WO2015152110A1

WO2015152110A1 - Urethane (meth)acrylate compound, active-energy-ray-curable resin composition, and coating agent

Info

Publication number: WO2015152110A1
Application number: PCT/JP2015/059837
Authority: WO
Inventors: 敏郎野田; 幸宗神田; 篤志辻本
Original assignee: 日本合成化学工業株式会社
Priority date: 2014-03-31
Filing date: 2015-03-30
Publication date: 2015-10-08

Abstract

The present invention is a urethane (meth)acrylate compound (A) which is produced by reacting a hydroxyl-group-containing (meth)acrylate compound (x) containing a structural moiety derived from ε-caprolactone with a polyfunctional isocyanate compound (y), wherein the average number of isocyante groups in the polyfunctional isocyanate compound (y) is 3.2 or more. When a cured coating film is formed using an active-energy-ray-curable resin composition containing the urethane (meth)acrylate compound, the resultant cured coating film has excellent restorability at such a level that the cured coating film can bear to practical use, also has excellent blocking resistance and surface hardness, and also has excellent transparency and adhesiveness to metallic base materials.

Description

Urethane (meth) acrylate-based compound, active energy ray-curable resin composition, and coating agent

The present invention relates to a urethane (meth) acrylate compound, an active energy ray-curable resin composition, and a coating agent. More specifically, the present invention is excellent in resilience against scratches, blocking resistance, and surface hardness. The present invention relates to an active energy ray-curable resin composition for forming a cured coating film excellent in material adhesion, and a coating agent using the same.

Conventionally, an active energy ray-curable resin composition is cured by irradiation with an active energy ray such as radiation for a very short time, so it is widely used as a coating agent, adhesive or anchor coating agent for various substrates. It has been.

Among them, as the coating agent, an active energy ray curable resin capable of forming a cured film on the surface of a plastic substrate and forming a cured coating film having resilience against scratches as a coating agent for protecting the outermost surface of the substrate. Development of a composition is desired. For example, an ultraviolet curable coating composition using a urethane acrylate oligomer obtained by reacting a polycaprolactone-containing polyfunctional alcohol, an isocyanate and a hydroxyl group-containing (meth) acrylate (for example, patent literature) 1) is proposed.

Japanese Patent Laid-Open No. 2004-35599

However, in the disclosed technique of the above-mentioned Patent Document 1, the polycaprolactone-containing polyfunctional alcohol is used as a constituent material of the urethane (meth) acrylate compound, so that it exhibits some resilience when a cured coating film is obtained. In addition to the polyvalent isocyanate compound and the hydroxyl group-containing acrylate, the urethane (meth) acrylate compound further reacts with a polyol, and it is necessary to react three kinds of constituent materials. It was difficult to achieve a high viscosity due to high molecular weight, and was highly likely to gel.

In addition, when a curable composition containing a high molecular weight urethane (meth) acrylate-based compound is used as a cured coating film, stickiness of the coating film (occurrence of tack) is likely to occur, that is, the blocking resistance tends to deteriorate. Also had a point.

Therefore, the present invention is a urethane (meth) acrylate compound that is excellent in resilience at a level that can withstand practicality, and also has excellent blocking resistance and transparency when used as a cured coating film under such a background. Furthermore, it is an object of the present invention to provide an active energy ray-curable resin composition comprising the urethane (meth) acrylate compound and a coating agent using the same.

However, as a result of intensive studies in view of such circumstances, the present inventors have made a urethane (meta) containing a hydroxyl group-containing (meth) acrylate compound containing a structural site derived from ε-caprolactone and a polyvalent isocyanate compound. ) In the acrylate compound, by using a polyisocyanate compound having a larger number of average functional groups than usual as the polyisocyanate of the constituent material, a relatively large number of branched structures are formed in the molecular structure of the urethane (meth) acrylate compound. In addition, a urethane (meth) acrylate compound with a lower molecular weight than that obtained by introducing a branched structure using a polyfunctional alcohol can be obtained, so that the cured coating film has excellent balance of resilience against scratches and blocking resistance. The present invention was completed.

That is, the gist of the present invention is a urethane (meth) acrylate compound obtained by reacting a hydroxyl group-containing (meth) acrylate compound (x) containing a structural site derived from ε-caprolactone and a polyvalent isocyanate compound (y). It is (A) and relates to a urethane (meth) acrylate compound characterized in that the polyisocyanate compound (y) has an average number of isocyanate groups of 3.2 or more.
The present invention also provides an active energy ray-curable resin composition containing the urethane (meth) acrylate compound and a coating agent.

Further, in the present invention, the urethane (meth) acrylate compound (B) is different from the urethane (meth) acrylate compound (A) in order to improve the surface hardness of the urethane (meth) acrylate compound (A). In addition, a polysiloxane structure-containing compound (C) is added to improve blocking resistance, or a phosphoric acid group-containing ethylenically unsaturated compound (D) is used to improve metal substrate adhesion. It is preferable to contain.

When the urethane (meth) acrylate-based compound of the present invention is used, an active energy ray-curable resin composition having an excellent effect in a good balance between the resilience to scratches and the blocking resistance when obtained as a cured coating film can be obtained. 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.

<Urethane (meth) acrylate compound (A)>
The urethane (meth) acrylate compound (A) of the present invention comprises a hydroxyl group-containing (meth) acrylate compound (x) containing a structural site derived from ε-caprolactone, and a polyvalent isocyanate having an average isocyanate group number of 3.2 or more. It is obtained by reacting the system compound (y).

The hydroxyl group-containing (meth) acrylate compound (x) containing a structural site derived from ε-caprolactone (hereinafter, sometimes referred to as “hydroxyl group-containing (meth) acrylate compound (x)”) may contain a hydroxyl group ( A compound obtained by ring-opening polymerization of ε-caprolactone to a (meth) acrylate compound is preferable, and examples thereof include compounds represented by the following general formula (1).

The value of n in the general formula (1) is 1 to 25, preferably 1 to 15, particularly preferably 1 to 10, and further preferably 2 to 5.
If the value of n is too large, the blocking resistance tends to be lowered.

Specific examples of the compound represented by the general formula (1) include a caprolactone adduct of 2-hydroxyethyl acrylate and a caprolactone adduct of 2-hydroxyethyl methacrylate, and trade names include, for example, Daicel. “Plaxel FA1”, “Plaxel FA1DDM”, “Plaxel FA2D”, “Plaxel FA5”, “Plaxel FA10L”, “Plaxel FM1”, “Plaxel FM1D”, “Plaxel FM2D”, “Plaxel FM3”, “Plaxel FM4” And “Placcel FM5”.

Among these, 2-hydroxyethyl acrylate caprolactone 1 mol adduct, 2-hydroxyethyl acrylate caprolactone 2 mol adduct, 2-hydroxyethyl acrylate caprolactone 5 mol in terms of an excellent balance between resilience and blocking resistance. Adducts are preferred, and 2-hydroxyethyl acrylate caprolactone 2-mole adducts are particularly preferred.

The number of ethylenically unsaturated groups of the hydroxyl group-containing (meth) acrylate compound (x) containing a structural site derived from ε-caprolactone is preferably 1 to 5, particularly preferably 1 to 3, and still more preferably. One.
When the number of such ethylenically unsaturated groups is too large, there is a tendency that it is difficult to obtain restorability.

The weight average molecular weight of the hydroxyl group-containing (meth) acrylate compound (x) containing a structural site derived from ε-caprolactone is preferably 100 to 2,500, particularly preferably 200 to 1,000, and more preferably. 300-500.
If the weight average molecular weight is too high, the blocking resistance tends to decrease, and if it is too low, the restoring property tends to be difficult to obtain.

As the polyvalent isocyanate compound (y) used in the present invention, the average number of isocyanate groups calculated by the following formula (1) needs to be 3.2 or more.

The isocyanate group concentration (% by weight) in the formula is a value measured by the method described in JIS K1603-1: 2007.

The number average molecular weight (Mn) in the formula is the number average molecular weight in terms of standard polystyrene molecular weight, and can be measured by high performance liquid chromatography (“Waters 2695 (main body)” and “Waters 2414 (detector)” manufactured by Nippon Waters). 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, It is a value measured by using three series of filler particle diameters: 10 μm).

The average number of isocyanate groups in the polyvalent isocyanate compound (y) needs to be 3.2 or more, preferably 3.5 or more, particularly preferably 3.8 or more, more preferably 4 or more, particularly Preferably, it is 4.5 or more. In addition, as an upper limit of an average isocyanate group number, it is 10 normally, Preferably it is 6.
If the average number of isocyanate groups in the polyvalent isocyanate compound (y) is too small, the restorability is poor.

The average number of isocyanate groups of the polyvalent isocyanate compound (y) can be adjusted, for example, by multimerizing diisocyanate compounds having two isocyanate groups and providing distribution of isocyanate compounds having different numbers of isocyanate groups.

Examples of the polyvalent isocyanate compound (y) include:
Aromatic diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane diisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylene diisocyanate, naphthalene diisocyanate;
Acyclic aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate;
Alicyclic diisocyanates such as hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane;
And polyisocyanates based on multimerization having an allophanate structure, a nurate structure, a biuret structure, and the like.

Among these, Preferably it is a polyvalent isocyanate type compound obtained using an acyclic aliphatic diisocyanate, Especially preferably, it is a polyvalent isocyanate type compound obtained using hexamethylene diisocyanate, More preferably, it is hexamethylene. A biuret type multimer or a nurate type multimer of diisocyanate, particularly preferably a biuret type multimer of hexamethylene diisocyanate.

The number average molecular weight of the polyvalent isocyanate compound (y) is preferably 500 to 5,000, particularly preferably 600 to 2,000, and more preferably 700 to 1,000. If the number average molecular weight is too high, the restoring property tends to be difficult to obtain, and if it is too low, the isocyanate compound tends to be difficult to increase in quantity.

The urethane (meth) acrylate compound (A) of the present invention is obtained by reacting the hydroxyl group-containing (meth) acrylate compound (x) with the polyvalent isocyanate compound (y). What is necessary is just to manufacture according to the manufacturing method of a well-known general urethane (meth) acrylate type compound. For example, the hydroxyl group-containing (meth) acrylate compound (x) and the polyvalent isocyanate compound (y) may be charged into the reactor or reacted separately.

The reaction molar ratio of the hydroxyl group-containing (meth) acrylate compound (x) and the polyvalent isocyanate compound (y) is, for example, one hydroxyl group of the hydroxyl group-containing (meth) acrylate compound (x), When the average isocyanate group of the isocyanate compound (y) is 3.5, the hydroxyl group-containing (meth) acrylate compound (x): polyvalent isocyanate compound (y) is about 3.5: 1, When the hydroxyl group-containing (meth) acrylate compound (x) has one hydroxyl group and the polyvalent isocyanate compound (y) has an average isocyanate group of 4.5, the hydroxyl group-containing (meth) acrylate compound (x ): The polyvalent isocyanate compound (y) is about 4.5: 1.

In the addition reaction of the hydroxyl group-containing (meth) acrylate compound (x) and the polyvalent isocyanate compound (y), the reaction is terminated when the residual isocyanate group content in the reaction system is 0.5% by weight or less. By making it, a urethane (meth) acrylate type compound (A) is obtained.

In the reaction of the hydroxyl group-containing (meth) acrylate compound (x) and the polyvalent isocyanate compound (y), it is also preferable to use a catalyst for the purpose of accelerating the reaction. Examples of such a catalyst include dibutyltin dilaurate. , Dibutyltin diacetate, trimethyltin hydroxide, tetra-n-butyltin, bis (acetylacetonato) zinc, bis (tetrafluoroacetylacetonato) zinc, zirconium monoacetylacetonate, zirconium ethylacetoacetate, zirconium tris ( Acetylacetonate) ethyl acetoacetate, zirconium tetraacetylacetonate, tetramethoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium, tetrabutoxytitanium and other organometallic compounds, tin octenoate, Zinc oxalate, zinc octenoate, zinc stearate, zirconium 2-ethylhexanoate, cobalt naphthenate, stannous chloride, stannic chloride, potassium acetate, metal salts such as triethylamine, triethylenediamine, benzyldiethylamine, 1, 4-diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [5,4,0] undecene, N, N, N ′, N′-tetramethyl-1,3-butanediamine, N-methylmorpholine In addition to amine catalysts such as N-ethylmorpholine, bismuth nitrate, bismuth bromide, bismuth iodide, bismuth sulfide, etc., organic bismuth compounds such as dibutyl bismuth dilaurate and dioctyl bismuth dilaurate, bismuth 2-ethylhexanoate, Bismuth naphthenate, bismuth isodecanoate, neodecanoic acid Smuth salt, bismuth laurate, bismuth maleate, bismuth stearate, bismuth oleate, bismuth linoleate, bismuth acetate, bismuth bisneodecanoate, bismuth disalicylate, bismuth digallate, etc. Examples thereof include bismuth-based catalysts such as organic acid bismuth salts, among which dibutyltin dilaurate and 1,8-diazabicyclo [5,4,0] undecene are preferred. These can be used alone or in combination of two or more.

In the reaction of the hydroxyl group-containing (meth) acrylate compound (x) and the polyvalent isocyanate compound (y), an organic solvent having no functional group that reacts with an isocyanate group, for example, methyl acetate, ethyl acetate, Organic solvents such as esters such as butyl acetate, 2-ethoxyethyl acetate and 2-methoxy-1-methylethyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and aromatics such as toluene and xylene can be used. .

The reaction temperature 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 number of ethylenically unsaturated groups contained in the urethane (meth) acrylate compound (A) obtained above is preferably 1 to 10, particularly preferably 3 to 8, and more preferably 4 ~ 6. If the number of ethylenically unsaturated groups is too small, the hardness of the coating film tends to be low, and if it is too large, the hardness of the coating film is too high and it is difficult to obtain restorability.

The ethylenically unsaturated group content (mmol / g) of the urethane (meth) acrylate compound (A) is preferably 0.1 to 10 mmol / g, particularly preferably 1 to 5 mmol / g, Preferably, it is 1 to 3 mmol / g. If the content of the ethylenically unsaturated group (mmol / g) of the urethane (meth) acrylate compound (A) is too small, the film-forming property after irradiation with active energy rays tends to decrease, and if too large, Hardness is too high and the resilience tends to decrease.

The urethane (meth) acrylate compound (A) preferably has a weight average molecular weight of 1,000 to 50,000, particularly preferably 2,000 to 10,000, and more preferably 3,000 to 5, 000. If the weight average molecular weight is too small, sufficient resilience tends to be difficult to obtain, and if the weight average molecular weight is too large, the viscosity of the coating agent tends to increase and coating tends to be difficult.

The above-mentioned weight average molecular weight (Mw) is a weight average molecular weight in terms of standard polystyrene molecular weight, and is used for high performance liquid chromatography (manufactured by Nippon Waters, “Waters 2695 (main body)” and “Waters 2414 (detector)”). : Shodex GPC KF-806L (exclusion limit molecular weight: 2 × 10 ⁷ , separation range: 100 to 2 × 10 ⁷ , theoretical plate number: 10,000 plates / piece, filler material: styrene-divinylbenzene copolymer, filler It is a value measured by using three series of particle diameters: 10 μm).

The viscosity of the urethane (meth) acrylate compound (A) at 60 ° C. is preferably 100 to 10,000 mPa · s, particularly 300 to 8,000 mPa · s, more preferably 500 to 5,000 mPa · s. It is preferable that When the viscosity is out of the above range, the coatability tends to be lowered.
The viscosity is measured with an E-type viscometer.

Thus, the urethane (meth) acrylate compound (A) of the present invention can be produced. And it can be set as an active energy ray-curable resin composition using this urethane (meth) acrylate type compound (A).

<Active energy ray-curable resin composition>
The active energy ray-curable resin composition of the present invention contains the urethane (meth) acrylate compound (A).

Further, in the present invention, those containing a urethane (meth) acrylate compound (B) (excluding the urethane (meth) acrylate compound (A)) are also preferred from the viewpoint of improving the surface hardness.

Furthermore, in this invention, in addition to the said urethane (meth) acrylate type compound (A) and a urethane (meth) acrylate type compound (B) (however, except a urethane (meth) acrylate type compound (A)), it is resistant. It is also preferable to contain a polysiloxane structure-containing compound (C) in order to improve blocking properties, or to contain a phosphoric acid group-containing ethylenically unsaturated compound (D) in order to improve adhesion to a metal substrate. .

<Urethane (meth) acrylate compound (B)>
The urethane (meth) acrylate compound (B) used in the present invention may be different from the urethane (meth) acrylate compound (A), but preferably a hydroxyl group-containing (meth) acrylate compound (b1). A urethane (meth) acrylate compound (B1) and / or a hydroxyl group-containing (meth) acrylate compound (b1) obtained by reacting a polyisocyanate compound (b2) and a polyol compound (b3), a polyisocyanate compound This is a urethane (meth) acrylate compound (B2) obtained by reacting the compound (b2).
Among these, urethane (meta) obtained by reacting a hydroxyl group-containing (meth) acrylate compound (b1), a polyvalent isocyanate compound (b2), and a polyol compound (b3) is particularly preferred from the standpoint of maintaining good restorability. ) Acrylate compound (B1).

Examples of the hydroxyl group-containing (meth) acrylate compound (b1) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) ) Acrylate, hydroxyalkyl (meth) acrylate such as 6-hydroxyhexyl (meth) acrylate, 2-hydroxyethyl acryloyl 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 pentaerythritol 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) An acrylate etc. are mentioned.

Among these, a hydroxyl group-containing (meth) acrylate compound having 1 to 3 ethylenically unsaturated groups is preferred from the standpoint of maintaining good restorability. A compound having one ethylenically unsaturated group is 2-hydroxy Hydroxyalkyl (meth) such as ethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylate As a compound having acrylate and two ethylenically unsaturated groups, glycerin di (meth) acrylate and a compound having three ethylenically unsaturated groups, pentaerythritol tri (meth) acrylate is excellent in reactivity and versatility. preferable. Among these, compounds having one ethylenically unsaturated group are preferable from the viewpoint that the curing shrinkage of the cured product when cured can be reduced, and in particular, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meta) ) Acrylate is preferred. Moreover, it is also preferable to use polyfunctional (meth) acrylate at the point which can improve surface hardness further.
These hydroxyl group-containing (meth) acrylate compounds (b1) can be used alone or in combination of two or more.

Examples of the polyvalent isocyanate compound (b2) 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 polyisocyanates, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate, hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis (isocyanate) Natomethyl) Cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane and other alicyclic polyisocyanates, or trimer compounds or multimer compounds of these polyisocyanates, allophanate type polyisocyanates, burette type polyisocyanates, water dispersion types Polyisocyanate etc. are mentioned.

Among these, a diisocyanate-based compound is preferable because it can maintain a good restorability. An alicyclic diisocyanate such as isophorone diisocyanate, norbornene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane is preferably used, and more preferably has a small curing shrinkage. Isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, norbornene diisocyanate Over preparative is used, particularly preferably hydrogenated diphenylmethane diisocyanate in view of excellent reactivity and versatility, 1,3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate is used.
The polyvalent isocyanate compound (b2) can be used alone or in combination of two or more.

Examples of the polyol compound (b3) include polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, polybutadiene polyols, (meth) acrylic polyols, polysiloxane polyols, 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 three types of components: a polycondensation product 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), 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, 1,4 -Arocyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, paraphenylenedicarboxylic acid, trimellitic acid, etc.

Examples of the cyclic ester include propiolactone, β-methyl-δ-valerolactone, and ε-caprolactone.

Examples of the polycarbonate polyol include a reaction product of a polyhydric alcohol and phosgene, a ring-opening polymer of a cyclic carbonate (alkylene carbonate, etc.), and the like.

Examples of the polyhydric alcohol include polyhydric alcohols exemplified in the description of the polyester-based polyol, and examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, hexamethylene carbonate, and the like. It is done.

The polycarbonate-based polyol may be a compound having a carbonate bond in the molecule and having a hydroxyl group at the end, and may have an ester bond together with the carbonate bond.

Examples of the polyolefin-based polyol include those having a homopolymer or copolymer such as ethylene, propylene, and butene as a saturated hydrocarbon skeleton, and having a hydroxyl group at the molecular end.

Examples of the polybutadiene-based polyol include those having a butadiene copolymer as a hydrocarbon skeleton and having a hydroxyl group at the molecular end.
The polybutadiene-based polyol may be a hydrogenated polybutadiene polyol in which all or part of the ethylenically unsaturated groups contained in the structure thereof are hydrogenated.

Examples of the (meth) acrylic polyol include those having at least two hydroxyl groups in the polymer or copolymer molecule of (meth) acrylic acid ester. As such (meth) acrylic acid ester, , For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, (meth) acrylic acid And (meth) acrylic acid alkyl esters such as 2-ethylhexyl, decyl (meth) acrylate, dodecyl (meth) acrylate, and octadecyl (meth) acrylate.

Examples of the polysiloxane polyol include dimethyl polysiloxane polyol and methylphenyl polysiloxane polyol.

Among these, polyester-based polyols and polyether-based polyols are preferable in terms of easy balance between resilience and coating surface hardness.

In the present invention, the polyol compound (b3) preferably has a number average molecular weight of 50 to 8,000, particularly 100 to 5,000, more preferably 200 to 3,000. When the number average molecular weight is too small, the restoring property of the coating film tends to be low, and when it is too large, the coating film surface hardness tends to decrease.

In addition, said number average molecular weight is a number average molecular weight by standard polystyrene molecular weight conversion, a column is put into a high performance liquid chromatography (Nippon Waters, "Waters 2695 (main body)" and "Waters 2414 (detector)"). : Shodex GPC KF-806L (exclusion limit molecular weight: 2 × 10 ⁷ , separation range: 100 to 2 × 10 ⁷ , theoretical plate number: 10,000 plates / piece, filler material: styrene-divinylbenzene copolymer, filler It is measured by using three series of particle diameters: 10 μm).

In the present invention, the urethane (meth) acrylate compound (B1) can be produced as follows.

For example, (1) A method in which the above hydroxyl group-containing (meth) acrylate compound (b1), polyvalent isocyanate compound (b2), and polyol compound (b3) are charged or reacted together in a reactor at a time (2 ) A method of reacting a hydroxyl group-containing (meth) acrylate compound (b1) with a reaction product obtained by reacting a polyol compound (b3) with a polyvalent isocyanate compound (b2) in advance; The reaction product obtained by reacting the isocyanate compound (b2) and the hydroxyl group-containing (meth) acrylate compound (b1) in advance can be reacted with the polyol compound (b3). The method (2) is preferred from the standpoint of properties and reduction of by-products.

For the reaction between the polyol compound (b3) and the polyvalent isocyanate compound (b2), known reaction means can be used. At that time, for example, the molar ratio of the isocyanate group in the polyvalent isocyanate compound (b2) to the hydroxyl group in the polyol compound (b3) is usually about 2n: (2n-2) (n is an integer of 2 or more). By doing this, it is possible to obtain a terminal isocyanate group-containing compound in which an isocyanate group remains, and after the compound is obtained, an addition reaction with the hydroxyl group-containing (meth) acrylate-based compound (b1) is enabled.

The addition reaction of the reaction product obtained by reacting the polyol compound (b3) and the polyvalent isocyanate compound (b2) in advance with the hydroxyl group-containing (meth) acrylate compound (b1) is also a known reaction. Means can be used.

The reaction molar ratio of the reaction product to the hydroxyl group-containing (meth) acrylate compound (b1) is, for example, that the reaction product has two isocyanate groups and the hydroxyl group-containing (meth) acrylate compound (b1) has one hydroxyl group. In the case of a single group, the reaction product: hydroxyl group-containing (meth) acrylate compound (b1) is about 1: 2, the reaction product has three isocyanate groups, and the hydroxyl group-containing (meth) acrylate compound (b1). ) Has one hydroxyl group, the reaction product: hydroxyl group-containing (meth) acrylate compound (b1) is about 1: 3.

In the addition reaction between the reaction product and the hydroxyl group-containing (meth) acrylate compound (b1), 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) is obtained.

In the reaction between the polyol compound (b3) and the polyvalent isocyanate compound (b2), and further in the reaction between the reaction product and the hydroxyl group-containing (meth) acrylate compound (b1), a catalyst is used for the purpose of promoting the reaction. It is also preferable to use, for example, organometallic compounds such as dibutyltin dilaurate, trimethyltin hydroxide, tetra-n-butyltin, zinc octenoate, tin octenoate, cobalt naphthenate, stannous chloride. Metal salts such as stannic chloride, triethylamine, benzyldiethylamine, 1,4-diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [5,4,0] undecene, N, N, N ′, Amine catalysts such as N'-tetramethyl-1,3-butanediamine and N-ethylmorpholine, bismuth nitrate, bromide Organic bismuth compounds such as dibutyl bismuth dilaurate and dioctyl bismuth dilaurate, bismuth 2-ethylhexanoate, bismuth naphthenate, bismuth isodecanoate, bismuth neodecanoate, lauryl Organic acid bismuth such as bismuth acid salt, bismuth maleate, bismuth stearate, bismuth oleate, bismuth linoleate, bismuth acetate, bismuth bisneodecanoate, bismuth disalicylate, bismuth digallate Examples thereof include bismuth-based catalysts such as salts, zirconium-based catalysts such as inorganic zirconium, organic zirconium and zirconium alone, and two or more types of catalysts such as zinc 2-ethylhexanoate / zirconium tetraacetylacetonate. Also, dibutyltin dilaurate, 1,8-diazabicyclo [5,4,0] undecene is preferred.

In the reaction between the polyol compound (b3) and the polyvalent isocyanate compound (b2), and further in the reaction between the reaction product and the hydroxyl group-containing (meth) acrylate compound (b1), it reacts with the isocyanate group. An organic solvent having no functional group, for example, esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and aromatic solvents such as toluene and xylene can be used.

The reaction temperature is usually 30 to 90 ° C., preferably 40 to 80 ° C., and the reaction time is usually 2 to 10 hours, preferably 3 to 8 hours.

Thus, the urethane (meth) acrylate compound (B1) is obtained.
The above description is about the urethane (meth) acrylate compound (B1) obtained by reacting the hydroxyl group-containing (meth) acrylate compound (b1), the polyvalent isocyanate compound (b2), and the polyol compound (b3). However, the urethane (meth) acrylate compound (B2) is also subjected to the above method, that is, without using the polyol compound (b3), and without containing the hydroxyl group-containing (meth) acrylate compound (b1). And a polyvalent isocyanate compound (b2) can be produced according to the above method.

The weight average molecular weight of the urethane (meth) acrylate compound (B) is preferably 500 to 40,000, particularly 1,000 to 30,000, and more preferably 1,500 to 20,000. preferable. If the weight average molecular weight is too small, the restoring property of the coating film tends to be low, and if it is too large, the coating film surface hardness tends to decrease.

The weight average molecular weight of the urethane (meth) acrylate compound (B1) is preferably 1,000 to 40,000, particularly 1,500 to 30,000, more preferably 2,000 to 20,000. The weight average molecular weight of the urethane (meth) acrylate compound (B2) is preferably 500 to 20,000, particularly 1,000 to 15,000, and more preferably 1,500 to 10 , 000 is preferable.

In addition, said weight average molecular weight is measured similarly to the measuring method of the weight average molecular weight of the said urethane (meth) acrylate type compound (A).

The viscosity of the urethane (meth) acrylate-based compound (B) is preferably 5,000 to 10,000,000 mPa · s, particularly 6,000 to 90,000 mPa · s, at 60 ° C. Further, it is preferably 7,000 to 80,000 mPa · s. If the viscosity is too high, handling tends to be difficult, and if it is too low, control of the film thickness tends to be difficult.
The viscosity is measured with an E-type viscometer.

The content of the urethane (meth) acrylate compound (B) is preferably 100 parts by weight or less, particularly 1 to 95 parts by weight with respect to 100 parts by weight of the urethane (meth) acrylate compound (A). Part, more preferably 5 to 90 parts by weight. If the content is too large, the restorability tends to decrease.

<Polysiloxane structure-containing compound (C)>
As the polysiloxane structure-containing compound (C) used in the present invention, a compound containing a known general polysiloxane structure may be used. For example, a polysiloxane structure-containing (meth) acrylate monomer, a polysiloxane structure-containing urethane (meth) acrylate -Based compound (C1), polysiloxane structure-containing polyether (meth) acrylate compound, polysiloxane structure-containing polyester (meth) acrylate compound, polysiloxane structure-containing poly (meth) acrylate such as polycarbonate (meth) acrylate compound containing polysiloxane structure Compounds;
A polyester compound containing a polysiloxane structure;
A polycarbonate compound containing a polysiloxane structure;
Polysiloxane structure-containing (meth) acrylic polymer;
Unsaturated group-containing polysiloxane structure-containing (meth) acrylate;
And compounds obtained by introducing a fluorine atom into the above compound.

Among these, a polysiloxane structure-containing (meth) acrylate compound is preferable from the viewpoint of forming a crosslinked structure when irradiated with ultraviolet rays to form a cured coating film and exhibiting excellent durability, and further, urethane ( A polysiloxane structure-containing urethane (meth) acrylate compound (C1) is preferred because it is excellent in compatibility with the (meth) acrylate compound.

The polysiloxane structure-containing urethane (meth) acrylate compound (C1) (hereinafter sometimes referred to as “urethane (meth) acrylate compound (C1)”) will be described.

The polysiloxane structure-containing urethane (meth) acrylate compound (C1) only needs to contain a polysiloxane structure in its structure, and in particular, as a component of the urethane (meth) acrylate compound, the following general formula A urethane (meth) acrylate compound (C1-1) obtained by using a polysiloxane compound having a hydroxyl group at one end represented by (2), a polyhydroxyl having hydroxyl groups at both ends represented by the following general formula (3) A urethane (meth) acrylate compound (C1-2) obtained by using a siloxane compound is preferable.
In addition, the said urethane (meth) acrylate type compound (C1) may have a structure site | part derived from both general formula (2) and (3).

First, a polysiloxane structure-containing urethane (meth) acrylate compound (C1-1) (hereinafter referred to as “urethane (meth)) obtained by using a polysiloxane compound having a hydroxyl group at one end represented by the general formula (2). The acrylate compound (C1-1) ”may be described.

The urethane (meth) acrylate compound (C1-1) is a polysiloxane compound (p1) having a hydroxyl group at one end represented by the general formula (2) (hereinafter referred to as “polysiloxane compound (p1)”). And a polyisocyanate compound (p2), a hydroxyl group-containing (meth) acrylate compound (p3) and, if necessary, a polyol compound (p4).

For such a polysiloxane compound (p1), R ¹ in the general formula (2) is an alkyl group, and the alkyl group preferably has a relatively short carbon number. Specifically, it usually has 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, particularly preferably 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group.

R ² in the general formula (2) is each independently an alkyl group, a cycloalkyl group, or a phenyl group.
The alkyl group preferably has a relatively short carbon number. Specifically, it usually has 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, particularly preferably 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group.
The carbon number of the cycloalkyl group is usually 3 to 10, preferably 5 to 8, and examples thereof include a cyclopentyl group, a cyclohexyl group, and a norbornyl group.

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.

R ³ in the general formula (2) is a hydrocarbon group or an organic group containing a hetero atom.
The hydrocarbon group usually has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, and examples thereof include divalent or trivalent hydrocarbon groups.
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.

A in the general formula (2) is an integer of 1 or more, preferably 5 to 200, particularly preferably an integer of 5 to 120. b is an integer of 1 to 3, and preferably an integer of 1 to 2.

The weight average molecular weight of the polysiloxane compound (p1) used in the present invention is usually preferably 100 to 50,000, particularly 500 to 10,000, and more preferably 1,000 to 10,000. It is preferable. If the weight average molecular weight is too low, the blocking resistance tends to decrease, and if it is too high, the transparency tends to decrease.

Specific examples of the polysiloxane compound (p1) represented by the general formula (2) include, for example, “X-22-170BX”, “X-22-170DX”, “X-22-2” manufactured by Shin-Etsu Chemical Co., Ltd. 176DX "," X-22-176F "," Silaplane FM-0411 "," Silaplane FM-0421 "," Silaplane FM-0425 "," Silaplane FM-DA11 "," Silaplane "manufactured by Chisso Corporation Products such as “FM-DA21” and “Silaplane FM-DA26”.

Examples of the polyisocyanate compound (p2) used in the present invention include tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate. Aromatic polyisocyanates, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate and other aliphatic polyisocyanates, hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis (isocyanato) Methyl) cyclohexane, 1, -Alicyclic polyisocyanates such as bis (isocyanatomethyl) cyclohexane, trimer compounds or multimeric compounds of these polyisocyanates, allophanate polyisocyanates, burette polyisocyanates, water-dispersed polyisocyanates (eg Tosoh) ("Aquanate 100", "Aquanate 105", "Aquanate 120", "Aquanate 210", etc.) manufactured by Co., Ltd.).
These can be used alone or in combination of two or more.
Among these, an isocyanate-based compound having 3 or more isocyanate groups in one molecule, particularly a polyisocyanate trimer or multimer compound, is a low unreacted cause of coating film hardness and bleeding. It is more preferable in that the molecular weight component can be reduced.

Examples of the hydroxyl group-containing (meth) acrylate compound (p3) used in the present invention include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 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 Cole 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 pentaerythritol 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. are mentioned. These can be used alone or in combination of two or more.
Among these, pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate are preferable in that a coating film having a relatively high hardness can be obtained.

Furthermore, a polyol compound (p4) may be used as long as the effects of the present invention are not impaired. Examples of the polyol compound (p4) include polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, polybutadiene polyols, (meth) acrylic polyols, and the like. About this polyol type compound (p4), the thing similar to the above-mentioned polyol type compound (b3) is mentioned.

The weight average molecular weight of the polyol compound (p4) is preferably 50 to 8,000, particularly preferably 100 to 5,000, and further preferably 200 to 3,000. If the weight-average molecular weight of the polyol compound (p4) is too large, mechanical properties such as coating film hardness tend to decrease during curing, and if it is too small, curing shrinkage tends to be large and stability tends to decrease.

The urethane (meth) acrylate-based compound (C1-1) preferably has one or more ethylenically unsaturated groups, and has three or more ethylenically unsaturated groups in terms of hardness of the cured coating film. It is particularly preferable that it has one, and further preferably one having 6 or more ethylenically unsaturated groups.
The upper limit of the ethylenically unsaturated group contained in the urethane (meth) acrylate compound (C1-1) is usually 30 and preferably 25 or less.

The method for producing the urethane (meth) acrylate compound (C1-1) is not particularly limited. For example,
(I): a polysiloxane compound (p1), a polyisocyanate compound (p2) (if necessary, a polyisocyanate compound (p2) previously reacted with a polyol compound (p4)), a hydroxyl group-containing (meta ) A method in which the acrylate compound (p3) is charged and reacted together,
(II): after reacting polysiloxane compound (p1) and polyisocyanate compound (p2) (if necessary, polyisocyanate compound (p2) previously reacted with polyol compound (p4)) , A method of reacting a hydroxyl group-containing (meth) acrylate compound (p3),
(III): Polyisocyanate compound (p2) (if necessary, a polyisocyanate compound (p2) previously reacted with a polyol compound (p4)) and a hydroxyl group-containing (meth) acrylate compound (p3) A method of reacting the polysiloxane compound (p1) after the reaction,
(IV): Polyisocyanate compound (p2) (if necessary, a polyisocyanate compound (p2) previously reacted with a polyol compound (p4)) and a hydroxyl group-containing (meth) acrylate compound (p3) A method in which after reacting a part, the polysiloxane compound (p1) is reacted, and the remaining hydroxyl group-containing (meth) acrylate compound (p3) is further reacted.
Among these, among these, the method (II) or (IV) is preferable, and the method (II) is particularly preferable from the viewpoint of stability of reaction control.

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 (p4) and a polyisocyanate type compound (p2) react beforehand.

In the method (II), after reacting the hydroxyl group of the polysiloxane compound (p1) with the isocyanate group of the polyisocyanate compound (p2) under the condition that the isocyanate group remains, the polyisocyanate compound ( The residual isocyanate group of p2) is reacted with the hydroxyl group of the hydroxyl group-containing (meth) acrylate compound (p3).

The reaction molar ratio between the polysiloxane compound (p1) and the polyisocyanate compound (p2) is, for example, that the polysiloxane compound (p1) has one hydroxyl group and the polyisocyanate compound (p2) has 2 isocyanate groups. In the case of polysiloxane compound (p1): polyisocyanate compound (p2) = 1: 0.8 to about 10, the polysiloxane compound (p1) has one hydroxyl group and is polyisocyanate compound. When the compound (p2) has three isocyanate groups, the polysiloxane compound (p1): polyisocyanate compound (p2) may be about 1: 0.2 to 5.

In the addition reaction between the reaction product and the hydroxyl group-containing (meth) acrylate compound (p3), the reaction is terminated when the residual isocyanate group in the reaction system is 0.5% by weight or less. ) An acrylate compound (C1-1) is obtained.

The weight of the structural portion derived from the polysiloxane compound (p1) contained in 100 parts by weight of the urethane (meth) acrylate compound (C1-1) is 0.1 to 80 within the above molar ratio range. It is preferable that it is a weight part.

In the above reaction, it is also preferable to use a catalyst for the purpose of accelerating the reaction, and examples of the catalyst include the same ones listed in the production of the urethane (meth) acrylate compound (B).

In the above reaction, an organic solvent having no functional group that reacts with an isocyanate group, for example, esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and aromatics such as toluene and xylene An organic solvent such as can be used.

The reaction temperature of the above 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 (C1-1) thus obtained is preferably 500 to 50,000, and more preferably 500 to 30,000. If the weight average molecular weight is too small, the blocking resistance tends to decrease, and if it is too large, the transparency of the cured coating film tends to decrease.

The viscosity of the urethane (meth) acrylate compound (C1-1) at 20 ° C. in a 40% methyl isobutyl ketone solution is preferably 5 to 5,000 mPa · s, more preferably 5 to 2,500 mPa · s, It is preferably 5 to 1,000 mPa · s. When the viscosity is out of the above range, the coatability tends to be lowered.
The viscosity is measured using a B-type viscometer.

The urethane (meth) acrylate compound (C1-1) may be used alone or in combination of two or more.

Next, a polysiloxane structure-containing urethane (meth) acrylate compound (C1-2) (hereinafter referred to as “urethane (meta)) obtained by using a polysiloxane compound having hydroxyl groups at both ends represented by the general formula (3). ) Acrylate compound (C1-2) ”).

The urethane (meth) acrylate compound (C1-2) is a polysiloxane compound (q1) having a hydroxyl group at both ends represented by the general formula (3) (hereinafter referred to as “polysiloxane compound (q1)”). And a polyisocyanate compound (q2), a hydroxyl group-containing (meth) acrylate compound (q3), and, if necessary, a polyol compound (q4).

For such polysiloxane compound (q1), R ³ in the general formula (3), each independently, an organic group containing a hydrocarbon group or a heteroatom.
The hydrocarbon group usually has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, and examples thereof include divalent or trivalent hydrocarbon groups.
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 (3) is each independently an alkyl group, a cycloalkyl group, or a phenyl group.
The alkyl group preferably has a relatively short carbon number. Specifically, it usually has 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, particularly preferably 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group.
The carbon number of the cycloalkyl group is usually 3 to 10, preferably 5 to 8, and examples thereof include a cyclopentyl group, a cyclohexyl group, and a norbornyl group.

A in the general formula (3) is an integer of 1 or more, preferably 5 to 200, particularly preferably an integer of 5 to 120. b and c are integers of 1 to 3, preferably integers of 1 to 2.

The weight average molecular weight of the polysiloxane compound (q1) is usually preferably 100 to 50,000, particularly 500 to 10,000, and more preferably 1,000 to 10,000. If the weight average molecular weight is too low, the blocking resistance tends to decrease, and if it is too high, the transparency tends to decrease.

Specific examples of the polysiloxane compound (q1) include “X-22-160AS”, “KF-6001”, “KF-6002”, “KF-6003” manufactured by Shin-Etsu Chemical Co., Ltd., “ Silaplane FM-4411, Silaplane FM-4421, Silaplane FM-4425, Momentive Performance Materials Japan XF42-B0970, Toray Dow Corning BY 16 -004 "," SF 8427 "," Macromonomer HK-20 "manufactured by Toagosei Co., Ltd.," DMS-C21 "," DMS-C23 "," DBL-C31 "," DMS-CA21 "manufactured by GELEST, etc. Products.

Examples of the polyisocyanate compound (q2) include the same compounds as those exemplified as the polyisocyanate compound (p2) in the description of the urethane (meth) acrylate (C1-1).

Examples of the hydroxyl group-containing (meth) acrylate compound (q3) are the same as those exemplified as the hydroxyl group-containing (meth) acrylate compound (p3) in the description of the urethane (meth) acrylate (C1-1). Can be mentioned.

Furthermore, the polyol compound (q4) may be used as long as the effects of the present invention are not impaired. For example, the polyol compound (p4) is exemplified in the description of the urethane (meth) acrylate (C1-1). The same thing as what was done is mentioned.

The urethane (meth) acrylate compound (C1-2) preferably has 2 or more ethylenically unsaturated groups, and has 4 or more ethylenically unsaturated groups in terms of hardness of the cured coating film. It is particularly preferable that it has one, and further preferably one having 6 or more ethylenically unsaturated groups.
Moreover, the upper limit of the ethylenically unsaturated group contained in the urethane (meth) acrylate compound (C1-2) is usually 30 and preferably 25 or less.

The method for producing the urethane (meth) acrylate compound (C1-2) is not particularly limited.
(I): polysiloxane compound (q1), polyisocyanate compound (q2) (if necessary, polyisocyanate compound (q2) previously reacted with polyol compound (q4)), hydroxyl group-containing (meta ) A method in which the acrylate compound (q3) is charged and reacted together,
(II): after reacting a polysiloxane compound (q1) and a polyisocyanate compound (q2) (if necessary, a polyisocyanate compound (q2) previously reacted with a polyol compound (q4)) , A method of reacting a hydroxyl group-containing (meth) acrylate compound (q3),
(III): a polyisocyanate compound (q2) (if necessary, a polyisocyanate compound (q2) previously reacted with a polyol compound (q4)) and a hydroxyl group-containing (meth) acrylate compound (q3). A method of reacting the polysiloxane compound (q1) after the reaction,
(IV): a polyisocyanate compound (q2) (if necessary, a polyisocyanate compound (q2) previously reacted with a polyol compound (q4)) and a hydroxyl group-containing (meth) acrylate compound (q3) A method of reacting a part of the polysiloxane compound (q1) and then reacting the remaining hydroxyl group-containing (meth) acrylate compound (q3);
Among these, the method (II) or (IV) is preferable, and the method (IV) is particularly preferable 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 (q4) and a polyisocyanate type compound (q2) react beforehand.

In the method (II), after reacting the hydroxyl group of the polysiloxane compound (q1) with the isocyanate group of the polyvalent isocyanate compound (q2) under the condition that the isocyanate group remains, the polyisocyanate compound is then reacted. The residual isocyanate group of (q2) is reacted with the hydroxyl group of the hydroxyl group-containing (meth) acrylate compound (q3).

The reaction molar ratio between the polysiloxane compound (q1) and the polyisocyanate compound (q2) is, for example, that the polysiloxane compound (q1) has 2 hydroxyl groups and the polyisocyanate compound (q2) has 2 isocyanate groups. In the case of the polysiloxane compound (q1): polyisocyanate compound (q2) = 1: 1.1 to 2.2, the polysiloxane compound (q1) has two hydroxyl groups, When the isocyanate compound (q2) has three isocyanate groups, the polysiloxane compound (q1): polyisocyanate compound (q2) may be about 1: 0.5 to 2.2.

In the addition reaction between the reactive organism and the hydroxyl group-containing (meth) acrylate compound (q3), the reaction is terminated when the residual isocyanate group in the reaction system becomes 0.5% by weight or less. ) Acrylate compound (C1-2) is obtained.

The weight of the structural portion derived from the polysiloxane compound (q1) contained in 100 parts by weight of the urethane (meth) acrylate compound (C1-2) is 0.1 to 80 weights within the above molar ratio range. Part.

In the above reaction, it is also preferable to use a catalyst for the purpose of accelerating the reaction, and examples of the catalyst include the same as described above.

The weight average molecular weight of the urethane (meth) acrylate compound (C1-2) thus obtained is usually preferably 500 to 50,000, more preferably 500 to 30,000. If the weight average molecular weight is too small, the blocking resistance tends to decrease, and if it is too large, the transparency of the cured coating film tends to decrease.

The viscosity at 20 ° C. of a 40% methyl isobutyl ketone solution of the urethane (meth) acrylate compound (C1-2) is preferably 5 to 5,000 mPa · s, more preferably 10 to 2,500 mPa · s, Is preferably 15 to 1,000 mPa · s. When the viscosity is out of the above range, the coatability tends to be lowered.
The viscosity is measured using a B-type viscometer.

The urethane (meth) acrylate compound (C1-2) may be used alone or in combination of two or more.

As the polysiloxane structure-containing urethane (meth) acrylate compound (C1), it is preferable to use the urethane (meth) acrylate compound (C1-1) and / or the urethane (meth) acrylate compound (C1-2). However, it is particularly preferable to use urethane (meth) acrylate (C1-2) in that an unreacted polysiloxane compound hardly remains.

When the urethane (meth) acrylate compounds (C1-1) and (C1-2) are used in combination, the urethane (meth) acrylate compound (C1-1) and the urethane (meth) acrylate compound (C1- The blending ratio (weight ratio) of 2) is preferably (C1-1) / (C1-2) = 5/95 to 95/5, particularly preferably (C1-1) / (C1-2) = 20 / 80 to 80/20.

The polysiloxane structure-containing compound (C) preferably has a silicon atom content of 0.1 to 80% by weight, particularly preferably 0.3 to 60% by weight, more preferably 0.5%, based on the total amount of (C). ~ 30% by weight.
If the silicon atom content is too large, the compatibility with other components tends to decrease, and if it is too small, the blending amount required for improving the blocking resistance increases, making it difficult to balance the physical properties of the coating film. Tend to be.

The content of the polysiloxane structure-containing compound (C) is a urethane (meth) acrylate compound (A) (in the case where the urethane (meth) acrylate compound (B) is blended, the sum of (A) and (B)) 100 The amount is preferably 0.01 to 100 parts by weight, particularly preferably 0.1 to 75 parts by weight, and more preferably 1 to 50 parts by weight with respect to parts by weight. When the content is too large, the compatibility tends to decrease, and when the content is too small, the blocking resistance tends to be difficult to improve.

<Phosphate group-containing ethylenically unsaturated compound (D)>
Examples of the phosphoric acid group-containing ethylenically unsaturated compound (D) used in the present invention include 2- (meth) acryloyloxyethyl phosphate (for example, “light ester P-1M”, “light acrylate” manufactured by Kyoeisha Chemical Co., Ltd.). P-1A ", etc.), methylene phosphate (meth) acrylate, ethylene phosphate (meth) acrylate, propylene (meth) acrylate phosphate, tetramethylene phosphate (meth) acrylate, alkylene phosphate (meth) acrylate, phosphorus 1-chloromethylethylene (meth) acrylate, phosphate ester of polyethylene glycol monomethacrylate (for example, “Sipomer PAM100”, “Sipomer PAM4000”, etc. manufactured by Rhodia Nikka Co., Ltd.), phosphate ester of polyethylene glycol monoacrylate (for example, For example, “Sipomer PAM5000” manufactured by Rhodia Nikka Co., Ltd.), phosphate ester of polypropylene glycol monomethacrylate (eg, “Sipomer PAM200” manufactured by Rhodia Nikka Co., Ltd.), phosphate ester of polypropylene glycol monoacrylate (eg Rhodia, etc.) A phosphate group-containing ethylenically unsaturated compound having one ethylenically unsaturated group such as a phosphate of polyalkylene glycol mono (meth) acrylate such as “Sipomer PAM300” manufactured by Nikka Corporation;
Bis (2- (meth) acryloyloxyethyl) phosphate (for example, “light ester P-2M”, “light acrylate P-2A”, etc. manufactured by Kyoeisha Chemical Co., Ltd.), ethylene oxide-modified phosphoric diacrylate, ethylene oxide-modified Phosphoric acid group-containing ethylenically unsaturated compounds having two or more ethylenically unsaturated groups such as phosphoric acid di (meth) acrylate and ethylene oxide-modified phosphoric acid tri (meth) acrylate;
Examples thereof include phosphoric acid group-containing ethylenically unsaturated compounds having 3 or more ethylenically unsaturated groups such as triacryloyloxyethyl phosphate (for example, Biscoat # 3PA manufactured by Osaka Organic Chemical Industry Co., Ltd.).
These phosphate group-containing ethylenically unsaturated compounds (D) may be used alone or in combination of two or more.

Among these, it is preferable to use 2- (meth) acryloyloxyethyl phosphate and bis (2-methacryloyloxyethyl) phosphate from the viewpoint that excellent adhesion to a metal surface can be easily obtained.

The content of the phosphoric acid group-containing ethylenically unsaturated compound (D) is urethane (meth) acrylate compound (A) (when blending urethane (meth) acrylate compound (B) (A) and (B). The total amount is preferably from 0.01 to 10 parts by weight, more preferably from 0.05 to 8 parts by weight, still more preferably from 0.1 to 5 parts by weight, particularly preferably from 0 to 100 parts by weight. .2 to 3 parts by weight. If the content of the phosphoric acid group-containing ethylenically unsaturated compound (D) is too small, the adhesion to the metal surface tends to decrease. If the content is too large, the metal surface is corroded or mechanical properties such as hardness are exhibited. There is a tendency to lower.

Thus, the active energy ray-curable resin composition of the present invention comprises the urethane (meth) acrylate compound (A), and further, the urethane (meth) acrylate compound (A) and the urethane (meta) ) Acrylate compound (B) (excluding urethane (meth) acrylate compound (A)) is preferred, and in particular, urethane (meth) acrylate compound (A) and urethane (meta) It is preferable to contain an acrylate compound (B), a polysiloxane structure-containing compound (C) and / or a phosphoric acid group-containing ethylenically unsaturated compound (D).

The active energy ray-curable resin composition of the present invention includes a photopolymerization initiator, an ethylenically unsaturated monomer other than the above (A) to (D), an ethylenically unsaturated oligomer, an acrylic resin, a surface, if necessary. Conditioners, leveling agents, polymerization inhibitors, etc. can be blended, and oil, antioxidants, flame retardants, antistatic agents, fillers, stabilizers, reinforcing agents, matting agents, abrasives, organic fine particles It is also possible to blend inorganic particles and the like.

Examples of the photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2- Methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1- ON, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propane 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 2-hydroxy Acetophenones such as -2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomer; benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, o-Benzoylmethyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 2,4,6 Benzo such as trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethananium bromide, (4-benzoylbenzyl) trimethylammonium chloride Phenones; 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy) -3 Thioxanthones such as 2,4-dimethyl-9H-thioxanthone-9-one mesochloride; 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl -Acyl phosphine oxides such as pentylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; In addition, only 1 type may be used for these photoinitiators, and 2 or more types may be used together.

Examples of these auxiliaries include triethanolamine, triisopropanolamine, 4,4′-dimethylaminobenzophenone (Michler ketone), 4,4′-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, 4-dimethylamino. Ethyl benzoate, ethyl 4-dimethylaminobenzoate (n-butoxy), isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4-diisopropylthio It is also possible to use xanthone or the like together.

Among these, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoin isopropyl ether, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2-hydroxy-2-methyl-1- It is preferable to use phenylpropan-1-one.

As content of a photoinitiator, urethane (meth) acrylate type compound (A) (when adding urethane (meth) acrylate type compound (B) further, it is the sum total of (A) and (B)) 100 weight The amount is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, and still more preferably 1 to 10 parts by weight with respect to parts. If the content of the photopolymerization initiator is too small, curing tends to be poor and film formation tends to be difficult, and if too large, yellowing of the cured coating film tends to occur, and coloring problems tend to occur.

The ethylenically unsaturated monomers and ethylenically unsaturated oligomers other than the above (A) to (D) include monofunctional monomers, bifunctional monomers, trifunctional or higher monomers, epoxy (meth) acrylate compounds, polyesters (meth) Examples include oligomers such as acrylate compounds.

Examples of such monofunctional monomers include styrene monomers such as styrene, vinyl toluene, chlorostyrene, α-methylstyrene, methyl (meth) acrylate, ethyl (meth) acrylate, acrylonitrile, 2-methoxyethyl (meth) acrylate, 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 Lilate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate (2-methyl-2-ethyl-1,3-dioxolan-4-yl) -methyl (meth) acrylate, cyclohexanespiro-2- (1,3-dioxolan-4-yl) -methyl (meth) acrylate, Cyclic trimethylolpropane formal acrylate, 3-ethyl-3-oxetanylmethyl (meth) acrylate, γ-butyrolactone (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 ( n = 2) (meth) acrylate, nonylphenol propylene oxide modified (n = 2.5) (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, etc. (Meth) acrylate, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, carbitol (meth) acrylate, benzyl (meth) acrylate of phthalic acid derivatives of (Meth) acrylate monomers such as butoxyethyl (meth) acrylate, allyl (meth) acrylate, (meth) acryloylmorpholine, polyoxyethylene secondary alkyl ether acrylate, 2-hydroxyethylacrylamide, N-methylol (meth) Examples include acrylamide, N-vinyl pyrrolidone, 2-vinyl pyridine, and vinyl acetate.

Examples of such bifunctional monomers 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, and di Propylene 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, cyclohexanedimethanol di (meth) acrylate, ethoxylated cyclohexanedimethanol di ( Acrylate), dimethylol dicyclopentane di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) ) Acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, hydroxypivalic acid modified neopentyl glycol di (meth) acrylate, isocyanuric acid Examples include ethylene oxide-modified diacrylate.

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) acryloyloxyethoxytrimethylolpropane, glycerin polyglycidyl ether poly (meth) acrylate, isocyanuric acid ethylene oxide modified triacrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol hexa (Meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate, cap Lactone modified pentaerythritol tetra (meth) acrylate, ethylene oxide modified dipentaerythritol penta (meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, ethylene oxide modified pentaerythritol tri (meth) acrylate, ethylene oxide modified pentaerythritol Examples include tetra (meth) acrylate and ethoxylated glycerin triacrylate.

Further, Michael adduct of acrylic acid or 2-acryloyloxyethyl dicarboxylic acid monoester can be used in combination. Examples of the Michael adduct of acrylic acid include acrylic acid dimer, methacrylic acid dimer, acrylic acid trimer, methacrylic acid trimer, An acrylic acid tetramer, a methacrylic acid tetramer, etc. are mentioned.

The 2-acryloyloxyethyl dicarboxylic acid monoester is a carboxylic acid having a specific substituent, such as 2-acryloyloxyethyl succinic acid monoester, 2-methacryloyloxyethyl succinic acid monoester, 2-acryloyloxyethyl. Examples thereof include phthalic acid monoester, 2-methacryloyloxyethyl phthalic acid monoester, 2-acryloyloxyethyl hexahydrophthalic acid monoester, and 2-methacryloyloxyethyl hexahydrophthalic acid monoester. Furthermore, other oligoester acrylates can also be mentioned.

Examples of the surface conditioner include cellulose resin and alkyd resin. The cellulose resin has an effect of improving the surface smoothness of the coating film, and the alkyd resin has an effect of imparting a film forming property at the time of application.

As the leveling agent, a known general leveling agent can be used as long as it has an effect of imparting wettability to the substrate of the coating liquid and a function of reducing the surface tension. For example, a silicone-modified resin, a fluorine-modified resin An alkyl-modified resin or the like can be used.

Examples of the polymerization inhibitor include p-benzoquinone, naphthoquinone, tolquinone, 2,5-diphenyl-p-benzoquinone, hydroquinone, 2,5-di-t-butylhydroquinone, methylhydroquinone, hydroquinone monomethyl ether, mono-t. -Butylhydroquinone, pt-butylcatechol and the like.

In addition, the active energy ray-curable resin composition of the present invention preferably uses an organic solvent for dilution, if necessary, in order to make the viscosity at the time of coating appropriate. Examples of such organic solvents include alcohols such as methanol, ethanol, propanol, n-butanol and i-butanol, ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone and cyclohexanone, cellosolves such as ethyl cellosolve, toluene, xylene And the like, glycol ethers such as propylene glycol monomethyl ether, acetates such as methyl acetate, ethyl acetate and butyl acetate, and diacetone alcohol. These organic solvents may be used alone or in combination of two or more.

In the case where two or more of the above are used in combination, it is preferable from the viewpoint of the coating film appearance that two or more of the glycol ethers, ketones and alcohols are selected and combined.

In the production of the active energy ray-curable resin composition of the present invention, the mixing method of the above components (A) to (D) and other components is not particularly limited, and the mixing is performed by various methods. can do.

The active energy ray-curable resin composition of the present invention is effectively used as a curable resin composition for coating film formation, such as a topcoat agent and an anchor coat agent on various substrates, and is active energy ray-curable. After applying the functional resin composition to the substrate (after further drying if the composition diluted with an organic solvent is applied), it is cured by irradiation with active energy rays.

Examples of the base material to which the active energy ray-curable resin composition of the present invention is applied include, for example, polyolefin resin, polyester resin, polycarbonate resin, acrylic resin acrylonitrile butadiene styrene copolymer (ABS). Metal (aluminum) such as plastic base materials such as polystyrene resins and moldings thereof (films, sheets, cups, etc.), composite base materials thereof, or composite base materials of the above materials mixed with glass fibers or inorganic substances , Copper, iron, SUS, zinc, magnesium, alloys thereof, metal-deposited films, etc.), and substrates having a primer layer on a substrate such as glass.

Examples of the coating method of the active energy ray-curable resin composition include wet coating methods such as spray, shower, dipping, dispenser, roll, spin, screen printing, and ink jet printing. Underneath, the substrate may be coated.

Further, the active energy ray-curable resin composition of the present invention is diluted with the above organic solvent so that the solid content concentration is usually 3 to 90% by weight, preferably 5 to 60% by weight. It is preferable to work.

The drying conditions for dilution with the organic solvent are as follows: the temperature is usually 40 to 120 ° C., preferably 50 to 100 ° C., and the drying time is usually 1 to 20 minutes, preferably 2 to 10 minutes. That's fine.

Active energy rays used for curing the active energy ray-curable resin composition coated on the substrate include rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, and infrared rays, and electromagnetic waves such as X-rays and γ rays. In addition, electron beams, proton beams, neutron beams, and the like can be used, but curing by ultraviolet irradiation is advantageous from the viewpoint of curing speed, availability of an irradiation device, price, and the like. In addition, when performing electron beam irradiation, it can harden | cure even if it does not use a photoinitiator.

When curing by ultraviolet irradiation, using a high-pressure mercury lamp, ultra-high pressure mercury lamp, carbon arc lamp, metal halide lamp, xenon lamp, chemical lamp, electrodeless discharge lamp, LED, etc. Usually, ultraviolet rays of 30 to 3000 mJ / cm ² (preferably 100 to 1500 mJ / cm ² ) may be irradiated.
After the ultraviolet irradiation, heating can be performed as necessary to complete the curing.

The coating thickness (thickness after curing) is related to the flaw depth assumed as the resilience to the flaw, so that the flaw depth does not exceed the coating thickness. In general, the photopolymerization initiator should be 3 to 1000 μm, preferably 5 to 500 μm, particularly preferably 10 to 200 μm, considering light transmission so that the photopolymerization initiator can react uniformly as an ultraviolet curable coating film. It is.

The urethane (meth) acrylate compound (A) of the present invention is obtained by reacting a hydroxyl group-containing (meth) acrylate compound (x) containing a structural site derived from ε-caprolactone and a polyvalent isocyanate compound (y). It is a urethane (meth) acrylate compound, and is an urethane (meth) acrylate compound characterized in that the polyisocyanate compound (y) has an average number of isocyanate groups of 3.2 or more. After making the energy ray curable resin composition, it is excellent in a good balance between the resilience to the scratches and the blocking resistance by using a cured coating film. Further, the urethane (meth) acrylate compound (B) (however, urethane (meth)) In the case of containing an acrylate compound (A), the surface hardness is excellent and the polysiloxane structure is contained. When the compound (C) is contained, the blocking resistance is also superior, and when the phosphoric acid group-containing ethylenically unsaturated compound (D) is contained, the adhesiveness to the metal substrate is also excellent. It is particularly useful as an outermost surface coating agent or a metal surface coating agent.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. In the examples, “parts” and “%” mean weight basis unless otherwise specified.

[1] A system using only the urethane (meth) acrylate compound (A).
<(A) alone>
The following were prepared as urethane (meth) acrylate compounds (A) (see Table 1).

<Example 1: Urethane (meth) acrylate compound (A-1)>
In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 353 g (0.37 mol) of biuret-type multimer (y) of hexamethylene diisocyanate having an average isocyanate group number of 4.9, 2 -647 g (1.88 mol) of 2-hydroxyethyl acrylate caprolactone adduct (x), 0.02 g of hydroquinone methyl ether as a polymerization inhibitor, and 0.02 g of dibutyltin dilaurate as a reaction catalyst were reacted at 60 ° C for 6 hours. The reaction was terminated when the residual isocyanate group reached 0.3%, and the urethane (meth) acrylate compound (A-1) (weight average molecular weight (Mw) 4,000; ethylenically unsaturated group content 1 .88 mmol / g) was obtained.

<Example 2: Urethane (meth) acrylate compound (A-2)>
In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser and nitrogen gas inlet, 342 g (0.46 mol) of biuret-type multimer (y) of hexamethylene diisocyanate having an average isocyanate group number of 4.1, 2 -658 g (1.91 mol) of caprolactone 2-mol adduct of hydroxyethyl acrylate (1.91 mol), 0.02 g of hydroquinone methyl ether as a polymerization inhibitor and 0.02 g of dibutyltin dilaurate as a reaction catalyst were reacted at 60 ° C for 6 hours. The reaction was terminated when the residual isocyanate group reached 0.3%, and the urethane (meth) acrylate compound (A-2) (weight average molecular weight (Mw) 3,600; ethylenically unsaturated group content 1 .91 mmol / g) was obtained.

<Example 3: Urethane (meth) acrylate compound (A-3)>
In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, isocyanurate type multimer (y) 330.6 g (0.40 mol) of hexamethylene diisocyanate having an average isocyanate group number of 4.2. ), 2-hydroxyethyl acrylate caprolactone 1 mol adduct (x) 669.4 g (1.95 mol), hydroquinone methyl ether 0.02 g as a polymerization inhibitor, and dibutyltin dilaurate 0.02 g as a reaction catalyst, The reaction was terminated when the residual isocyanate group reached 0.3%, and the urethane (meth) acrylate compound (A-3) (weight average molecular weight (Mw) 4,930; A saturated group content of 1.95 mmol / g) was obtained.

<Example 4: Urethane (meth) acrylate compound (A-4)>
In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser and nitrogen gas inlet, isocyanurate type multimer (y) of hexamethylene diisocyanate having an average isocyanate group number of 3.4 (0.6) (0.65 mol) ), 2-hydroxyethyl acrylate caprolactone 1 mol adduct (x) 599.4 g (2.60 mol), hydroquinone methyl ether 0.02 g as a polymerization inhibitor, and dibutyltin dilaurate 0.02 g as a reaction catalyst, The reaction was terminated when the residual isocyanate group reached 0.3%, and the urethane (meth) acrylate compound (A-4) (weight average molecular weight (Mw) 2,920; A saturated group content of 2.60 mmol / g) was obtained.

<Comparative Example 1: Urethane (meth) acrylate compound (A'-1)>
In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser, and nitrogen gas inlet, 350.3 g (0.63 mol) of hexamethylene diisocyanate biuret multimer (y) having an average isocyanate group number of 3.0 2-hydroxyethyl acrylate caprolactone 2-mol adduct (x) 649.7 g (1.89 mol), hydroquinone methyl ether 0.02 g as a polymerization inhibitor, and dibutyltin dilaurate 0.02 g as a reaction catalyst were charged at 60 ° C. The reaction was terminated for 6 hours, and when the residual isocyanate group reached 0.3%, the reaction was terminated, and the urethane (meth) acrylate compound (A′-1) (weight average molecular weight (Mw) 3,470; A saturated group content of 1.89 mmol / g) was obtained.

<Comparative Example 2: 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, isocyanurate type multimer (y) 409.8 g (0.54 mol) of isophorone diisocyanate having an average isocyanate group number of 3.0 2-hydroxyethyl acrylate caprolactone 2-mol adduct (x) 590.2 g (1.72 mol), hydroquinone methyl ether 0.02 g as a polymerization inhibitor, and dibutyltin dilaurate 0.02 g as a reaction catalyst were charged at 60 ° C. The reaction was terminated for 6 hours. When the residual isocyanate group reached 0.3%, the reaction was terminated, and the urethane (meth) acrylate compound (A′-2) (weight average molecular weight (Mw) 4,260; A saturated group content of 1.72 mmol / g) was obtained.

<Active energy ray-curable resin composition>
Urethane (meth) acrylate compounds (A-1 to A-4) obtained in Examples 1 to 4 and urethane (meth) acrylate compounds (A′-1, A) obtained in Comparative Examples 1 and 2 '-2) 100 parts, 4 parts of photopolymerization initiator ("Irgacure 184", manufactured by BSF Corporation), toluene blended to a solid content concentration of 80%, active energy ray curable resin A composition was obtained.
About the obtained active energy ray-curable resin composition, the restorability and blocking resistance were evaluated as follows. The evaluation results are shown in Table 1.

<Restorability>
The active energy ray-curable resin composition obtained above was applied to a black polycarbonate substrate (manufactured by Nippon Test Panel Co., 2 × 70 × 150 mm) so that the cured coating film had a thickness of 40 μm with an applicator, After drying at 90 ° C. for 6 minutes, using one high pressure mercury lamp 80W, 3 passes of UV irradiation (cumulative irradiation amount 1000 mJ / cm ² ) at a conveyor speed of 3.4 m / min from a height of 18 cm. A cured coating film was obtained.
Using the cured coating film obtained above, under a condition of 23 ° C. and 50% Rh, using a brass two-digit brush, scratches the coating film 5 times, and the scratch cannot be visually confirmed. Was measured and evaluated according to the following evaluation criteria.

(Evaluation criteria)
○: Scratch could not be confirmed within 1 minute. Δ: Scratch could not be confirmed within 10 minutes after over 1 minute. ×: Scratch could be confirmed even after over 10 minutes.

<Blocking resistance>
The active energy ray-curable resin composition obtained above was applied to a black polycarbonate substrate (manufactured by Nippon Test Panel Co., 2 × 70 × 150 mm) so that the cured coating film had a thickness of 40 μm with an applicator, After drying at 90 ° C. for 6 minutes, using one high pressure mercury lamp 80W, 3 passes of UV irradiation (cumulative irradiation amount 1000 mJ / cm ² ) at a conveyor speed of 3.4 m / min from a height of 18 cm. A cured coating film was obtained.
Using the cured coating film obtained above, a polyethylene terephthalate (PET) film was placed on the surface side of the cured coating film at 23 ° C. and 50% Rh, and the film was pasted once by a 2 kg load roller. After 5 minutes, the PET film was peeled off to measure the tackiness of the cured coating film surface and evaluated according to the following evaluation criteria.

(Evaluation criteria)
◎: PET film does not adhere at all ○: PET film adheres slightly, but no trace of peeling remains Δ: PET film adheres, but no trace of peeling remains ×: PET film adheres and peels off Traces remain

From the above evaluation results, the cured coating films obtained from the active energy ray-curable resin compositions obtained by using the urethane (meth) acrylate compounds (A-1 to A-4) of Examples 1 to 4 are recoverable. It can be seen that the blocking resistance is excellent in a well-balanced manner.
On the other hand, active energy ray-curable resin compositions obtained by using urethane (meth) acrylate compounds (A′-1 to A′-2) made of polyvalent isocyanate compounds having a small average number of isocyanate groups in Comparative Examples 1 and 2 It turns out that the cured coating film obtained from a thing is inferior to the resilience of what is excellent in blocking resistance.

[2] A system comprising a urethane (meth) acrylate compound (A) and another urethane (meth) acrylate compound (B).
<Combination system of (A) + (B)>
<Examples 5 to 10>
The above urethane (meth) acrylate compound (A-2) and the following urethane (meth) acrylate compounds (B-1 to B-3) have the composition shown in Table 2, and a photopolymerization initiator (“Irgacure 184”). 4 parts, manufactured by BASF), methyl isobutyl ketone was blended so as to have a solid content concentration of 80%, and an active energy ray-curable resin composition was obtained.
About the obtained active energy ray-curable resin composition, the restorability, blocking resistance, and surface hardness were evaluated as follows. The evaluation results are shown in Table 2.

<Reference Example 1>
Evaluation was performed in the same manner as in Example 5 except that 100 parts of the urethane (meth) acrylate compound (A-2) was used and the urethane (meth) acrylate compound (B) was not blended. The evaluation results are shown in Table 2.

<Urethane (meth) acrylate compound (B-1)>
In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 37.5 g (0.17 mol) of isophorone diisocyanate, 25.5 g of polytetramethylene glycol diol (hydroxyl value 167 mg KOH / g; hydroxyl group) Molecular weight 672 calculated from the valence; 0.04 mol), polyester triol 13.4 g (hydroxyl value 262 mg KOH / g; molecular weight calculated from the hydroxyl value 642; 0.02 mol), and dibutyltin dilaurate 0.02 g as the reaction catalyst. Charged and reacted at 80 ° C. When the residual isocyanate group became 11% or less, 23.6 g (0.2 mol) of 2-hydroxyethyl acrylate and 0.04 g of methoxyphenol as a polymerization inhibitor were further added and reacted at 60 ° C. The reaction was terminated at a point of time of 0.3% or less to obtain urethane (meth) acrylate compound (B-1) (functional group number: 2-3, weight average molecular weight: about 3,500).

<Urethane (meth) acrylate compound (B-2)>
In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser and nitrogen gas inlet, 29.9 g (0.14 mol) of isophorone diisocyanate, 54.2 g of polycarbonate diol (hydroxyl value 139.5 mgKOH / g; hydroxyl value) The molecular weight calculated from the formula (804; 0.07 mol) was charged with 0.02 g of dibutyltin dilaurate as a reaction catalyst and reacted at 60 ° C. When the residual isocyanate group became 6.7% or less, 15.9 g (0.14 mol) of 2-hydroxyethyl acrylate and 0.04 g of methoxyphenol as a polymerization inhibitor were further charged and reacted at 60 ° C. The reaction was terminated when the isocyanate group became 0.3% or less, and a urethane (meth) acrylate compound (B-2) (functional group number: 2, weight average molecular weight: about 5,000) was obtained.

<Urethane (meth) acrylate compound (B-3)>
A 4-neck flask equipped with a thermometer, stirrer, water-cooled condenser, and nitrogen gas inlet is charged with 60.4 g (0.10 mol) of hexamethylene diisocyanate trimer, and hydroquinone methyl ether 0 as a polymerization inhibitor. .2 g was added, and 39.6 g (0.30 mol) of 2-hydroxypropyl acrylate was added dropwise so that the internal temperature did not exceed 70.degree. C., and the reaction was carried out at 70.degree. The reaction was terminated when the residual isocyanate concentration became 0.3% or less to obtain urethane (meth) acrylate compound (B-3) (number of functional groups: 3, weight average molecular weight: about 2,300).

<Restorability>
The active energy ray-curable resin composition obtained above was applied to a black polycarbonate substrate (manufactured by Nippon Test Panel Co., 2 × 70 × 150 mm) so that the cured coating film had a thickness of 40 μm with an applicator, After drying at 90 ° C. for 5 minutes, two passes of UV irradiation (accumulated dose of 800 mJ / cm ² ) are performed at a conveyor speed of 3.4 m / min from a height of 18 cm using a high pressure mercury lamp 80 W and one lamp. A cured coating film was obtained.
Using the cured coating film obtained above, under a condition of 23 ° C. and 50% Rh, using a brass two-digit brush, scratches the coating film 5 times, and the scratch cannot be visually confirmed. Was measured and evaluated according to the following evaluation criteria.

<Blocking resistance>
The active energy ray-curable resin composition obtained above was applied to a black polycarbonate substrate (manufactured by Nippon Test Panel Co., 2 × 70 × 150 mm) so that the cured coating film had a thickness of 40 μm with an applicator, After drying at 90 ° C. for 5 minutes, two passes of UV irradiation (accumulated dose of 800 mJ / cm ² ) are performed at a conveyor speed of 3.4 m / min from a height of 18 cm using a high pressure mercury lamp 80 W and one lamp. A cured coating film was obtained.
Using the cured coating film obtained above, put the PET film on the surface side of the cured coating film under the conditions of 23 ° C. and 50% Rh, and after reciprocating once with a roller of 2 kg load for 5 minutes. Later, the PET film was peeled off to measure the adhesiveness of the cured coating film surface, and evaluated according to the following evaluation criteria.

<Surface hardness>
The active energy ray-curable resin composition obtained above was applied to a 125 μm easy-adhesive PET film (“A4300”, manufactured by Toyobo Co., Ltd.) using an applicator so that the cured coating film had a thickness of 40 μm. After drying for 5 minutes, using a high pressure mercury lamp lamp 80W and one lamp, UV irradiation of 2 passes (accumulated dose of 800 mJ / cm ² ) is performed at a conveyor speed of 3.4 m / min from a height of 18 cm to cure. A coating film was obtained.
The pencil hardness of the cured coating film obtained above was measured according to JIS K 5600-5-4.

From the above evaluation results, it can be seen that the cured coating films obtained from the active energy ray-curable resin compositions of Examples 5 to 10 are excellent in balance between resilience and blocking resistance and excellent in surface hardness. Moreover, in surface hardness, it is superior to the cured coating film obtained from the active energy ray-curable resin composition of Reference Example 1 that does not contain other urethane (meth) acrylate compounds (B).

[3] A system comprising a polysiloxane structure-containing compound (C) together with a urethane (meth) acrylate compound (A).

[3-1] Combined system of urethane (meth) acrylate compound (A) + polysiloxane structure-containing compound (C).
<Examples 11 to 15, Reference Example 2>
The above urethane (meth) acrylate compound (A-2) and the following polysiloxane structure-containing compounds (C-1, C-2) are blended as shown in Table 3, and a photopolymerization initiator (“Irgacure 184”) is used. 4 parts of BAS, Inc.) and methyl isobutyl ketone were blended to a solid content concentration of 40% to obtain an active energy ray-curable resin composition.
About the obtained active energy ray curable resin composition, the restorability, blocking resistance, and transparency (haze) were evaluated as follows. The evaluation results are shown in Table 3.

<Polysiloxane structure-containing compound (C-1)>
In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas blowing port, 69.1 g of hexamethylene diisocyanate trimer (q2) (isocyanate group content 21.0%), general formula (3 polysiloxane compound represented ^{_{_{by) (q1) (R 1 =}}} -C 2 H 4 OC 3 H 6 -, R 2 = ^{_{_{_{methyl, R 3 = -C 3 H 6}}}} OC 2 H 4 -, b = 1, c = 1, weight average molecular weight 6000) 172.6 g, methyl isobutyl ketone 500 g, hydroquinone methyl ether 1.0 g as a polymerization inhibitor, and dibutyltin dilaurate 0.1 g as a reaction catalyst, reacted at 60 ° C. for 3 hours, and residual isocyanate Is 4.0%, dipentaerythritol pentaacrylate (q3) [dipentaerythritol pentaacrylate And 258.3 g of a mixture of dipentaerythritol hexaacrylate (hydroxyl value 50 mg KOH / g)], 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 A compound (C-1) solution (solid concentration: 50%) was obtained.

<Polysiloxane structure-containing compound (C-2)>
In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas blowing port, 115.7 g of isophorone diisocyanate trimer (q2) (isocyanate group content 17.2%), general formula (3) A polysiloxane compound (q1) (R ¹ = —C ₂ H ₄ OC ₃ H ₆ —, R ² = methyl group, R ³ = —C ₃ H ₆ OC ₂ H ₄ —, b = 1, c = 1, weight average molecular weight 6000) 236.7 g, methyl isobutyl ketone 500 g, 2,6-di-tert-butylcresol 0.5 g as a polymerization inhibitor, dibutyltin dilaurate 0.05 g as a reaction catalyst, and 3 at 60 ° C. When the residual isocyanate is 3.8% after reacting for a period of time, pentaerythritol triacrylate [pentaerythritol triacrylate and The mixture (q3) of pentaerythritol tetraacrylate (hydroxyl value 120 mgKOH / g)] 147.6 g was charged, 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 type A compound (C-2) solution (solid concentration: 50%) was obtained.

<Restorability>
The active energy ray-curable resin composition obtained above was applied to a black polycarbonate substrate (manufactured by Nippon Test Panel Co., 2 × 70 × 150 mm) so that the cured coating film had a thickness of 40 μm with an applicator, After drying at 90 ° C. for 5 minutes, two passes of UV irradiation (accumulated dose of 800 mJ / cm ² ) are performed at a conveyor speed of 3.4 m / min from a height of 18 cm using a high pressure mercury lamp 80 W and one lamp. A cured coating film was obtained.
Using the cured coating film obtained above, under a condition of 23 ° C. and 50% Rh, using a brass two-digit brush, scratches the coating film 5 times, and the scratch cannot be visually confirmed. Was measured and evaluated according to the following evaluation criteria. The results are shown in Table 3 below.

<Blocking resistance>
The active energy ray-curable resin composition obtained above was applied to a black polycarbonate substrate (manufactured by Nippon Test Panel Co., 2 × 70 × 150 mm) so that the cured coating film had a thickness of 40 μm with an applicator, After drying at 90 ° C. for 5 minutes, two passes of UV irradiation (accumulated dose of 800 mJ / cm ² ) are performed at a conveyor speed of 3.4 m / min from a height of 18 cm using a high pressure mercury lamp 80 W and one lamp. A cured coating film was obtained.
Using the cured coating film obtained above, put the PET film on the surface side of the cured coating film under the conditions of 23 ° C. and 50% Rh, and after reciprocating once with a roller of 2 kg load for 5 minutes. Later, the PET film was peeled off to measure the adhesiveness of the cured coating film surface, and evaluated according to the following evaluation criteria. The results are shown in Table 3 below.

<Transparency>
The active energy ray-curable resin composition obtained above was applied to a 125 μm easy-adhesive PET film (“A4300”, manufactured by Toyobo Co., Ltd.) using an applicator so that the cured coating film had a thickness of 40 μm. After drying for 5 minutes, using a high pressure mercury lamp lamp 80W and one lamp, UV irradiation of 2 passes (accumulated dose of 800 mJ / cm ² ) is performed at a conveyor speed of 3.4 m / min from a height of 18 cm to cure. A coating film was obtained.
The haze value which combined the PET film and the cured coating film was measured with respect to the cured coating film obtained above using the haze meter (the Nippon Denshoku Industries Co., Ltd. make, "NDH 2000"). The haze value of the PET film itself was 0.52%.
The evaluation criteria are as follows.

(Evaluation criteria)
○ ・・・ Haze value is less than 1.0% Δ ・・・ Haze value is 1.0% or more, less than 3.0% × ・・・ Haze value is 3.0% or more

From the above evaluation results, the cured coating film obtained from the active energy ray-curable resin compositions of Examples 11 to 15 in which the urethane (meth) acrylate compound (A) and the polysiloxane structure-containing compound (C) are used in combination It can be seen that it is excellent in resilience, blocking resistance and transparency. Moreover, in blocking resistance, it is superior to the cured coating film obtained from the active energy ray-curable resin composition of Reference Example 2 that does not contain the polysiloxane structure-containing compound (C).

[3-2] Combined system of urethane (meth) acrylate compound (A) + other urethane (meth) acrylate compound (B) + polysiloxane structure-containing compound (C).
<Examples 16 to 20>
Table 4 shows the urethane (meth) acrylate compound (A-2), the urethane (meth) acrylate compound (B-1), and the polysiloxane structure-containing compound (C-1, C-2). The composition shown in FIG. 4 is used, and 4 parts of photopolymerization initiator ("Irgacure 184", manufactured by BSF Corporation) and methyl isobutyl ketone are blended so that the solid content concentration is 40%, and the active energy ray curability is obtained. A resin composition was obtained.
About the obtained active energy ray curable resin composition, as above-mentioned, restoration property, blocking resistance, transparency (haze), and also surface hardness were evaluated as follows. The evaluation results are shown in Table 4.

<Reference Example 3>
The same procedure as in Example 16 except that the urethane (meth) acrylate compound (A-2) was 100 parts and the urethane (meth) acrylate compound (B) and the polysiloxane structure-containing compound (C) were not blended. Made and evaluated. The evaluation results are shown in Table 4.

From the above evaluation results, the cured coating films obtained from the active energy ray-curable resin compositions of Examples 16 to 20 are excellent in restoration properties and particularly good in blocking resistance, and further, transparency and surface of the coating films It can be seen that the hardness is also excellent. Moreover, in blocking resistance and surface hardness, it is obtained from the active energy ray-curable resin composition of Reference Example 3 that does not contain other urethane (meth) acrylate compound (B) and polysiloxane structure-containing compound (C). It is superior to a cured coating film.

[4] A system comprising a phosphoric acid group-containing ethylenically unsaturated compound (D) together with a urethane (meth) acrylate compound (A).

[4-1] Combined system of urethane (meth) acrylate compound (A) + phosphoric acid group-containing ethylenically unsaturated compound (D).
<Examples 21 to 26, Reference Example 4>
The above urethane (meth) acrylate compound (A-2) and the following phosphoric acid group-containing ethylenically unsaturated compounds (D-1 to D-3) are blended as shown in Table 5, and a photopolymerization initiator (Irgacure 184, “manufactured by BSF Corporation”) and 4 parts of methyl isobutyl ketone were blended so as to have a solid concentration of 40% to obtain an active energy ray-curable resin composition.
About the obtained active energy ray curable resin composition, the restorability, metal base-material adhesiveness, and transparency (haze) were evaluated as follows. The evaluation results are shown in Table 5.

The following were prepared as the phosphoric acid group-containing ethylenically unsaturated compound (D).
<Phosphate group-containing ethylenically unsaturated compound (D-1)>
2-Methacryloyloxyethyl acid phosphate (manufactured by Kyoeisha Chemical Co., Ltd .: trade name “Light Ester P-1M”)

<Phosphate group-containing ethylenically unsaturated compound (D-2)>
Bis (2-methacryloyloxyethyl) acid phosphate (manufactured by Kyoeisha Chemical Co., Ltd .: trade name “Light Ester P-2M”)

<Phosphoric group-containing ethylenically unsaturated compound (D-3)>
Triacryloyloxyethyl phosphate (manufactured by Osaka Organic Chemical Industry Co., Ltd .: trade name “Biscoat # 3PA”)

<Restorability>
The active energy ray-curable resin composition obtained above was applied to a black polycarbonate substrate (manufactured by Nippon Test Panel Co., 2 × 70 × 150 mm) so that the cured coating film had a thickness of 40 μm with an applicator, After drying at 90 ° C. for 5 minutes, two passes of UV irradiation (accumulated dose of 800 mJ / cm ² ) are performed at a conveyor speed of 3.4 m / min from a height of 18 cm using a high pressure mercury lamp 80 W and one lamp. A cured coating film was obtained.
Using the cured coating film obtained above, under a condition of 23 ° C. and 50% Rh, using a brass two-digit brush, scratches the coating film 5 times, and the scratch cannot be visually confirmed. Was measured and evaluated according to the following evaluation criteria. The results are shown in Table 5 below.

<Metal substrate adhesion>
The active energy ray-curable resin composition obtained in the above Examples was prepared using an aluminum base (manufactured by Nippon Test Panel; “A1050P”; 1.0 × 70 × 150 mm), dried at 90 ° C. for 5 minutes, and then irradiated with 2 passes of UV light at a conveyor speed of 3.4 m / min from a height of 18 cm using a high pressure mercury lamp 80 W and 1 lamp (integrated) Irradiation amount was 800 mJ / cm ² ) to obtain a cured coating film.
About the obtained cured coating film, metal base-material adhesiveness was evaluated by the following evaluation criteria by the cross-cut tape method according to JISK5400 (1990 edition).

(Evaluation criteria)
○: 50% or more of the coating film remains on the substrate even after the tape test (50/100 or more)
X: Less than 50% of the coating film remains on the substrate after the tape test (less than 50/100)

From the above evaluation results, it is obtained from the active energy ray-curable resin compositions of Examples 21 to 26 in which the urethane (meth) acrylate compound (A) and the phosphoric acid group-containing ethylenically unsaturated compound (D) are used in combination. It can be seen that the cured coating film is excellent in resilience, metal substrate adhesion, and transparency. Moreover, in metal base-material adhesiveness, it is a thing superior to the cured coating film obtained from the active energy ray curable resin composition of the reference example 4 which does not contain a phosphoric acid group containing ethylenically unsaturated compound (D).

[4-2] Combined system of urethane (meth) acrylate compound (A) + other urethane (meth) acrylate compound (B) + phosphoric acid group-containing ethylenically unsaturated compound (D).
<Examples 27 to 32>
The urethane (meth) acrylate compound (A-2), the urethane (meth) acrylate compound (B-1), and the phosphoric acid group-containing ethylenically unsaturated compound (D-1 to D-3). ) With a composition shown in Table 6, 4 parts of a photopolymerization initiator ("Irgacure 184", manufactured by BASF), and methyl isobutyl ketone are blended so as to have a solid content concentration of 40%. An energy ray curable resin composition was obtained.
About the obtained active energy ray-curable resin composition, the restorability, blocking resistance, metal substrate adhesion, and surface hardness were evaluated as follows. The evaluation results are shown in Table 6.

<Reference Example 5>
Example except that the urethane (meth) acrylate compound (A-2) is 100 parts and the urethane (meth) acrylate compound (B) and the phosphoric acid group-containing ethylenically unsaturated compound (D) are not blended. Evaluation was performed in the same manner as in No. 27. The evaluation results are shown in Table 6.

<Metal substrate adhesion>
The active energy ray-curable resin composition obtained in the above Examples was prepared using an aluminum base (manufactured by Nippon Test Panel; “A1050P”; 1.0 × 70 × 150 mm), dried at 90 ° C. for 5 minutes, and then irradiated with 2 passes of UV light at a conveyor speed of 3.4 m / min from a height of 18 cm using a high pressure mercury lamp 80 W and 1 lamp (integrated) Irradiation amount was 800 mJ / cm ² ) to obtain a cured coating film.
About the obtained cured coating film, metal base-material adhesiveness was evaluated by the cross-cut tape method according to JISK5400 (1990 edition).

From the above evaluation results, the cured coating films obtained from the active energy ray-curable resin compositions of Examples 27 to 32 are excellent in resilience and blocking resistance, and are also excellent in metal substrate adhesion and surface hardness. I understand. Moreover, in metal base-material adhesiveness and surface hardness, the active energy ray sclerosis | hardenability of the reference example 5 which does not contain another urethane (meth) acrylate type compound (B) and a phosphate group containing ethylenically unsaturated compound (D). It is superior to the cured coating film obtained from the resin composition.

[4-3] Combined system of urethane (meth) acrylate compound (A) + polysiloxane structure-containing compound (C) + phosphate group-containing ethylenically unsaturated compound (D).
<Example 33, Reference Example 6>
The urethane (meth) acrylate compound (A-2), the polysiloxane structure-containing compound (C-2) and the phosphoric acid group-containing ethylenically unsaturated compound (D-2) have the composition shown in Table 7. , 4 parts of a photopolymerization initiator (Irgacure 184, “manufactured by BSF Corporation”) and methyl isobutyl ketone were blended to a solid content concentration of 40% to obtain an active energy ray-curable resin composition It was.
About the obtained active energy ray-curable resin composition, resilience, blocking resistance, and transparency (haze) were evaluated as described above, and further, metal substrate adhesion was evaluated as described above. The evaluation results are shown in Table 7.

From the above evaluation results, the active energy ray curing of Example 33 using the urethane (meth) acrylate compound (A), the polysiloxane structure-containing compound (C), and the phosphoric acid group-containing ethylenically unsaturated compound (D) in combination. It can be seen that the cured coating film obtained from the conductive resin composition is excellent in resilience, blocking resistance, and transparency, and is also excellent in metal substrate adhesion. Moreover, in blocking resistance and metal base-material adhesiveness, the active energy ray curable resin composition of the reference example 6 which does not contain a polysiloxane structure containing compound (C) and a phosphoric acid group containing ethylenically unsaturated compound (D). It is superior to the cured coating film obtained from 1.

[4-4] Urethane (meth) acrylate compound (A) + other urethane (meth) acrylate compound (B) + polysiloxane structure-containing compound (C) + phosphate group-containing ethylenically unsaturated compound (D) Combination system.
<Example 34>
The urethane (meth) acrylate compound (A-2), the urethane (meth) acrylate compound (B-1), the polysiloxane structure-containing compound (C-1), and the phosphate group-containing ethylene The unsaturated compound (D-2) has the composition shown in Table 8, 4 parts of a photopolymerization initiator (Irgacure 184, “manufactured by BASF”), and methyl isobutyl ketone at a solid content concentration of 40%. The active energy ray-curable resin composition was obtained.
About the obtained active energy ray-curable resin composition, the restorability, blocking resistance, transparency (haze), metal substrate adhesion, and surface hardness were evaluated as described above. The evaluation results are shown in Table 8.

From the above evaluation results, it can be seen that the cured coating film obtained from the active energy ray-curable resin composition of Example 34 is excellent in resilience, blocking resistance, transparency, and metal substrate adhesion and surface hardness. .

In the above embodiments, specific forms in the present invention have been described. However, the above embodiments are merely examples and are not construed as limiting. Various modifications apparent to those skilled in the art are contemplated to be within the scope of this invention.

The urethane (meth) acrylate compound of the present invention has an excellent balance of resilience and blocking resistance to scratches by making a cured coating film after making an active energy ray-curable resin composition, so that paint, ink, Useful for coating agents. In particular, it is useful as an outermost surface coating agent, a metal surface coating agent, and an ink jet ink.

Claims

a urethane (meth) acrylate compound (A) obtained by reacting a hydroxyl group-containing (meth) acrylate compound (x) containing a structural site derived from ε-caprolactone and a polyvalent isocyanate compound (y),
The urethane (meth) acrylate compound, wherein the polyisocyanate compound (y) has an average number of isocyanate groups of 3.2 or more.
The urethane (meth) acrylate compound according to claim 1, wherein the hydroxyl group-containing (meth) acrylate compound (x) is a hydroxyl group-containing (meth) acrylate compound containing one ethylenically unsaturated group. .
The urethane (meth) acrylate compound according to claim 1 or 2, wherein the polyvalent isocyanate compound (y) is an acyclic aliphatic diisocyanate.
The urethane (meth) acrylate compound according to any one of claims 1 to 3, wherein the polyvalent isocyanate compound (y) has a number average molecular weight of 500 to 5,000.
The urethane (meth) acrylate compound according to any one of claims 1 to 4, wherein the urethane (meth) acrylate compound (A) has an ethylenically unsaturated group content of 0.1 to 10 mmol / g. .
The urethane (meth) acrylate compound according to any one of claims 1 to 5, wherein the urethane (meth) acrylate compound (A) has a weight average molecular weight of 1,000 to 50,000.
An active energy ray-curable resin composition comprising the urethane (meth) acrylate compound (A) according to any one of claims 1 to 6.
The active energy ray-curable resin composition according to claim 7, comprising a urethane (meth) acrylate compound (B) (excluding the urethane (meth) acrylate compound (A)). .
Urethane (meth) acrylate compound (B) is a urethane (meth) acrylate compound obtained by reacting a hydroxyl group-containing (meth) acrylate compound (b1), a polyvalent isocyanate compound (b2), and a polyol compound (b3). The urethane (meth) acrylate compound (B2) obtained by reacting the compound (B1) and / or the hydroxyl group-containing (meth) acrylate compound (b1) and the polyvalent isocyanate compound (b2). Item 9. The active energy ray-curable resin composition according to Item 8.
The content of the urethane (meth) acrylate compound (B) is 100 parts by weight or less with respect to 100 parts by weight of the urethane (meth) acrylate compound (A). An active energy ray-curable resin composition.
The active energy ray-curable resin composition according to any one of claims 7 to 10, comprising a polysiloxane structure-containing compound (C).
The active energy ray-curable resin composition according to claim 11, wherein the polysiloxane structure-containing compound (C) is a polysiloxane structure-containing urethane (meth) acrylate compound (C1).
The content of the polysiloxane structure-containing compound (C) is 0.01 to 100 parts by weight with respect to 100 parts by weight of the urethane (meth) acrylate compound (A). Active energy ray-curable resin composition.
The active energy ray-curable resin composition according to any one of claims 7 to 13, comprising a phosphoric acid group-containing ethylenically unsaturated compound (D).
The content of the phosphoric acid group-containing ethylenically unsaturated compound (D) is 0.01 to 10 parts by weight with respect to 100 parts by weight of the urethane (meth) acrylate compound (A). 14. The active energy ray-curable resin composition according to 14.
A coating agent comprising the active energy ray-curable resin composition according to any one of claims 7 to 15.
The coating agent according to claim 16, wherein the coating agent is used as an outermost surface coating agent.
The coating agent according to claim 16, wherein the coating agent is used as a coating agent for a metal surface.