-1) in the text.

・ <Production of ethylenically unsaturated compound [B-2]>
In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser and nitrogen gas inlet, 111.8 g of isophorone diisocyanate trimer (a2) (isocyanate group content 17.3%) and 0.1 g of dibutyltin dilaurate Then, 500 g of methyl ethyl ketone was charged, and 143.0 g of pentaerythritol triacrylate (a3) [mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (hydroxyl value 120 mg KOH / g)] at 60 ° C. or less, and 1 g of methylhydroquinone were dropped over about 1 hour. The reaction was continued at 60 ° C., and the reaction was terminated when the isocyanate group disappeared, and the ethylenically unsaturated compound [B-2] (based on the total amount of [B-2] and [B-4]) 75%) and pentaerythritol tetraacrylate [B- ] To obtain a mixture solution of ([25% based on the total weight of the B-2] and [B-4]) (solid concentration 50%).
The ethylenically unsaturated compound [B-2] corresponds to the urethane (meth) acrylate compound (B1-1) in the text.

・ <Ethylenically unsaturated monomer [B-3]>
Dipentaerythritol hexaacrylate (corresponding to (B2)) was used.

・ <Ethylenically unsaturated monomer [B-4]>
Pentaerythritol tetraacrylate (corresponding to (B2)) was used.

  As a photopolymerization initiator (C), 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF Japan, “Irgacure 184”) [C-1] was prepared.

  As the surface conditioner (D), polyether-modified polydimethylsiloxane (BIC Chemie Japan, “BYK-UV 3510”) [D-1] was prepared.

<Examples 1 to 5 and Comparative Examples 1 and 2>
[Production of active energy ray-curable resin composition]
The above polysiloxane structure-containing urethane (meth) acrylate [A], ethylenically unsaturated compound [B], and photopolymerization initiator [C] are blended so as to have the ratio shown in Table 1 in terms of solid content, and photopolymerization is performed. It diluted with methyl ethyl ketone so that solid content except an initiator might be 50% concentration, and the active energy ray hardening-type resin composition solution was obtained.
Next, the active energy ray-curable resin composition solution was applied onto a triacetyl cellulose (TAC) film using a bar coater so that the film thickness after drying was 10 μm, and at 60 ° C. for 5 minutes. After drying, using a high pressure mercury lamp 80W and one lamp, two passes of UV irradiation (cumulative irradiation amount 500 mJ / cm ² ) are carried out at a conveyor speed of 5 m / min from a height of 18 cm, and a cured coating film (film thickness) 10 μm) and the following evaluation was performed.

<Comparative Example 3>
The above-mentioned ethylenically unsaturated compound [B], photopolymerization initiator [C], and surface conditioner [D] were blended so as to have the ratio shown in Table 1 in terms of solid content, and the solid excluding the photopolymerization initiator The active energy ray-curable resin composition solution was obtained by diluting with methyl ethyl ketone so that the concentration became 50%.
Next, the active energy ray-curable resin composition solution was applied onto a triacetyl cellulose (TAC) film using a bar coater so that the film thickness after drying was 10 μm, and at 60 ° C. for 5 minutes. After drying, using a high pressure mercury lamp 80W and one lamp, two passes of UV irradiation (cumulative irradiation amount 500 mJ / cm ² ) are carried out at a conveyor speed of 5 m / min from a height of 18 cm, and a cured coating film (film thickness) 10 μm) and the following evaluation was performed.

[Appearance of coating film]
The appearance of the cured coating film was observed and evaluated as follows.
(Evaluation)
○ ・ ・ ・ Transparent and free of foreign matter × ・ ・ ・ White turbidity or aggregate on the surface of the cured coating

[Anti-fouling performance]
A one-way line was drawn on the cured coating film with a black oil-based pen and allowed to stand for 24 hours, followed by dry wiping with a waste cloth. The cured coating film after wiping was observed and evaluated as follows.
(Evaluation)
○ ・ ・ ・ Can be wiped clean △ ・ ・ ・ While it can be wiped off

[chemical resistance]
・ [Initial water contact angle]
The PET film on which the cured coating film was formed was allowed to stand for 24 hours in an atmosphere of 23 ° C. and 50% RH. Then, about the cured coating film, the contact angle of purified water was measured using DCA-VZ150 by Kyowa Interface Science Co., Ltd.
・ [Water contact angle after chemical resistance test]
The PET film on which the cured coating film was formed was immersed in a 1.5N NaOH solution at 50 ° C. for 2 minutes, and then the coating film surface was washed with purified water and allowed to stand in a 23 ° C. atmosphere for 24 hours. Then, about the cured coating film, the contact angle of purified water was measured using DCA-VZ150 by Kyowa Interface Science Co., Ltd., and evaluated as follows.
(Evaluation)
○: Water contact angle after initial and chemical resistance test is both 90 ° or more ×… Water contact angle after initial and chemical resistance test or either value is 90 ° or less

[Abrasion resistance]
About the said cured coating film, the surface damage degree after steel wool # 0000 which applied the load of 300g was reciprocated 10 times on the cured coating film surface was observed visually, and it evaluated as follows.
(Evaluation)
◎ ・ ・ ・ No damage at all ○ ・ ・ ・ Slightly scratched △ ・ ・ ・ Slightly scratched × ・ ・ ・ Thin film is whitened due to damage

  The evaluation results of the above examples and comparative examples are shown together in Table 1.

  The cured coating film obtained from the active energy ray-curable resin composition containing the urethane (meth) acrylate-based compound (A) of Examples 1 to 5 has good wiping properties for oil-based pens for antifouling performance, The water contact angle is 90 ° or more at the initial stage and exhibits water repellency. Further, even after a chemical resistance (alkaline resistance) test, the water contact angle is less than 90 ° and the water repellency is maintained. It can be seen that a cured coating film having excellent properties and chemical resistance was obtained.

On the other hand, since the cured coating film of Comparative Example 1 using the polysiloxane structure-containing urethane (meth) acrylate compound (A) containing only four ethylenically unsaturated double bonds is insufficiently cured, it is antifouling. It is inferior in performance (dirt removal), chemical resistance (alkali resistance), and scratch resistance.
Moreover, the cured coating film of Comparative Example 2 using the polysiloxane structure-containing urethane (meth) acrylate compound (A) obtained by using a polysiloxane compound having a weight average molecular weight of less than 2,000 has antifouling performance ( The result was inferior in soil removal property and chemical resistance (alkali resistance).
Further, Comparative Example 3 using a polyether-modified polydimethylsiloxane compound having a weight average molecular weight of 5,000 and not containing an ethylenically unsaturated double bond without using a polysiloxane structure-containing urethane (meth) acrylate compound The cured coating film had a very poor chemical resistance (alkali resistance).

The active energy ray-curable resin composition of the present invention is excellent in antifouling properties such as adhesion of dirt, antifouling performance such as dirt removal and chemical resistance such as alkali resistance, and excellent in coating film hardness and scratch resistance. Therefore, it can be usefully used mainly for coating applications such as a coating agent, an anchor coating agent, and a magnetic powder coating binder.
It can also be used as a paint, ink, pressure-sensitive adhesive, adhesive, adhesive or the like.

Claims (8)

Polysiloxane structure-containing urethane (meth) obtained by reacting a polysiloxane compound (a1) having two or more hydroxyl groups, a polyvalent isocyanate compound (a2), and a hydroxyl group-containing (meth) acrylate compound (a3). An acrylate compound (A),
The weight average molecular weight of the polysiloxane compound (a1) having two or more hydroxyl groups is 2,000 or more,
And,
A polysiloxane structure-containing urethane (meth) acrylate compound containing 10 or more ethylenically unsaturated double bonds. The polysiloxane structure according to claim 1, wherein the polysiloxane compound (a1) having two or more hydroxyl groups is a polysiloxane compound having hydroxyl groups at both ends represented by the following general formula (1). Contains urethane (meth) acrylate compounds.

[Wherein R ¹ and R ³ represent a hydrocarbon group or an organic group containing a hetero atom, R ² independently represents an alkyl group, a cycloalkyl group or a phenyl group, and a is an integer of 10 or more, b and c are integers of 1 to 3. ] ^{3. The} polysiloxane structure-containing urethane (meth) acrylate compound according to claim 2, wherein R ¹ and R ³ in the general formula (1) are organic groups having an ether bond.   The polysiloxane structure-containing urethane (meth) acrylate compound according to any one of claims 1 to 3, wherein the polyisocyanate compound (a2) is a polyisocyanate compound having an isocyanurate structure.   An active energy ray-curable resin composition comprising the polysiloxane structure-containing urethane (meth) acrylate compound according to claim 1.   The active energy ray-curable resin composition according to claim 5, comprising an ethylenically unsaturated compound (B).   A coating agent comprising the active energy ray-curable resin composition according to claim 4 or 5.   The coating agent according to claim 7, wherein the coating agent is used as an outermost surface coating agent.