WO2006006402A1

WO2006006402A1 - Active energy ray-curable resin composition, method for producing same, and coating composition using same

Info

Publication number: WO2006006402A1
Application number: PCT/JP2005/011944
Authority: WO
Inventors: Toshirou Noda; Hitoshi Matsunami; Hiromitsu Koumoto
Original assignee: The Nippon Synthetic Chemical Industry Co., Ltd.
Priority date: 2004-07-08
Filing date: 2005-06-29
Publication date: 2006-01-19
Also published as: JP5235263B2; TW200615286A; KR20070032363A; JP2006045504A; KR100998116B1

Abstract

Disclosed is an active energy ray-curable resin composition which is useful for forming a coating layer having excellent antifouling property, coating film hardness, abrasion resistance, solvent resistance and adhesiveness. Also disclosed are a method for producing such a resin composition and a coating composition using such a resin composition. Specifically disclosed is an active energy ray-curable resin composition containing a polysiloxane-containing polyisocyanate derivative [A] obtained by reacting a polysiloxane compound (a1) represented by the general formula (1) below and having a terminal hydroxyl group, a polyisocyanate compound and a hydroxyl group-containing (meth)acrylate compound, and a compound [B] having one or more ethylenically unsaturated groups in one molecule. Also disclosed are a method for producing such a resin composition and a coating composition using such a resin composition. [In the formula, R1 represents an alkyl group; R2's independently represent an alkyl group, a cycloalkyl group or a phenyl group; R3 represents a hydrocarbon group or an organic group containing an oxygen atom; a represents an integer of not less than 1; and b represents an integer of 1-3.]

Description

Specification

Active energy ray-curable resin composition, method for producing the same, and coating agent composition using the same

Technical field

[0001] The present invention relates to an active energy one-line curable resin composition containing a polysiloxane-containing polyisocyanate derivative, more specifically, excellent antifouling properties, coating film hardness, and scratch resistance. The present invention relates to an active energy one-line curable resin composition useful for forming a coating layer having excellent properties, solvent resistance, and adhesion, a method for producing the same, and a coating agent composition using the same.

Background art

[0002] Conventionally, when the surface of a base material such as a high-quality material, a paper-based material, a non-combustible building material, glass, or a plastic material is contaminated with magic or the like, the dirt is not removed even if it is wiped with a waste cloth. For the purpose of preventing contamination of the surface of the substrate, which is a problem, a coating agent made of a photocurable resin composition for top coating has been studied.

[0003] Examples of the resin composition used in such a coating agent include, for example, a photocurable (meth) acrylate resin, a photocurable polysiloxane urethane (meth) acrylate resin, and a photocurable silicone block. A resin composition containing a (meth) acrylate-based resin and a photopolymerization initiator has been proposed (see, for example, JP-A-2003-192751).

Disclosure of the invention

[0004] However, as a result of detailed studies by the present inventors, the technique disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 2003-192751 is mainly polyisocyanate and polydimethyl having one hydroxyl group at both ends. Uses a photocurable resin composition made of urethane (meth) acrylate obtained by reacting siloxane diol with hydroxyalkyl (meth) acrylates, and is a powerful urethane (meth) acrylate. Power that has a certain degree of decontamination in the use of, which requires further improvement with the recent increase in performance requirements o

[0005] When a molded article made of plastic is used as a base material, it is lightweight and transparent. Although it is excellent and easy to form and economical, it is widely used. On the other hand, it is soft and easily scratched, so a coating agent is often applied to protect the plastic surface. . However, the technique disclosed in the above Japanese Patent Laid-Open No. 2003-192751 requires further improvements that are not satisfactory in terms of scratch resistance, solvent resistance, and adhesion to plastic substrates. ing.

[0006] Therefore, in the present invention, an active energy useful for forming a coating layer having excellent antifouling properties and excellent coating film hardness, scratch resistance, solvent resistance, and adhesiveness under such a background. The object of the present invention is to provide a lug-line curable resin composition, a method for producing the composition, and a coating agent composition using the composition.

[0007] However, the present inventor has conducted extensive studies in view of intensive efforts. As a result, the polysiloxane compound (al) having a hydroxyl group at one end represented by the following general formula (1), a polyisocyanate compound, and a hydroxyl group A polysiloxane-containing polyisocyanate derivative [A] obtained by reacting a containing (meth) acrylate compound and a compound [B] having one or more ethylenically unsaturated groups in one molecule The present inventors have found that the active energy ray-curable resin composition meets the above-mentioned purpose and completed the present invention.

[0008] [Chemical 1]

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

In the present invention, further, a polysiloxane compound (cl) having a hydroxyl group at both ends represented by the following general formula (2), a polyisocyanate compound, and a hydroxyl group-containing (meth) acrylate compound It is preferable in terms of transparency and scratch resistance that it contains a polyisocyanate derivative [C] obtained by reaction.

[0010] [Chemical 2] (2)

[In the formula, each R ⁴ independently represents an organic group containing a hydrocarbon group or an oxygen atom, each R ⁵ independently represents an alkyl group, a cycloalkyl group, or a full group, and c is 1 or more. It is an integer, and d and e are integers of 1 to 3. ]

[0011] In the present invention, the compound [B] having one or more ethylenically unsaturated groups in one molecule is represented by the urethane (meth) atalylate compound (B1) and Z represented by the following general formula (3): Or an ethylenically unsaturated monomer (excluding (B1)) (B2) is preferred from the viewpoint of coating film hardness, and further, a urethane (meth) acrylate compound represented by the following general formula (4) [D] The combination of these is preferred in terms of flexibility and crack resistance.

[0012] [Chemical 3]

[In the formula, R ° is a urethane bond residue of the polyisocyanate compound (bl), R ⁷ is a urethane bond residue of the hydroxyl group-containing (meth) acrylate compound (b2), and f is an integer of 2 to 50 It is. ] [Chemical 4]

[Wherein R ⁸ is a urethane bond residue of a polyisocyanate compound (dl), R ⁹ is a urethane bond residue of a hydroxyl group-containing (meth) acrylate compound (d2), R ^1Q is a polyol compound ( d3) urethane bond residue, g is an integer of 1 to 50, and h is an integer of 2 to 50. ]

The active energy ray-curable resin composition of the present invention comprises a polysiloxane compound (al) having a hydroxyl group at one end represented by the general formula (1), a polyisocyanate compound, Because it contains a polysiloxane-containing polyisocyanate derivative [A] obtained by reacting a hydroxyl group-containing (meth) acrylate compound and a compound [B] having one or more ethylenically unsaturated groups in one molecule The resulting coating film is excellent in antifouling properties and exhibits excellent effects in coating film hardness, scratch resistance, solvent resistance, and adhesion. Paint, ink, protective coating agent, anchor coating agent It is useful as various film forming materials such as magnetic powder coating binders, pressure-sensitive adhesives, adhesives, and adhesives. Especially, it is very useful as a coating agent composition for top coating of various plastics and optical films.

BEST MODE FOR CARRYING OUT THE INVENTION

[0015] The present invention is described in detail below.

The active energy ray-curable resin composition of the present invention comprises a polysiloxane-containing polyisocyanate derivative [A] and a compound [B] having one or more ethylenically unsaturated groups in one molecule. is there.

First, the powerful polyisocyanate derivative [A] will be described.

[0016] The polyisocyanate derivative [A] includes a polysiloxane compound (al) having a hydroxyl group at one end represented by the general formula (1), a polyisocyanate compound, and a hydroxyl group-containing (meth) atariate. It is obtained by reacting a rate compound.

[0017] The powerful polysiloxane compound (al) is not particularly limited as long as it is a compound having a structure represented by the general formula (1). In the general formula (1), R ¹ represents an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc.), and each R ² independently represents an alkyl group (for example, a methyl group, an ethyl group, a propyl group). , A butyl group, etc.), a cycloalkyl group or a phenyl group, and R ³ represents a hydrocarbon group or an organic group containing an oxygen atom. a is an integer of 1 or more, preferably 9 to 120, and b is an integer of 1 to 3, preferably 1 to 2.

[0018] The weight average molecular weight of the polysiloxane compound (al) used in the present invention is not particularly limited. The force is preferably 100-30, 000, particularly 500 to 10,000, more preferably 1,000. A power of -10,000 S is preferred. When the weight average molecular weight is less than 100, the antifouling performance is lowered. When the weight average molecular weight is more than 30,000, the coating film hardness is undesirably lowered.

[0019] Specific examples of the polysiloxane compound (al) represented by the general formula (1) include Shin-Etsu Chemical Co., Ltd. “-22-1700”, “X-22-4015” manufactured by Kogyo Co., Ltd. “Silaplane FM-0411”, “Silaplane FM—0412”, “Silaplane FM—0425” manufactured by Chisso Corporation , “Sylaplane FM—DA11”, “Silaplane FM—DAI 2”, “Silaplane FM—DA25”, etc.

[0020] The polyisocyanate compound used in the present invention is not particularly limited, and examples thereof include aromatic, aliphatic, and alicyclic polyisocyanates. Cyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, polymethanemethane polyisocyanate, modified diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, xylylene diisocyanate Cyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane , Range-isocyanate, lysine disiocyanate, Polyisocyanates such as N-triisocyanate and naphthalene diisocyanate, or trimer or multimer compounds of these polyisocyanates, burette-type polyisocyanates, water-dispersed poly Isocyanate (for example, “Aquanate 100”, “Aquanate 110”, “Aquanate 200”, “Aquanate 210”, etc.) manufactured by Nippon Polyurethane Industry Co., Ltd.), or these polyisocyanates and polyols The reaction product etc. are mentioned. Among them, an isocyanate compound having three or more isocyanate groups in one molecule, particularly a polyisocyanate trimer or multimer compound, is required to have a coating film hardness, scratch resistance and solvent resistance. , And more preferable because it can reduce unreacted low molecular weight components that cause bleeding.

[0021] Examples of such polyols include, but are not limited to, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene dallicol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, poly Butylene glycol, 1,6-hexane diol, neopentyl glycol, cyclohexane dimethanol, hydrogenated bisphenol A, polypropylene, trimethylololeethane, trimethylololepropane, polytrimethylololepropane , Pentaerythritol, polypentaerythritol, sonolebithonole, mannitol, glycerin, poly Polyhydric alcohols such as glycerin and polytetramethylene glycol, polyether polyols having a structure of at least one of block or random copolymerization of polyethylene oxide, polypropylene oxide, ethylene oxide Z propylene oxide, the polyhydric alcohol Or polyether polyol and maleic anhydride, maleic acid, fumaric acid

Polyester polyols, which are condensates with polybasic acids such as itaconic anhydride, itaconic acid, adipic acid, isophthalic acid, etc. Caplatato-modified polyols such as force prolatatone-modified polytetramethylene polyol, polyolefin-based polyols, hydrogenated polybutadiene polyols Examples thereof include polybutadiene-based polyols.

Furthermore, as such polyol, for example, 2,2-bis (hydroxymethyl) butyric acid, tartaric acid, 2,4 dihydroxybenzoic acid, 3,5 dihydroxybenzoic acid, 2,2 bis (hydroxymethyl) propion Acid, 2,2-bis (hydroxyethyl) propionic acid, 2,2-bis (hydroxypropyl) propionic acid, dihydroxymethylacetic acid, bis (4-hydroxyphenol) acetic acid, 4,4-bis (4-hydroxyphenol) -Ru) Powerful ruxyl group-containing polyols such as pentanoic acid and homogentisic acid, and sulphonic acid group or sulfonate group-containing polyols such as sodium 1,4 butanediol sulfonate.

[0023] When a reaction product of a polyisocyanate and a polyol is used, for example, it may be used as a urethane polyol obtained by reacting the polyol with the polyisocyanate. In the reaction of a powerful polyisocyanate and a polyol, a metal catalyst such as dibutyltin dilaurate or an amine catalyst such as 1,8 diazabicyclo [5.4.0] undecene-7 is used for the purpose of accelerating the reaction. Also preferred to use.

[0024] The hydroxyl group-containing (meth) acrylate compound used in the present invention is not particularly limited, and examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2 Hydroxybutyl (meth) atarylate, 4 Hydroxybutyl (meth) atrelate, 2-Hydroxyethyl allyloyl phosphate, 2- (meth) atariloy cicchitil— 2 Hydroxypropyl phthalate, 2 Hydroxy 1- (meth) atariloy Roxypropyl (meth) acrylate, force prolataton modified 2-hydroxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, cap latataton modified dipentaerythritol penta (Meta) Atarirate, Power Rataton modified pen Examples include taerythritol tri (meth) acrylate, ethylene oxide modified dipentaerythritol penta (meth) acrylate, ethylene oxide modified penta erythritol tri (meth) acrylate, and the like. These can be used alone or in combination.

[0025] In the present invention, the method for producing the polysiloxane-containing polyisocyanate derivative [A] is not particularly limited.

(I) a method of charging and reacting a polysiloxane compound (al), a polyisocyanate compound, and a hydroxyl group-containing (meth) atalylate compound all together,

(Mouth) A method of reacting a hydroxyl group-containing (meth) acrylate compound after reacting the polysiloxane compound (al) with the polyisocyanate compound,

(C) a method of reacting a polysiloxane compound (al) after reacting a polyisocyanate compound with a hydroxyl group-containing (meth) acrylate compound,

From the viewpoint of stability of reaction control, the (mouth) method is preferable.

[0026] In this (mouth) method, the hydroxyl group of the polysiloxane compound (al) and the isocyanate group of the polyisocyanate compound are reacted under the conditions in which the isocyanate group remains, and then the polyisocyanate is reacted in the following manner. The residual isocyanate group of the cyanate compound is reacted with the hydroxyl group of the hydroxyl group-containing (meth) acrylate compound.

[0027] In addition, for such a reaction, for the purpose of promoting the reaction, a metal catalyst such as dibutyltin dilaurate, an amine catalyst such as 1,8 diazabicyclo [5.4.0] undecene 7, etc. Further, the reaction temperature is preferably 30 to 90 ° C, particularly preferably 40 to 70 ° C.

[0028] Power to obtain polyisocyanate derivative [A] by force The weight average molecular weight of the obtained polyisocyanate derivative [A] is preferably 500 to 50,000, and moreover, The force S is preferably 500 to 30,000. When the weight average molecular weight is less than 500, the film forming property is deteriorated. When the weight average molecular weight is more than 50,000, the viscosity becomes high and the film is difficult to handle.

[0029] The weight average molecular weight of the polyisocyanate derivative [A] is a weight average molecular weight in terms of standard polystyrene molecular weight, and is determined by high performance liquid chromatography (Nippon “Waters 2695 (main unit)” and “Waters 2414 (detector)” manufactured by Orters Co., Ltd.), column: Shodex GPC KF—806L (exclusion limit molecular weight: 2 X 10 ⁷ , separation range: 100-2 X 1 0 Theoretical plate number: 10,000 plate Z Measured by using three series of Z, filler material: styrene-dibutylbenzene copolymer, filler particle size: 10 m).

[0030] Hereinafter, the measurement of the weight average molecular weight of the urethane (meth) acrylate compound described below is performed according to the above method.

[0031] In obtaining the active energy ray-curable rosin composition of the present invention, it is preferable that Sarako contains a compound [B] having one or more ethylenically unsaturated groups in one molecule. It is necessary in terms of coating film hardness, and such a compound [B] is not particularly limited, but is a urethane (meth) acrylate compound (B1) represented by the above general formula (3) and Z or ethylenically unsaturated Monomers [excluding (B1)] (B2) are preferred. In the general formula (3), R ⁶ is a urethane bond residue of the polyisocyanate compound (bl), R ⁷ is a urethane bond residue of the hydroxyl group-containing (meth) acrylate compound (b2), and f is 2 to 50 It is an integer.

The urethane (meth) acrylate compound (B1) represented by the general formula (3) is obtained by reacting a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate compound. The isocyanate compound is not particularly limited, and examples thereof include those similar to the polyisocyanate compound, and the hydroxyl group-containing (meth) acrylate compound is not particularly limited, but the hydroxyl group-containing (meth) acrylate is not particularly limited. Examples thereof are the same as those of the series compounds.

[0033] Further, as the strong ethylenically unsaturated monomer (excluding (B1)) (B2), any monomer having one or more ethylenically unsaturated groups in one molecule may be used. Bifunctional monomers and tri- or higher functional monomers are listed.

[0034] Examples of the monofunctional monomer include styrene, butyltoluene, chlorostyrene, _a -methylstyrene, methyl (meth) acrylate, ethyl (meth) acrylate, acrylonitrile, butyl acetate, 2-hydroxyethyl ( (Meth) attalylate, 2-hydroxypropyl (meth) attali

—Phenoxy 2-hydroxypropyl (meth) acrylate, 2-hydroxy 3 phenoxy propyl (meth) acrylate, 3 1-hydroxy propyl (meth) acrylate, Glycerin mono (meth) acrylate, glycidyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodeca

-Lu (meth) acrylate, dicyclopentyl (meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, no- (Meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, n-stearyl (meth) acrylate, benzyl (meth) acrylate, phenol ethylene oxide modified ( Half (meth) acrylate, furfuryl (meta) of phthalic acid derivatives such as (meth) acrylate, nouryl phenol propylene oxide modified (meth) acrylate, 2- (meth) tertyloxyl-2-hydroxypropyl phthalate ) Atalylate, carbitol (meth) atarylate, benzyl (meth) Tallylate, butoxychetyl (meth) acrylate, aryl (meth) acrylate, allyloyl morpholine, 2-hydroxyxetyl acrylamide, N-methylol (meth) acrylamide, N-butyrpyrrolidone, 2-butyl pyridine, 2- (Meth) ataryl oxychetyl acid phosphate monoester and the like.

Examples of the bifunctional monomer include 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 Type A 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 (meta ) Atari Glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene diol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meta) ) Atarylate, hydroxybivalic acid-modified neopentyldaricol di (meth) atalylate, isocyanuric acid ethylene oxide-modified diatalylate, 2- (meth) atalyloyloxychetyl acid phosphate diester, and the like. [0036] Examples of the tri- or higher functional monomer include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate. , Dipentaerythritol hexa (meth) acrylate, tri (meth) attaroyloxyethoxytrimethylolpropane, glycerin polyglycidyl ether poly (meth) acrylate, isocyanuric acid ethylene oxide modified triatalylate, ethylene oxide modified dipenta Erythritol penta (meth) atrelate, ethylene oxide-modified dipentaerythritol hexa (meth) acrylate, ethylene oxide-modified pentaerythritol tri (meth) atrelate , Ethylene oxide-modified base pentaerythritol tetra (meth) Atari rate, succinic acid-modified pentaerythritol tri (meth) Atari rate, and the like.

[0037] Other examples include acrylic acid Michael-added products or 2-ataryl oxychetyl dicarboxylic acid monoester. Examples of acrylic acid Michael adducts include acrylic acid dimer, methacrylic acid dimer, acrylic acid. Examples include acid trimer, methacrylic acid trimer, acrylic acid tetramer, and methacrylic acid tetramer. In addition, the 2-ataryl oxyschetil dicarboxylic acid monoester is a carboxylic acid having a specific substituent, such as 2-acryloyl oxystilyl succinic acid monoester, 2-methacryloyl oxysche. Tylsuccinic acid monoester, 2-Atalyloxyxetyl phthalic acid monoester, 2-Methacryloyl oxychetyl phthalic acid monoester, 2-Atalyloxyxetylhexahydrophthalic acid monoester, 2-methacryloyl Oxetylhexahydrophthalic acid monoester and the like. Furthermore, other oligoester acrylates are also included.

[0038] These urethane (meth) acrylate compounds (B1) and ethylenically unsaturated monomers (except (B1)) (B2) may be used alone or in combination of two or more. Also good.

[0039] When the urethane (meth) acrylate compound (B1) represented by the general formula (3) is contained, the content is not particularly limited, but the polysiloxane-containing polyisocyanate derivative [A ] 100 weight 咅 for 1 ~: LO, 000 weight 咅 ^ Special 〈ίMA 5 〜 5,000 咅さら ^ 【【This is preferably 10 to 5,000 parts by weight 1 weight If it is less than 10 parts by weight, no improvement in coating film hardness is observed, and if it exceeds 10,000 parts by weight, the antifouling performance is lowered, which is not preferable.

[0040] Ethylenically unsaturated monomer (excluding (B1)) (Β2) Although not limited to this, polysiloxane-containing polyisocyanate derivatives [A] 100 parts by weight [In contrast, 1 to: LO, 000 wt. It is preferable that the amount is 10 to 5,000 parts by weight. If the amount is less than 1 part by weight, the coating film hardness is not improved, and if it exceeds 10,000 parts by weight, the antifouling performance is lowered.

[0041] Further, when the urethane (meth) acrylate compound (B1) represented by the general formula (3) and the ethylenically unsaturated monomer (excluding (Β1)) (Β2) are used in combination, Without limitation, each of the above range forces may be appropriately selected and used. As a compound [Β] having one or more ethylenically unsaturated groups in one molecule, polyisocyanate derivative [Α] 100 parts by weight 2 to 20,000 parts by weight, particularly 5 to L0,000 parts by weight is preferable in terms of coating film hardness.

[0042] In the present invention, when the polysiloxane-containing polyisocyanate derivative [化合物] and the compound [1] having one or more ethylenically unsaturated groups are blended, (1) each obtained separately [Α] ] And [Β] and (2) [方法] and [Β] are reacted in the same reaction system and manufactured as a mixture of [Α] and [Β]. However, (2) is preferred in terms of manufacturing stability and transparency of the coating.

[0043] In carrying out the method (2), the polysiloxane compound (al) having a hydroxyl group at one end represented by the general formula (1) from the viewpoint of achieving both antifouling properties and coating film hardness. 0. From 001 to 20% by weight, 1 to 40% by weight of polyisocyanate compound and 50 to 98% by weight of hydroxyl group-containing (meth) atalyte compound Until the isocyanate group of the polyisocyanate compound disappears It is preferable to react. Particularly preferred are a polysiloxane compound (al) 1 to 20% by weight, a polyisocyanate compound 10 to 40% by weight, and a hydroxyl group-containing (meth) acrylate compound 50 to 89% by weight.

[0044] Further, the present invention further comprises a polysiloxane compound (cl) having a hydroxyl group at both ends represented by the general formula (2), a polyisocyanate compound, and a hydroxyl group-containing (meth) atrelate compound. The polysiloxane-containing polyisocyanate derivative [C] obtained by reaction is preferably contained in terms of antifouling property, transparency and scratch resistance.

[0045] The polysiloxane compound (cl) having hydroxyl groups at both ends represented by the general formula (2) is not particularly limited as long as it is a compound having a structure represented by the general formula (2). General formula ( In 2), R ⁴ represents a hydrocarbon group or an organic group containing an oxygen atom, and R ⁵ each independently represents an alkyl group (eg, a methyl group, an ethyl group, a propyl group, a butyl group), a cycloalkyl group or a phenyl group. -Represents a ru group. c is an integer of 1 or more, preferably 9 to 120, and d and e are integers of 1 to 3, preferably 1 to 2.

[0046] The weight average molecular weight of the polysiloxane compound (cl) used in the present invention is not particularly limited. The force is preferably 100-30, 000, particularly 500 to 10,000, more preferably 1,000. A power of -10,000 S is preferred. When the weight average molecular weight is less than 100, the antifouling performance is lowered, and when it exceeds 30,000, transparency and scratch resistance are lowered.

[0047] Specific examples of the polysiloxane compound (cl) represented by the general formula (2) include "X-22-160AS", "KF-6001", "KF-" manufactured by Shin-Etsu Chemical Co., Ltd. “6002”, “KF—6003”, “Silaplane FM—4411”, “Silaplane FM—4412”, “Silaplane FM—4425” manufactured by Chisso Corporation, “Macromonomer HK” manufactured by Toagosei Co., Ltd. — 20 ”and so on.

[0048] The polyisocyanate compound used in the present invention is not particularly limited, and examples thereof include those similar to the above polyisocyanate compound. Examples of the hydroxyl group-containing (meth) acrylate compound include It is not particularly limited, and examples thereof include those similar to the above hydroxyl group-containing (meth) acrylate compound.

[0049] In obtaining the polyisocyanate derivative [C] in the present invention, the production method is not particularly limited,

(I) a method in which a polysiloxane compound (cl), a polyisocyanate compound, and a hydroxyl group-containing (meth) atalylate compound are charged together and reacted;

(Mouth) A method in which a polysiloxane compound (cl) and a polyisocyanate compound are reacted, and then a hydroxyl group-containing (meth) acrylate compound is reacted,

(C) a method of reacting a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate compound, and then reacting a polysiloxane compound (cl),

[0050] In this (mouth) method, the hydroxyl group of the polysiloxane compound (cl) After reacting the isocyanate group of the cyanate compound under the condition that the isocyanate group remains, the remaining isocyanate group of the polyisocyanate compound and the hydroxyl group-containing (meth) acrylate compound of The hydroxyl group is reacted.

[0051] In addition, for such a reaction, for the purpose of promoting the reaction, a metal catalyst such as dibutyltin dilaurate, an amine catalyst such as 1,8 diazabicyclo [5.4.0] undecene 7, etc. Further, the reaction temperature is preferably 30 to 90 ° C, particularly preferably 40 to 70 ° C.

[0052] Force to obtain polyisocyanate derivative [C] by force The weight average molecular weight of the obtained polyisocyanate derivative [C] is preferably 500 to 50,000, and moreover, The force S is preferably 500 to 30,000. When the weight average molecular weight is less than 500, the film-forming property is deteriorated. When the weight average molecular weight is more than 50,000, the viscosity becomes high and it is difficult to handle, and the hardness and scratch resistance of the cured coating film are remarkably inferior.

[0053] The content of the strong polyisocyanate derivative [C] is not particularly limited. However, the polyisocyanate derivative [A] is 1 to 500 parts by weight, particularly 1 to: LOO weight with respect to 100 parts by weight. 1 to 50 parts by weight is preferred. If the amount is less than 1 part by weight, the solvent resistance is not improved, and if it exceeds 500 parts by weight, the repellency of the cured coating film surface decreases, which is not preferred.

[0054] In the present invention, a blend of a polysiloxane-containing polyisocyanate derivative [A], a compound [B] having at least one ethylenically unsaturated group and a polysiloxane-containing polyisocyanate derivative [C] In such cases, (1) a method in which [A], [B], and [C] obtained separately are combined, or (2) [A], [B], and [C] are reacted in the same reaction system [ A), [B] and [C] are produced and blended, and (2) is preferred in terms of production stability and transparency of the paint! / ,.

[0055] In carrying out the method (2), the polysiloxane compound (al) having a hydroxyl group at one end represented by the general formula (1) from the viewpoint of achieving both antifouling properties and coating film hardness. 0.1 to 20% by weight and a polysiloxane compound having a hydroxyl group at both ends represented by the general formula (2) (c 1) 0.001 to 20% by weight and a polyisocyanate compound 1 to 40% by weight Hydroxyl group-containing (meth) acrylate compound 50 to 98% by weight of polyisocyanate compound It is preferable to react until the cyanate group disappears. Particularly preferred ratios are as follows: polysiloxane compound (al) 1-20% by weight, polysiloxane compound (cl) 1-20% by weight, polyisocyanate compound 10-40% by weight, hydroxyl group-containing (meth) It is 50 to 88% by weight of the attalylate compound.

[0056] Further, in the present invention, it is preferable from the viewpoint of flexibility that a urethane (meth) acrylate compound [D] represented by the general formula (4) is further contained. In the general formula (4), R ⁸ is a urethane bond residue of a polyisocyanate compound (dl), R ⁹ is a urethane bond residue of a hydroxyl group-containing (meth) acrylate compound (d2), and R ^1Q is a polyol compound. (D3) urethane bond residue, g is an integer of 1 to 50, and h is an integer of 2 to 50.

[0057] The urethane (meth) acrylate compound [D] represented by the general formula (4) is obtained by reacting a polyisocyanate compound, a hydroxyl group-containing (meth) acrylate compound and a polyol compound. The polyisocyanate compound is not particularly limited, and examples thereof include those similar to the polyisocyanate compound, and the hydroxyl group-containing (meth) acrylate compound is not particularly limited. Although the same thing as the said hydroxyl-containing (meth) acrylate-type compound is mentioned, Although it does not specifically limit as a polyol-type compound, The thing similar to said polyol is mentioned.

[0058] The content of the urethane (meth) acrylate compound [D] represented by the general formula (4) is not particularly limited. However, the polysiloxane-containing polyisocyanate derivative [A] is 100 parts by weight. , 0.1 ~: LOO weight 咅 ^ special こ ί or 咅 5 【【こ 5 5 さらさらさらさらさら【ここ..... 5 5 ではではではではFlexibility is not obtained, and if it exceeds 100 parts by weight, the scratch resistance is lowered, which is preferable.

[0059] The photopolymerization initiator [Ε] used in the present invention is not particularly limited as long as it generates a radical by the action of light. For example, 4-phenoxydichloroacetophenone, 4- t-Butyl-dichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl 1-phenolpropane 1-one, 1- (4-isopropylenephenol) 2-hydroxy-2-methyl Propane-1-one, 1- (4-dodecylphenol) -2-hydroxy-2-methylpropane-1-one, 4- (2-hydroxyethoxy) monophenyl (2-hydroxy-2-propyl) ketone, 1 —Hydroxycyclohexyl phenyl ketone, 2-methyl 1 1 [4 (Methylthio) phenol] 2 Morpholinopropane 1, Benzoin, Benzoin Methinoreethenore, Benzoinetinoreethenole, Benzoinisopropinoreethenore, Benzoinisobutylether, Benzyldimethyl ketal, Benzophenone, Benzoyl benzoate Acid, methyl benzoylbenzoate, 4-phenol benzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3, 3'-dimethyl-4-methoxybenzophenone, thixanthone, 2-chlorothioxanthone, 2-Methylthixanthone, 2,4 Dimethylthioxanthone, Isopropylthixanthone, Camphorquinone, Dibenzosuberone, 2-Ethylanthraquinone, 4 ', A "— Jetylisophthalate Phenon, 3, 3', 4, 4 ' -Tetra (t Ruperoxycarbol) benzophenone, OC—facilitate oxime ester, acyl phosphine oxide, methyl phenol glyoxylate, benzyl, 9, 10 phenanthrenequinone, 4- (2-hydroxyethoxy) phenol 2-hydroxy-2-propyl) ketone, among others, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoin isopropyl ether, 4- (2-hydroxyethoxy) monophenyl (2-hydroxy mono 2) (Propyl) ketone, 2-hydroxy-1-2-methyl 1-phenolpropane 1-one is preferably used.

[0060] Further, triethanolamine, triisoprono V-lamine, 4,4'-dimethylaminobenzophenone (Michler's ketone), 4,4'-jetylaminoben zophenone, 2dimethylamino as an auxiliary for photopolymerization initiator Ethylbenzoic acid, 4-dimethylaminobenzoic acid ethyl, 4 dimethylaminobenzoic acid (n-butoxy) ethyl, 4 dimethylaminobenzoic acid isamyl, 4-dimethylaminobenzoic acid 2 ethylhexyl, 2, 4 jetylthioxanthone, 2, 4 Diisopropylthioxanthone and the like can be used in combination.

[0061] In the present invention, the amount of the photopolymerization initiator [E] is such that the polysiloxane-containing polyisocyanate derivative [A] and one or more ethylenically unsaturated groups per molecule. 100 parts by weight of the total amount of the compound [B] (When the polysiloxane-containing polyisocyanate derivative [C] and the urethane (meth) acrylate compound [D] are added, [A], [B], [ C] and [D] in total 100 parts by weight) 1 to: L0 parts by weight is preferred, 1 to 8 parts by weight, particularly preferably 1 to 5 parts by weight. If the amount is less than 1 part by weight, the curing rate in the case of UV curing will be extremely slow, and if it exceeds 10 parts by weight, the curability will be It is useless without improving.

[0062] In the present invention, the polysiloxane-containing polyisocyanate derivative [A], the compound having one or more ethylenically unsaturated groups in one molecule [B], the polysiloxane-containing polyisocyanate In addition to isocyanate derivatives [C], urethane (meth) acrylate compounds [D], photoinitiators [E], fillers, electrolyte salts, dyes, pigments, oils, plasticizers, waxes, dry Agents, dispersants, wetting agents, emulsifiers, gelling agents, stabilizers, antifoaming agents, leveling agents, thixotropic agents, antioxidants, flame retardants, fillers, reinforcing agents, matting agents, crosslinkers Etc. can also be blended.

[0063] In addition to these, unsaturated polyester resin, vinyl urethane resin, vinyl ester urethane resin, polyisocyanate, polyepoxide, acrylic resin, alkyd for the purpose of suppressing the curing shrinkage of the coating film. Coffins, urea resins, melamine coffins, polyacetate butyl, acetate butyl copolymers, polygen elastomers, saturated polyesters, saturated polyesters and celluloses such as -trocellulose and cellulose acetate butyrate You can add polymers such as derivatives.

[0064] The polysiloxane-containing polyisocyanate derivative of the present invention [A] and a compound having at least one ethylenically unsaturated group in one molecule [B], preferably a polysiloxane-containing polyisocyanate. An active energy ray-curable resin composition containing an nate-based derivative [C] and a urethane (meth) acrylate-based compound [D] is obtained.

[0065] If necessary, this composition can be used by blending an organic solvent and adjusting the viscosity. Examples of powerful organic solvents include cellosolves such as ethyl acetate, butyl acetate, toluene, xylene, methanol, ethanol, propanol, butanol, acetone, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, and ethyl acetate sorb. Examples include propylene glycolenoatenoles such as propylene glycolenomonomethylenoatenole and diacetone alcohol. These can be used alone or in combination.

[0066] The active energy ray-curable resin composition of the present invention is cured by irradiating with an active energy ray after applying it to an object.

There are no particular limitations on the object to be applied. For example, polyethylene, polypropylene, Polyolefin resin such as licyclopentagen, polycarbonate, polyester,

Examples include ABS resin, acrylic resin, molded products (films, sheets, cups, etc.), metals, and glass.

[0067] As active energy rays to be generated, in addition to electromagnetic rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays and infrared rays, X rays and γ rays, electron rays, proton rays, neutron rays and the like can be used. Curing by ultraviolet irradiation is advantageous from the viewpoint of curing speed, availability of irradiation equipment, price, etc. In addition, when performing electron beam irradiation, it can be cured without using a photopolymerization initiator [Ε].

[0068] 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, etc. Irradiation with about 100 to 3000 mjZcm ^{2 is} sufficient.

After the ultraviolet irradiation, heating can be performed as necessary to complete the curing.

[0069] As a result, the active energy ray-curable resin composition of the present invention comprises a polysiloxane-containing polyisocyanate derivative [A] and a compound having one or more ethylenically unsaturated groups in one molecule [B]. Preferably, it further comprises a polysiloxane-containing polyisocyanate derivative [C] N-urethane (meth) atalylate compound [D], so that it is excellent in antifouling properties, and has coating film hardness and scratch resistance. , An active energy one-line curable resin composition that forms a coating layer with excellent solvent resistance and adhesion. Paint, ink, protective coating agent, anchor coating agent, magnetic powder coating binder, adhesive, adhesive It is useful as various film forming materials such as adhesives. Among them, it is very useful as a coating agent for various plastics and optical film top coats. Example

Hereinafter, the present invention will be described more specifically with reference to examples.

In the examples, “%” and “parts” are based on weight unless otherwise specified.

[0071] [Polysiloxane-containing polyisocyanate derivative [A]]

(Synthesis of polysiloxane-containing polyisocyanate derivatives [A-1])

Trimer of hexamethylene diisocyanate (isocyanate group content 21.0%) in a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser and nitrogen gas inlet 41. 8 g (0.070 mol), polysiloxane compound (al) represented by general formula (1) (R ¹ : methyl group, R ² = methyl group, R ³ = —CH OC H—, a = 80, b = l) 307. 8 g (0. 070 mol),

3 6 2 4

60. Charged with dibutyltin dilaurate 0. 10 g and methyl ethyl ketone 500 g. When the residual isocyanate group was 0.69% after reacting with C for 3 hours, dipentaerythritol pentaatalylate (a mixture of dipentaerythritol pentaatalylate and dipentaerythritol hexaatalylate acrylate (hydroxyl group) 150.4 K (0.14 mol), 2,6-di-tert-butyltalesole 0.4 g was added dropwise over about 1 hour, and the reaction was continued as it was, and the isocyanate group disappeared. At the time, the reaction was completed, and a polysiloxane-containing polyisocyanate derivative [A-1] solution was obtained (solid content concentration 50%).

[0072] (Synthesis of polysiloxane-containing polyisocyanate derivative [A-2])

A four-necked flask equipped with a thermometer, stirrer, water-cooled condenser, and nitrogen gas inlet is charged with isophorone diisocyanate (isocyanate group content: 37.8%), 37.7 g (0.17 mol), general formula ( 1) Polysiloxane compound (al) (= methyl group, R ² = methyl group, R ³ = —CH ³ OCH C (CH 2) (CH 2)-, a = 80, b = 2) 279. 2g ( 0.085 mol), di

3 6 2 3 2 5 2

60. Charged with butyltin dilaurate 0. 10 g and methyl ethyl ketone 500 g. When the residual isocyanate group is 0.87% after reacting for 3 hours with C, dipentaerythritol monopentaatalylate [dipentaerythritol pentaatalylate and dipentaerythritol hexaoxalate Attalate mixture (hydroxyl value 52 mg KOH / g)] 183. lg (0.17 mol), 2,6-di-tert-butyl talesol 0.4 g was added dropwise for about 1 hour, and the reaction was continued. The reaction was terminated when the isocyanate group disappeared, and a polysiloxane-containing polyisocyanate derivative [A-2] solution was obtained (solid content concentration 50%).

[Compound having at least one ethylenically unsaturated group in one molecule [B]]

(Synthesis of Urethane (Meth) Atalylate Compound (B1-1))

Trimer of hexamethylene diisocyanate (isocyanate group content 21.0%) 77. lg (0.13) in a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser and nitrogen gas inlet Mol) and dibutyltin dilaurate (0.10 g) and methyl ethyl ketone (500 g), and dipentaerythritol pentaatalylate (mixture of dipentaerythritol pentaatalylate and dipentaerythritol hexaatalylate acrylate (hydroxyl group) at 60 ° C or lower. (52 mg KOHZg)] 422.9 g (0.39 mol), 2,6 di-tert-butyltalesol 0.4 g was added dropwise in about 1 hour, and the reaction was continued at 60 ° C, when the isocyanate group disappeared. The reaction was terminated with a urethane (meth) acrylate compound (B1-1) (solid content 50%)

[0074] (Synthesis of urethane (meth) atalylate compound (B1-2))

In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser, and nitrogen gas inlet, isophorone diisocyanate (isocyanate group content 21.3%) 96. Og (0.43 mol) and dibutyltin dilaurate 0 10 g and 500 g of methyl ethyl ketone were charged, and pentaerythritol triatalylate [mixture of pentaerythritol triatalylate and pentaerythritol tetraatalylate (hydroxyl value 120 mg KOH / g)] at 60 ° C or lower 404. Og (0. 86 mol), 2,6 di-tert-butyltaresole (0.4 g) was added dropwise in about 1 hour, and the reaction was continued at 60 ° C. When the isocyanate group disappeared, the reaction was terminated. Attallate-based compound (B1-2) was obtained (solid content concentration 50%).

[0075] (ethylenically unsaturated monomer (B2-1))

Dipentaerythritol hexaatalylate (manufactured by Nippon Kayaku Co., Ltd., “KAYARAD DPH A”) was used.

[Polysiloxane-containing polyisocyanate derivatives [C]]

(Synthesis of polysiloxane-containing polyisocyanate derivatives [C 1])

Trimer of hexamethylene diisocyanate (isocyanate group content 21.0%) 88.7 g (0.15) in a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser and nitrogen gas inlet Mol), polydimethylsiloxanediol having one hydroxyl group at both ends (cl) (manufactured by Shin-Etsu Chemical Co., Ltd., “KF6003”) 377. Og (0.074 mol), dibutyltin dilaurate 0.10 g, methyl Ethyl ketone 500g was charged and reacted at 60 ° C for 2 hours. When the remaining isocyanate group was 1.29%, further 34.3 g (0.30 mol) of 2-hydroxyethyl atyrate, 2, 6 Di-tert-butyl talesole 0.4g, dibutyltin dilaurate 0.02g was added dropwise over about 1 hour, and the reaction was continued as it was. When the isocyanate group disappeared, the reaction was terminated and polysiloxane contained Polyisocyanate derivatives [C- 1] A solution was obtained (solid concentration 50%). [0077] Examples 1 to 6 and Comparative Examples 1 to 3

[Production of active energy ray-curable resin composition]

Polysiloxane-containing polyisocyanate derivative [A], compound having one or more ethylenically unsaturated groups in one molecule [B], polysiloxane-containing polyisocyanate derivative [C], urethane ( The meta) acrylate compound [D] and the photopolymerization initiator [E] (Ciba 'Specialty' Chemicals Co., Ltd., “Darocur 1173”) are adjusted to the ratio shown in Table 1 in terms of solid content. The active energy ray-curable resin composition solution was obtained by blending and diluting with methyl ethyl ketone so that the solid content excluding the photopolymerization initiator was 30%.

[0078] Example 7

[Production of polysiloxane-containing polyisocyanate derivative [A-1] and urethane (meth) acrylate compound (B1-1) as a mixture)

Trimer of hexamethylene diisocyanate (isocyanate group content 21.0%) 76.2 g (0.13) in a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser and nitrogen gas inlet Mol), a polysiloxane compound represented by the general formula (1) (al) (= methyl group, R ² = ^ / V¾, R ³ = -CH OC H—

3 6 2 4, a = 80, b = l) 16.8 g (0.0038 mole), dibutyltin dilaurate 0.10 g, methyl ethyl ketone 500 g are charged 60. When the residual isocyanate group is 0.69% after reacting with C for 3 hours, dipentaerythritol monopentaatalylate [dipentaerythritol pentaatalylate and dipentaerythritol hexaoxalate Mixture of acrylate (hydroxyl value 52 mgKOH / g)] 406.9 g (0.38 mol), 2,6-di-tert-butyltalesol 0.4 g was added dropwise for about 1 hour, and the reaction was continued. The reaction was terminated when the isocyanate group disappeared, and a mixed solution of the polysiloxane-containing polyisocyanate derivative [A-1] and the urethane (meth) acrylate compound (B1-1) was obtained. (Weight ratio of [A-1] and (B1-1) = 6:94, solid content concentration 50%).

[Manufacture of active energy ray-curable resin composition]

A mixture of the above polysiloxane-containing polyisocyanate derivative [A] and a compound [B] having one or more ethylenically unsaturated groups in one molecule and a photopolymerization initiator [E] (Ciba 'Specialty' Chemicals Co., Ltd., “Darocur 1173”) was adjusted to the ratio shown in Table 1 in terms of solid content, and the solid content excluding the photopolymerization initiator was adjusted to a concentration of 30%. Dilution with ethyl ketone gave an active energy ray-curable resin composition solution.

[0080] Example 8

[Manufacturing as a mixture of polysiloxane-containing polyisocyanate derivative [A-1], urethane (meth) acrylate compound (B1-1) and ethylenically unsaturated monomer (B2-1)) Thermometer, stirring Hexamethylene diisocyanate trimer (isocyanate group content 21.0%) 65. Og (0.11 mol), general, in a four-necked flask equipped with a vacuum condenser, water-cooled condenser and nitrogen gas inlet Polysiloxane compound (al) represented by formula (1) (= methyl group, R ² = ^ / V¾, R ³ = -CH OC H—, a = 80, b = l) 20. Og (0. 0045 Mol), di

3 6 2 4

60. Charged with butyltin dilaurate 0. 10 g and methyl ethyl ketone 500 g. When the remaining isocyanate group is 2.30% after reacting with C for 3 hours, dipentaerythritol monopentatalylate [dipentaerythritol pentatalylate and dipentaerythritol hexaoxatalylate Mixture of acrylate (hydroxyl value 52 mg KOHZg)] 415.0 g (0.38 mol), 2,6 di-tert-butyl tallesol 0.4 g was added dropwise over about 1 hour, and the reaction was continued. The reaction was terminated when the isocyanate group disappeared, and the polyisocyanate-containing polyisocyanate derivative [A-1], urethane (meth) acrylate compound (B1-1) and (meth) acrylate compound (B2 — A mixed solution of 1) was obtained (weight ratio of [A-1], (B11) and (B2-1)) = 7:80:13, solid content concentration 50%).

[0081] [Production of active energy ray-curable resin composition]

A mixture of the above polysiloxane-containing polyisocyanate derivative [A] and a compound [B] having one or more ethylenically unsaturated groups in one molecule and a photopolymerization initiator [E] (Ciba 'Specialty' Chemicals Co., Ltd., “Darocur 1173”) was adjusted to the ratio shown in Table 1 in terms of solid content, and the methyl ethyl ketone was adjusted so that the solid content excluding the photopolymerization initiator would be 30% concentration. To obtain an active energy ray-curable resin composition solution.

[0082] [Evaluation]

Apply the resin composition solutions obtained in Examples 1 to 8 and Comparative Examples 1 to 3 on a glass plate using a 150 m applicator so that the film thickness after drying is 15 m. After drying for 5 minutes at 60 ° C, using a high pressure mercury lamp lamp 80W, 1 lamp, 2 passes of UV irradiation at a conveyor speed of 5.lm / min from a height of 18cm (accumulated dose 450mj / cm ² ) Then, a cured coating film (film thickness 15 m) was formed, and the following evaluation was performed.

[0083] (Anti-fouling property)

(1) Ink wiping

The cured coating film was reciprocated once with blue magic ink, and then left for 24 hours. The coating film after wiping with a waste cloth was observed and evaluated as follows.

〇 ...

△ ...

X · · · · Can not wipe

(2) repellency

After drawing a line back and forth with blue magic ink on the cured coating film, the mark of the magic ink was observed and evaluated as follows.

〇 ·· “Repels ink, and the traces of the lines are dotted.

△ · · 'The ink is repelled and the traces of the lines become thin.

X · · · Do not repel ink

[0084] (Coating hardness)

For the cured coating film, the pencil hardness was measured according to JIS K 5600-5-4.

[0085] (Abrasion resistance)

The cured film was visually observed for the degree of scratching on the surface after steel wool # 0000 with a load of 500 g was reciprocated 10 times on the surface of the cured film, and evaluated as follows.

◎ ... No scratches

○ · · · Slightly scratched

△ · · · Slightly scratched

X · · 'The paint film whitened due to scratches

[0086] (Solvent resistance)

The surface of the cured coating film was wiped 10 times with a cloth soaked with ethanol, and then the above ink wiping property was observed. The coating film was observed and evaluated as follows.

〇 ... △ ...

X · · · · Can not wipe

[0087] Further, the obtained active energy ray-curable resin composition was coated on a polycarbonate panel using a bar coater No. 14 so that the film thickness after drying was 5 m, After drying at 60 ° C for 5 minutes, using a high pressure mercury lamp lamp 80 W, 1 lamp, 2 passes of UV irradiation (cumulative irradiation dose 450 mi / cm ² ) from a height of 18 cm at a conveyor speed of 5. lm / min As a result, a cured coating film was formed and the following evaluation was performed.

[0088] (Plastic adhesion)

According to the above 6JIS K 5600-5-6, make 100 lmm grids on the cured coating film, conduct adhesion test with adhesive tape, observe the peeling state of the grids, and check the number of remaining grids It was evaluated with.

[0089] Table 1 shows the evaluation results of Examples and Comparative Examples.

[0090] [Table 1]

. : ^ Table 1

[]

Figures in parentheses indicate the solid content ratio, and “” indicates no addition.

Regarding the transparency in the paint state, Examples 7 to 8 were better than Examples 1 to 6. However, the transparency in the cured coating film was good in both Examples and Comparative Examples.

Industrial applicability

The active energy ray-curable resin composition of the present invention has an excellent antifouling property and an active energy ray-curable resin that forms a coating layer having excellent coating film hardness, scratch resistance, solvent resistance, and adhesion. It becomes a composition and is useful as a coating film forming material such as paints, inks, protective coating agents, anchor coating agents, magnetic powder coating binders, adhesives, adhesives, and adhesives. Among them, it is very useful as a coating agent for various plastics and optical film top coats.

Claims

Claims [1] A polysiloxane compound (al) having a hydroxyl group at one end represented by the following general formula (1), a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate compound are reacted. A polysiloxane-containing polyisocyanate derivative [A] and a compound [B] having at least one ethylenically unsaturated group in one molecule, an active energy line-curable resin Composition.

[Chemical 1]

R ² R ²

[2] Further, a polysiloxane compound (cl) having a hydroxyl group at both ends represented by the following general formula (2), a polyisocyanate compound, and a hydroxyl group-containing (meth) acrylate compound are reacted. 2. The active energy ray-curable resin composition according to claim 1, comprising a polysiloxane-containing polyisocyanate derivative [C].

[Chemical 2]

(2)

[Wherein R ⁴ independently represents a hydrocarbon group or an organic group containing an oxygen atom, R ⁵ independently represents an alkyl group, a cycloalkyl group, or a phenyl group, and c represents an integer of 1 or more. And d and e are integers of 1 to 3. ]

[3] A compound having at least one ethylenically unsaturated group in one molecule [B] is a urethane (meth) acrylate compound (B1) represented by the following general formula (3) and Z or ethylenically unsaturated 3. The active energy ray-curable resin composition according to claim 1 or 2, which is a sum monomer (excluding (B1)) (B2).

[Chemical 3]

[Wherein R ⁶ is a urethane bond residue of the polyisocyanate compound (bl), R ⁷ is a urethane bond residue of the hydroxyl group-containing (meth) acrylate compound (b2), and f is an integer of 2 to 50 It is. ]

[4] The method according to any one of claims 1 to 3, further comprising a urethane (meth) acrylate compound [D] represented by the following general formula (4): An active energy line curable resin composition.

[Chemical 4]

[5] The polyisocyanate compound power is an active energy ray-curable cocoon according to claim 1 or 2, which is a polyisocyanate compound having 3 or more isocyanate groups in one molecule. Fat composition.

[6] The active energy ray-curable resin composition according to any one of claims 1 to 5, further comprising a photopolymerization initiator [E].

[7] In producing the active energy ray-curable resin composition according to claim 1 or 3, a polysiloxane compound having a hydroxyl group at one end represented by the general formula (1) (A 1) Polyisocyanate compound at a ratio of 0.001 to 20% by weight, polyisocyanate compound 1 to 40% by weight and hydroxyl group-containing (meth) acrylate compound 50 to 98% by weight A process for producing an active energy ray-curable resin composition characterized by reacting until the isocyanate group disappears.

[8] In producing the active energy ray-curable resin composition according to claim 2 or 3, a polysiloxane compound having a hydroxyl group at one end represented by the general formula (1) (Al) 0.001 to 20% by weight and a polysiloxane compound having a hydroxyl group at both ends represented by the general formula (2) (cl) 0.001 to 20% by weight and a polyisocyanate compound 1 to 40 And a hydroxyl group-containing (meth) acrylate compound 50 to 98% by weight in a ratio of 50 to 98% by weight until the isocyanate group of the polyisocyanate compound disappears, and a method for producing an active energy ray-curable resin composition .

[9] A coating agent composition comprising the active energy ray-curable resin composition according to any one of claims 1 to 6.

[10] A coating agent composition comprising an active energy ray-curable resin composition obtained by the production method according to claim 7 or 8.