JP2000211249A - Activation-energy-beam-curing composition for ink-jet ink receiving layer, and information recording medium having receiving layer obtained by curing the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition being excellent in activation-energy-beam- curing properties and used for forming an ink-jet ink receiving layer which is obtained by curing the composition and constitutes an information recording medium excellent in any of ink fixing properties, water resistance and coat strength. SOLUTION: This composition contains an alkylene oxide modified multifunctional (meta) acrylate monomer and a compound containing two or more maleimide skeletons in a molecule. A receiving layer which is obtained by laminating the above composition and by curing the laminate by an activation energy beam and which enables recording with ink by an ink jet recording method is provided on the surface of an information recording medium.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an active energy ray-curable ink receiving layer composition suitably used for ink jet recording and an information recording medium having a receiving layer obtained by curing the composition. The present invention relates to an active energy ray-curable inkjet ink receiving layer composition containing a maleimide compound which is cured by ultraviolet rays.

[0002]

2. Description of the Related Art An active energy ray-curable composition which is polymerized by an active energy ray such as an ultraviolet ray, a visible ray or an electron beam cures quickly and has high productivity.
(OC) is low, and in fields where solvent-borne paints such as printing inks, clear coatings and overprint varnishes have been used in the past, they have been rapidly commercialized as high productivity and environmentally friendly alternative paints. Have been.

In the ink-jet ink receiving layer composition, the solvent or water evaporates, and the dried coating film is replaced with a solvent-type or aqueous receiving layer composition that forms the receiving layer. Various things have been proposed. For example, JP-A-10-217605 discloses that polyvinyl alcohol is used as a water-absorbing polymer resin, and flour such as wheat flour is used as an essential component for improving the fixability of the ink, and a photopolymerization initiator and an ethylenically unsaturated compound are used. Compositions comprising the same have been proposed. Also, Japanese Patent Application Laid-Open No. 8-279179
In Japanese Patent Application Publication No. H11-264, a composition containing a dialkylamino (meth) acrylate, a photopolymerization initiator, and fine particles is proposed.
These are all proposed as a composition containing a photopolymerization initiator, contain fine particles or a filler for adjusting the water absorption of the ink, and further ensure the fixing property of the ink.
It is configured to contain a tertiary or quaternary nitrogen-containing polymer or monomer. Conventionally, a monofunctional monomer has been used as a tertiary or quaternary nitrogen-containing monomer in an active energy ray-curable inkjet ink receiving layer composition. Here, in order to enhance the fixing property of the ink, it was necessary to considerably increase the amount of addition of the nitrogen-containing monomer. For this reason, the cured coating has tackiness,
There was a problem that the strength and water resistance of the coating film deteriorated. Further, the active energy ray-curable composition also causes a reduction in the active energy ray-curable property. As for the photopolymerization initiator, in order to reduce the active energy ray for curing the composition, it is necessary to increase the addition amount of the photopolymerization initiator to about 5 to 15% by weight according to the required productivity. Therefore, with the increase in the amount of addition of the photopolymerization initiator, there has been a problem that the mechanical deformation (curl, warp, etc.) of the information recording medium becomes large, particularly after a high-temperature and high-humidity test.

[0004]

SUMMARY OF THE INVENTION To solve these problems, the present inventors have proposed an active energy ray-curing method using a maleimide compound which is a polyfunctional nitrogen-containing compound and has a photopolymerization initiation function. The composition was studied, and the present invention was reached.

The receiving layer obtained by curing the ink-jet ink receiving layer composition of the present invention is excellent in productivity because the ink has good fixability, water resistance and coating strength, and has good active energy ray curability. is there.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using a specific maleimide compound, and have completed the present invention. Was.

That is, in order to solve the above-mentioned problems, the present invention provides a compound containing two or more alkylene oxide-modified polyfunctional (meth) acrylates and a maleimide skeleton in a molecule.
More preferably, the following general formula (1) (where m and n are
Each represents 1 or more independent integers. R ₁₁ and R ₁₂ are
Each independently represents a hydrocarbon bond composed of an aliphatic group and / or an aromatic group. G ₁ and G ₂ each independently represent an ether bond, an ester bond, a urethane bond, or a carbonate bond. R ₂ represents an aliphatic group and / or an aromatic group
(a) ether bond, (b) ester bond, (c) urethane bond and (d) average molecular weight of 40-1 linked by at least one bond selected from the group consisting of carbonate bond.
(A) (poly) ether linked chain or (poly) ether, (B) (poly) ester linked chain or (poly) ester residue, (C) (poly) urethane linked chain or (poly) urethane A residue or (D) a (poly) carbonate linking chain or a (poly) carbonate residue. )
The present invention provides an active energy ray-curable inkjet ink receiving layer composition containing a maleimide compound represented by the formula: and an information recording medium having a receiving layer obtained by curing the composition.

General formula (1)

Embedded image

[0009]

DETAILED DESCRIPTION OF THE INVENTION As the alkylene oxide-modified polyfunctional (meth) acrylate used in the present invention, a (meth) acrylate obtained by modifying a polyol from a diol with an alkylene oxide, particularly preferably ethylene oxide and / or propylene oxide, is used. it can. Examples of the bifunctional one include (meth) acrylates obtained by modifying ethylene glycol, propylene glycol, butanediol, neopentyl glycol, hexanediol and the like with ethylene oxide and / or propylene oxide. Examples of the trifunctional or higher functional groups include (meth) acrylates obtained by modifying trimethylolpropane, glycerin, pentaerythritol, isocyanurate, ditrimethylolpropane, dipentaerythritol and the like with ethylene oxide and / or propylene oxide.

[0010] Of these, it is preferable to use one having three or more functionalities from the viewpoint of ultraviolet curability and the strength of the coating film obtained by curing. As for the degree of alkylene oxide modification, from the viewpoint of ink receptivity in ink jet recording, those having a large degree of modification, and as a modified structure,
An ethylene oxide structure is preferred.

The amount of the alkylene oxide-modified polyfunctional (meth) acrylate used in the composition depends on the structure of the maleimide derivative used in combination. It is compounded by.

In the maleimide compound suitably used in the present invention, m and n in the above formula (1) each independently represent an integer of 1 or more. In particular, since it is liquid at room temperature and forms a cured film by itself,
And n are each independently an integer of 1 to 5, and a compound in which m + n is an integer of 2 to 6 is recommended.

R ₁₁ and R ₁₂ each independently represent a hydrocarbon bond consisting of an aliphatic and / or aromatic group. Among them, a hydrocarbon bond selected from the group consisting of an alkylene group, a cycloalkylene group, an arylalkylene group and a cycloalkylalkylene group is particularly preferred. Here, the alkylene group may be linear or branched, and the arylalkylene group or the cycloalkyl-alkylene group may be an aryl group or a cycloalkyl group in a main chain or a branched chain, respectively. May be provided.

Specific examples of R ₁₁ and R ₁₂ include, for example,
Linear alkylene groups such as methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group 1-methylethylene group, 1-
Methyl-trimethylene group, 2-methyl-trimethylene group, 1-methyl-tetramethylene group, 2-methyl-tetramethylene group, 1-methyl-pentamethylene group, 2-methyl-pentamethylene group, 3-methyl-pentamethylene An alkylene group having a branched alkyl group such as a neopentyl group; a cycloalkylene group such as a cyclopentylene group or a cyclohexylene group; a benzylene group, a 2,2-diphenyl-trimethylene group, a 1-phenyl-ethylene group,
Arylalkylene groups having an aryl group in the main chain or side chain such as 1-phenyl-tetraethylene group and 2-phenyl-tetraethylene group; cyclohexylmethylene group, 1
-Cyclohexyl-ethylene group, 1-cyclohexyl-
Examples thereof include a cycloalkyl-alkylene group having a cycloalkyl group in a main chain or a side chain such as a tetraethylene group and a 2-cyclohexyl-tetraethylene group, but are not limited thereto.

R ₂ has an aliphatic group and / or an aromatic group represented by (a)
Average molecular weight of 40 to 10 linked by at least one bond selected from the group consisting of an ether bond, (b) an ester bond, (c) a urethane bond, and (d) a carbonate bond.
000 (A) (poly) ether linked chains or (poly) ether residues, (B) (poly) ester linked chains or (poly) ester residues, (C) (poly) urethane linked chains or (poly) ) Represents a urethane residue or (D) a (poly) carbonate linking chain or a (poly) carbonate residue. R ₂ may be a connecting chain composed of an oligomer or a polymer in which these connecting chains are repeated as one unit and are repeated.

Specific examples of the linking chain or residue representing R ₂ include: (a) at least one carbon atom selected from the group consisting of a linear alkylene group, a branched alkylene group, a cycloalkylene group and an aryl group; A connecting chain or a residue composed of (poly) ether (poly) ol having an average molecular weight of 40 to 100,000 and having one or a repeating unit of a hydrogen group bonded by an ether bond:

(B) at least one hydrocarbon group selected from the group consisting of a straight-chain alkylene group, a branched alkylene group, a cycloalkylene group and an aryl group is formed by one or a repeating unit thereof bonded by an ester bond; A linking chain or residue composed of a (poly) ester (poly) ol having an average molecular weight of 40 to 100,000:

(C) at least one hydrocarbon group selected from the group consisting of a straight-chain alkylene group, a branched alkylene group, a cycloalkylene group and an aryl group is one or more repeating units linked by an ether bond; Obtained by esterifying (poly) ether (poly) ol having an average molecular weight of 40 to 100,000 and di-hexa-carboxylic acid (hereinafter abbreviated as polycarboxylic acid).
Linking chain or residue composed of (poly) carboxylic acid {(poly) ether (poly) ol} ester having a polycarboxylic acid residue at the end:

(D) at least one hydrocarbon group selected from the group consisting of a straight-chain alkylene group, a branched alkylene group, a cycloalkylene group and an aryl group, wherein one or more of them are bonded by an ether bond and an ester bond, or (Poly) carboxylic acid {(poly) ester whose polycarboxylic acid residue is obtained by esterifying (poly) ester (poly) ol having a repeating unit and having an average molecular weight of 40 to 100,000 with polycarboxylic acid Linking chain or residue composed of (poly) all｝ ester:

(E) at least one hydrocarbon group selected from the group consisting of a straight-chain alkylene group, a branched alkylene group, a cycloalkylene group and an aryl group is one or more repeating units linked by an ether bond; A linking chain or residue obtained by ring-opening a (poly) epoxide having an average molecular weight of 100 to 40,000:

(F) at least one hydrocarbon group selected from the group consisting of a straight-chain alkylene group, a branched alkylene group, a cycloalkylene group and an aryl group has one or more repeating units linked by an ether bond; A linking chain or residue composed of a (poly) ether (poly) isocyanate obtained by urethane-forming a (poly) ether (poly) ol having an average molecular weight of 40 to 100,000 and an organic (poly) isocyanate:

(G) at least one hydrocarbon group selected from the group consisting of a straight-chain alkylene group, a branched alkylene group, a cycloalkylene group and an aryl group is one or a repeating unit thereof bonded by an ester bond; A linking chain or residue composed of a (poly) ester (poly) isocyanate obtained by urethane-forming a (poly) ester (poly) ol having an average molecular weight of 40 to 100,000 and an organic (poly) isocyanate:

(H) at least one hydrocarbon group selected from the group consisting of a straight-chain alkylene group, a branched alkylene group, a cycloalkylene group and an aryl group is one or more repeating units linked by an ether bond; A linking chain or a residue composed of a carbonate ester of (poly) ether (poly) ol having an average molecular weight of 40 to 100,000, but is not limited thereto.

Examples of the (poly) ether (poly) ol constituting the linking chain or residue (a) include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polybutylene glycol and polytetramethylene glycol; Ethylene glycol, propanediol, propylene glycol, tetramethylene glycol, pentamethylene glycol, hexanediol, neopentyl glycol, glycerin,
Trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane, alkylene glycols such as dipentaerythritol, ethylene oxide modified, propylene oxide modified, butylene oxide modified, tetrahydrofuran modified, and the like, among these And various modified products of alkylene glycols.

Further, the (poly) ether (poly) ol constituting the linking chain (a) includes a copolymer of ethylene oxide and propylene oxide, a copolymer of propylene glycol and tetrahydrofuran, and a copolymer of ethylene glycol and tetrahydrofuran. Polymers, hydrocarbon polyols such as polyisoprene glycol, hydrogenated polyisoprene glycol, polybutadiene glycol, hydrogenated polybutadiene glycol, and polyhydric hydroxyl compounds such as polytetramethylene hexaglyceryl ether (tetrahydrofuran-modified hexaglycerin), etc. But are not limited to these.

Examples of the (poly) ester (poly) ol constituting the linking chain or residue (b) include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polybutylene glycol and polytetramethylene glycol; Or alkylene glycols such as ethylene glycol, propanediol, propylene glycol, tetramethylene glycol, pentamethylene glycol, hexanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane, dipentaerythritol ,
ε-caprolactone modified, γ-butyrolactone modified, δ-valerolactone modified or methylvalerolactone modified; aliphatic dicarboxylic acids such as adipic acid and dimer acid, and polyols such as neopentyl glycol and methylpentanediol. Aliphatic polyester polyol which is an esterified product; polyester polyol such as an aromatic polyester polyol which is an esterified product of an aromatic dicarboxylic acid such as terephthalic acid and a polyol such as neopentyl glycol; polycarbonate polyol, acrylic polyol, polytetramethylene hexaglyceryl Polyhydric hydroxyl compound such as ether (modified tetrahydrofuran of hexaglycerin), fumaric acid, phthalic acid, isophthalic acid, itaconic acid, adipic acid, sebacic acid, maleic Esterified products with a dicarboxylic acid such as an acid; polyhydric hydroxyl-containing compounds such as monoglyceride obtained by transesterification of a polyhydric hydroxyl-containing compound such as glycerin with an animal or plant fatty acid ester; and the like. It is not limited.

Examples of the (poly) carboxylic acid {(poly) ether (poly) ol} ester in which the terminal constituting the linking chain or residue (c) is a polycarboxylic acid include (1) succinic acid, Adipic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, fumaric acid, isophthalic acid, itaconic acid, adipic acid, sebacic acid, maleic acid, trimellitic acid, pyromellitic acid, benzenepentacarboxylic acid, benzenehexacarboxylic acid (2) a polycarboxylic acid having a terminal obtained by esterification of a polycarboxylic acid such as citric acid, tetrahydrofurantetracarboxylic acid, or cyclohexane bird carboxylic acid with (poly) ether (poly) ol shown in (a) above; (Poly) carboxylic acid {(poly) ether (poly) ol} ester But it is not limited thereto.

Examples of the (poly) carboxylic acid {(poly) ester (poly) ol} ester in which the terminal constituting the linking chain or the residue (d) is a polycarboxylic acid include (1) succinic acid, Adipic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, fumaric acid, isophthalic acid, itaconic acid, adipic acid, sebacic acid, maleic acid, trimellitic acid, pyromellitic acid, benzenepentacarboxylic acid, benzenehexacarboxylic acid Di-hexa-carboxylic acid such as citric acid, tetrahydrofuran tetracarboxylic acid, cyclohexane bird carboxylic acid,
(2) The (poly) carboxylic acid {(poly) ester (poly) ol} ester having a polycarboxylic acid terminal obtained by esterification with the (poly) ester (poly) ol shown in the above (b) is But not limited thereto.

Examples of the (poly) epoxide constituting the above-mentioned linking chain or residue (e) include (methyl) epichlorohydrin and epichlorohydrin synthesized from bisphenol A or bisphenol F and ethylene oxide or propylene oxide modified products thereof. Modified bisphenol type epoxy resin; (methyl) epichlorohydrin, hydrogenated bisphenol A, hydrogenated bisphenol F,
Epichlorohydrin-modified hydrogenated bisphenol-type epoxy resins and epoxy novolak resins synthesized from ethylene oxide-modified products, propylene oxide-modified products, and the like; phenols, biphenols, and the like, and reaction products of (methyl) epichlorohydrin; terephthalic acid, isophthalic acid, or Aromatic epoxy resins such as glycidyl ester of pyromellitic acid; glycols such as (poly) ethylene glycol, (poly) propylene glycol, (poly) butylene glycol, (poly) tetramethylene glycol, neopentyl glycol, and their alkylene oxides Modified polyglycidyl ether; trimethylolpropane, trimethylolethane, glycerin, diglycerin, erythritol, pentaerythritol, sorbitol, 1, -Glycidyl ethers of aliphatic polyhydric alcohols such as butanediol and 1,6-hexanediol, and their alkylene oxide modified products; glycidyl esters of carboxylic acids such as adipic acid, sebacic acid, maleic acid and itaconic acid; Glycidyl ethers of polyester polyols with alcohols and polycarboxylic acids; copolymers of glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate; glycidyl esters of higher fatty acids, epoxidized linseed oil, epoxidized soybean oil, epoxidized castor oil And aliphatic epoxy resins such as epoxidized polybutadiene, but are not limited thereto.

Examples of the (poly) ether (poly) isocyanate constituting the linking chain or residue (f) include, for example, methylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate Aliphatic diisocyanate compounds such as 2,4-tolylene diisocyanate, dimer of 2,4-tolylene diisocyanate,
2,6-tolylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 4,
Aromatic diisocyanate compounds such as 4'-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, and 3,3'-dimethylbiphenyl-4,4'-diisocyanate; isophorone diisocyanate;
4'-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2,6) diisocyanate, 1,3- (isocyanatomethylene)
(Poly) ether (poly) isocyanate obtained by urethanization reaction of polyisocyanate such as cycloaliphatic diisocyanate such as cyclohexane and (poly) ether (poly) ol, and the like, but are not limited thereto. is not.

Examples of the (poly) ether (poly) ol used in the reaction with the polyisocyanate include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polybutylene glycol, and polytetramethylene glycol;
Modified ethylene oxide of alkylene glycols such as propanediol, propylene glycol, tetramethylene glycol, pentamethylene glycol, hexanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane, dipentaerythritol And modified products of propylene oxide, butylene oxide, and modified products of tetrahydrofuran. Of these, various modified products of alkylene glycols are preferable.

Further, the (poly) ether (poly) ol used for the reaction with the polyisocyanate includes a copolymer of ethylene oxide and propylene oxide, a copolymer of propylene glycol and tetrahydrofuran, a copolymer of ethylene glycol and tetrahydrofuran, Hydrocarbon polyols such as isoprene glycol, hydrogenated polyisoprene glycol, polybutadiene glycol, and hydrogenated polybutadiene glycol; and polyhydric hydroxyl compounds such as polytetramethylene hexaglyceryl ether (tetrahydrofuran-modified hexaglycerin). However, the present invention is not limited to these.

The (poly) ester (poly) isocyanate constituting the linking chain or residue (g) includes, for example, the polyisocyanates listed for the linking chain (a),
Examples include (poly) ester (poly) isocyanate obtained by urethanation with (poly) ester (poly) ol, but are not limited thereto.

Examples of the (poly) ester (poly) ol used in the reaction with the polyisocyanate include ethylene glycol, propanediol, propylene glycol, tetramethylene glycol, pentamethylene glycol, hexanediol, neopentyl glycol, glycerin, and trimethylol. Of alkylene glycols such as propane, pentaerythritol, diglycerin, ditrimethylolpropane, and dipentaerythritol,
ε-caprolactone modified, γ-butyrolactone modified, δ-valerolactone modified, methylvalerolactone modified; aliphatic dicarboxylic acids such as adipic acid and dimer acid, and polyols such as neopentyl glycol and methylpentanediol Aliphatic polyester polyol which is an esterified product; polyester polyol such as an aromatic polyester polyol which is an esterified product of an aromatic dicarboxylic acid such as terephthalic acid and a polyol such as neopentyl glycol; polycarbonate polyol, acrylic polyol, polytetramethylene hexagon Polyhydric hydroxyl compound such as glyceryl ether (tetrahydrofuran modified hexaglycerin), fumaric acid, phthalic acid, isophthalic acid, itaconic acid, adipic acid, sebacic acid, maleic acid Esterified products with a dicarboxylic acid such as glycerin; and polyhydric hydroxyl group-containing compounds such as monoglyceride obtained by transesterification of a polyvalent hydroxyl-containing compound such as glycerin with a fatty acid ester of an animal or a plant, but are not limited thereto. It is not done.

The (poly) ether (poly) ol constituting the above-mentioned connecting chain or residue (h) includes, but is not limited to, the (poly) ether (poly) ol described in (a) above. Not something.

As the compound used for the esterification with (poly) ether (poly) ol, diethyl carbonate, dipropyl carbonate, phosgene and the like can be mentioned.
Further, polycarbonate can be obtained by alternate polymerization of epoxide and carbon dioxide, but is not limited thereto.

Among these, R ₂ is selected from the group consisting of (1) a C 2-24 straight-chain alkylene group, a C 2-24 branched alkylene group, a C 2-24 alkylene group having a hydroxyl group, a cycloalkylene group, and an aryl group. Group having an average molecular weight of 100 to 100,000, wherein at least one organic group selected from the group consisting of a group and an arylalkylene group is connected by at least one bond selected from the group consisting of (a) an ether bond and (b) an ester bond. (A) a (poly) ether-linked chain or a (poly) ether residue or (B) a (poly) ester-linked chain or a (poly) ester residue, and particularly (2) a straight chain having 2 to 24 carbon atoms A repeating unit containing an alkylene group, a branched alkylene group having 2 to 24 carbon atoms, an alkylene group having 2 to 24 carbon atoms having a hydroxyl group and / or an aryl group; It becomes the average molecular weight 100 to 100,000 (poly) ether linking chain or (poly) ether residue or (3) 2 carbon atoms
Having an average molecular weight of 100 to 100,000, which is composed of a repeating unit containing a linear alkylene group having 2 to 24 carbon atoms, a branched alkylene group having 2 to 24 carbon atoms, an alkylene group having 2 to 24 carbon atoms and / or an aryl group having a hydroxyl group. Poly (ester) linking chains or (poly) ester residues are preferred.

In recent years, active energy ray-curable compositions, particularly in the field of ultraviolet-curable compositions, have been required to have rapid curability. For that purpose, R ₁₁ and R ₁₂ are
Each independently represents an alkylene group having 1 to 5 carbon atoms;
₁ and G ₂ are each independently an ester bond represented by —COO— or —OCO—, and R ₂ has ₂ carbon atoms.
-6 straight-chain alkylene group, C2-C6 branched alkylene group and / or C2-C2 hydroxyl group having a hydroxyl group.
It is particularly recommended to use a maleimide compound (derivative) that is a (poly) ether connecting chain or a (poly) ether residue having an average molecular weight of 100 to 1,000 and consisting of 6 repeating units containing an alkylene group.

The maleimide compound (derivative) represented by the general formula (1) used in the active energy ray-curable inkjet ink receiving layer composition of the present invention includes, for example,
(A) a maleimide compound having a carboxyl group (a-
From (1) and a compound (a-2) that reacts with a carboxyl group, or (b) from a maleimide compound (b-1) having a hydroxyl group and a compound (b-2) having a carboxyl group, It can be synthesized using techniques.

The maleimide compound (a-1) having a carboxyl group is, for example, as shown in the following reaction formula:
From maleic anhydride and primary aminocarboxylic acid, a known technique [for example, DH Rich
Et al., "Journal of Medical Chemistry", Vol. 18, No. 10
04-1010 (1975)].

Reaction formula

Embedded image

The maleimide compound (b-1) having a hydroxyl group can be prepared, for example, from maleimide and formaldehyde as shown in the following reaction formula, or from maleic anhydride as shown in the following reaction formula. 1
And a known technique (for example, US Pat. No. 2,526,517, JP-A-2-26815).
No. 5) or the like.

Reaction formula

[0044]

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Reaction formula

[0046]

Embedded image

The primary aminocarboxylic acid used in the above reaction includes, for example, asparagine, alanine, β-alanine, arginine, isoleucine, glycine, glutamine, tryptophan, threonine, valine, phenylalanine, homophenylalanine, α-methyl-phenylalanine , Lysine, leucine, cycloleucine, 3-
Aminopropionic acid, α-aminobutyric acid, 4-aminobutyric acid, aminovaleric acid, 6-aminocaproic acid, 7-aminoheptanoic acid, 2-aminocaprylic acid, 3-aminocaprylic acid, 6-aminocaprylic acid, 8-amino Caprylic acid,
2-aminononanoic acid, 4-aminononanoic acid, 9-aminononanoic acid, 2-aminocapric acid, 9-aminocapric acid, 10-aminocapric acid, 2-aminoundecanoic acid, 10-aminoundecanoic acid, 11-aminoundecanoic acid 2-aminolauric acid, 11-aminolauric acid, 12-aminolauric acid, 2-aminotridecanoic acid, 13-aminotridecanoic acid, 2-aminomistinic acid, 14-aminomistinic acid, 2-aminopentadecanoic acid, 15-amino Pentadecanoic acid, 2-aminopalmitic acid, 16-aminopalmitic acid, 2-aminoheptadecanoic acid, 17-aminoheptadecanoic acid, 2-aminostearic acid, 18-aminostearic acid, 2-aminoeicosanonic acid, 20 -Aminoeicosanonic acid, aminocyclohexanecarboxylic acid, Nomethylcyclohexanecarboxylic acid, 2-amino-3-propionic acid, 3-amino-3-phenylpropionic acid, and the like, but are not limited thereto, and any primary aminocarboxylic acid can be used. Can also be used. Also, pyrrolidone, δ-
Lactams such as valerolactam and ε-caprolactam can also be used.

The primary amino alcohol used in the above reaction includes, for example, 2-aminoethanol, 1-amino-2-propanol, 3-amino-1-propanol, 2-amino-2-methyl-1-propanol, 2-
Amino-3-phenyl-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 2-amino-1-butanol
Amino-3-methyl-1-butanol, 2-amino-4
-Methylthio-1-butanol, 2-amino-1-pentanol, 5-amino-1-pentanol, (1-aminocyclopentane) methanol, 6-amino-1-hexanol, 2-amino-1-hexanol, 7-amino-1-heptanol, 2- (2-aminoethoxy) ethanol, N- (2-aminoethyl) ethanolamine,
4-amino-1-piperazineethanol, 2-amino-
1-phenylethanol, 2-amino-3-phenyl-
Examples thereof include 1-propanol, 1-aminomethyl-1-cyclohexanol, and aminotrimethylcyclohexanol, but are not limited thereto, and any primary amino alcohol can be used.

Compounds which react with carboxyl groups (a-
As 2), for example, at least one hydrocarbon group selected from the group consisting of a linear alkylene group, a branched alkylene group, a cycloalkylene group, and an aryl group is bonded by an ether bond and / or an ester bond. Alternatively, the average molecular weight having these repeating units is from 100 to 1,
For example, 2,000,000 bifunctional to hexafunctional polyols or polyepoxides.

Compounds which react with hydroxyl groups (b-
As 2), for example, at least one hydrocarbon group selected from the group consisting of (b-2-1) a linear alkylene group, a branched alkylene group, a cycloalkylene group, and an aryl group is an ether bond and / or an ester. Di-hexa-carboxy having 2 to 6 carboxyl groups, ether bond and / or ester bond in one molecule having an average molecular weight of 100 to 1,000,000 and having one or a repeating unit thereof bonded by a bond Acid, (b-2-2) (poly) isocyanate, or (b-2-3) carbonate, phosgene, and the like.

A maleimide compound (a-1) having a carboxyl group and a compound (a-
The reaction with a polyol, which is one of the 2), is not particularly limited, but may be carried out by a known technique [for example, CE Rehberg et al., “Org. Synth. Collective Volume (Org. Synth. Collective Volume)”).
Volume), Vol. III, p. 46 (1955)], and the maleimide derivative represented by the general formula (1) can be synthesized.

This reaction is carried out at room temperature to 1 under normal pressure or reduced pressure.
It is preferable to perform the dehydration in a temperature range of 50 ° C. while using a catalyst. Examples of the catalyst include acid catalysts such as sulfuric acid, phosphoric acid, metasulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and strongly acidic cation exchange resin. The addition amount of the catalyst is preferably in the range of 0.01 to 10% by weight based on the whole charged amount.

In this reaction, an organic solvent azeotropic with water can be used as a reaction solvent. Examples of such an organic solvent include toluene, benzene, butyl acetate, ethyl acetate, diisopropyl ether, dibutyl ether, and the like.

A maleimide compound (a-1) having a carboxyl group and a compound (a-
The reaction with polyepoxide, which is one of 2), is not particularly limited, but may be performed by a known technique [for example, JP-A-4-2285.
No. 29] can be used to synthesize the maleimide derivative represented by the general formula (1).

This reaction is carried out in a temperature range from room temperature to 150 ° C., and it is desirable to use a catalyst. Examples of the catalyst include imidazoles such as 2-methylimidazole, quaternary ammonium salts such as tetramethylammonium chloride, trimethylbenzylammonium chloride and tetramethylammonium bromide, and amines such as trimethylamine, triethylamine, benzylmethylamine and tributylamine. Phosphines such as triphenylphosphine and tricyclohexylphosphine; lauric esters such as dibutyltin laurate; basic alkali metal salts such as potassium acetate, potassium tertiary phosphate, sodium acrylate and sodium methacrylate; sodium methylate And alkali metal alcoholates such as potassium ethylate and anion exchange resins. The addition amount of the catalyst is preferably in the range of 10 to 10,000 ppm based on the whole charged amount.

In this reaction, an organic solvent containing no active hydrogen can be used as a reaction solvent. Such organic solvents include, for example, toluene,
Aromatic hydrocarbons such as ethylbenzene, tetralin, cumene and xylene; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; formate, methyl acetate, ethyl acetate and n-acetic acid
And esters such as butyl.

A maleimide compound (b-1) having a hydroxyl group and a compound (b-
Compound (b-) having a carboxyl group which is one of 2)
Although the reaction with 2-1) is not particularly limited, a known technique [for example, CE Rehber (CE Rehber)
g), “Org. Synth. Collective Volume” III
Volume, p. 46 (1955)] can be used to synthesize the maleimide derivative represented by the general formula (1).

This reaction is carried out at room temperature to 1 under normal pressure or reduced pressure.
It is preferable to perform the dehydration in a temperature range of 50 ° C. while using a catalyst. Examples of the catalyst include acid catalysts such as sulfuric acid, phosphoric acid, metasulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and a strongly acidic cation exchange resin.
And the like. The addition amount of the catalyst is preferably in the range of 0.01 to 10% by weight based on the whole charged amount.

At this time, an organic solvent azeotropic with water can be used as a reaction solvent. Such organic solvents include, for example, toluene, benzene, butyl acetate, ethyl acetate, diisopropyl ether, dibutyl ether,
And the like. A maleimide compound (b-1) having a hydroxyl group and (poly) isocyanate (b) which is one of the compounds (b-2) reacting with the hydroxyl group
The reaction with -2-2) is not particularly limited, but the maleimide derivative represented by the general formula (1) can be synthesized by a known urethane reaction.

This reaction is carried out under a nitrogen atmosphere, for example, in a temperature range from room temperature to 90 ° C., and it is preferable to use a catalyst. As the catalyst, for example, organic titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, and tetraethyl titanate, tin octylate, dibutyl tin oxide, organic tin compounds such as dibutyl tin laurate, stannous iodide, and the like can be used. . The addition amount of the catalyst is preferably in the range of 10 to 10,000 ppm based on the whole charged amount.

In this reaction, various active hydrogen-free organic solvents can be used as a reaction solvent. Such organic solvents include, for example, aromatic hydrocarbons such as toluene, ethylbenzene, tetralin, cumene and xylene; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; formate, methyl acetate, ethyl acetate, Esters such as n-butyl acetate are exemplified.

A maleimide compound (b-1) having a hydroxyl group and a compound (b-
The reaction with the carbonate ester (b-2-3), which is one of 2), is not particularly limited, but the maleimide derivative represented by the general formula (1) can be synthesized by a known transesterification reaction.

This reaction is carried out at room temperature to 1 under normal pressure or reduced pressure.
It is preferable to carry out the reaction while distilling off the alcohol formed in a temperature range of 50 ° C. and use a catalyst. Examples of the catalyst include sulfuric acid, phosphoric acid, metasulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, an acid catalyst such as a strongly acidic cation exchange resin, an organic titanium compound such as tetrabutyl titanate, tetrapropyl titanate, and tetraethyl titanate; Examples include organotin compounds such as tin octylate, dibutyltin oxide, and dibutyltin laurate; and aluminum alkoxides such as aluminum triisopropoxide. The amount of the catalyst added was 0.1 to the total charge.
The range of 01 to 10% by weight is preferred.

At this time, the reaction solvent may not be used, but an organic solvent azeotropic with the produced alcohol can be used. Such organic solvents include, for example, toluene,
Examples thereof include benzene, hexane, heptane, butyl acetate, ethyl acetate, diisopropyl ether, dibutyl ether and the like.

In any of the above reactions, it is desirable to use a radical polymerization inhibitor for the purpose of suppressing the radical polymerization of the maleimide group. Examples of the radical polymerization inhibitor include hydroquinone, tert-butylhydroquinone, methoquinone, 2,4-dimethyl-6-te
Phenolic compounds such as rt-butylphenol, catechol, tert-butylcatechol; phenothiazine, p
Amines such as phenylenediamine and diphenylamine; and copper complexes such as copper dimethyldithiocarbamate, copper diethyldithiocarbamate and copper dibutyldithiocarbamate. These polymerization inhibitors can be used alone or in combination of two or more. The amount of the polymerization inhibitor to be added is 10 to 1 with respect to the total charged amount.
A range of 0.00000 ppm is preferred.

Compounds which react with carboxyl groups (a-
Examples of the polyol used as 2) include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polybutylene glycol, and polytetramethylene glycol; ethylene glycol, propanediol, propylene glycol, butanediol, butylene glycol, hexanediol, and the like. Modified ethylene oxide, alkylene glycols such as neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane, dipentaerythritol, ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, ε-caprolactone Denatured product, γ
-Butyrolactone modified, δ-valerolactone modified,
Methyl valerolactone modified product;

Copolymers such as copolymers of ethylene oxide and propylene oxide, copolymers of propylene glycol and tetrahydrofuran, copolymers of ethylene glycol and tetrahydrofuran, polyisoprene glycol, hydrogenated polyisoprene glycol, polybutadiene glycol, and hydrogenated polybutadiene glycol Hydrogen-based polyols; aliphatic polyester polyols which are ester reactants of aliphatic dicarboxylic acids such as adipic acid and dimer acid with polyols such as neopentyl glycol and methylpentanediol; aromatic dicarboxylic acids such as terephthalic acid and Aromatic polyester polyols which are ester reactants with polyols such as pentyl glycol; polycarbonate polyols; acrylic polyols; Polyhydric hydroxyl compounds such as tylene hexaglyceryl ether (tetrahydrofuran-modified hexaglycerin); mono- and polyhydric hydroxyl-containing compounds having terminal ether groups of the above polyhydric hydroxyl-containing compounds; and the above-mentioned polyhydric hydroxyl-containing compounds and fumaric acid Polyhydric hydroxyl-containing compounds obtained by esterification with dicarboxylic acids such as phthalic acid, isophthalic acid, itaconic acid, adipic acid, sebacic acid, and maleic acid; polyhydric hydroxyl compounds such as glycerin; and fatty acid esters of animals and plants And polyhydric hydroxyl group-containing compounds such as monoglyceride obtained by transesterification reaction with the same. Can also be used.

Compounds which react with carboxyl groups (a-
As the polyepoxide used as 2), for example,
(Methyl) epichlorohydrin, bisphenol A,
Epichlorohydrin-modified bisphenol type epoxy resin synthesized from bisphenol F, their ethylene oxide, propylene oxide modified products, etc .; (methyl) epichlorohydrin, hydrogenated bisphenol A, hydrogenated bisphenol F, their ethylene oxide, propylene oxide modified products, etc. Epichlorohydrin-modified hydrogenated bisphenol-type epoxy resin and epoxy novolak resin synthesized from phenol and biphenol with (methyl) epichlorohydrin; aromatic epoxy such as glycidyl ester of terephthalic acid, isophthalic acid and pyromellitic acid Resins; (poly) ethylene glycol, (poly) propylene glycol, (poly) butylene glycol, (poly) tetramethylene glycol,
Glycols such as neopentyl glycol, polyglycidyl ethers of alkylene oxide modified products thereof;
Trimethylolpropane, trimethylolethane, glycerin, diglycerin, erythritol, pentaerythritol, sorbitol, 1,4-butanediol,
Glycidyl ethers of aliphatic polyhydric alcohols such as 1,6-hexanediol and alkylene oxide modified products thereof; Glycidyl esters of carboxylic acids such as adipic acid, sebacic acid, maleic acid and itaconic acid; Polyhydric alcohols and polycarboxylic acids Glycidyl ethers of polyester polyols with acids; copolymers of glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate;
Glycidyl esters of higher fatty acids, epoxidized linseed oil, epoxidized soybean oil, epoxidized castor oil, aliphatic epoxy resins such as epoxidized polybutadiene, and the like.

Compounds having a carboxyl group (b-2-
Examples of the di-hexa-carboxylic acid having 2 to 6 carboxyl groups, ether bond and ester bond in one molecule used as 1) include fumaric acid, phthalic acid, and the like.
Isophthalic acid, itaconic acid, adipic acid, sebacic acid,
A dicarboxylic acid such as maleic acid, succinic acid, adipic acid, hexahydrophthalic acid, tetrahydrophthalic acid, or pyromellitic acid, or the following general formula (2) obtained by esterifying the dicarboxylic acid and the polyol, wherein ,
X ′ represents a dicarboxylic acid residue, Y ′ represents a polyol residue, and n represents an integer of 1 to 5. ), But are not limited thereto.

Formula (2)

[0071]

Embedded image

(Poly) isocyanate compound (b-2-
Examples of 2) include aliphatic diisocyanate compounds such as methylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethylene diisocyanate, lysine diisocyanate, and dimer diisocyanate; 2,4-tolylene diisocyanate, 2,4-tolylene diisocyanate Dimer of isocyanate, 2,6-tolylene diisocyanate,
p-xylene diisocyanate, m-xylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3,3'-
Aromatic diisocyanate compounds such as dimethylbiphenyl-4,4'-diisocyanate; isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2,6) diisocyanate, 1,3- (isocyanate An alicyclic diisocyanate compound such as methyl) cyclohexane; a diisocyanate compound which is a reaction product of a diol and a diisocyanate such as an adduct of 1 mol of 1,3-butylene glycol and 2 mol of tolylene diisocyanate; Terminal isocyanate compounds represented by the following general formula (3) (wherein X represents a polyisocyanate residue, Y represents a polyol residue, and n represents an integer of 1 to 5).

General formula (3)

[0074]

Embedded image

The polyols usable in the above reaction include, for example, polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polybutylene glycol and polytetramethylene glycol; ethylene glycol, propanediol, propylene glycol, butanediol, butylene Glycol,
Hexanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol,
Alkylene glycols such as diglycerin, ditrimethylolpropane and dipentaerythritol, ethylene oxide modified, propylene oxide modified, butylene oxide modified, tetrahydrofuran modified, ε-caprolactone modified, γ-butyrolactone modified, δ-
Modified valerolactone, modified methylvalerolactone;
A copolymer of ethylene oxide and propylene oxide, a copolymer of propylene glycol and tetrahydrofuran,
A copolymer of ethylene glycol and tetrahydrofuran,
Hydrocarbon polyols such as polyisoprene glycol, hydrogenated polyisoprene glycol, polybutadiene glycol, hydrogenated polybutadiene glycol;

Aliphatic polyester polyol which is a reaction product of an aliphatic dicarboxylic acid such as adipic acid or dimer acid and a polyol such as neopentyl glycol or methylpentanediol;

Polyester polyols such as aromatic polyester polyols which are reaction products of aromatic dicarboxylic acids such as terephthalic acid and polyols such as neopentyl glycol; polycarbonate polyols, acrylic polyols, polytetramethylene hexaglyceryl ether ( Polyhydric hydroxyl compound such as hexaglycerin modified with tetrahydrofuran); mono- and polyhydric hydroxyl-containing compounds having terminal ether groups of the above polyhydric hydroxyl-containing compound; polyhydric hydroxyl-containing compound, fumaric acid, phthalic acid, and isophthalic acid Polyhydric hydroxyl-containing compounds obtained by esterification with dicarboxylic acids such as acid, itaconic acid, adipic acid, sebacic acid, and maleic acid; by the transesterification reaction of polyhydric hydroxyl compounds such as glycerin with fatty acid esters of animals and plants Profit Polyhydric hydroxyl group-containing compound of monoglycerides or the like, and the like, but is not limited thereto, as long as 2-6 functional polyol, either can be used.

Examples of the carbonate (b-2-3) include carbonates such as dimethyl carbonate, diethyl carbonate and dipropyl carbonate. Incidentally, phosgene, methyl chlorocarbonate, ethyl chlorocarbonate and the like can also be used.

The maleimide compound (derivative) represented by the general formula (1) used in the active energy ray-curable ink jet ink receiving layer composition of the present invention can be obtained by the above-described production method. The production method of the compound used is not limited to these. The amount of the compound containing two or more maleimide skeletons in the molecule of the ink-jet ink receiving layer composition of the present invention is preferably in the range of 20% by weight to 50% by weight.
The mixing ratio with the alkylene oxide-modified polyfunctional (meth) acrylate is determined from the viewpoint of the required coating film properties and active energy ray curability.

An active energy ray-curable ink jet ink receiving layer composition containing the alkylene oxide-modified polyfunctional (meth) acrylate and a compound containing two or more maleimide skeletons in the molecule of the present invention further forms a receiving layer. It is preferable to add another compound having an unsaturated double bond in consideration of adhesion to the substrate. For example, monofunctional (meth) acrylate monomers such as carbitol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and cyclohexyl (meth) acrylate, and / or 1,6-hexanediol di (meth) acrylate, neopentyl Glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate,
1,9-nonanediol di (meth) acrylate,
Use of a bifunctional (meth) acrylate monomer such as 4-butanediol di (meth) acrylate may be used in combination.

Further, a compound having an acryloyloxy group or a methacryloyloxy group is added to the active energy ray-curable inkjet ink receiving layer composition of the present invention in order to adjust the physical properties of the receiving layer and the curability of the active energy ray. It is possible.

These are roughly classified into (A-1); (poly) ester (meth) acrylate, (A-2); urethane (meth) acrylate, (A-3); epoxy (meth) acrylate, (A) -4); (poly) ether (meth) acrylate, (A-5); alkyl (meth) acrylate or alkylene (meth) acrylate, (A-
6); (meth) acrylate having an aromatic ring, (A-
7); (meth) acrylates having an alicyclic structure, and the like, but are not limited thereto.

The (poly) ester (meth) acrylate (A-1) which can be used in combination with the active energy ray-curable ink jet ink receiving layer composition of the present invention is (meth) having at least one ester bond in the main chain. As a general term for acrylate, urethane (meth) acrylate (A-2)
As a general term for (meth) acrylates having one or more urethane bonds in the main chain, epoxy acrylate (A-3) refers to a (meth) acrylate obtained by reacting one or more functional epoxides with (meth) acrylic acid. Collectively,
Alkyl (meth) acrylate or alkylene (meth)
The acrylate (A-4) has a main chain of a straight-chain alkyl, a branched alkyl, a straight-chain alkylene group or a branched alkylene group, and may have a halogen atom and / or a hydroxyl group on a side chain or at a terminal (meth) ) A generic term for acrylates
(Meth) acrylate having an aromatic ring (A-5)
As a general term for (meth) acrylates having an aromatic ring in the main chain or side chain, (meth) acrylates (A-6) having an alicyclic structure are an oxygen atom or a nitrogen atom as a structural unit in the main chain or a side chain. Is used as a generic term for (meth) acrylates having an alicyclic structure which may contain

Examples of the (poly) ester (meth) acrylate (A-1) which can be used in combination with the active energy ray-curable ink jet ink receiving layer composition of the present invention include, for example,
Alicyclic modified neopentyl glycol (meth) acrylate ("R-629" or "R-6" manufactured by Nippon Kayaku Co., Ltd.)
44 "), monofunctional (poly) ester (meth) acrylates such as caprolactone-modified 2-hydroxyethyl (meth) acrylate, ethylene oxide-modified succinic acid (meth) acrylate, and caprolactone-modified tetrahydrofurfuryl (meth) acrylate; pivalic acid ester Neopentyl glycol di (meth) acrylate,
Caprolactone-modified hydroxypivalic acid ester neopentylglycol di (meth) acrylate, epichlorohydrin-modified phthalic acid di (meth) acrylate; 1 mol or more of ε-caprolactone, γ-butyrolactone, δ- Mono-, di- or tri (meth) acrylate of triol obtained by adding a cyclic lactone compound such as valerolactone or methylvalerolactone;

One mole or more of ε-caprolactone per mole of pentaerythritol or ditrimethylolpropane,
Mono, di, tri or tetra (meth) acrylate of triol obtained by adding a cyclic lactone compound such as γ-butyrolactone, δ-valerolactone or methylvalerolactone; 1 mol or more of ε per mol of dipentaerythritol
Mono-triol obtained by adding a cyclic lactone compound such as caprolactone, γ-butyrolactone, δ-valerolactone or methylvalerolactone, or poly (meth) acrylate such as triol, tetraol, pentaol or hexaol. Mono (meth) acrylate or poly (meth) acrylate of a polyhydric alcohol;

Diol components such as (poly) ethylene glycol, (poly) propylene glycol, (poly) tetramethylene glycol, (poly) butylene glycol, (poly) pentanediol, (poly) methylpentanediol and (poly) hexanediol And maleic acid, fumaric acid, succinic acid, adipic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, heptic acid, hymic acid, chlorendic acid, dimer acid, alkenyl succinic acid, Sebacic acid, azelaic acid, 2,2,4-trimethyladipic acid, 1,
4-cyclohexanedicarboxylic acid, terephthalic acid, 2-
Sodium sulfoterephthalic acid, 2-potassium sulfoterephthalic acid, isophthalic acid, 5-sodium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid, orthophthalic acid, 4-sulfophthalic acid, 1,10-decamethylenedicarboxylic acid, muconic acid, shu (Meth) acrylates of polyester polyols composed of polybasic acids such as acid, malonic acid, glutanic acid, trimellitic acid, and pyromellitic acid; the diol component, polybasic acid, ε-caprolactone, γ-butyrolactone, and δ-valerolactone Or polyfunctional (poly) ester (meth) acrylates such as (meth) acrylate of a cyclic lactone-modified polyester diol composed of methyl valerolactone, but is not limited thereto.

Urethane (meth) acrylate (A-2) usable in combination with the active energy ray-curable ink of the present invention
Is a general term for (meth) acrylates obtained by reacting a hydroxy compound (A-2-1) having at least one (meth) acryloyloxy group with an isocyanate compound (A-2-2).

Examples of the hydroxy compound (A-2-1) having at least one (meth) acryloyloxy group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
-Hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate , Trimethylolpropane di (meth) acrylate, trimethylolethanedi (meth) acrylate, pentaerythritol tri (meth)
Acrylate or glycidyl (meth) acrylate-
(Meth) acrylic acid adducts, 2-hydroxy-3-phenoxypropyl (meth) acrylate and other various hydroxyl-containing (meth) acrylate compounds, and the above-mentioned hydroxyl-containing (meth) acrylate compounds and ε-caprolactone Ring-opening reactants and the like.

As the isocyanate compound (A-2-2), for example, p-phenylenediisocyanate, m-
Phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate,
Aromatic diisocyanates such as 3,3'-dimethyldiphenyl-4,4'-diisocyanate, 3,3'-diethyldiphenyl-4,4'-diisocyanate, naphthalene diisocyanate; isophorone diisocyanate, hexamethylene diisocyanate, 4,4 ' -Aliphatic or alicyclic diisocyanates such as dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate and lysine diisocyanate; one or more burettes of isocyanate monomers or isocyanurates obtained by trimerizing the diisocyanate compound Polyisocyanate;
The above isocyanate compound and various polyols (A-2-
And polyisocyanate obtained by urethanation reaction with 3).

The polyol (A-2-3) used for producing the polyisocyanate includes, for example, (poly) ethylene glycol, (poly) propylene glycol, (poly) butylene glycol and (poly) tetramethylene glycol. (Poly) alkylene glycols; ethylene glycol, propanediol, propylene glycol, tetramethylene glycol, pentamethylene glycol, hexanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane, dipentaerythritol Alkylene glycols such as ethylene oxide-modified, propylene oxide-modified, butylene oxide-modified, tetrahydrofuran-modified, ε-capro Lactone-modified products, .gamma.-butyrolactone modified products, .delta.-valerolactone-modified products, and methyl valerolactone-modified product;

Copolymers such as copolymers of ethylene oxide and propylene oxide, copolymers of propylene glycol and tetrahydrofuran, copolymers of ethylene glycol and tetrahydrofuran, polyisoprene glycol, hydrogenated polyisoprene glycol, polybutadiene glycol, and hydrogenated polybutadiene glycol Hydrogen-based polyols; aliphatic polyester polyols which are esterification products of aliphatic dicarboxylic acids such as adipic acid and dimer acid with polyols such as neopentyl glycol and methylpentanediol; aromatic dicarboxylic acids such as terephthalic acid Polyester polyols, which are esterification products of phenol and polyols such as neopentyl glycol; polycarbonate polyols; acrylic polyols; Polyhydric hydroxyl compounds such as methylene hexaglyceryl ether (tetrahydrofuran modified product of hexaglycerin); mono- and polyhydric hydroxyl-containing compounds having terminal ether groups of the above-mentioned polyhydric hydroxyl-containing compounds; and the above-mentioned polyhydric hydroxyl-containing compounds and fumaric acid Polyhydric hydroxyl-containing compounds obtained by esterification with dicarboxylic acids such as phthalic acid, isophthalic acid, itaconic acid, adipic acid, sebacic acid, and maleic acid; polyhydric hydroxyl compounds such as glycerin; and fatty acid esters of animals and plants And a polyvalent hydroxyl group-containing compound such as monoglyceride obtained by transesterification with thiol, but are not limited thereto.

The epoxy (meth) acrylate (A-3) which can be used in combination with the active energy ray-curable ink jet ink receiving layer composition of the present invention is obtained by reacting a monofunctional or higher functional epoxide with (meth) acrylic acid. (Meth) acrylate. Examples of the epoxide (A-3-1) serving as a raw material of the epoxy (meth) acrylate include (methyl) epichlorohydrin, hydrogenated bisphenol A, hydrogenated bisphenol S, hydrogenated bisphenol F, and ethylene oxide and propylene oxide modified thereof. Epichlorohydrin-modified hydrogenated bisphenol-type epoxy resin synthesized from a product or the like; alicyclic epoxy resin such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis- (3,4-epoxycyclohexyl) adipate An alicyclic epoxide such as an epoxy resin containing a hetero ring such as triglycidyl isocyanurate;

Epichlorohydrin-modified bisphenol type epoxy resin synthesized from (methyl) epichlorohydrin and bisphenol A, bisphenol S, bisphenol F, ethylene oxide and propylene oxide modified products thereof; phenol novolak type epoxy resin; cresol novolak type epoxy resin Epoxidized products of various dicyclopentadiene-modified phenolic resins obtained by reacting dicyclopentadiene with various phenols; epoxidized products of 2,2 ′, 6,6′-tetramethylbiphenol, and aromatic epoxides such as phenylglycidyl ether ;

(Poly) ethylene glycol, (poly) propylene glycol, (poly) butylene glycol,
(Poly) glycidyl ethers of glycols such as (poly) tetramethylene glycol and neopentyl glycol; (poly) glycidyl ethers of glycols modified with alkylene oxide; trimethylolpropane, trimethylolethane, glycerin, diglycerin, erythritol, Pentaerythritol, sorbitol,
Alkylene-type epoxides such as (poly) glycidyl ether of aliphatic polyhydric alcohol such as 1,4-butanediol and 1,6-hexanediol; (poly) glycidyl ether of alkylene oxide-modified aliphatic polyhydric alcohol;

Glycidyl esters of carboxylic acids such as adipic acid, sebacic acid, maleic acid and itaconic acid; glycidyl ethers of polyester polyols of polyhydric alcohols and polycarboxylic acids; glycidyl (meth) acrylate, methyl glycidyl (meth) Copolymers of acrylates, including, but not limited to, glycidyl esters of higher fatty acids, epoxidized linseed oil, epoxidized soybean oil, epoxidized castor oil, and aliphatic epoxy resins such as epoxidized polybutadiene .

Examples of the alkyl (meth) acrylate or alkylene (meth) acrylate (A-4) which can be used in combination with the active energy ray-curable inkjet ink receiving layer composition of the present invention include, for example, methyl (meth) acrylate, ethyl ( (Meth) acrylate, propyl (meth)
Acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, neopentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate,
Decyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, pentadecyl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, neryl (meth) acrylate,
Geranyl (meth) acrylate, farnesyl (meth)
Monofunctional (meth) acrylates such as acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, docosyl (meth) acrylate, trans-2-hexene (meth) acrylate;

1,2-butylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 1,10-decanediol di Di (meth) of hydrocarbon diol of (meth) acrylate
Acrylates;

Mono (meth) acrylate, di (meth) acrylate or tri (meth) acrylate of trimethylolpropane
Acrylate (hereinafter, "poly" is used as a generic term for polyfunctional such as di, tri, tetra, etc.), glycerin mono (meth) acrylate or poly (meth) acrylate, pentaerythritol mono (meth) acrylate or poly (meth) A) mono (meth) acrylate or poly (meth) acrylate of acrylate, ditrimethylolpropane, mono (meth) acrylate of dipentaerythritol or mono (meth) acrylate of poly (meth) acrylate (Meth) acrylates or poly (meth) acrylates;

2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4
Hydroxy-containing (meth) acrylates such as -hydroxybutyl (meth) acrylate and 3-chloro-2-hydroxyethyl (meth) acrylate; 2,3-dibromopropyl (meth) acrylate, tribromophenyl (meth) acrylate, ethylene oxide (Meth) acrylates having a bromine atom, such as modified tribromophenyl (meth) acrylate and ethylene oxide-modified tetrabromobisphenol A di (meth) acrylate;

Trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, dodecafluoroheptyl (meth) acrylate, hexadecafluorononyl (meth) Acrylate, hexafluorobutyl (meth) acrylate, 3-perfluorobutyl-2-hydroxypropyl (meth) acrylate, 3-perfluorohexyl-2-hydroxypropyl (meth) acrylate, 3-perfluorooctyl-2-hydroxypropyl (Meth) acrylate, 3- (perfluoro-5-
Methylhexyl) -2-hydroxypropyl (meth) acrylate, 3- (perfluoro-7-methyloctyl) -2-hydroxypropyl (meth) acrylate,
(Meth) acrylates having a fluorine atom, such as 3- (perfluoro-8-methyldecyl) -2-hydroxypropyl (meth) acrylate, and the like,
It is not limited to these.

Examples of the (meth) acrylate (A-5) having an aromatic ring which can be used in combination with the active energy ray-curable ink jet ink receiving layer composition of the present invention include, for example, phenyl (meth) acrylate and benzyl acrylate. Functional (meth) acrylates; bisphenol A
Examples include, but are not limited to, diacrylates, diacrylates such as bisphenol F diacrylate, and bisphenol S diacrylate.

Examples of the (meth) acrylate (A-6) having an alicyclic structure which can be used in combination with the active energy ray-curable ink jet ink receiving layer composition of the present invention include:
Cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, cycloheptyl (meth) acrylate, bicycloheptyl (meth) acrylate, isobornyl (meth) acrylate, bicyclopentyl di (meth) acrylate, tricyclodecyl (meth) acrylate, bicyclopentenyl (Meth) acrylate,
Norbornyl (meth) acrylate, bicyclooctyl (meth) acrylate, tricycloheptyl (meth)
Monofunctional (meth) acrylates having an alicyclic structure such as acrylates and cholesteroid skeleton substituted (meth) acrylates; di (meth) of hydrogenated bisphenols such as hydrogenated bisphenol A, hydrogenated bisphenol F and hydrogenated bisphenol S Acrylates, di (meth) acrylates of hydrogenated trisphenols, di (meth) acrylates of hydrogenated p, p'-biphenols;"KayaradR684"
Polyfunctional (meth) acrylates having a cyclic structure such as dicyclopentane-based di (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, and bisphenol fluorenedihydroxy (meth) acrylate such as Nippon Kayaku Co., Ltd. : Tetrahydrofurfuryl (meth) acrylate, morpholinoethyl (meth)
Alicyclic acrylate having an oxygen atom and / or a nitrogen atom in a structure such as acrylate, and the like,
It is not limited to this.

The compound having an acryloyl group or a methacryloyl group which can be used in combination with the active energy ray-curable inkjet ink receiving layer composition of the present invention includes:
In addition to the above compounds, for example, a reaction product of a (meth) acrylic acid polymer and glycidyl (meth) acrylate or a glycidyl (meth) acrylate polymer and (meth)
Poly (meth) acryl (meth) acrylate such as a reaction product with acrylic acid; (meth) acrylate having an amino group such as dimethylaminoethyl (meth) acrylate; isocyanurate such as tris ((meth) acryloxyethyl) isocyanurate (Meth) acrylate; phosphazene (meth) acrylate such as hexakis [((meth) acryloyloxyethyl) cyclotriphosphazene]; (meth) acrylate having a polysiloxane skeleton; polybutadiene (meth) acrylate; melamine (meth) acrylate Can also be used. Among these compounds having an acryloyl group or a methacryloyl group, a compound having 1 to 6 acryloyl groups or methacryloyl groups in one molecule is preferable.

Examples of the (meth) acrylamide derivative that can be used in combination with the active energy ray-curable inkjet ink receiving layer composition of the present invention include monofunctional (meth) acrylamides such as N-isopropyl (meth) acrylamide and acryloylmorpholine. And polyfunctional (meth) acrylamides such as methylenebis (meth) acrylamide.

The amount of the compound having an acryloyloxy group or a methacryloyloxy group which can be used in combination in the composition of the present invention is from 2% by weight to 20% by weight.
% By weight.

The ink jet ink receiving layer of the present invention comprises:
It is preferable to add a component for forming a heterogeneous structure in the receiving layer in order to enhance the ink absorbency. As a method for forming a heterogeneous structure in the receiving layer, addition of inorganic and / or organic fine particles / pigments and the like can be mentioned.

As the inorganic and / or organic fine particles and pigments, those which are insoluble in the cured product of the composition of the present invention are preferably used.

[0108] Colloidal silica, synthetic silica powder, clay, talc, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate,
Aluminum silicate, synthetic zeolite, smectite,
Montmorolinite group minerals, synthetic mica, alumina, zinc oxide, titanium white, protein powder such as leather powder, silk powder, protein, chitin, chitosan, starch derivatives, sugars such as pullulan, dextrin, acrylic resin, styrene resin, urea Organic polymer fine particles such as formaldehyde resin, benzoguanamine resin, silicone resin, and fluororesin are exemplified. The amount of addition varies depending on what is used, but is 2% by weight to 30% by weight.

The ink jet ink receiving layer composition of the present invention may contain a surfactant for the purpose of adjusting the surface tension to increase the affinity with the base material and to smooth the cured coating film. Can be done. Surfactants that can be used include commercially available surfactants as leveling agents, and modified silicones, acrylic copolymers, fluorine surfactants, acetylene glycol surfactants, and the like are recommended. Examples thereof include Disparon # 1700 surface modifier (Kusumoto Kasei Co., Ltd.), perenol acrylic copolymer (Henkel Hakusui Co., Ltd.), paintat modified silicone (Dow Corning Co., Ltd.), Megafac fluorine Surfactants (Dainippon Ink and Chemicals, Inc.), Dynol 604 acetylene glycol-based surfactant (Air Products Japan, Ltd.) and the like. It goes without saying that the present invention is not limited to the exemplified compounds.

The active energy ray-curable ink-jet ink receiving layer composition of the present invention can be used for ink-jet paper such as ink-jet dedicated paper and OHP sheets, discs such as CD-R (write-once compact disc) and DVD (digital versatile disc). It is useful for an information recording medium such as a shape recording medium and a card recording medium such as an IC card.

The active energy ray-curable ink-jet ink-receiving layer composition of the present invention has an inherent spectral sensitivity at 200 to 400 nm, and in the absence of a photopolymerization initiator, an ultraviolet or visible light having a wavelength of 180 to 500 nm. 254 nm,
Light having a wavelength of 308 nm, 313 nm, 365 nm is effective for curing the active energy ray-curable ink of the present invention.
Further, the active energy ray-curable ink of the present invention can be cured by irradiation with energy rays other than ultraviolet rays or by heat. Further, the active energy ray-curable ink of the present invention can be cured either in the air and / or in an inert gas.

Examples of light sources of ultraviolet or visible light having a wavelength of 180 to 500 nm include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, chemical lamps, black light lamps, xenon flash lamps, and mercury-free lamps. Xenon lamps, excimer lamps, short arc lamps, helium / cadmium lasers, argon lasers, excimer lasers, and sunlight.

Further, the active energy ray-curable ink jet ink receiving layer composition of the present invention may further comprise a coupling agent, a tackifier, an antifoaming agent, a plasticizer, an oxidizing agent, depending on the intended use, in addition to those exemplified above. An inhibitor, an ultraviolet absorber, a flame retardant and the like can be used in combination as appropriate.

The coupling agent which can be used in combination with the active energy ray-curable ink jet ink receiving layer composition of the present invention is not particularly limited as long as it is a known and commonly used one.
For example, a silane coupling agent such as γ-glycidoxypropyltrimethoxysilane or γ-chloropropyltrimethoxysilane; tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis ( Dioctyl pyrophosphate) titanate coupling agents such as ethylene titanate;
Aluminum-based coupling agents such as acetoalkoxyaluminum diisopropylate; acetylacetone.
Examples include zirconium-based coupling agents such as zirconium complexes, but are not limited thereto.

The tackifier, defoamer, plasticizer, antioxidant, ultraviolet absorber and flame retardant which can be used in combination with the active energy ray-curable ink jet ink receiving layer composition of the present invention include:
Any known and commonly used ones, their curability,
It can be used without any particular limitation as long as the resin properties are not impaired.

In order to obtain the active energy ray-curable inkjet ink receiving layer composition of the present invention, the above-mentioned components may be mixed, and the order and method of mixing are not particularly limited.

The active energy ray-curable ink-jet ink receiving layer composition of the present invention does not substantially require a solvent. It is also possible to dilute the active energy ray-curable ink of the present invention with other commonly used organic solvents such as acetates, aromatic hydrocarbons such as benzene, toluene and xylene.

[0118]

EXAMPLES The composition of the present invention is an ink jet ink receiving layer composition which is excellent in active energy ray curability, coating film strength and ink jet printability and has little mechanical deformation. Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited to the scope of the following Examples.

(Synthesis Example 1) Glycine 3 was placed in a 1-L three-necked flask equipped with a dropping funnel, a condenser, and a stirrer.
7.5 g and 400 ml of acetic acid were charged, and a solution consisting of 49.0 g of maleic anhydride and 300 ml of acetic acid was dropped from the dropping funnel over 2 hours while stirring at room temperature. After completion of the dropwise addition, stirring was further continued for 1 hour, and then the reaction was terminated. The resulting precipitate was collected by filtration and recrystallized from a mixed solvent of water: methanol = 3: 7 (volume ratio) to give maleimide acetic acid 1
1 g was obtained.

<Physical properties of maleimide acetic acid> ¹ H NMR (300 MHz, DMSO-d6): 7.0 pp
m (s, 2H, -C = C-), 4.1 ppm (s, 2H,-
^{_{CH 2 -) IR: 3170cm -1}} (-COOH), 1750cm -1, 1
719 cm ^-1 (C = O), 831 cm ^-1 , 696 cm ^-1 (-C
= C-) Elemental analysis (CHN): Calculated value: C 46.5%, H 3.87%, N 9.03% Analysis value: C 46.2%, H 4.05%, N 8.70%

(Synthesis Example 2) Polytetramethylene glycol having a number average molecular weight of 250 (B.A.
S.F. Japan “Poly (THF25)”
0 ", polystyrene equivalent value by GPC: number average molecular weight 440, weight average molecular weight 470) 5 g, maleimide acetic acid 6.8 g obtained in Synthesis Example 1, p-toluenesulfonic acid 1.
2 g, 2,6-tert-butyl-p-cresol 0.06
g and 15 ml of toluene, 240 torr,
The reaction was continued while stirring for 4 hours while removing water generated at 80 ° C. The reaction mixture was dissolved in 200 ml of toluene and washed three times with 100 ml of saturated sodium bicarbonate and once with 100 ml of saturated saline. The organic phase was concentrated to obtain 9 g of a pale yellow liquid of a maleimide compound MIA250 represented by the following formula (4).

Equation (4)

[0123]

Embedded image

<Physical properties of maleimide compound MIA250> IR: 1750 cm ^-1 , 1719 cm ^-1 (C = O), 831
^{cm -1, 698cm -1 (C =} C) 1 H NMR (300MHz, CDCl 3): 6.7ppm
(S, 4H, -CH = CH-), 4.3 ppm [s, 4
_{H, N-CH 2 - (} C = O) -], 4.1ppm (t, 4
H, - (C = O) -O-CH 2 -), 3.4~3.5ppm
_{(M, -O-CH 2 -} ), 1.6~1.7ppm (m, -C
H ₂ −) ¹³ C NMR (75 MHz, CDCl ₃ ): 170 ppm [N
-( C = O)], 167 ppm [-( C = O) -O], 1
35ppm (- C H = C H -), 64.5~70.9ppm
_{(-O- C H 2 -),} 38.7ppm (N- C H 2 -) 25.7~26.6ppm (- C H 2 -) molecular weight by GPC distribution analysis (in terms of polystyrene): number average molecular weight 730 , Weight average molecular weight 750

(Synthesis Example 3) In Synthesis Example 2, polytetramethylene glycol having a number average molecular weight of 250 (“Poly (THF)” manufactured by BSF Japan Ltd.) was used.
250 ", polystyrene equivalent value by GPC: number average molecular weight 440, weight average molecular weight 470) polytetramethylene glycol having a number average molecular weight of 650 (" PTG650SN "manufactured by Hodogaya Chemical Co., Ltd.) (Number average molecular weight 1,200, weight average molecular weight 1,600) 16 g of a pale yellow liquid of a maleimide compound MIA650 represented by the following formula (5) was obtained in the same manner as in Synthesis Example 2 except for using 13 g.

Equation (5)

[0127]

Embedded image

<Physical properties of maleimide compound MIA650> IR: 1750 cm ^-1 , 1719 cm ^-1 (C = O), 831
^{cm -1, 698cm -1 (C =} C) 1 H NMR (300MHz, CDCl 3): 6.8ppm
(S, 4H, -CH = CH-), 4.3 ppm [s, 4
_{H, N-CH 2 - (} C = O) -], 4.2ppm [t, 4
H, - (C = O) -O-CH 2 -], 3.4ppm (m, -
_{O-CH 2 -), 1.6~1.7ppm} (m, -CH 2 -) 13 C NMR (75MHz, CDCl 3): 170ppm [N
-( C = O)], 167 ppm [-( C = O) -O], 1
34ppm (- C H = C H -), 65.7ppm, 70.0~
_{70.7ppm (-O- C H 2 -)} , 38.6ppm (N- C
H ₂ −), 25.4-26.5 ppm (−CH ₂ −) Elemental analysis (CHN): Calculated value: C 61.3%, H 8.27%, N 3.03% Analysis value: C 58.3%, H7.50%, N1.80% Molecular weight distribution analysis result by GPC (polystyrene conversion): number average molecular weight 2,100, weight average molecular weight 2,5
00

(Examples 1 and 2, Comparative Examples 1 and 2) Alkylene oxide-modified polyfunctional acrylate and maleimide compound
Comparative Example 1 using nitrogen-containing acrylate instead of maleimide compound and two examples of the composition of the present invention based on the combination of MIA250 and MIA650, and using hydroxyl-containing polyfunctional monomer instead of alkylene oxide-modified polyfunctional acrylate A composition of Comparative Example 2 was prepared.

[0130]

[Table 1]

<Description of Compounds in Table 1> SR415: Ethylene oxide (20 mol) modified trimethylolpropane triacrylate T-200EA: Ethylene oxide (45 mol) modified trimethylolpropane triacrylate DMAPAA: N, N-dimethylaminopropylacrylamide M-305: Pentaerythritol triacrylate CBA: Ethyl carbitol acrylate Irg. 184: 1-hydroxycyclohexyl phenyl ketone aerosil 200: Synthetic silica fine particles manufactured by Nippon Aerosil Co., Ltd.

The composition of Table 1 was placed on a white PET film E-22 (188 μm thick) A4 size manufactured by Toray Industries, Inc.
Coating was performed with a 4-bar coater. Thereafter, the coating film was cured with an ultraviolet curing device manufactured by Eye Graphics Inc. (equipped with a high-pressure mercury lamp of 120 W / cm and a condensing cold mirror).
Curing was performed at 150 mJ / cm ² and 300 mJ / cm ² (the integrated light amount was measured using a light meter UVPF-3 manufactured by Eye Graphics Co., Ltd.)
6 use), and the resulting coating film was evaluated as follows. The thickness was about 9 μm.

1) Evaluation of curability The surface of the coating film was gently rubbed with a Kim wipe paper impregnated with methanol. If it is not cured, it is attacked by methanol and the coating film surface becomes cloudy. If cured, there is no change in surface appearance.

2) Evaluation of coating film strength After the surface of the cured coating film was lightly scratched with a nail, the appearance of the coating film was observed. A sample without any breakage of the coating film or large scratches was evaluated as OK. On the contrary, a case where the film was broken or large scratches were observed was judged as NG.

3) Evaluation of Mechanical Deformation The curl at the end of the film was observed.

4) Evaluation of ink printability Inkjet printer BJC-600 manufactured by Canon Inc.
C, the above-prepared film with the receiving layer was set, and a printing test of printer settings of OS / WINDOWS 95 manufactured by Microsoft Corporation was performed. Immediately after printing,
The printed surface was rubbed with Kimwipe paper, and the remaining ink was visually observed.

Table 2 shows the results of applying the above evaluations to the compositions shown in Table 1.

[0138]

[Table 2]

As is clear from the results in Table 2, the composition of the present invention is excellent in ultraviolet curability and coating film strength, has little mechanical deformation, and is excellent in printability of ink jet recording.

[0140]

The active energy ray-curable ink-jet ink-receiving layer composition of the present invention is excellent in active energy ray-curable property and excellent in printability of ink-jet recording, satisfying both problems of coating film strength and mechanical deformation. I have. Further, by applying the present composition to an information recording medium, a highly reliable recording medium with little deformation can be obtained.

Claims (9)

[Claims] 1. An alkylene oxide-modified polyfunctional (meth)
An active energy ray-curable inkjet ink receiving layer composition containing a compound containing two or more acrylates and a maleimide skeleton in a molecule. 2. A compound containing two or more maleimide skeletons in a molecule is represented by the following general formula (1) (wherein, m and n each independently represent an integer of 1 or more; R ₁₁ and R ₁₂ each represent G ₁ and G ₂ each independently represent a hydrocarbon bond consisting of an aliphatic group or an aromatic group, and G ₁ and G ₂ each independently represent an ether bond, an ester bond, a urethane bond, or a carbonate bond.
R ₂ is an aliphatic group or an aromatic group having (a) an ether bond,
(A) a (poly) ether-linked chain having an average molecular weight of 40 to 100,000 linked by at least one bond selected from the group consisting of (b) an ester bond, (c) a urethane bond, and (d) a carbonate bond; (Poly) ether residue, (B) (poly) ester linked chain or (poly) ester residue, (C) (poly) urethane linked chain or (poly) urethane residue or (D) (poly) carbonate linked chain or Represents a (poly) carbonate residue. The active energy ray-curable inkjet ink-receiving layer composition according to claim 1, which is represented by the formula: General formula (1) 3. R ₁₁ and R ₁₂ are each independently a hydrocarbon bond selected from the group consisting of an alkylene group, a cycloalkylene group, an arylalkylene group and a cycloalkylalkylene group, and G ₁ and G ₂ are are each independently -COO- or -OCO- ester bond represented by, R ₂ is a straight-chain alkylene group, a branched alkylene group, an alkylene group having a hydroxyl group, cycloalkylene group, aryl group and an aryl alkylene group At least one organic group selected from the group consisting of (a) an ether bond and (b) at least one bond selected from the group consisting of an ester bond;
3. The activity according to claim 2, which contains 00000 maleic compounds which are (A) (poly) ether linked chains or (poly) ether residues or (B) (poly) ester linked chains or (poly) ester residues. Energy ray curable inkjet ink receiving layer composition. 4. R ₂ is a linear alkylene group having 2 to 24 carbon atoms, a branched alkylene group having 2 to 24 carbon atoms, an alkylene group having 2 to 24 carbon atoms having a hydroxyl group and / or an aryl group. The active energy ray-curable ink jet ink receiving layer composition according to claim 3, which contains a maleimide compound that is a (poly) ether linked chain or a (poly) ether residue having an average molecular weight of 100 to 100,000 and consisting of a repeating unit containing: . 5. The active energy ray-curable ink jet ink receiving layer composition according to claim 1, wherein the alkylene oxide is ethylene oxide. 6. The active energy ray-curable ink-jet ink receiving layer composition according to claim 5, wherein the polyfunctional (meth) acrylate has three or more functional groups. 7. The method according to claim 1, further comprising at least one selected from the group consisting of inorganic fine particles, organic fine particles, and pigments.
The active energy ray-curable inkjet ink receiving layer composition according to the above. 8. An information recording medium comprising a receiving layer formed by curing the composition according to claim 1, wherein the active energy ray is ultraviolet light. 9. The method according to claim 1, wherein the active energy ray is ultraviolet light, and further includes at least one selected from the group consisting of inorganic fine particles, organic fine particles, and pigments.
An information recording medium having a receiving layer obtained by curing the composition according to item 6.