JPH10310620A - Composition curable by actinic radiation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition excellent in curability, tight adhesion and chemical resistance, having high coefficient of dynamic friction and having both non-slip characteristics and blocking resistance, by using as the constituents aluminum atoms bound through a primary bond, a chelate bond or a hydrogen bond, and unsaturated groups curable by actinic radiation. SOLUTION: This composition comprises, e.g. a resin which has a number- average molecular weight of 500 to 15,000 and whose skeleton contains unsaturated groups curable by actinic radiation, in an amount of 0.2-6 mol/kg in terms of solids concentration and Al atoms bound through a primary bond, a chelate bond or a hydrogen bond, in an amount of 0.1-10% solids by weight. This composition is obtained by esterifying a part of the polyol of, e.g. a polyester resin skeleton, a polyether resin skeleton or a polyurethane resin skeleton, or the epoxy groups of an epoxy resin skeleton with (meth)acrylic acid, and reacting the remaining hydroxyl groups with, e.g. trialkoxyaluminum.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to paints for wooden building materials, coating agents for decorative paper for building materials, coating agents for decorative plastic sheets for building materials, glossy varnishes for paper, metal plates such as aluminum, iron, tinplate and galvanized sheet, metal materials. The present invention relates to a composition useful as a coating material for coatings, packaging materials, a coating agent for cardboard, etc., and an ink such as gravure ink and flexo ink.

[0002]

2. Description of the Related Art Paints for wood-based building materials, coating materials for decorative paper for building materials, glossy varnishes for paper, metal plates such as aluminum, iron, tinplate, galvanized sheet, paints for metal materials, cardboard, various plastic films, etc. Active energy ray curing with a short curing time is applied as a curing method in the fields of paints, coatings, coatings used as inks, coating agents and inks. However, in practical use, after passing through processes such as painting and printing, active energy rays are irradiated and cured, and immediately after processing or packing, the UV lamp may be heated during the ultraviolet irradiation process. Therefore, it is difficult to satisfy various characteristics. In other words, if flexibility is emphasized in order to obtain the appropriateness of the bending process and the non-slip property of the coating film, blocking between the coating films or between the object to be coated and the coating film in the next step, and damage to the coating film surface during processing. Inconveniences such as sticking and abrasion occur.

[0003] As a specific application of a non-slip coating material, in particular, a coating material which is hard to slip even when walking with a sock on a surface of a floor or a stair member is used to prevent an infant or an elderly person from falling over at home. Paints have been considered.

[0004] Non-slip paints are used for flooring and stairs, but a paint made of an active energy ray-curable composition applied to the surface of wood or a decorative sheet has a high coefficient of friction when cured with active energy rays. , Socks, stockings and slippers should not slip when walking. However, in the application of the non-slip paint and the subsequent steps, the packaging operation is started immediately after the coating and curing, and several floor materials having the painted surfaces are bundled and packed. At this time, the higher the coefficient of kinetic friction and the higher the non-slip property, the softer the coating film and the easier the blocking. Therefore, a coating material having a high dynamic friction coefficient is actually difficult to be put into practical use.

[0005] In this non-slip coating, an ultraviolet-curable coating composition containing an ultraviolet-curable polyester or polyurethane having rubber elasticity in order to achieve both the flexibility and the blocking property of a coating film for imparting a non-slip property (Japanese Patent Laid-Open Publication No. Hei 8 (1994)).
-188742, JP-A-8-188743). However, the non-slip property is also effective when the kinetic friction coefficient is 0.4 or more. However, even when the kinetic friction coefficient is 0.4 or more, it does not sufficiently prevent blocking, but also the flexibility of the coating film. It is difficult to say that the blocking property is compatible. The same applies to other fields such as coating agents and protective coating agents that have a slipless function to prevent collapse of plastics, metal products, paper, and cardboard when piled up. It is not compatible with other fields.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to trade off the flexibility of a coating film for imparting a non-slip property and the good blocking property in paints, coatings and inks comprising an active energy ray-curable vehicle. An object of the present invention is to obtain an active energy ray-curable composition for obtaining a coated or printed material having the following characteristics.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that by introducing an aluminum compound into a vehicle having a high dynamic friction coefficient, the blocking property of the coating film is significantly improved. discovered. Also,
Similarly, it was found that even when a paper container and a cardboard were coated with the ink and the coating made of the composition of the present invention, they could be prevented from slipping and falling during stacking and blocking each other's surfaces.

That is, the present invention provides an aluminum atom bonded through a primary bond, a chelate bond or a hydrogen bond,
The present invention relates to an active energy ray-curable composition containing an active energy ray-curable unsaturated group. or,
In the present invention, the above-mentioned aluminum atom bonded through a primary bond, a chelate bond or a hydrogen bond, and the above-mentioned active energy ray-curable unsaturated group have a number average molecular weight of 5
The present invention relates to an active energy ray-curable composition present in a molecule of a resin skeleton of 00 to 15,000.

Further, the present invention relates to the present invention, wherein the above-mentioned aluminum atom bonded via a primary bond, a chelate bond or a hydrogen bond, and the above-mentioned active energy ray-curable unsaturated group are the same molecule having a number average molecular weight of 300 to 5,000. Active-energy radiation curable composition present therein.

Further, according to the present invention, the weight ratio of the aluminum atom bonded through a primary bond, a chelate bond or a hydrogen bond in the composition is from 0.1 to 10% by weight of solid content, and The present invention relates to an active energy ray-curable composition having an energy ray-curable unsaturated group having a solid content of 0.5 to 6 mol / kg.

The present invention also provides the above active energy ray-curable composition, wherein the resin skeleton is a polyester resin skeleton, a polyether resin skeleton, a polyether polyester resin skeleton, a polycarbonate resin skeleton, a polybutadiene resin skeleton, a polyolefin resin. The present invention relates to an active energy ray-curable composition which is at least one resin skeleton selected from a skeleton, an epoxy resin skeleton, and a polyurethane resin skeleton.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The active energy ray-curable composition of the present invention is carried out in the following modes. That is, (I) the resin skeleton having a number average molecular weight of 500 to 15,000 has an active energy ray-curable unsaturated group in a solid content concentration of 0.2 to 6 mol / kg, preferably 1.0 to 3 mol / kg, A composition containing an active energy ray-curable resin composition containing 0.1 to 10 solids by weight of an aluminum atom to a resin skeleton through a primary bond or a chelate bond or a hydrogen bond, or
(II) An active energy ray-curable unsaturated group having a solid content concentration of 0.5 to 6 mol / kg, preferably 1.0 to 3 mol / kg in a molecule, and a primary bond, a chelate bond, or Aluminum atoms bonded through hydrogen bonds 0.1 to
Number average molecular weight of 300 to 10% by solid content
A composition containing 5000 active energy ray-curable compounds, and (III) a number average molecular weight of 500 to 1
An active energy ray-curable unsaturated group is contained in a resin skeleton of 5000 at a solid content concentration of 0.2 to 6 mol / kg, preferably 1.0 to 1.0 mol / kg.
Composition containing an active energy ray-curable resin composition having 3 mol / kg and a compound having 0.1 to 10% by weight of solid content of aluminum atoms bonded through primary bond, chelate bond or hydrogen bond. It is implemented in the form of a thing.

The active energy ray-curable resin composition having a resin skeleton according to the present invention includes a polyester resin skeleton, a polyether resin skeleton, a polyether polyester resin skeleton, a polycarbonate resin skeleton, a polybutadiene resin skeleton, a polyolefin resin skeleton or a polyurethane resin. At least one selected from a skeleton or an epoxy resin skeleton
It is obtained from a seed resin skeleton.

The above-mentioned active energy ray-curable composition has an active energy ray-curable unsaturated group in a molecule of a resin skeleton having an average molecular weight of 500 to 15,000, and a primary bond or a chelate bond or a hydrogen bond in the same resin skeleton. Representative methods for obtaining an active energy ray-curable composition (I) having an aluminum atom bonded via a polyester resin skeleton, a polyether resin skeleton, a polyether polyester resin skeleton, a polycarbonate resin skeleton A part of a polyol such as a polybutadiene resin skeleton, a polyolefin resin skeleton, and a polyurethane resin skeleton, or an epoxy group of an epoxy resin skeleton is esterified with acrylic acid or methacrylic acid, and the remaining hydroxyl groups are trialkoxy aluminum and dialkoxy aluminum chelate compounds. ,
Any one or more aluminum compounds (A-3) of the aluminum trichelate compound have an aluminum atom concentration of 0.1 to 10% by weight, and an active energy ray-curable unsaturated group has a solid content of 0.2 to 6%. Mol / kg preferably 1.
It is obtained by reacting so as to be 0 to 3.0 mol / kg.

For example, in the case of a polyester resin skeleton, first, the hydroxyl group of the polyester polyol resin skeleton synthesized using the polyol (B-1) and the polybasic acid (A-1) as raw materials is esterified with acrylic acid or methacrylic acid. To obtain an active energy ray-curable polyester resin skeleton. The remaining hydroxyl group or carboxyl group of the polyester skeleton is substituted with at least one of aluminum compounds (A-3) of trialkoxyaluminum, dialkoxyaluminum chelate compound and aluminum trichelate compound at an aluminum atom concentration of 0.1 to 0.1%. 10
% By weight of the active energy ray-curable unsaturated group
It is obtained by reacting at 6 mol / kg, preferably 1.0-3 mol / kg.

Alternatively, the above-mentioned polyol having a resin skeleton is subjected to a dealcoholation reaction with a dialkoxyaluminum chelate compound in an equimolar amount or more to form a terminal alkoxyaluminum chelate compound, and a compound having an active energy ray-curable unsaturated double bond and a hydroxyl group (B -2) and the concentration of aluminum atoms is reduced to 0.1 to
The active energy ray-curable unsaturated group is contained in 10% by weight.
It is obtained by reacting to 2 to 6 mol / kg, preferably 1.0 to 3 mol / kg.

Alternatively, the unsaturated polybasic acid (A-1), which is a raw material of the polyester skeleton, may be partially or entirely replaced with an unsaturated dibasic acid such as maleic acid, fumaric acid or maleic anhydride. The hydroxyl group or carboxyl group of the active energy ray-curable resin composition having a polyester skeleton has an aluminum compound (A-3) having an aluminum atom concentration of 0.1 to 10% by weight and an active energy ray-curable unsaturated group having a concentration of 0.1 to 10% by weight. 2-6 mol / kg, preferably 1.0-3
It is obtained by reacting so as to be mol / kg.

As a typical method for obtaining the resin composition (I) having an active energy ray-curable polyurethane skeleton, a polyisocyanate compound (A-2) having two or more functional groups and a polyol (B- 1) and a polyol having a resin skeleton; a compound (B-2) having an active energy ray-curable unsaturated double bond and a hydroxyl group; and a carboxyl group of a compound obtained by reacting a dihydroxyalkanoic acid (A-4). Any one or more aluminum compounds of trialkoxyaluminum, dialkoxyaluminum chelate compound, and aluminum trichelate compound (A-
3) When the concentration of aluminum atoms is 0.1 to 10% by weight
And an active energy ray-curable unsaturated group is reacted at 0.2 to 6 mol / kg, preferably 1.0 to 3 mol / kg.

The above dihydroxyalkanoic acid (A-4)
Is, for example, 2,2-dihydroxypropionic acid, 2,2
-Dihydroxybutanoic acid and 2,2-dihydroxypropionic acid, and carboxyl group-containing polycaprolactone diol obtained by reacting 2,2-dihydroxybutanoic acid with ε-caprolactone.

Another typical method for obtaining the active energy ray-curable polyurethane skeleton resin composition (I) is as follows.
One of the hydroxyl groups of the polyurethane compound obtained by reacting the polyisocyanate compound (A-2) having a higher functionality or higher with the polyol (B-1) having an average functionality of two or more and the polyol of the resin skeleton so as to have an excess hydroxyl group. And reacting diisocyanate having two isocyanate groups having different reactivities with monohydroxymonoacrylate, monohydroxydi (meth) acrylate, etc., and half-urethane having an unsaturated group obtained by the reaction of monoisocyanate. Aluminum compound (A-
3), when the concentration of aluminum molecules is 0.1 to 10% by weight and the active energy ray-curable unsaturated group is 0.2 to 6 mol / kg, preferably 1.0 to 3 mol / kg.
kg.

Further, as a typical method for obtaining a resin composition (I) having an active energy ray-curable polyurethane skeleton, a bifunctional or higher functional polyol resin is reacted with half-urethane having an unsaturated group so that a hydroxyl group remains. In addition to the hydroxyl group of the active energy ray-curable polyurethane skeleton resin obtained by the above, any one or more of the aluminum compounds (A-3) and the active energy ray-curable unsaturated group are preferably 0.2 to 6 mol / kg. Is obtained by reacting so as to have a concentration of 1.0 to 3 mol / kg and a concentration of aluminum molecules of 0.1 to 10% by weight.

Further, an acetylacetone group is introduced by subjecting a part of the hydroxyl group of the polyol resin to a tertiary butyl acetylacetone or the like by a dealcoholization reaction, and half urethane having an unsaturated group in the remaining hydroxyl group is reacted to activate an active energy ray. A resin having a curable polyurethane skeleton is obtained. Further, the acetylacetone group introduced into this resin and any one or more of trialkoxyaluminum and dialkoxyaluminum chelate compounds are added with an active energy ray-curable unsaturated group in an amount of 0.2 to 6 mol / kg, preferably 1.0 to 1.0 mol / kg. And a method of obtaining a resin having an active energy ray-curable polyurethane skeleton by reacting so that the concentration of aluminum molecules is 0.1 to 10% by weight.

In the resin composition having an active energy ray-curable polyurethane skeleton of the present invention, an unsaturated polyester polyol having a double bond at the α and β positions can be used as a polyester polyol component of the polyester urethane resin skeleton. The double bond at the α and β positions is an unsaturated dibasic acid having a double bond at the α and β positions such as maleic acid, fumaric acid and itaconic acid as a part of the dibasic acid constituting the polyester component. Introduced using

When the polyester polyol having a double bond at the α- and β-positions is used as the component (B-1), a compound having an active energy ray-curable unsaturated double bond of a polyester urethane resin skeleton and a hydroxyl group (B As -2), it is particularly preferable to use a hydroxyvinyl ether such as hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, or cyclohexane dimethanol monovinyl ether from the viewpoint of high alternating copolymerizability. Polyurethane resin obtained by using as an polyol component (B-1) an unsaturated polyester polyol having a double bond at the α and β positions, introduced using an unsaturated dibasic acid having a double bond at the α and β positions. The equivalent ratio of the unsaturated group of the vinyl ether to 1 equivalent of the unsaturated group of the skeleton is preferably from 0.3 to 3, and more preferably from 0.5 to 2
More desirably, it is prepared in the range of

These reactions can be carried out at 20 to 80 ° C. by adding a solvent which does not react with isocyanate, and known polymerization inhibitors and reaction catalysts can be arbitrarily added in appropriate amounts.

The reaction for producing the polyurethane resin skeleton composition can be carried out in an organic solvent, and if necessary, a known urethane catalyst and a polymerization inhibitor can be added.

The active energy ray-curable polyurethane composition having a polyurethane resin skeleton of the present invention is usually produced in a state of being dissolved in an organic solvent, but can be reacted without a solvent.

As the organic solvent, it is preferable to use, for example, acetone, methyl ethyl ketone, ethyl acetate or the like having a low boiling point in consideration of a drying step after coating and printing. Of course, there is no problem in using an organic solvent having a high boiling point as long as the drying property of ink or paint is not impaired.

Examples of the urethane catalyst include tin catalysts such as dibutyltin laurate and stannous octoate;
An amine catalyst such as triethylenediamine is exemplified.

The compound in the composition (II) described as the second embodiment of the embodiment, that is, an active energy ray-curable unsaturated group in a molecule and a primary bond or a chelate bond or a hydrogen bond in the same molecule As a typical method for obtaining an active energy ray-curable compound having a number average molecular weight of 300 to 5000 and having an aluminum molecule bonded through a hydroxyl group, a hydroxyl group reacting with an aluminum compound (A-3) and an active energy ray Compounds having a curable unsaturated group in the same molecule (B-
2) A compound having a functional group such as an acetylacetone group and an active energy ray-curable unsaturated group in the same molecule or a compound having an acetylacetone group and an active energy ray-curable unsaturated group in the same molecule and an aluminum compound Obtained by reaction.

A typical example of the above compound having an acetylacetone group and an active energy ray-curable unsaturated group in the same molecule is acetylacetone ethyl methacrylate.

The reaction of the above-mentioned hydroxyl group, alkyl acetoacetate group or carboxyl group with the aluminum compound (A-3) proceeds by dealcoholation and dealkylacetone when heated and reduced in pressure at 60 to 160 ° C. When the group is present, there is a risk of gelation,
It is desirable to adopt a synthesis method that takes into consideration the prevention of gelation for the molar ratio of the reactants, the reaction temperature, and the like.

As described in the third embodiment,
The composition (III) is combined with an active energy ray-curable resin composition having a resin skeleton having a number average molecular weight of 500 to 15,000 having an active energy ray-curable unsaturated group via a primary bond or a chelate bond or a hydrogen bond. A compound having bound aluminum molecules, the concentration of aluminum atoms is from 0.1 to 10% by weight, the active energy ray-curable unsaturated group is from 0.2 to 6 mol / kg, preferably from 1.0 to 10 mol / kg.
It is mixed and prepared to be 3 mol / kg.

As a typical example of the compound having an aluminum molecule bonded through a primary bond, a chelate bond or a hydrogen bond, the aluminum compound (A-3) described above can be mentioned.

The polyol component (B-1) comprises at least one polyol resin selected from the group consisting of polyester polyols, polyether polyols, polyester polyether polyols, polycarbonate polyols, polybutadiene polyols and polyolefin polyol resins, and other components. (B-1).

As typical examples of other polyols (b-1), first, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 2-methyl-1 , 3-propanediol, dipropylene glycol, 1,3-butylene glycol,
1,4 butylene glycol, neopentyl glycol,
1,6 hexanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol,
Examples thereof include 2-butyl-2ethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, spiro glycols, monoglycidyl ethers, and monoepoxides.

Next, examples of the trivalent or higher polyol component include polyhydric alcohols such as glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol, or compounds having an equivalent effect. Further, a polybutadiene polyol, a polypentadiene polyol, an epoxy resin or the like can be mentioned as an alcohol component or a component having an equivalent effect.

The polyisocyanate compound (A-
Specific examples of 2) include ethylene diisocyanate, 1,6-hexamethylene diisocyanate,
2,4-trimethylhexamethylene diisocyanate,
Aliphatic diisocyanate such as 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, norbornane diisocyanatomethyl, isopropyl Examples include alicyclic diisocyanates such as lidenedicyclohexyl-4,4'-diisocyanate or diisocyanates such as aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, and tolylene diisocyanate. I can do it.

Further, the diisocyanate (A-
Adduct of the polymer of 2) or diisocyanate (A-2) with a polyol such as trimethylolpropane or ethylene glycol, or diisocyanate (A-
The urea modified product, buret modified product, carbodiimide modified product, uretonimine modified product, allohanate modified product, etc. of 2) are applicable.

Specific examples of the above aluminum compound (A-3) include aluminum alcoholate such as aluminum triethylate, aluminum triisopropylate, aluminum trisecondary butyrate monosecondary butoxyaluminum diisopropylate, and ethyl acetoacetate. Aluminum diisopropylate,
Dialkoxyaluminum monochelate compounds such as alkyl acetoacetate aluminum diisopropylate Trialuminum chelates such as aluminum tris (acetylacetate), aluminum tris (ethylacetoacetate), aluminum monoacetylacetatebis (ethylacetoacetate) and the above aluminum compounds (A-3) such as a dimerized compound in which two molecules react with each other and the alkoxy or chelate compound in each molecule deviates one molecule at a time, or a trimerized aluminum compound such as cyclic aluminum oxide triisopropylate. Can be mentioned.

The above-mentioned polyester polyol can be obtained by various known methods, and typical methods are shown below. One method for obtaining a polyester polyol is by subjecting a polyhydric alcohol or a compound having an equivalent effect to a polyhydric alcohol to a dehydration or dealcoholation reaction or an addition reaction. Alternatively, the above-mentioned polyols, polyhydroxy compounds or amines are used as starting materials, and a lactone monomer such as ε-caprolactone or β-methyl-δ-valerolactone is subjected to addition polymerization to obtain a polyether as one type of polyester polyol. A lactone polyester polyol is obtained.

As representatives of the above polybasic acids, succinic acid,
4 to 2 carbon atoms such as succinic anhydride, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid
Compounds having the same effect as dicarboxylic acids, such as aliphatic dicarboxylic acids and dimethyl esters thereof, and fatty acids such as hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, hexahydrophthalic acid, and tetrahydrophthalic acid. Aromatic dicarboxylic acids, such as aromatic dicarboxylic acids, orthophthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, and dimethyl terephthalate, or compounds having the same effect, trimellitic acid, pyromellitic anhydride, methyl maleate Cyclohexene tetrabasic acid anhydride (for example, manufactured by Dainippon Ink and Chemicals, Inc., trade name: Epicron B4400), and the like.

Examples of the polyhydric alcohol used as a raw material of the polyester polyol include, among the polyols (b-1) mentioned above as representatives of other polyols, diols, compounds having the same effect as diols, polyhydric alcohols Or a compound having an effect equivalent thereto.

Such a polyester polyol may be added with a titanate such as tetraisopropyl titanate or tetrabutyl titanate or a tin catalyst such as dibutyltin oxide as an esterification catalyst, if necessary, or to promote dehydration. To a solvent such as xylene, Solvesso 100, or Solvesso 150, and further, a known method such as adding an additive such as triphenyl phosphite or trinonyl phenyl phosphite to prevent oxidative coloring. Obtained by alcohol condensation. The average molecular weight of the polyol and the number of functional groups of the hydroxyl group can be determined by blending the hydroxyl equivalent of the alcohol component with an equivalent ratio of at least 1 equivalent to the carboxyl equivalent of the acid component. However, when an acid or alcohol component having three or more functionalities or a component having an effect equivalent thereto is used, it is desirable to adopt a synthesis method that takes into consideration the prevention of gelation during synthesis.

Examples of the polyether polyol include the polyols mentioned above, and 4,4-dihydroxydiphenyl-2,2-propane (bisphenol A),
Examples thereof include polyhydroxy compounds such as dihydroxydiphenyl-2,2-methane, and polyether polyols obtained by addition-polymerizing ethylene oxide, propylene oxide, tetrahydrofuran, or the like using amines or the like as a starting material.

As the polyol having a polyester polyether skeleton, ethylene oxide, propylene oxide,
It is obtained by addition polymerization of tetrahydrofuran or the like. Alternatively, the polyether polyol may be obtained by addition polymerization of a lactone monomer such as ε-caprolactone or β-methyl-δ-valerolactone using the above polyether polyol as a starting material.

A typical example of the polyol having a polycarbonate resin skeleton is a polycarbonate diol manufactured by Daicel Chemical.

Examples of the polyol having a polybutadiene resin skeleton include a polybutadiene polyol manufactured by Nippon Soda and a polyol manufactured by Idemitsu Kosan.

As a polyol having a polyolefin resin skeleton, a polyol manufactured by Nippon Soda obtained by hydrogenating a polybutadiene polyol can be exemplified.

The epoxy resin is bisphenol A,
Bisphenol epoxy resins synthesized from bisphenol F, bisphenol AD, etc. and epichlorohydrin, novolak epoxy resins synthesized from phenol novolak, cresol novolak, etc. and epichlorohydrin, dibasic acids such as phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid Glycidyl ester-based epoxy resins synthesized from phenol and epichlorohydrin, glycidyl ether-based epoxy resins synthesized from polyol and epichlorohydrin, and alicyclic epoxy resins.

Representative examples of the compound (B-2) having an active energy ray-curable unsaturated double bond and a hydroxyl group include 2-hydroxyethyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate.
Monohydroxy mono (meth) acrylate such as hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, or glycerin di (meth) acrylate, Biscoat 214HP (manufactured by Osaka Organic Co., Ltd.)
Monohydroxytriacrylate such as monohydroxydi (meth) acrylate and pentaerythritol triacrylate, dihydroxymono (meth) acrylate such as glycerin mono (meth) acrylate, and addition polymerization of ethylene oxide, propylene oxide and tetrahydrofuran to these. Or a compound obtained by addition polymerization of ε-caprolactone or the like. Furthermore,
A product obtained by reacting half-urethane obtained by reacting a diisocyanate having two isocyanate groups having different reactivities with monohydroxy monoacrylate, monohydroxy di (meth) acrylate, and dialkanolamine is also referred to as (B) -2) can be cited as a typical example.

Representative examples of the diisocyanates having two isocyanate groups having different reactivities include isophorone diisocyanate and tolylene diisocyanate.

Representative of the above dialkanolamines are diethanolamine, diisopropanolamine,
Examples thereof include dipropanolamine and dibutanolamine.

It is preferable to use a polymerization inhibitor in the reaction of introducing an acryloyl group or a methacryloyl group of the present invention, or in other reactions after the introduction of an acryloyl group or a methacryloyl group. Representative examples of such a polymerization inhibitor include tertiary butyl hydroquinone, methoquinone, and the like.

The active energy ray-curable composition of the present invention may be diluted with an organic solvent such as alcohol, and may be diluted with pigments, dyes, surfactants, matting agents, thickeners, heat stabilizers, leveling. Agent, defoamer, filler, anti-settling agent, antioxidant, plasticizer, well-known acryloyl group or methacryloyl group, vinyl active energy ray-curable crosslinking agent having at least one vinyl group in the molecule Composition of various resins such as wax, polymerization initiator for active energy ray curing, thermal decomposition radical initiator, known polyester resin, polyamide resin, shellac or modified shellac, rosin derivative, polyurethane resin, acrylic copolymer, etc. May be added.

Examples of the colorant include pigments and dyes each alone or in combination, such as soluble or insoluble organic pigments such as azo, phthalocyanine, and naphthol, titanium oxide, red iron oxide, carbon black, calcium carbonate, and the like. Inorganic pigments such as barium sulfate, organic dyes of metal complex salts and the like, alone or in combination.

The paint or printing ink may be prepared by any method, and for example, can be prepared according to the following formula. That is, the colorant is usually a mixture of the active energy ray-curable composition of the present invention or another active energy ray-curable composition, or another resin composition alone, and if necessary, a dispersing aid or Ball mill,
The mixture is dispersed in a conventional meat mill such as a sand mill or other media mill and used as a colorant base. The colorant base is mixed with other resin components including the remaining active energy ray-curable composition and, if necessary, a solvent, an antifoaming agent, and other additives, and is mixed with a desired paint or printing ink for active energy rays. It is finally prepared as a curable composition.

The active energy ray-curable composition of the present invention can be cured by a known method. For example, in the case of curing with an electron beam, after coating on the adherend and evaporating and drying water and a small amount of an organic solvent when included,
Acceleration voltage 20 to 2000 KeV, preferably 150 to 3
Using a 00 KeV electron beam irradiation device, a cured product is obtained by irradiation in an inert gas atmosphere containing or not containing a small amount of oxygen so that the total irradiation dose becomes 5 to 200 KGy, preferably 20 to 150 KGy. I can do it.

Further, in the present invention, other curing means, for example, a method of curing in air or an inert gas atmosphere by ultraviolet rays obtained from a mercury lamp, a xenon lamp, or the like, or energy related to heat such as infrared rays, high frequency waves or microwaves , Ie, a method of curing by heating. When using high-energy ionizing radiation having an action of emitting secondary electrons by being absorbed by a substance such as the above-mentioned electron beam, X-ray, and gamma ray, it is not particularly necessary to add a polymerization initiator. When heat curing or ultraviolet curing is used, it is preferable to add a photopolymerization initiator or a thermal polymerization initiator. In addition, one kind selected from the above-described curing method using ionizing radiation, a curing method using ultraviolet light, and a method using heat curing can be used alone, or two or more methods can be used simultaneously or before and after each other.

Examples of these polymerization initiators by heat or light include 2,2′-azobisisobutyronitrile,
2,2′-azobis (2-methylbutyronitrile),
Azo initiators such as 2,2'-azobis (2,4-dimethylvaleronitrile) and 1,1'azobis (cyclohexane-1-carbonitrile), ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide , Hydroperoxides such as cumene hydroperoxide and tert-butyl peroxide, dialkyl peroxides such as di-tert-butyl peroxide and dicumyl peroxide, tert-butylperoxylaurate, t
Peroxide esters such as peroxyesters such as tert-butylperoxybenzoate can be exemplified.

Further, examples of photopolymerization initiators include intermolecular hydrogen abstraction initiators such as benzyl, benzophenone, Michler's ketone, dibenzosuberone, 2-ethylanthraquinone, isobutylthioxanthone, benzoin ethyl ether, diethoxyacetophenone, and the like. Benzyl methyl ketal, 1-hydroxycyclohexyl phenyl ketone 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one,
Acylphosphine oxide, 2-methyl-1- [4
A known and commonly used organic phase radical polymerization initiator such as an initiator of an intramolecular bond cleavage type such as-(methylthio) phenyl] -2-morpholinopropane-1 can be used.

The amount of the polymerization initiator used may be appropriately selected from the range of 0.2 to 20% per solid content excluding the colorant, but is particularly preferably in the range of 0.5 to 10%.

The active energy ray-curable composition of the present invention can be applied to objects to be coated and to-be-printed including wood, metal, glass, cloth, leather, paper, and plastic, and can be applied by brush coating, spray coating, flow coating. Various coating methods and printing methods such as dip coating, vacuum coating, roll coating, gravure printing, and flexographic printing are applicable.

[0064]

Next, the present invention will be described more specifically with reference examples and examples. In the following, all parts and percentages are by weight unless otherwise specified. In the following text, viscosity represents Gardner viscosity.

[Preparation Example 1] Pespol 2 was placed in a reactor equipped with a stirrer equipped with a reflux condenser, an air inlet, and a thermometer.
00 (molecular weight: 1368, polyester diol manufactured by Toagosei Co., Ltd.): 396 parts, Kuraray polyol P-530
(Polyester diol manufactured by Kuraray Co., Ltd.) 147 parts, P
-75S (Ethyl acetoacetate aluminum diisopropylate manufactured by Kawaken Fine Chemical Co., Ltd.) 319
And 86 parts of ethyl acetate, and the temperature was raised to 55 ° C. in 0.5 hour with stirring, the air introduction was stopped, and the reaction was carried out at 55 to 60 ° C. under reduced pressure of 20 to 30 mmHg. After the reaction for 2 hours, the pressure was stopped and light ester G-201P (glycerin acrylate methacrylate manufactured by Kyoeisha Chemical Co., Ltd.) 13
8 parts and 0.5 part of methquinone were added, and pressure reduction was started again.
The mixture was reacted at 60 to 65 ° C. for 3 hours to obtain a viscous liquid (J-1) having a polyester resin skeleton having a Gardner viscosity of Z1.

[Preparation Example 2] PolyTH was added to a reactor equipped with a stirrer equipped with a reflux condenser, an air inlet, and a thermometer.
F1000 (molecular weight: 1014, polytetramethylene ether diol manufactured by BASF) 455 parts, P-75S (ethyl acetoacetate aluminum diisopropylate manufactured by Kawaken Fine Chemical Co., Ltd.) 331 parts, ethyl acetate 15
0 parts, and while stirring, the temperature was raised to 55 ° C. in 0.5 hours, the air introduction was stopped, and the temperature was increased to 55 to 60 ° C. and 20 to 30 mmH.
g. After the reaction for 2 hours, the pressure reduction was stopped, 214 parts of light ester G-201P (glycerin acrylate methacrylate manufactured by Kyoeisha Chemical Co., Ltd.) and 0.5 part of methoquinone were added, and the pressure reduction was started again.
The mixture was allowed to react for a period of time to obtain a viscous liquid (J-2) having a polyether resin skeleton and a Gardner viscosity of -Z.

[Preparation Example 3] 397 parts of Kuraray polyol P-1010 (a polyester diol manufactured by Kuraray Co., Ltd.) and butylethylpropanediol 20 were placed in a reactor equipped with a stirrer equipped with a reflux condenser, a nitrogen inlet, and a thermometer. .9
Parts, dimethylolpropionic acid 13.4 parts, TDI80
/ 20 (tolylene diisocyanate manufactured by Mitsui Toatsu Chemicals, Inc.) and 150 parts of ethyl acetate were added, and the temperature was raised to 70 ° C. in 0.5 hour while stirring, and reacted at 70 to 75 ° C. for 3 hours. The introduction pipe was switched to an air introduction pipe, and 155 parts of Biscoat # 214HP (glycerin acrylate methacrylate manufactured by Osaka Organic Co., Ltd.) and methquinone 0.4 were used.
Parts, 3.8 parts of trinonylphenyl phosphite, 0.23 parts of stannous octoate, and 39 parts of methyl ethyl ketone, and reacted again at 70 to 75 ° C. for 6 hours to obtain a solution of the poly (ester) urethane resin skeleton. Obtained. After cooling to 60 ° C., 27.3 parts of ALCH (ethylacetoaluminum diisopropylate manufactured by Kawaken Fine Chemical Co., Ltd.) and 27.3 parts of isopropyl alcohol are preliminarily mixed and gradually added to this solution. The mixture was kept for 30 minutes to obtain a viscous liquid (J-3) having a Gardner viscosity of -Z.

Preparation Example 4 754 parts of FA-4 (molecular weight: 572, lactone polyester acrylate manufactured by Daicel Chemical Co., Ltd.) and P-75S were placed in a reactor equipped with a reflux condenser, an air inlet, and a thermometer and equipped with a stirrer. (Ethyl acetoacetate aluminum diisopropylate manufactured by Kawaken Fine Chemical Co., Ltd.) 246 parts, 150 parts of ethyl acetate and 0.5 part of methquinone were added, and the temperature was raised to 60 ° C. in 0.5 hour with stirring, and air was introduced. And the pressure was reduced at 20 to 30 mmHg at 55 to 60 ° C. for 3 hours to give a solution of a polyester resin skeleton, a viscous liquid having a Gardner viscosity of + Y (J-
4) was obtained.

[Preparation Example 5] 384 parts of hydroxybutyl vinyl ether (manufactured by BASF) was placed in a reactor equipped with a stirrer equipped with a reflux condenser, an air inlet, and a thermometer.
Add 616 parts of -75P (ethyl acetoaluminum diisopropylate 75% isopropanol solution manufactured by Kawaken Fine Chemicals Co., Ltd.) and 0.5 part of methoquinone, stir the mixture, raise the temperature to 60 ° C in 0.5 hours, and introduce air. Was stopped and the pressure was reduced at 20 to 30 mmHg at 55 to 60 ° C. for 3 hours to obtain a viscous liquid (J-5) having a Gardner viscosity of + Y.

[Preparation Example 6] 555 parts of light ester G-201P (glycerin acrylate methacrylate manufactured by Kyoeisha Chemical Co., Ltd.) and S-75P were placed in a reactor equipped with a stirrer equipped with a reflux condenser, an air inlet, and a thermometer. (Kawaken Fine Chemical Co., Ltd. ethylacetoaluminum diisopropylate 75% isopropanol solution) 445
Parts, 0.5 part of methoquinone and 60 ° C. while stirring.
Temperature in 0.5 hours until the air introduction is stopped and 55-60
The pressure was reduced at 20 to 30 mmHg at 3 ° C. for 3 hours to obtain a viscous liquid (J-6) having a Gardner viscosity of Z4-Z5.

[Preparation Example 7] 317 parts of light ester G-201P (glycerin acrylate methacrylate manufactured by Kyoeisha Chemical Co., Ltd.) was placed in a reactor equipped with a stirrer equipped with a reflux condenser, an air inlet, and a thermometer. (Manufactured by Osaka Organic Co., Ltd.) 177 parts, S-75P
(Ethylacetoaluminum diisopropylate 75% isopropanol solution manufactured by Kawaken Fine Chemical Co., Ltd.)
507 parts and 0.5 part of methoquinone were added, and the temperature was raised to 60 ° C. in 0.5 hours while stirring, and the introduction of air was stopped.
The pressure was reduced at 20 to 30 mmHg at -60 ° C for 3 hours to obtain a viscous liquid (J-7) having a Gardner viscosity of Z3.

[Preparation Example 8] In a reactor equipped with a stirrer equipped with a rectification column, a reflux condenser, a nitrogen inlet tube, and a thermometer, 190 parts of ethylene glycol, 425 parts of ethylbutylpropanediol, 332 parts of maleic anhydride, Adipic acid 193
Part, SCAT-24 (manufactured by Sankyokisei Co., Ltd.) 0.5
And 2 parts of triphenyl phosphite, stirred and heated to 220 ° C. for 3.5 hours, reacted at 220 ° C. for 4 hours, and cooled when the acid value became 2 or less.
50 parts, at 75 ° C. or lower, to obtain an unsaturated polyester resin composition (J-8) having a nonvolatile content of 80%, a viscosity of CD, and a light yellow transparent appearance.

[Comparative Preparation Example 1] In a reactor equipped with a stirrer equipped with a reflux condenser, a nitrogen inlet, and a thermometer, 562.8 parts of Kuraray polyol P-2010 (Kuraray polyester diol), TDI80 / 20 (tolylene diisocyanate manufactured by Mitsui Toatsu Chemicals, Inc.), 99.1 parts of ethyl acetate, and 199.1 parts of ethyl acetate were added, and the mixture was heated to 70 ° C. for 0.5 hour with stirring and reacted at 70 to 75 ° C. for 3 hours. After that, the nitrogen inlet pipe was switched to an air inlet pipe, and Viscort # 214 was used.
134.5 parts of HP (glycerin acrylate methacrylate manufactured by Osaka Organic Co., Ltd.), 0.4 part of methoquinone, 4 parts of trinonylphenyl phosphite, 0.24 parts of stannous octoate were added, and the mixture was heated again at 70 to 75 ° C. The mixture was reacted for 6 hours to obtain an active energy ray-curable composition (H-1) having a nonvolatile content of 80%, a viscosity of Z1, and a pale yellow transparent poly (ester) urethane resin skeleton.

[Comparative Preparation Example 2] PolyT was placed in a reactor equipped with a stirrer equipped with a reflux condenser, a nitrogen inlet, and a thermometer.
HF-2000 (polytetramethylene ether diol manufactured by BASF) 616.8 parts, TDI80 / 20
(Mitsui Toatsu Chemical Co., Ltd. Tolylene diisocyanate) 1
After adding 08.0 parts and 198 parts of ethyl acetate, the temperature was raised to 70 ° C. in 0.5 hour with stirring and the reaction was carried out at 70 to 75 ° C. for 3 hours. (Hydroxypropyl acrylate manufactured by Osaka Organic Co., Ltd.) 73.0 parts, methoquinone 0.4 part, trinonylphenyl phosphite 4 parts, stannous octoate 0.2
4 parts, and reacted again at 70-75 ° C. for 6 hours.
Nonvolatile content: 80%, viscosity: X, appearance: pale yellow transparent active energy ray-curable composition (H-2) having a poly (ether) urethane resin skeleton.

[Examples 1 to 3 as clear paint test examples]
10, Comparative Examples 1 to 4] Active energy ray-curable compositions (J-1 to J-8) obtained in Preparation Examples, ALCH-TR
Example composition 1 in which [Aluminum Tris (ethyl acetoacetate) manufactured by Kawaken Fine Chemical Co., Ltd.] and (H-1 to H-2) obtained in Comparative Preparation Examples were blended as shown in Tables 1, 3, and 5. To 10 and Comparative Examples 1 to 4 were prepared. The following tests were performed on the 14 compositions thus prepared. Further, the coated test piece was applied to a veneer plywood and art paper using a bar coater so that the thickness of the dried coating film became 23 to 27 μm, and dried at 60 ° C. for 5 minutes with a blow dryer. Thereafter, the irradiation amount was 450 mJ / cm ^{2 using a} 120 W high-pressure mercury lamp.
UV irradiation. After the UV irradiation, veneer plywood,
MEK resistance test, cellophane peel test, sensation slip test, blocking test,
The dynamic friction coefficient was measured. The test methods are shown below, and the test results are shown in Tables 2, 4, and 6.

(MEK rubbing test) Absorbent cotton wrapped in gauze was mixed with methyl ethyl ketone (MEK), and 2 kg
Rubbing the coating film by applying a load of
It measures the number of rubbings until 0% exposure.
The measurement was performed using an IC type rubbing tester type I (manufactured by Riken Engineering Co., Ltd.).

(Cellophane Tape Peeling Test) According to one method of the adhesion strength test, a cut line having a depth reaching the base material is formed on the surface of the test piece in a crosswise shape, and a cellophane tape (manufactured by Nichiban Co., Ltd.) having a width of 24 mm is formed. After pasting, quickly 18 by hand
Peel 0 degree. The adhesion strength test results are shown by examining the remaining state of the coating film. When the coating film does not peel at all (（), when it peels slightly along the cross (△), when it peels off, it shows (x). I do.

(Spontaneous Slip Test) A cotton towel cloth was rolled to a diameter of about 5 cm, and the surface of the test piece was rubbed by hand. If there is no resistance, slip (○), if there is some resistance but slip (△), if there is no resistance, slip (×)

(Blocking test) Painted 10 × 1
The coated surface of the test piece of 0 cm is coated and coated, and the pressing temperature: 40 ° C., the pressing pressure: 5 kg, the pressing time: 1
Evaluation was performed in a state where the test piece was peeled off by pressing for 6 hours. When peeling can be performed with little resistance, or when there is slight resistance but easy peeling is possible (○), when there is resistance but no trace of crimping is left (△), there is quite strong resistance and trace of crimping remains In this case, or when the material cannot be removed unless it is pryed apart with a spatula or the like and causes material destruction, it is indicated by (x).

(Measurement of Dynamic Friction Coefficient) The measurement conditions were as follows:
200 g, pulling speed: 1200 mm / sec, measurement start time: 0.5 sec, measurement time: 5.0 sec, surface material: cotton gauze, measurement temperature: 25 ° C, number of measurements: 3 times, dynamic friction measured under the above conditions A simple average of three coefficient measurements is shown.

[0081]

[Table 1]

[0082]

[Table 2]

In the table, "TMPTA" is "trimethylolpropane triacrylate", "ACMO" is "Acroylmorpholine", "Darocur" is "Darocur D-1173", and "Silica" is "Fuji Silysia". "Silica matting agent Sylysia 446" manufactured by Kagaku Co., Ltd., "solid aluminum content%" refers to "content of aluminum molecules in solid content", "MEK resistance" refers to "MEK resistance test", "cellotape peeling""" Indicates a "cellophane tape peeling test", and "blocking" indicates a "blocking resistance test".

[0084]

[Table 3]

[0085]

[Table 4]

"ALCH-TR" in the table means "aluminum tris (ethyl acetoacetate)" and "LX-6".
"60" represents "Dick Dry LX-660 manufactured by Dainippon Ink and Chemicals, Inc." and "DVE-3" represents "RAPI-CURE DVE-3 manufactured by ASP Japan Co., Ltd."

[0087]

[Table 5]

[0088]

[Table 6]

[0089]

As is clear from the above results, the active energy ray-curable composition of the present invention is excellent in curability, adhesion and chemical resistance, has a high dynamic friction coefficient, and has non-slip properties and blocking resistance. Are compatible, and it is much better. Therefore, the active energy ray-curable composition of the present invention comprises
Non-slip coatings for building materials such as stairs and floors, coatings or coatings on metals, plastics, corrugated cardboard, paper, etc. to provide slipless functions such as preventing collapse of cargo, coatings, glossy varnishes, gravure inks, flexo inks It is extremely useful as a vehicle for such applications.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09D 167/06 C09D 167/06 171/00 171/00 A 175/16 175/16

Claims (5)

[Claims] 1. An active energy ray-curable composition comprising an aluminum atom bonded through a primary bond, a chelate bond or a hydrogen bond, and an active energy ray-curable unsaturated group. 2. The method according to claim 1, wherein the aluminum atom bonded through a primary bond, a chelate bond or a hydrogen bond, and the active energy ray-curable unsaturated group are in a molecule of a resin skeleton having a number average molecular weight of 500 to 15,000. The active energy ray-curable composition according to claim 1, which is present in the composition. 3. The aluminum atom bonded via a primary bond, a chelate bond or a hydrogen bond, and the active energy ray-curable unsaturated group are present in the same molecule having a number average molecular weight of 300 to 5000. The active energy ray-curable composition according to claim 1. 4. The composition according to claim 1, wherein the weight ratio of the aluminum atom bonded through the primary bond, the chelate bond or the hydrogen bond in the composition is 0.1 to 10% by weight of the solid content, and When the solid concentration of the unsaturated group is 0.
The active energy ray-curable composition according to claim 1, wherein the composition is 5 to 6 mol / kg. 5. The resin skeleton is at least selected from the group consisting of a polyester resin skeleton, a polyether resin skeleton, a polyether polyester resin skeleton, a polycarbonate resin skeleton, a polybutadiene resin skeleton, a polyolefin resin skeleton, an epoxy resin skeleton, and a polyurethane resin skeleton. The active energy ray-curable composition according to any one of claims 1 to 4, which is one kind of resin skeleton.