JP4282732B2 - Polymerizable compound and curable composition - Google Patents

Description

The present invention relates to a polymerizable compound and a curable composition that are excellent in hydrolysis resistance, curability by heat or active energy rays, and water resistance of a cured product. More specifically, the present invention relates to a curable composition that can be suitably used in various fields such as various paints, resists, printing inks such as inkjet inks, and adhesives.

Conventionally, as a method for forming an image, a technique using a paint or ink that is cured by heat energy or active energy rays is known.

For example, curable inks are also known in the field of inkjet printing, and a curable resin composition prepared by making a non-aqueous polymerizable monomer into an emulsion in an aqueous solvent (Patent Document 1), a water-soluble polymerizable monomer. (Patent Documents 2 and 3) using a polyol, an esterification reaction product of a polyol and (meth) acrylic acid (Patent Document 4), and a polyvinyl alcohol having a (meth) acrylic acid ester group introduced into a side chain (Patent Document 5) , 6 and 7).

In addition, although not intended for inkjet printing, materials that can be assumed to be replaceable from the above examples include polyvinyl alcohol having a (meth) acrylic acid ester group introduced in the side chain (Patent Document 8), side chain Examples thereof include polyvinyl alcohol having a (meth) acrylamide group introduced therein (Patent Documents 9, 10 and 11), and a saccharide having a (meth) acrylamide structure introduced through an ether bond or a urethane bond (Patent Document 12).

However, the ink for ink jet printing used for the ink jet recording method needs to be a material having low viscosity and good flow characteristics. When a water-soluble polymer such as polyvinyl alcohol or cellulose is used, the viscosity of the ink is not sufficiently low and it is not suitable for high-density nozzles, and is not suitable for precision printing.

The water-soluble polymerizable compound having a (meth) acrylic acid ester group is, for example, when an anionic aqueous dye or an aqueous pigment dispersion is used as a coloring material, As the acrylic acid is generated by the above, the pH of the ink is lowered, and the aqueous dye may be precipitated or the pigment dispersion may be aggregated, and the storage stability of the ink and the curability by irradiation with active energy rays are lowered.

As a method for solving such problems, a low molecular weight polyfunctional monomer using (meth) acrylamide as a polymerizable group has been proposed, and N-methylol (meth) acrylamide or N-alkoxymethyl (meth) acrylamide and A reaction product of a polyol (Patent Document 13) has been proposed. This reaction product satisfies the level required for the ink jet ink in terms of the viscosity of the aqueous solution, and is excellent in cured physical properties by active energy rays.

However, the reaction product of N-methylol (meth) acrylamide or N-alkoxymethyl (meth) acrylamide and polyol in Patent Document 13 cannot actually suppress hydrolysis and generates (meth) acrylamide and formaldehyde. Therefore, in addition to the storage stability of the ink, it is not preferable for environmental hygiene.
JP-A-8-48922 JP-A-3-216379 JP-A-7-224241 JP2002-187918 JP2007-182513 JP2007-70604 JP2007-84636 Special table 2000-506282 JP 62-32110 A JP-A-7-88850 JP 2006-193526 A Special table 10-507768 JP 2004-323753 A

The present invention has been made in view of the above situation, and is excellent in hydrolysis resistance, curability by heat or active energy rays and water resistance of the cured product, and further, the solution has a low viscosity required for ink jet printing. It aims at providing the polymeric compound and curable composition which satisfy | fill.

  As a result of intensive investigations to achieve the above-mentioned problems, the present inventors have found that a polymerizable compound obtained by an acetalization reaction between a compound containing a (meth) acrylamide group having a specific structure and a sugar is resistant to water. Decomposability, curability by heat or active energy rays, and water resistance of the cured product, and the viscosity of the solution of the polymerizable compound satisfies the low viscosity required for inkjet, so it is also useful for inkjet printing ink applications It discovered that it was a thing and came to this invention.

  As means for achieving the above object, the invention of claim 1 is a polymerizable compound obtained by an acetalization reaction between a compound represented by the following general formula (1) or (2) and a sugar.

(Wherein n is 0 or 1, R ₁ is a hydrogen atom or a C1-C4 alkyl group, R ₂ is a hydrogen atom or a C1-C6 alkyl group, and R ₃ is n = 0. —C (R ₁ ) ═CH ₂ or, if n = 1, a —C (R ₆ ) (R ₇ ) — or —C (R ₆ ) (R ₇ ) —CH ₂ — bridging group R ₄ is a C1 to C6 alkylene group , and may further include an arylene group, an aralkylene group, an alkylene ether group, an arylene ether group, an aralkylene ether group, an alkylene thioether group, an arylene thioether group, or an aralkylene thioether group. , R ₅ is a C1-C4 alkyl group, and R ₆ and R ₇ are each independently a hydrogen atom, a C1-C4 alkyl group or an aryl group.)

The invention according to claim 2 is the polymerizable compound according to claim 1, wherein the sugar is a monosaccharide, disaccharide, trisaccharide, oligosaccharide or cyclodextrin.

The invention according to claim 3 is the polymerizable compound according to claim 1, wherein the sugar is a non-reducing sugar selected from trehalose, isotrehalose, neotrehalose and sucrose.

The invention according to claim 4 is the polymerizable compound according to claim 1, wherein the sugar is a sugar alcohol selected from mannitol, sorbitol and xylitol.

Invention of Claim 5 contains the polymeric compound as described in any one of Claims 1-4, and also at least 1 type selected from a thermal-polymerization initiator and a photoinitiator. It is a curable composition.

The invention according to claim 6 is the curable composition according to claim 5, further comprising at least one selected from an organic dye, an organic pigment, and inorganic fine particles.

The invention according to claim 7 is the aqueous curable composition according to claim 6, which is for inkjet recording.

<Invention of Claim 1>

  A compound obtained by acetalization reaction of a compound represented by the general formula (1) or (2) with a sugar (hereinafter referred to as a polymerizable compound of the present invention) has an acrylamide structure in the side chain of the sugar. It is possible to provide a polymerizable compound having hydrolysis resistance and radical polymerizability and excellent in water resistance and substrate adhesion of a cured film obtained by polymerization.

<Invention of Claim 2>

  The compound of the general formula (1) or (2) forms a 1,2-dioxolane structure or a 1,2-dioxane structure by an acetalization reaction with a compound having 1,2-diol or 1,3-diol. And combine. Monosaccharides, disaccharides, trisaccharides, oligosaccharides or cyclodextrins have a 1,2-diol bond or a 1,3-diol bond, and are therefore preferably used to provide the polymerizable compound of the present invention.

<Invention of Claim 3>

Among the sugars, trehalose, isotrehalose, neotrehalose and sucrose, which are non-reducing sugars, are highly reactive and do not have unstable aldehyde groups or keto groups, so they form glycosidic bonds or react with other hydroxyl groups. Therefore, it is preferably used for providing the polymerizable compound of the present invention.

<Invention of Claim 4>

Among sugars, the sugar alcohols mannitol, sorbitol, and xylitol have no reactive labile aldehyde group or keto group, so there are no side reactions such as formation of glycosidic bonds and reactions with other hydroxyl groups. Therefore, it is preferably used for providing the polymerizable compound of the present invention.

<Invention of Claim 5>

The polymerizable compound according to any one of claims 1 to 4, wherein the thermal polymerization initiator acts as a catalyst by heating, or the photopolymerization initiator acts as a catalyst by receiving irradiation of active energy rays such as ultraviolet rays, Since radical polymerization proceeds, excellent curability can be obtained by containing at least one selected from a thermal polymerization initiator and a photopolymerization initiator.

<Invention of Claim 6>

  Since the curable composition according to claim 5 exhibits radical polymerization due to heat or active energy rays and can form and cure a three-dimensional network structure, it further comprises an organic dye, an organic pigment, and inorganic fine particles. By containing at least one selected, a curable composition that can hold the particles in the cured product can be obtained.

<Invention of Claim 7>

  Since the composition of Claim 6 uses the polymerizable compound of Claims 1-4, it is water-soluble or hydrophilic. Furthermore, since the viscosity and fluidity of the composition satisfy the level required for inkjet ink, it is useful as an aqueous curable composition for inkjet recording.

Hereinafter, embodiments of the present invention will be described in detail.
The polymerizable compound of the present invention can adjust a curable composition that undergoes radical polymerization by heat or active energy rays by blending a thermal polymerization initiator or a photopolymerization initiator, and is excellent in hydrolysis resistance. The cured film was found to have good crosslink density, water resistance, and substrate adhesion and satisfy the low viscosity level required for inkjet inks, leading to the present invention.

The compound of the general formula (1) or (2) is bonded to a 1,2-diol or 1,3-diol of a sugar by an acetalization reaction with the sugar, and a 1,2-dioxolane structure or 1,2-dioxane Form and bond structures. That is, the curable composition according to claims 6 and 7 of the present invention (hereinafter referred to as the curable composition of the present invention) is at least selected from structural units represented by the following general formulas (3) and (4). Have a kind.

(In the formula, k is an integer of 1 or more, n is 0 or 1, R ₁ is a hydrogen atom or a C1-C4 alkyl group, and R ₂ is a hydrogen atom or a C1-C6 alkyl group. , R ₃ is —C (R ₁ ) ═CH ₂ if n = 0, or —C (R ₆ ) (R ₇ ) — or —C (R ₆ ) (R ₇ ) if n = 1. A —CH ₂ — crosslinking group, R ₄ is a C1 to C6 alkylene group , and an arylene group, an aralkylene group, an alkylene ether group, an arylene ether group, an aralkylene ether group, an alkylene thioether group, an arylene thioether group or aralkylene may include a thioether group, _{R 5} is an alkyl group C1 -C4, _{R 6} and _{R 7,} independently of one another, a hydrogen atom, C1 -C4 alkyl or aryl In is.)

R ₁ in the general formulas (1) and (2) includes a hydrogen atom, a chain alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group, an aryl group such as a phenyl group and a tolyl group, and an alkenyl group. It is done. Among these, a hydrogen atom or a methyl group is preferable.

R ₂ in the general formulas (1) and (2) includes a hydrogen atom, a chain alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, an aryl group such as a phenyl group and a tolyl group, and an alkenyl group. It is done. Among these, a hydrogen atom or a methyl group is preferable.

R ₄ in the general formulas (1) and (2) is a methylene group, ethylene group, n- or isopropylene group, n-, sec- or tert-butylene group, n- or iso-pentene group, hexene group, And a linear or branched alkylene group such as a heptene group or an octene group, and an arylene group, an aralkylene group, an alkylene ether group, an arylene ether group, an aralkylene ether group, an alkylene thioether group, an arylene thioether group, or an aralkylene thioether. Groups may be included. Among these, a methylene group, an ethylene group, and an n-propylene group are preferable.

Examples of R ₅ in the general formula (1) include a linear or branched alkyl group such as a methyl group, an ethyl group, an n- or isopropyl group, or an n-, sec- or tert-butyl group. Among these, a methyl group and an ethyl group are preferable.

R ₆ and R ₇ in the general formulas (1) and (2) are, independently of each other, a hydrogen atom, a methyl group, an ethyl group, an n- or isopropyl group or an n-, sec- or tert-butyl group, etc. Examples thereof include an aryl group such as an alkyl group, a phenyl group, and a tolyl group, an alkenyl group, and a cyclohexyl group. Among these, a hydrogen atom or a methyl group is preferable.

N in the general formula (1) is 0 or 1.

The sugar that can be used in the present invention is not particularly limited, but erythrose, threorose, erythrulose, ribose, lyxose, xylose, arabinose, apiose, ribulose, xylulose, allose, talose, gulose, glucose, altrose, mannose, galactose Monosaccharides such as Idos, fructose, psicose, sorbose, tagatose, cedoheptulose, coliose, trehalose, isotrehalose, cordierbiose, sophorose, nigerose, laminaribiose, saccharose, maltose, isomaltose, cellobiose, gentiobiose, lactose , Raffinose, gentianose, meretitol, maltotriose, cellotriose, manninotriose and other trisaccharides, stachyose Tetrasaccharides such as erythritol, isomalt, lactitol, maltitol, mannitol, sorbitol, xylitol, etc., deoxy sugars such as deoxyribose, fucose, rhamnose, uronic acids such as galacturonic acid, α-, β- or γ- Examples include cyclodextrin, hydroxypropylcyclodextrin, branched cyclodextrin, cyclitols such as inositol.

Among these, reducing sugars have an aldehyde group or a keto group, and thus are highly reactive and unstable, and cause side reactions such as the formation of glycoside bonds and reactions with other hydroxyl groups. Therefore, non-reducing sugars such as trehalose, isotrehalose, neotrehalose and sucrose, and sugar alcohols such as mannitol, sorbitol and xylitol are more preferable.

  The reaction between the compound represented by the general formula (1) or (2) and the saccharide is preferably 2 or more molecules, more preferably 3 or more molecules per saccharide. In the case of one molecule, radical polymerization proceeds only linearly even when irradiated with heat or active energy rays, and the crosslinking density is low, so that sufficient curability cannot be obtained. In the case of two or more molecules, since the polymerizable compounds of the present invention are three-dimensionally cross-linked, the cross-linking density tends to be high, and a cured film having high hardness, water resistance, and substrate adhesion can be obtained.

The reaction between the compound represented by the general formulas (1) and (2) and the sugar is usually carried out in solution with heat, an acid catalyst or a combination thereof.

The solvent constituting the solution is not particularly limited, but a composition that dissolves sugar is preferable. As an example, water; alcohols such as methanol, ethanol, n-propanol, and iso-propanol; ethylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol; ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, and ethylene glycol Glycol ethers such as diethyl ether and diethylene glycol dimethyl ether; Glycol ether acetates such as ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate and diethylene glycol monobutyl ether acetate; Propylene glycols such as propylene glycol, dipropylene glycol and tripropylene glycol Propylene glycol ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol diethyl ether, Propylene glycol ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate; dimethyl sulfoxide, N-methylpyrrolidone, dimethylformamide , Dimethylacetamide and the like. These may be used alone or in combination of two or more.

The acid catalyst used in the reaction is not limited, but examples include inorganic acids such as sulfuric acid, phosphoric acid, nitric acid, perchloric acid, formic acid, acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid. Examples thereof include organic carboxylic acids such as acid and phthalic acid, organic sulfonic acids such as methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid and dodecylbenzenesulfonic acid, and acidic cation exchange resins.

After the reaction, these acids are preferably neutralized with an alkali compound such as sodium hydroxide, potassium hydroxide, ammonia, organic amine or a solution thereof, or removed using a basic ion exchange resin.

The reaction temperature largely depends on the types of compounds and sugars represented by the general formulas (1) and (2), the type of acid catalyst, and the concentration, but usually a range of room temperature to 100 ° C. is preferably used.

Thus, when comprising the composition of Claims 5-7 of this invention using the polymeric compound of Claims 1-4 of this invention, the hardening reaction by a heat | fever or an active energy ray is expressed or accelerated | stimulated. For this purpose, known materials such as a thermal polymerization initiator, a redox initiator, and a photopolymerization initiator can be used.

The thermal polymerization initiator to be applied is not particularly limited. For example, methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tert-butylperoxy) 3,3 , 5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane, 1,1-bis (tert-hexylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (tert-hexyl) Peroxy) cyclohexane, 1,1-bis (tert-butylperoxy) cyclododecane, isobutyl peroxide, lauroyl peroxide, oxalic acid peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, octa Noil par Koxide, stearoyl peroxide, diisopropyl peroxydicarbonate, dinormalpropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di-2-methoxybutyl peroxydicarb Bonate, bis- (4-tert-butylcyclohexyl) peroxydicarbonate, (α, α-bis-neodecanoylperoxy) diisopropylbenzene, peroxyneodecanoic acid cumyl ester, peroxyneodecanoic acid octyl ester, peroxyneodecane Acid hexyl ester, peroxyneodecanoic acid-tert-butyl ester, peroxypivalic acid-tert-hexyl ester, peroxypivalic acid-tert-butyl ester, , 5-Dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, peroxy-2-ethylhexanoic acid- tert-hexyl ester, peroxy-2-ethylhexanoic acid-tert-butyl ester, peroxy-2-ethylhexanoic acid-tert-butyl ester, peroxy-3-methylpropionic acid-tert-butyl ester, peroxylauric acid-tert -Butyl ester, tert-butylperoxy-3,5,5-trimethylhexanoate, tert-hexylperoxyisopropyl monocarbonate, tert-butylperoxyisopropyl carbonate, 2,5-dimethyl-2,5- Bis (benzoylperoxy) hexane Peroxide-based polymerization initiators such as peracetic acid-tert-butyl ester, perbenzoic acid-tert-hexyl ester, perbenzoic acid-tert-butyl ester, 1,1-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (2-methyl-butyronitrile), 2,2′-azobisbutyronitrile, 2,2′-azobis (2,4-dimethyl-valeronitrile), 2,2′-azobis (2 , 4-Dimethyl-4-methoxyvaleronitrile), 2,2′-azobis (2-amidino-propane) hydrochloride, 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) Propane] hydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] hydrochloride, 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) The Pan], 2,2′-azobis [2-methyl-N- (1,1-bis (2-hydroxymethyl) -2-hydroxyethyl) propionamide], 2,2′-azobis [2-methyl-N -(2-hydroxyethyl) propionamide], 2,2′-azobis (2-methyl-propionamide) dihydrate, 4,4′-azobis (4-cyano-valeric acid, 2,2′-azobis ( 2-hydroxymethylpropionitrile), 2,2′-azobis (2-methylpropionic acid) dimethyl ester (dimethyl 2,2′-azobis (2-methylpropionate)), cyano-2-propylazoformamide, etc. And an azo polymerization initiator. Furthermore, a reducing agent may be added to the peroxide polymerization initiator described above and used as a redox initiator.

The photopolymerization initiator and photosensitizer to be applied are not particularly limited, but examples include benzophenone, hydroxybenzophenone, bis-N, N-dimethylaminobenzophenone, bis-N, N-diethylaminobenzophenone, 4-methoxy. Benzophenones such as -4'-dimethylaminobenzophenone, thioxanthones such as thioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, chlorothioxanthone, isopropoxychlorothioxanthone, anthraquinones such as ethyl anthraquinone, benzanthraquinone, aminoanthraquinone, chloroanthraquinone , Acetophenones, benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, 2,4,6-tri Romethyltriazines, 1-hydroxycyclohexyl phenyl ketone, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole Dimer, 2- (o-fluorophenyl) -4,5-phenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2, -di (p-methoxyphenyl) -5-phenylimidazole dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer 2,4,5-triarylimidazole dimers, such as benzyldimethyl ketal, 2-benzyl-2-dimethylamino- -(4-morpholinophenyl) -butan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-hydroxy-2-methyl-1-phenyl-propane -1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, phenanthrenequinone, 9,10-phenanthrenequinone, methylbenzoin Benzoins such as ethylbenzoin, 9-phenylacridine, acridine derivatives such as 1,7-bis (9,9'-acridinyl) heptane, bisacylphosphine oxide, and mixtures thereof.

In addition to these initiators, accelerators and the like can also be added. Examples include ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, ethanolamine, diethanolamine, triethanolamine and the like.

Moreover, a polymerizable monomer can be added to the curable composition of the present invention for the purpose of improving the curing speed and the physical properties of the cured product. Examples include polyethylene glycol diacrylate (having 2 to 14 ethylene groups), polyethylene glycol dimethacrylate (having 2 to 14 ethylene groups), trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, trimethylol. Methylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylolpropane ethoxytriacrylate, trimethylolpropane ethoxytrimethacrylate, trimethylolpropane propoxytriacrylate, trimethylolpropane propoxytrimethacrylate, tetramethylol methane triacrylate, tetramethylol methane trimethacrylate , Tetramethylol methane tetraacrylate, tetramethylol methane tetra Lamethacrylate, polypropylene glycol diacrylate (having 2 to 14 propylene groups), polypropylene glycol dimethacrylate (having 2 to 14 propylene groups), dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, di Pentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethoxylated pentaerythritol tetraacrylate (with ethoxy group of 40 or less), propoxylated pentaerythritol tetraacrylate (with propoxy group of 40 or less), ethoxylated trimethylolpropane triacrylate (Ethoxy group having 40 or less), propoxylated trimethylolpropane triacrylate (propoxy group having 40 or less) ), Bisphenol A polyoxyethylene diacrylate, bisphenol A polyoxyethylene dimethacrylate, bisphenol A dioxyethylene diacrylate, bisphenol A dioxyethylene dimethacrylate, bisphenol A trioxyethylene diacrylate, bisphenol A trioxyethylene dimethacrylate Bisphenol A deoxyoxyethylene diacrylate, bisphenol A deoxyoxyethylene dimethacrylate, isocyanuric acid ethoxy-modified triacrylate, polyvalent carboxylic acid (phthalic anhydride, etc.) and a compound having a hydroxyl group and an ethylenically unsaturated group (β-hydroxyethyl Acrylates, β-hydroxyethyl methacrylate, etc.), alkyl esters of acrylic acid or methacrylic acid (Acrylic acid methyl ester, methacrylic acid methyl ester, acrylic acid ethyl ester, methacrylic acid ethyl ester, acrylic acid butyl ester, methacrylic acid butyl ester, acrylic acid 2-ethylhexyl ester, methacrylic acid 2-ethylhexyl ester, etc.), 2- Quaternary chloride of hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, N, N-dimethylacrylamide, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl acrylate with methyl chloride , Quaternary chlorides of N, N-dimethylaminopropylacrylamide with methyl chloride, acryloylmorpholine, N-isopropylacrylamide, N, N-diethyl Such as acrylamide and the like.

In addition, a polymer compound can be added to the curable composition of the present invention for the purpose of improving curability and adjusting viscosity. Examples include polyvinyl alcohols, polyvinyl acetals, polyvinyl pyrrolidones, polyalkylene oxides such as polyethylene oxide and polypropylene oxide, polyacrylic acid, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene-methacrylic acid. Styrene acrylate resin such as acid-acrylic acid ester copolymer, styrene-α-methylstyrene-acrylic acid copolymer, styrene-α-methylstyrene-acrylic acid-acrylic acid ester copolymer, styrene-maleic acid copolymer Polymers, acrylic resins such as styrene-maleic anhydride copolymer, acrylic acid-acrylonitrile copolymer, vinyl acetate-acrylic ester copolymer, or acrylic acid-acrylic ester copolymer, cellulose, hydride Celluloses such as loxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, vinyl naphthalene-acrylic acid copolymer, vinyl naphthalene-maleic acid copolymer, vinyl acetate-ethylene copolymer, vinyl acetate-fatty acid vinyl ethylene copolymer And vinyl acetate copolymers such as vinyl acetate-maleic acid ester copolymer, vinyl acetate-crotonic acid copolymer, vinyl acetate-acrylic acid copolymer, and salts thereof, gelatin, casein and the like. Among these, in particular, polyvinyl alcohols and polyvinyl acetals are subjected to an acetalization reaction with the compound represented by the general formula (1) or (2) according to claim 1 of the present invention, and (meth) acrylamide in the side chain. It can also be added as a polymerizable polymer compound having a group.

These polymer compounds can be used singly or in combination of two or more, and particularly when used in the curable composition according to claim 7, 30 parts by weight per 100 parts by weight of the component of the curable composition. The range is preferably not more than parts by weight, more preferably not more than 20 parts by weight. When the addition amount exceeds 30 parts by weight, the viscosity of the curable composition becomes too high, and the printing performance may be deteriorated.

The organic dye that can be dispersed in the curable composition of the present invention includes, for example, Acid Yellow 11, Acid Yellow 17, Acid Yellow 23, Acid Yellow 25, Acid Yellow 29, Acid Yellow 42, and Acid Yellow. 49, Acid Yellow 61, Acid Yellow 71, Direct Yellow 12, Direct Yellow 24, Direct Yellow 26, Direct Yellow 44, Direct Yellow 86, Direct Yellow 87, Direct Yellow 98, Direct Yellow 100, Direct Yellow 130, Direct Yellow 132 and Direct yellow 142 etc. are mentioned.

Examples of the magenta red dye include Acid Red 1, Acid Red 6, Acid Red 8, Acid Red 32, Acid Red 35, Acid Red 37, Acid Red 51, Acid Red 52, Acid Red 80, Acid Red 85, and Acid. Red 87, Acid Red 92, Acid Red 94, Acid Red 115, Acid Red 180, Acid Red 254, Acid Red 256, Acid Red 289, Acid Red 315, Acid Red 317, Direct Red 1, Direct Red 4, Direct Red 13 , Direct Red 17, Direct Red 23, Direct Red 28, Direct Red 31, Direct Red 62, Direct Red 79, Direct Red 81, Die Kutoreddo 83, Direct Red 89, Direct Red 227, Direct Red 240, such as Direct Red 242 and Direct Red 243, and the like.

Examples of cyan dyes include Acid Blue 9, Acid Blue 22, Acid Blue 40, Acid Blue 59, Acid Blue 93, Acid Blue 102, Acid Blue 104, Acid Blue 113, Acid Blue 117, Acid Blue 120, and Acid Blue 167. Acid Blue 229, Acid Blue 234, Acid Blue 254, Direct Blue 6, Direct Blue 22, Direct Blue 22, Direct Blue 25, Direct Blue 71, Direct Blue 78, Direct Blue 86, Direct Blue 90, Direct Blue 106 and Direct Blue 199, etc. Is mentioned.

As the organic pigment that can be dispersed in the curable composition of the present invention, the following can be used as appropriate. Examples of achromatic pigments include carbon black, titanium oxide, and calcium carbonate. Examples of chromatic organic pigments include insoluble azo pigments such as Toluidine Red, Toluidine Maroon, Hansa Yellow, Benzidine Yellow, and Pyrazolone Red; soluble azo pigments such as Ritolol Red, Helio Bordeaux, Pigment Scarlet, and Permanent Red 2B; Alizarin, Indantron Derivatives from vat dyes such as thioindigo maroon; phthalocyanine organic pigments such as phthalocyanine blue and phthalocyanine green; quinacridone organic pigments such as quinacridone red and quinacridone magenta; perylene organic pigments such as perylene red and perylene scarlet; Isoindolinone organic pigments such as indolinone yellow and isoindolinone orange; pyranthrone organic pigments such as pyranthrone red and pyranthrone orange; thioindigo Organic pigments; condensed azo organic pigments; benzimidazolone organic pigments; quinophthalone organic pigments such as quinophthalone yellow; isoindoline organic pigments such as isoindoline yellow; other pigments such as flavanthrone yellow, acylamide yellow, nickel Azo Yellow, Copper Azomethine Yellow, Perinone Orange, Anthrone Orange, Dianthraquinonyl Red, Dioxazine Violet.

The amount of the colorant used in the curable composition of the present invention is preferably in the range of 0.5 to 30 parts by weight with respect to 100 parts by weight of the components of the curable composition. More preferably, it is the range.

Examples of the inorganic powder that can be dispersed in the curable composition of the present invention include ZnO: Zn, Zn ₃ (PO ₄ ) 2: Mn, Y ₂ SiO ₅ : Ce, CaWO ₄ : Pb, BaMgAl ₁₄ O ₂₃ : Eu. , ZnS: (Ag, Cd) , Y 2 O 3: Eu, Y 2 SiO 5: Eu, Y 3 Al 5 O 12: Eu, YBO 3: Eu, (Y, Gd) BO 3: Eu, GdBO 3: Eu, ScBO ₃ : Eu, LuBO ₃ : Eu, Zn ₂ SiO ₄ : Mn, BaAl ₁₂ O ₁₉ : Mn, SrAl ₁₃ O ₁₉ : Mn, CaAl ₁₂ O ₁₉ : Mn, YBO ₃ : Tb, BaMgAl ₁₄ O ₂₃ : Mn, LuBO ₃ : Tb, GdBO ₃ : Tb, ScBO ₃ : Tb, Sr ₆ Si ₃ O ₃ Cl ₄ : Eu, ZnS: (Cu, Al), ZnS: Ag, Y ₂ O ₂ S: Eu, ZnS: Zn, _{(Y, Cd) BO 3:} Eu, Ba Gal ₁₀ O17: phosphor powder such as Eu, PbO-SiO _{2 system, PBO-B 2 O 3 -SiO} 2 system, ZnO-SiO _{2 system, ZnO-B 2 O 3 -SiO} 2 system, BiO-SiO ₂ system , BiO—B ₂ O ₃ —SiO ₂ -based lead borosilicate glass, zinc borosilicate glass, borosilicate bismuth glass, etc., cobalt oxide, iron oxide, chromium oxide, nickel oxide, copper oxide, manganese oxide, oxidation Neodymium, vanadium oxide, cerium oxide yellow, cadmium oxide, alumina, silica, magnesia, spinel and other oxides such as Na, K, Mg, Ca, Ba, Ti, Zr, Al, iron, nickel, copper, Examples thereof include conductive particles such as aluminum, silver, and gold.

These inorganic powders can be used alone or in combination of two or more thereof, and are preferably blended in the range of 0.5 to 2400 parts by weight with respect to 100 parts by weight of the components of the curable composition. When it is larger than 2400 parts by weight, curability by heat or active energy rays is lowered.

The curable composition of the present invention includes, as other components, an ultraviolet absorber, a polymerization inhibitor, a plasticizer, an antifoaming agent, a surfactant, a coupling agent, a leveling agent, a drying inhibitor, an antisettling agent, and a dilution. A conventionally known solvent such as water or an organic solvent can be blended as necessary.

The curable composition of the present invention can be suitably used in a wide range of fields such as various paints, resists, printing inks, and adhesives.

In addition, a known conductive polymer such as conductive polyaniline, conductive polypyrrole, conductive polythiophene, polyethylenedioxythiophene and polystyrene sulfonic acid complex is blended in the curable composition of the present invention, and an antistatic coating agent, It can also be suitably used in fields such as conductive coating agents, electrode materials, and electromagnetic shielding materials.

As a coating method of the curable composition of the present invention, a coating method using a brush, a bar coater, a spray coater, a spinner, a roll coater, screen printing, ink jet, or the like can be used.

Furthermore, when applying the curable composition of this invention for an inkjet printing use, it is necessary to perform pH adjustment and viscosity adjustment as needed.

The pH adjustment described above is neutral to alkaline, preferably 7.0 to 12.0, more preferably 7.5, in order to improve the storage stability of the ink and effectively prevent corrosion of the ink jet recording apparatus. It is desirable to maintain it at ˜11.5.

Examples of basic compounds used for pH adjustment include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkali metal carbonates such as lithium carbonate, sodium carbonate and potassium carbonate; triethanol Examples thereof include organic amines such as amine, methyl diethanolamine, ethyl diethanolamine, dimethyl ethanolamine, diethyl ethanolamine, and morpholine, and these can be used alone or in admixture of two or more.

The viscosity adjustment is preferably carried out at 25 ° C. within a range of 20 mPa · s or less, and more preferably 15 mPa · s or less, in order to adapt to a fine high density and high drive frequency nozzle.

  In order to cure the curable composition of the present invention having the components described above with active energy rays, for example, a light source such as an electron beam, an ultraviolet ray, an α ray, a β ray, a γ ray, and an X ray is used. Can do. Among these, electron beams and ultraviolet rays are preferable because they are dangerous to the human body, easy to handle, and are widely used industrially. In the present invention, ultraviolet rays are particularly preferable.

When using an electron beam, the amount of the electron beam to be irradiated is preferably in the range of 0.1 to 30 Mrad. If it is less than 0.1 Mrad, a sufficient irradiation effect cannot be obtained, and if it exceeds 30 Mrad, the support or the like may be deteriorated.

  When ultraviolet rays are used, the light source is, for example, a low pressure, medium pressure, high pressure mercury lamp, metal halide lamp, xenon lamp having a light emission wavelength in the ultraviolet region, cold cathode tube, hot cathode tube having an operating pressure of several hundred Pa to 1 MPa. A conventionally well-known thing, such as LED, is used.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples at all.
[1] Synthesis example of compound described in general formula (1)

[Synthesis Example 1]
A 3 L reaction vessel equipped with a stirrer and a cooling device was charged with 0.8 L of dichloromethane and 210 g of aminoacetaldehyde dimethyl acetal, and cooled to 10 ° C. or lower with ice cooling and stirring. To this solution, 209 g of methacryloyl chloride and 202 g of triethylamine were added dropwise at about 10 ° C. or less over about 3 hours. After completion of the reaction, the reaction mixture was washed with 300 mL of ion exchange water, then washed with 300 mL of 1N hydrochloric acid, and further washed with 300 mL of ion exchange water. The dichloromethane layer was dehydrated with anhydrous sodium sulfate, and dichloromethane was distilled off under reduced pressure to obtain 308 g of light yellow viscous liquid N- (2,2-dimethoxyethyl) -2-methyl-2-propenamide (recovery). Rate 89%).

[Synthesis Example 2]
A 3 L reaction vessel equipped with a stirrer and a cooling device was charged with 0.8 L of dichloromethane and 266 g of 4-aminobutyraldehyde dimethyl acetal, and cooled to 10 ° C. or lower with ice cooling and stirring. To this solution, 209 g of methacryloyl chloride and 202 g of triethylamine were added dropwise at about 10 ° C. or less over about 3 hours. After completion of the reaction, the reaction mixture was washed with 300 mL of ion exchange water, then washed with 300 mL of 1N hydrochloric acid, and further washed with 300 mL of ion exchange water. The dichloromethane layer was dehydrated with anhydrous sodium sulfate, and dichloromethane was distilled off under reduced pressure to obtain 366 g of light yellow viscous liquid N- (2,2-dimethoxybutyl) -2-methyl-2-propenamide (recovery). 91%).

[2] Synthesis example of polymerizable compound according to claim 1

[Synthesis Example 3]
In a 1 L reaction vessel equipped with a stirrer and a heating device, 200 mL of water, 91 g of mannitol, 201 g of N- (2,2-dimethoxybutyl) -2-methyl-2-propenamide, 4.5 g of phosphoric acid were placed, and 80 The reaction was carried out at 20 ° C. for 20 hours. The end point of the reaction was confirmed by disappearance of the peak of N- (2,2-dimethoxybutyl) -2-methyl-2-propenamide by HPLC analysis. After cooling to room temperature, it was neutralized with a 5% aqueous sodium hydroxide solution and further diluted with ion exchange water to a concentration of 50% to obtain an aqueous solution of mannitol (A) having a methacrylamide group.

[Synthesis Example 4]
In a 1 L reaction vessel equipped with a stirrer and a heating device, 300 mL of water, 171 g of anhydrous trehalose, 173 g of N- (2,2-dimethoxyethyl) -2-methyl-2-propenamide, and 8.5 g of phosphoric acid were added. And reacted at 80 ° C. for 20 hours. The end point of the reaction was confirmed by disappearance of the peak of N- (2,2-dimethoxymethyl) -2-methyl-2-propenamide by HPLC analysis. After cooling to room temperature, it was neutralized with a 5% aqueous sodium hydroxide solution and further diluted with ion-exchanged water to a concentration of 50% to obtain an aqueous solution (B) of trehalose having a methacrylamide group.
[3] Examples 1-2 and Comparative Examples 1-2

Using the aqueous solutions (A) and (B) obtained from Synthesis Examples 3 to 4, an active energy ray-curable curable composition for inkjet printing is prepared, and the curability, water resistance and storage stability are evaluated. It was.

Table 1 shows the composition and results of the curable composition. The viscosities of Examples 1 and 2 were 5.0 mPa · s and 4.8 mPa · s, respectively, at 25 ° C., satisfying the low viscosity required for inkjet.

“NK Oligo EA-5822” shown in Table 1 is polyethylene glycol diglycidyl ether acrylate (EO = 4) (manufactured by Shin-Nakamura Chemical Co., Ltd.), and “NK Oligo EA-5920” is propylene glycol. It is a reaction product of diglycidyl ether and acrylic acid (manufactured by Shin-Nakamura Chemical Co., Ltd.), and Irgacure 2959 (manufactured by Ciba Specialty Chemicals) is 1- [4- (2-hydroxyethoxy) -phenyl ] -2-Hydroxy-2-methyl-1-propan-1-one. Moreover, the unit of the compounding quantity of Table 1 is a weight part.

The ink evaluation method is as follows.

(Curing method)
Each ink composition shown in Table 1 is filled in a printer having a piezo head (PX-V500 manufactured by Seiko Epson Corporation), printed on fine paper, and then a belt-type UV irradiator (ECS manufactured by Eye Graphics Co., Ltd.). -151 U; 120 W high pressure mercury lamp).

(Curable)
A printing portion, the integrated light quantity of 400 mJ / cm ² from 100 mJ / cm ² (measured by Eye Graphics Co. PD-365) was irradiated with 100 mJ / cm ² intervals to confirm the curability. As an evaluation standard, “X” was used when the ink was transferred by pressing the high-quality paper against the printed portion, and “◯” when the ink was not transferred.

(water resistant)
The printed portion was irradiated with an integrated light amount of 400 mJ / cm ² and immersed in water for 1 minute. As evaluation criteria, when printing was blurred, it was set as x, and when not printed, it was marked as o.

(Storage stability)
Each ink was stored at 60 ° C. for 30 days and tested for its curability and water resistance.
[4] Examination of test results

  The ink compositions of Examples 1 and 2 had good curability and water resistance, and no change was observed after the storage stability test. However, the ink composition of Comparative Example 1 obtained sufficient curability. However, the ink composition of Comparative Example 2 had good curability and water resistance immediately after preparation, but could not ensure storage stability.

  The polymerizable compound used in the ink composition of Comparative Example 2 is a monomer having an acrylate group, whereas the ink compositions of Examples 1 and 2 have methacrylamide groups having good hydrolysis resistance. It has sugar. Therefore, in the composition of Example 1 or 2, since hydrolysis was suppressed, the curability of the ink composition did not change, and the storage stability could be ensured.

Since the polymerizable compound and the curable composition of the present invention are excellent in hydrolysis resistance, curability by heat or active energy rays and water resistance of the cured product, they are widely used in various fields such as various paints, resists, printing inks, and adhesives. It is useful in.

Claims (7)

A polymerizable compound obtained by an acetalization reaction between a compound represented by the general formula (1) or (2) and a sugar.
(Wherein n is 0 or 1, R ₁ is a hydrogen atom or a C1-C4 alkyl group, R ₂ is a hydrogen atom or a C1-C6 alkyl group, and R ₃ is n = 0. —C (R ₁ ) ═CH ₂ or, if n = 1, a —C (R ₆ ) (R ₇ ) — or —C (R ₆ ) (R ₇ ) —CH ₂ — bridging group R ₄ is a C1 to C6 alkylene group , and may further include an arylene group, an aralkylene group, an alkylene ether group, an arylene ether group, an aralkylene ether group, an alkylene thioether group, an arylene thioether group, or an aralkylene thioether group. , R ₅ is a C1-C4 alkyl group, and R ₆ and R ₇ are each independently a hydrogen atom, a C1-C4 alkyl group or an aryl group.)
  The polymerizable compound according to claim 1, wherein the sugar is a monosaccharide, disaccharide, trisaccharide, oligosaccharide or cyclodextrin. The polymerizable compound according to claim 1, wherein the sugar is a non-reducing sugar selected from trehalose, isotrehalose, neotrehalose and sucrose. The polymerizable compound according to claim 1, wherein the sugar is a sugar alcohol selected from mannitol, sorbitol and xylitol. A curable composition comprising the polymerizable compound according to claim 1 and at least one selected from a thermal polymerization initiator and a photopolymerization initiator.
6. The curable composition according to claim 5, further comprising at least one selected from an organic dye, an organic pigment, and inorganic fine particles. An aqueous curable composition, wherein the composition of claim 6 is for inkjet recording.