JP2023008774A - Polymer-containing aqueous dispersion and water-based ink - Google Patents

Abstract

To provide an emulsion particle-containing aqueous dispersion that has high adhesion to a substrate, particularly to olefinic substrates such as biaxially oriented polypropylene (OPP), an also has excellent scratch resistance, and a water-based ink.SOLUTION: An aqueous dispersion contains a polymer (A) having a structural unit derived from a cyclic aliphatic group-containing monomer and a wax component (B).SELECTED DRAWING: None

Description

The present invention relates to polymer-containing aqueous dispersions. and an aqueous ink containing the polymer-containing aqueous dispersion. The water-based ink of the present invention can be suitably used as, for example, water-based ink for inkjet, ink for flexographic printing, ink for offset printing, ink for lithographic printing, ink for gravure printing, ink for screen printing, and the like. The water-based ink of the present invention is particularly suitable for use as an inkjet water-based ink.

Inks are roughly classified into two types: organic solvent-based inks in which an organic solvent is used as the main component of the solvent, and water-based inks in which water is used as the main component of the solvent.

The organic solvent-based ink composition has good water resistance because the main component of the solvent is the organic solvent. However, the organic solvent-based ink composition is inferior in safety to the human body and generates an odor derived from the organic solvent. Therefore, in recent years, water-based inks have attracted attention.

For example, Patent Document 1 describes a pigment, a polymeric pigment dispersant, polymer particles, a hydrophilic organic solvent, water, a water-soluble acidic compound having a content of 50 to 1000 ppm and a molecular weight of 200 or less, and the water-soluble and at least one salt of an acidic compound.

JP 2010-202765

In recent years, inkjet recording methods have also been used for resin recording media such as PET (polyethylene terephthalate), PP (polypropylene), PVC (polyvinyl chloride), etc., which have conventionally been printed with solvent-based inks and UV curable inks. is required, and it has been found that the water-based ink described in Patent Document 1 lacks adhesion to resin-made recording media and scratch resistance.

An object of the present invention is to provide emulsion particles that have excellent adhesion to substrates, especially to olefinic substrates such as biaxially oriented polypropylene (OPP), and have good scratch resistance, even without a primer or the like. An object is to provide an aqueous dispersion as well as an aqueous ink.

The inventors conducted studies in view of the above problems, and found that an aqueous dispersion containing a polymer (A) having a structural unit derived from a cycloaliphatic group-containing monomer and a wax component (B), When used as a water-based ink, it has excellent adhesion to substrates, especially to olefinic substrates such as biaxially oriented polypropylene (OPP), and has good scratch resistance. completed.

According to the present invention, a polymer-containing water-soluble polymer having excellent adhesion to substrates, particularly excellent adhesion to olefinic substrates such as biaxially oriented polypropylene (OPP) without a primer or the like, and having good scratch resistance. Dispersions as well as water-based inks are provided.

The polymer-containing aqueous dispersion of the present invention is characterized by being an aqueous dispersion containing a polymer (A) having a structural unit derived from a cycloaliphatic group-containing monomer and a wax component (B).

Since the aqueous dispersion is used, the water-based ink of the present invention exhibits good adhesion to substrates, particularly adhesion to olefinic substrates such as biaxially oriented polypropylene (OPP) without a primer or the like. excellent scratch resistance.

<Polymer (A)>
The polymer (A) of the present disclosure is preferably a polymer having a structural unit derived from a cycloaliphatic group-containing monomer. By having a structural unit derived from a cycloaliphatic group-containing monomer, it has excellent adhesion to substrates, especially to olefinic substrates such as biaxially oriented polypropylene (OPP). It can be expected that a polymer with good adhesion can be obtained.

The structural unit derived from the cycloaliphatic group-containing monomer of the present disclosure may have the same structure as the structure in which at least one carbon-carbon double bond of the cycloaliphatic group-containing monomer is replaced with a carbon-carbon single bond. However, it is not limited to structural units formed by polymerization of a cycloaliphatic group-containing monomer, and may be structural units formed by post-reaction after polymerization, for example.

The structural unit derived from the cycloaliphatic group-containing monomer is preferably represented by the following formula (1). In formula (1) below, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² represents a cycloaliphatic group.

Cycloaliphatic groups in formula (1) include cyclopentyl group, adamantyl group, isobornyl group, dicyclopentanyl group, dicyclopentenyl group and the like, preferably cyclopentyl group, cyclohexyl group and isobornyl group, cyclohexyl group, An isobornyl group is more preferred.

The cycloaliphatic group-containing monomer of the present disclosure is preferably a monomer having a carbon-carbon double bond, and includes (meth)acrylate monomers having a cycloaliphatic hydrocarbon group.

The (meth)acrylate monomer having a cycloaliphatic hydrocarbon group is preferably a compound having a monovalent cycloaliphatic hydrocarbon group and a monovalent (meth)acrylate group, and a monovalent cycloaliphatic The hydrocarbon group and the monovalent (meth)acrylate group are directly bonded. Cycloaliphatic hydrocarbon groups include monocyclic groups, polycyclic groups, and bridged ring groups. The cycloaliphatic hydrocarbon group preferably has 4 to 20 carbon atoms. As the cycloaliphatic hydrocarbon group, a cycloaliphatic group having 4 to 20 carbon atoms, particularly 5 to 12 carbon atoms is preferred. The number of carbon atoms in the cycloaliphatic hydrocarbon group is particularly preferably 15 or less, for example 10 or less. A carbon atom in the ring of the cycloaliphatic hydrocarbon group is preferably directly bonded to the ester group in the (meth)acrylate group. Specific examples of cycloaliphatic hydrocarbon groups are cyclohexyl, t-butylcyclohexyl, isobornyl, dicyclopentanyl and dicyclopentenyl groups. The (meth)acrylate group is an acrylate group or a methacrylate group, preferably a methacrylate group.

Specific examples of monomers having a cyclic aliphatic hydrocarbon group include cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyl (meth)acrylate, cyclopentyl (meth)acrylate, Cyclohexyl (meth)acrylate and isobornyl (meth)acrylate are preferred, and cyclohexyl (meth)acrylate and isobornyl (meth)acrylate are more preferred.

These cycloaliphatic group-containing monomers can be used alone or in combination.

The content of structural units derived from a monomer having a cycloaliphatic hydrocarbon group in 100 parts by mass of the polymer (A) of the present disclosure may be 30 parts by mass or more from the viewpoint of adhesion, and may be 35 parts by mass or more. is preferably 40 parts by mass or more, more preferably 45 parts by mass or more, and may be 95 parts by mass or less, preferably 90 parts by mass or less, and more preferably 85 parts by mass or less.

The polymer (A) of the present disclosure may have structural units derived from monomers other than the structural units derived from the cycloaliphatic group-containing monomer.

Structural units derived from other monomers are not limited to structural units formed by polymerizing other monomers described below, for example, structural units formed by post-reaction after polymerization. good.

Other monomers include monofunctional monomers and polyfunctional monomers. Monofunctional monomers and polyfunctional monomers may be used alone or in combination.

Monofunctional monomers include (meth)acrylic acid esters having a linear alkyl group, (meth)acrylic acid esters having a branched alkyl group, acid group-containing monomers, hydroxyl group-containing (meth)acrylates, oxo Group-containing monomer, fluorine atom-containing monomer, nitrogen atom-containing monomer, epoxy group-containing monomer, alkoxyalkyl (meth)acrylate, silane group-containing monomer, carbonyl group-containing monomer, aziridinyl group Included monomers, styrenic monomers, aralkyl (meth)acrylates, addition-polymerizable oxazolines, and the like, but are not limited to these examples.

Examples of (meth)acrylic acid esters having a linear alkyl group of the present disclosure include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and (meth)acrylate. Pentyl acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, (meth)acrylic cetyl acid, stearyl (meth)acrylate, behenyl (meth)acrylate, methoxyethyl (meth)acrylate, ethyl carbitol (meth)acrylate, ethoxypolyethylene glycol (meth)acrylate, aminoethyl (meth)acrylate , chloroethyl (meth)acrylate, trifluoroethyl (meth)acrylate and heptadecafluorooctylethyl (meth)acrylate. ) ethyl acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, (meth) acrylate Decyl acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate are preferred, methyl (meth) acrylate, (meth) ) ethyl acrylate, butyl (meth)acrylate, octyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, and behenyl (meth)acrylate are more preferred.

The (meth)acrylic acid esters having a branched alkyl group of the present disclosure include isopropyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, Neopentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, isostearyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, methoxytripropylene glycol (meth)acrylate and (meth) hexafluoropropyl acrylate, etc., and from the viewpoint of adhesion and scratch resistance, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, (meth) ) neopentyl acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, isostearyl (meth) acrylate, preferably isobutyl (meth) acrylate, t-butyl (meth) acrylate, (meth) ) 2-ethylhexyl acrylate and isostearyl (meth)acrylate are more preferred.

Acid group-containing monomers of the present disclosure include, for example, (meth)acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, maleic anhydride, maleic acid monomethyl ester, maleic acid monobutyl ester, Examples include carboxyl group-containing aliphatic monomers such as monomethyl itaconate, monobutyl itaconate, and vinyl benzoic acid, but the present invention is not limited to these examples. Each of these acid group-containing monomers may be used alone, or two or more of them may be used in combination. Among these acid group-containing monomers, acrylic acid and methacrylic acid are preferred from the viewpoint of improving the dispersion stability, adhesion and scratch resistance of the aqueous dispersion when the polymer (A) is emulsion particles. and itaconic acid are preferred, acrylic acid and methacrylic acid are more preferred.

Examples of hydroxyl group-containing (meth)acrylates of the present disclosure include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, Examples include hydroxyl group-containing (meth)acrylates having an ester group with 1 to 18 carbon atoms such as 4-hydroxybutyl (meth)acrylate, but are not limited to these examples.
Among these hydroxyl group-containing monomers, 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate are preferred from the viewpoint of improving adhesion and scratch resistance.

These hydroxyl group-containing (meth)acrylates may be used alone or in combination of two or more.

Examples of oxo group-containing monomers of the present disclosure include (di)ethylene glycol (methoxy ) (meth)acrylate and the like, but are not limited to these examples. Each of these oxo group-containing monomers may be used alone, or two or more of them may be used in combination.

Examples of fluorine atom-containing monomers of the present disclosure include fluorine having an ester group having 2 to 6 carbon atoms, such as trifluoroethyl (meth)acrylate, tetrafluoropropyl (meth)acrylate, and octafluoropentyl (meth)acrylate. Atom-containing alkyl (meth)acrylates and the like are included, but are not limited to these examples. These fluorine atom-containing monomers may be used alone, respectively, or two or more of them may be used in combination.

Nitrogen-containing monomers of the present disclosure include, for example, (meth)acrylamide, N-monomethyl(meth)acrylamide, N-monoethyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, Nn-propyl (Meth)acrylamide, N-isopropyl(meth)acrylamide, methylenebis(meth)acrylamide, N-methylol(meth)acrylamide, N-butoxymethyl(meth)acrylamide, dimethylaminoethyl(meth)acrylamide, N,N-dimethylamino Acrylamide compounds such as propylacrylamide and diacetone acrylamide, nitrogen atom-containing (meth)acrylate compounds such as dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate, N-vinylpyrrolidone, (meth)acrylonitrile, and the like. However, it is not limited only to such examples. Each of these nitrogen atom-containing monomers may be used alone, or two or more of them may be used in combination.

Examples of epoxy group-containing monomers of the present disclosure include epoxy group-containing (meth)acrylates such as glycidyl (meth)acrylate, α-methylglycidyl (meth)acrylate, and glycidyl allyl ether, but only such examples is not limited to These epoxy group-containing monomers may be used alone or in combination of two or more. Among these epoxy group-containing monomers, glycidyl (meth)acrylate is preferred from the viewpoint of improving adhesion and scratch resistance.

Alkoxyalkyl (meth)acrylates of the present disclosure include, for example, methoxyethyl (meth)acrylate, methoxybutyl (meth)acrylate, ethoxybutyl (meth)acrylate, trimethylolpropane tripropoxy (meth)acrylate, etc. It is not limited only to such examples. These alkoxyalkyl (meth)acrylates may be used alone or in combination of two or more.

Silane group-containing monomers of the present disclosure include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(methoxyethoxy)silane, γ-(meth)acryloyloxypropyltrimethoxysilane, 2-styrylethyltrimethoxysilane. , vinyltrichlorosilane, γ-(meth)acryloyloxypropylhydroxysilane, γ-(meth)acryloyloxypropylmethylhydroxysilane, etc., but are not limited to these examples. These silane group-containing monomers may be used alone or in combination of two or more.

Examples of the carbonyl group-containing monomers of the present disclosure include acrolein, borumylstyrene, vinyl ethyl ketone, (meth)acryloxyalkylpropenal, acetonyl (meth)acrylate, diacetone (meth)acrylate, 2-hydroxypropyl ( meth)acrylate acetylacetate, butanediol-1,4-acrylate acetylacetate, 2-(acetoacetoxy)ethyl (meth)acrylate and the like, but are not limited to these examples. These carbonyl group-containing monomers may be used alone or in combination of two or more.

The aziridinyl group-containing monomers of the present disclosure include, for example, (meth)acryloylaziridine, 2-aziridinylethyl (meth)acrylate, and the like, but are not limited to these examples. These aziridinyl group-containing monomers may be used alone or in combination of two or more.

Styrenic monomers of the present disclosure include, for example, styrene, α-methylstyrene, p-methylstyrene, tert-methylstyrene, chlorostyrene, vinyltoluene, etc., but are not limited to these examples. Absent. These styrenic monomers may be used alone or in combination of two or more. Styrenic monomers have functional groups such as alkyl groups such as methyl groups and tert-butyl groups, nitro groups, nitrile groups, alkoxyl groups, acyl groups, sulfone groups, hydroxyl groups and halogen atoms on the benzene ring. may Among the styrene-based monomers, styrene is preferred from the viewpoint of enhancing water resistance.

Aralkyl (meth)acrylates of the present disclosure include, for example, aralkyl groups having 7 to 18 carbon atoms, such as benzyl (meth)acrylate, phenylethyl (meth)acrylate, methylbenzyl (meth)acrylate, and naphthylmethyl (meth)acrylate. and aralkyl (meth)acrylates having, but are not limited to only these examples. These aralkyl (meth)acrylates may be used alone or in combination of two or more.

Examples of addition polymerizable oxazolines of the present disclosure include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2 -oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, etc., but only such examples is not limited to Each of these addition-polymerizable oxazolines may be used alone, or two or more of them may be used in combination. Among these addition-polymerizable oxazolines, 2-isopropenyl-2-oxazoline is preferred because of its easy availability.

Examples of polyfunctional monomers include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, ethylene oxide-modified 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, propylene oxide-modified neopentyl glycol di(meth)acrylate, Di(meth)acrylates of polyhydric alcohols having 1 to 10 carbon atoms, such as tripropylene glycol di(meth)acrylate; Alkyl di(meth)acrylates having 2 to 50 moles of alkylene oxide groups having 2 to 4 carbon atoms, such as polypropylene glycol di(meth)acrylate having 2 to 50 and tripropylene glycol di(meth)acrylate; ethoxylation Glycerin tri(meth)acrylate, propylene oxide-modified glycerol tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol monohydroxy tri(meth)acrylate, trimethylolpropane Tri(meth)acrylates of polyhydric alcohols having 1 to 10 carbon atoms such as triethoxytri(meth)acrylate; pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate Tetra (meth) acrylate of polyhydric alcohol having 1 to 10 carbon atoms such as; Penta(meth)acrylate; hexa(meth)acrylate of polyhydric alcohol having 1 to 10 carbon atoms such as pentaerythritol hexa(meth)acrylate; bisphenol A di(meth)acrylate, 2-(2'-vinyloxyethoxyethyl) Epoxy group-containing (meth)acrylates such as (meth)acrylates and epoxy (meth)acrylates; polyfunctional (meth)acrylates such as urethane (meth)acrylates; Examples include acrylate and the like, but are not limited to these examples. Each of these polyfunctional monomers may be used alone, or two or more of them may be used in combination.

From the viewpoint of imparting UV stability or UV absorbability, the polymer (A) of the present disclosure contains UV-stable monomers, UV-absorbing monomers, etc. in the monomer component within a range in which the object of the present invention is not hindered. is preferred.

UV-stable monomers of the present disclosure include, for example, 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloylamino-2,2,6,6-tetramethyl Piperidine, 4-(meth)acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4-(meth)acryloyl-1-methoxy-2,2,6,6-tetramethylpiperidine, 4-cyano -4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 1-(meth)acryloyl-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 4- Crotonoylamino-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloylamino-1,2,2,6,6-pentamethylpiperidine, 4-cyano-4-(meth)acryloylamino- 2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 1-(meth)acryloyl-4-cyano-4-(meth)acryloylamino-2 , 2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, and other piperidine group-containing monomers. It is not limited only to such examples. These monomers may be used alone, respectively, or two or more of them may be used in combination. Among these UV-stable monomers, 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloyloxy-1, 4-(meth)acryloyloxy-1, Piperidyl group-containing (meth)acrylates such as 2,2,6,6-pentamethylpiperidine and 4-cyano-4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine are preferred.

Examples of UV-absorbing monomers of the present disclosure include benzotriazole-based UV-absorbing monomers and benzophenone-based UV-absorbing monomers, but the present invention is not limited to these examples. These monomers may be used alone, respectively, or two or more of them may be used in combination.

Benzotriazole-based UV-absorbing monomers include, for example, 2-[2′-hydroxy-5′-(meth)acryloyloxymethylphenyl]-2H-benzotriazole, 2-[2′-hydroxy-5′-(meth) ) acryloyloxyethylphenyl]-2H-benzotriazole, 2-[2′-hydroxy-5′-(meth)acryloyloxymethylphenyl]-5-tert-butyl-2H-benzotriazole, 2-[2′-hydroxy -5′-(meth)acryloylaminomethyl-5′-tert-octylphenyl]-2H-benzotriazole, 2-[2′-hydroxy-5′-(meth)acryloyloxypropylphenyl]-2H-benzotriazole, 2-[2′-hydroxy-5′-(meth)acryloyloxyhexylphenyl]-2H-benzotriazole, 2-[2′-hydroxy-3′-tert-butyl-5′-(meth)acryloyloxyethylphenyl ]-2H-benzotriazole, 2-[2′-hydroxy-3′-tert-butyl-5′-(meth)acryloyloxyethylphenyl]-5-chloro-2H-benzotriazole, 2-[2′-hydroxy -5'-tert-butyl-3'-(meth)acryloyloxyethylphenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(meth)acryloyloxyethylphenyl]-5-chloro-2H -benzotriazole, 2-[2'-hydroxy-5'-(meth)acryloyloxyethylphenyl]-5-cyano-2H-benzotriazole, 2-[2'-hydroxy-5'-(meth)acryloyloxyethyl Phenyl]-5-tert-butyl-2H-benzotriazole, 2-[2′-hydroxy-5′-(β-(meth)acryloyloxyethoxy)-3′-tert-butylphenyl]-4-tert-butyl -2H-benzotriazole and the like, but the present invention is not limited to such examples. These monomers may be used alone, respectively, or two or more of them may be used in combination.

Benzophenone-based UV-absorbing monomers include, for example, 2-hydroxy-4-(meth)acryloyloxybenzophenone, 2-hydroxy-4-[2-hydroxy-3-(meth)acryloyloxy]propoxybenzophenone, 2-hydroxy- 4-[2-(meth)acryloyloxy]ethoxybenzophenone, 2-hydroxy-4-[3-(meth)acryloyloxy-2-hydroxypropoxy]benzophenone, 2-hydroxy-3-tert-butyl-4-[2 -(Meth)acryloyloxy]butoxybenzophenone and the like, but the present invention is not limited only to such examples. These monomers may be used alone, respectively, or two or more of them may be used in combination.

As the other monomers of the present disclosure, piperidine group-containing monomers, nitrogen atom-containing monomers, and addition polymerizable oxazolines are preferred from the viewpoint of further improving adhesion to corona-treated PET, OPP, and the like. , piperidine group-containing monomers, addition polymerizable oxazolines are more preferred, 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloyloxy-1,2,2, More preferred are 6,6-pentamethylpiperidine and 2-isopropenyl-2-oxazoline. In addition, when the hydroxyl group-containing (meth)acrylate is contained as a monofunctional monomer, emulsion particles free from coarse particles can be easily obtained, and the ink containing the emulsion particles has excellent ejection stability, from the viewpoint of further improving adhesion. , a hydroxyl group-containing (meth)acrylate.

The content ratio of structural units derived from other monomers in 100 parts by mass of the polymer (A) of the present disclosure may be 5 parts by mass or more from the viewpoint of improving adhesion and scratch resistance, and may be 10 parts by mass or more. , more preferably 15 parts by mass or more, may be 70 parts by mass or less, preferably 65 parts by mass or less, more preferably 60 parts by mass or less, and even more preferably 55 parts by mass or less.

The acid value of the polymer (A) of the present disclosure may not have an acid value, but may be 50 mgKOH/g or less, preferably 40 mgKOH/g or less, and 35 mgKOH/g or less. is more preferable, and 30 mgKOH/g or less is even more preferable. When the acid value of the polymer (A) is within the above range, it is possible to obtain a water-based ink with a preferable viscosity as an inkjet ink, and an effect of improving the scratch resistance can be expected.

In addition, the acid value of the polymer (A) of the present disclosure may be 1 mgKOH/g or more from the viewpoint of suppressing aggregates and suppressing viscosity change when used as an ink.

The glass transition temperature of the polymer (A) of the present disclosure may be −10° C. or higher, preferably 0° C. or higher, more preferably 5° C. or higher, even more preferably 10° C. or higher, and may be 90° C. or lower. , preferably 80° C. or lower, more preferably 70° C. or lower, and even more preferably 60° C. or lower.

The glass transition temperature of the polymer is the glass transition temperature (Tg), using the glass transition temperature of the homopolymer of the monomer used in the monomer component used as the raw material of the polymer, using the formula:
1/Tg=Σ(Wm/Tgm)/100
[In the formula, Wm is the content (% by mass) of the monomer m in the monomer component for the inner layer constituting the resin layer, and Tgm is the glass transition temperature (absolute temperature: K) of the homopolymer of the monomer m]. Means the temperature determined based on the Fox equation.

In the present specification, the glass transition temperature of a polymer means the glass transition temperature determined based on the Fox formula, unless otherwise specified.

The polymer (A) of the present disclosure may be emulsion particles. The emulsion particles of the present disclosure may have a single layer or may have a multilayer structure. When the emulsion particles of the present disclosure have a multilayer structure, it preferably has 2 to 4 layers, more preferably 2 or 3 layers. In the emulsion particle having a multilayer structure resin layer, the inner layer means the innermost layer of the emulsion particle, the outer layer means the layers other than the innermost layer, and the outermost layer means the layer formed on the outermost side. .

When the polymer (A) of the present disclosure is an emulsion particle, the volume average particle diameter (nm) is 25 nm or more from the viewpoint of blocking resistance, adhesion and scratch resistance to a substrate, ejection stability, and image quality improvement. It is preferably 500 nm or less, more preferably 50 nm or more and 400 nm or less, and most preferably 100 nm or more and 300 nm or less.
The volume average particle size of the polymer (A) is not particularly limited, but can be measured by a dynamic light scattering method, a laser diffraction/scattering method, a Coulter counter, a microscope method, or the like.
The average particle size of the present disclosure is determined by the photon correlation method using a multi-sample nanoparticle size measurement system [manufactured by Otsuka Electronics Co., Ltd., trade name: nanoSAQLA], which is a particle size measurement device based on the dynamic light scattering method. is the average particle diameter (hydrodynamic diameter) obtained by cumulant analysis.

When the polymer (A) of the present disclosure is an emulsion particle having a multilayer structure, the content of structural units derived from a monomer having a cyclic aliphatic hydrocarbon group in 100 parts by mass of the monomer component forming the inner layer may be 30 parts by mass or more, preferably 35 parts by mass or more, more preferably 40 parts by mass or more, even more preferably 45 parts by mass or more, may be 95 parts by mass or less, preferably 90 parts by mass or less, 85 parts by mass or less is more preferable.

When the polymer (A) of the present disclosure is an emulsion particle having a multilayer structure, the content of structural units derived from other monomers in 100 parts by mass of the monomer component forming the inner layer is 5 parts by mass or more. preferably 10 parts by mass or more, more preferably 15 parts by mass or more, may be 70 parts by mass or less, preferably 65 parts by mass or less, more preferably 60 parts by mass or less, and even more preferably 55 parts by mass or less.

When the polymer (A) of the present disclosure is an emulsion particle having a multi-layered structure, 2-hydroxyethyl (meth) Acrylate, (meth)acrylic acid, 2-ethylhexyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, lauryl (meth)acrylate, (meth)acrylic acid Stearyl, behenyl (meth)acrylate, (meth)acrylonitrile, glycidyl (meth)acrylate, styrene, 2-isopropenyl-2-oxazoline, 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine , 4-(meth)acryloyloxy-1,2,2,6,6-pentamethylpiperidine, are more preferred.

When the polymer (A) of the present disclosure is an emulsion particle having a multilayer structure, the content of structural units derived from a monomer having a cyclic aliphatic hydrocarbon group in 100 parts by mass of the monomer component forming the outer layer may be 30 parts by mass or more, preferably 35 parts by mass or more, more preferably 40 parts by mass or more, even more preferably 45 parts by mass or more, may be 95 parts by mass or less, preferably 90 parts by mass or less, 85 parts by mass or less is more preferable.

When the polymer (A) of the present disclosure is an emulsion particle having a multilayer structure, the content of structural units derived from other monomers in 100 parts by mass of the monomer component forming the outer layer is 5 parts by mass or more. preferably 10 parts by mass or more, more preferably 15 parts by mass or more, may be 70 parts by mass or less, preferably 65 parts by mass or less, more preferably 60 parts by mass or less, and even more preferably 55 parts by mass or less.

When the polymer (A) of the present disclosure is an emulsion particle having a multi-layered structure, 2-hydroxyethyl (meth) Acrylate, (meth)acrylic acid, 2-ethylhexyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, lauryl (meth)acrylate, (meth)acrylic acid Stearyl, behenyl (meth)acrylate, (meth)acrylonitrile, glycidyl (meth)acrylate, styrene, 2-isopropenyl-2-oxazoline, 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine , 4-(meth)acryloyloxy-1,2,2,6,6-pentamethylpiperidine, are more preferred.

When the polymer (A) of the present disclosure is an emulsion particle having a multi-layered structure, 100 parts by mass of the monomer component forming the outermost layer contains structural units derived from a monomer having a cyclic aliphatic hydrocarbon group. The amount may be 30 parts by mass or more, preferably 35 parts by mass or more, more preferably 40 parts by mass or more, even more preferably 45 parts by mass or more, and may be 95 parts by mass or less, preferably 90 parts by mass or less. , 85 parts by mass or less.

When the polymer (A) of the present disclosure is an emulsion particle having a multilayer structure, the content of structural units derived from other monomers in 100 parts by mass of the monomer component forming the outermost layer is 5 parts by mass or more. 10 parts by mass or more, more preferably 15 parts by mass or more, may be 70 parts by mass or less, preferably 65 parts by mass or less, more preferably 60 parts by mass or less, and even more preferably 55 parts by mass or less .

When the polymer (A) of the present disclosure is an emulsion particle having a multilayer structure, 2-hydroxyethyl (meth ) acrylate, (meth) acrylic acid, 2-ethylhexyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, (meth) acrylic Stearyl acid, behenyl (meth)acrylate, (meth)acrylonitrile, glycidyl (meth)acrylate, styrene, 2-isopropenyl-2-oxazoline, 4-(meth)acryloyloxy-2,2,6,6-tetramethyl More preferred are piperidine, 4-(meth)acryloyloxy-1,2,2,6,6-pentamethylpiperidine.

The mass ratio of the polymer layer composing the inner layer to the polymer layer composing the outer layer of the present disclosure (mass of the polymer composing the inner layer/mass of the polymer composing the outer layer) is , From the viewpoint of improving flexibility, blocking resistance, adhesion to substrates and scratch resistance, preferably 10/90 to 90/10, more preferably 20/80 to 80/20, still more preferably 30 /70 to 70/30, even more preferably 40/60 to 60/40.

The mass ratio of the polymer layer forming the inner layer to the polymer layer forming the outermost layer of the present disclosure (polymer layer forming the inner layer/polymer layer forming the outermost layer) is , From the viewpoint of improving flexibility, blocking resistance, adhesion to substrates and scratch resistance, preferably 10/90 to 90/10, more preferably 20/80 to 80/20, still more preferably 30 /70 to 70/30, even more preferably 40/60 to 60/40.

The acid value of the polymer constituting the inner layer of the present disclosure may not have an acid value, but may be 50 mgKOH/g or less, preferably 40 mgKOH/g or less, and 35 mgKOH/g or less. is more preferably 30 mgKOH/g or less. By having the acid value of the inner layer of the polymer (A) within the above range, it is possible to obtain a viscosity water-based ink suitable for use as an inkjet ink, and effects of improving adhesion, scratch resistance, and ejection stability can be expected. In addition, the acid value of the polymer constituting the inner layer of the present disclosure may be 1 mgKOH/g or more from the viewpoint of suppressing aggregates and suppressing viscosity change when used as an ink.

The acid value of the polymer constituting the outer layer of the present disclosure may not have an acid value, but may be 50 mgKOH/g or less, preferably 40 mgKOH/g or less, and 35 mgKOH/g or less. is more preferably 30 mgKOH/g or less. When the acid value of the outer layer of the polymer (A) is within the above range, a water-based ink with a viscosity suitable for inkjet ink can be obtained, and effects of improving adhesion, scratch resistance, and ejection stability can be expected. In addition, the acid value of the polymer constituting the outer layer of the present disclosure may be 1 mgKOH/g or more from the viewpoint of suppressing aggregates and suppressing viscosity change when used as ink.

The acid value of the polymer constituting the outermost layer of the present disclosure may not have an acid value, but may be 50 mgKOH/g or less, preferably 40 mgKOH/g or less, and 35 mgKOH/g or less. more preferably 30 mgKOH/g or less. When the acid value of the outermost layer of the polymer (A) is within the above range, a water-based ink with a viscosity preferable as an inkjet ink can be obtained, and effects of improving adhesion, scratch resistance, and ejection stability can be expected. In addition, the acid value of the polymer constituting the outermost layer of the present disclosure may be 1 mgKOH/g or more from the viewpoint of suppressing aggregates and suppressing viscosity change when used as an ink.

The glass transition temperature of the polymer constituting the inner layer of the present disclosure is −10° C. or higher, preferably 0° C. or higher, from the viewpoint of adhesion and scratch resistance. From the viewpoint of scratch resistance, the temperature is preferably 120° C. or lower, more preferably 100° C. or lower. The glass transition temperature of the polymer forming the inner layer can be adjusted by adjusting the type and amount of the monomer forming the inner layer.

The glass transition temperature of the polymer constituting the outer layer of the present disclosure is 0° C. or higher, preferably 10° C. or higher, from the viewpoint of adhesion, scratch resistance, and film-forming properties, and the upper limit of the glass transition temperature is From the viewpoint of adhesion and scratch resistance, the temperature is preferably 100° C. or lower, more preferably 90° C. or lower. The glass transition temperature of the polymer forming the outer layer can be adjusted by adjusting the type and amount of the monomer forming the outer layer.

The glass transition temperature of the polymer constituting the outermost layer of the present disclosure is 0° C. or higher, preferably 10° C. or higher, from the viewpoint of adhesion, scratch resistance, and film-forming properties, and the upper limit of the glass transition temperature is , from the viewpoint of adhesion and scratch resistance, the temperature is preferably 100° C. or less, more preferably 90° C. or less. The glass transition temperature of the polymer forming the outermost layer can be adjusted by adjusting the type and amount of the monomer forming the outermost layer.

Unless otherwise specified, the glass transition temperature of the polymer constituting each layer means the glass transition temperature obtained based on the Fox equation, similarly to the glass transition temperature of the polymer (A).

<Method for producing polymer (A)>
The method for producing the polymer (A) of the present disclosure can be obtained by polymerizing a monomer containing a cycloaliphatic group-containing monomer. Examples of polymerization methods include emulsion polymerization, bulk polymerization, solution polymerization, and suspension polymerization, but the present invention is not limited to these examples. Among the methods for polymerizing the monomer component, the emulsion polymerization method is preferable because an environmentally friendly aqueous dispersion can be directly obtained when the monomer component is polymerized by an emulsion polymerization method.

As a method for emulsion polymerization of the monomer component, for example, an aqueous medium containing a water-soluble organic solvent such as a lower alcohol such as methanol and water, or an emulsifier is dissolved in a medium such as water, and the monomer is stirred under stirring. A method of dropping a component and a polymerization initiator, and a method of dropping a monomer component previously emulsified using an emulsifier and water into water or an aqueous medium, etc., but are limited only to such methods. is not. In addition, the amount of the medium may be appropriately set in consideration of the amount of non-volatile matter contained in the obtained emulsion. The medium may be charged into the reaction vessel in advance, or may be used as a pre-emulsion. In addition, the medium may be used, if necessary, during emulsion polymerization of the monomer components to produce an emulsion.

When emulsion polymerization of the monomer component is carried out, the emulsion polymerization may be carried out after mixing the monomer component, the emulsifier and the medium. Alternatively, the emulsion polymerization may be carried out by mixing at least one of the monomer component, emulsifier and medium with the rest of the pre-emulsion. The monomer component, emulsifier and medium may be added all at once, added in portions, or added dropwise continuously.

The monomers and the composition of the monomers used in polymerizing the polymer (A) of the present disclosure are as described above. The monomers and the composition of the monomers used when the polymer (A) of the present disclosure is an emulsion particle having a multilayer structure are as described above.

When the polymer (A) of the present disclosure is an emulsion particle having a multilayer structure, when forming an outer layer composed of the outer layer polymer component on the emulsion particles contained in the emulsion obtained above, the above An outer layer can be formed on the emulsion particles by subjecting the monomer component to emulsion polymerization in the emulsion in the same manner as described above. Further, in the case of forming an outer layer on the emulsion particles on which the outer layer (intermediate layer) is formed, the monomer component is emulsion-polymerized in the emulsion in the same manner as described above to form an additional layer on the emulsion particles. An outer layer comprising other outer layer polymer components can be formed. Thus, emulsion particles having a multilayer structure (core-shell emulsion particles) can be prepared by the multistage emulsion polymerization method.

When preparing the core-shell emulsion particles, one-stage or multiple-stage emulsion polymerization may be performed prior to the emulsion polymerization for forming the inner layer composed of the polymer component for the inner layer. and the emulsion polymerization for forming the intermediate layer, one or more stages of emulsion polymerization may be carried out. Further, between the emulsion polymerization for forming the intermediate layer and the emulsion polymerization for forming the outer layer, one or more stages of emulsion polymerization may be performed. Further, one-stage or multiple-stage emulsion polymerization may be carried out after the emulsion polymerization for forming the outer layer.

Examples of emulsifiers used during polymerization of the polymer (A) of the present disclosure include anionic emulsifiers, nonionic emulsifiers, cationic emulsifiers, amphoteric emulsifiers, polymer emulsifiers, etc. These emulsifiers may be used alone. Well, you may use two or more types together.

Examples of anionic emulsifiers include alkylsulfate salts such as ammonium dodecylsulfate and sodium dodecylsulfate; alkylsulfonate salts such as ammonium dodecylsulfonate, sodium dodecylsulfonate and sodium alkyldiphenylether disulfonate; ammonium dodecylbenzenesulfonate, sodium dodecylnaphthalenesulfonate and the like. polyoxyethylene alkylsulfonate salts; polyoxyethylene alkylsulfate salts; polyoxyethylene alkylarylsulfate salts; dialkylsulfosuccinates; arylsulfonic acid-formalin condensates; Fatty acid salt; bis(polyoxyethylene polycyclic phenyl ether) methacrylate sulfonate salt, propenyl-alkyl sulfosuccinate ester salt, (meth)acrylic acid polyoxyethylene sulfonate salt, (meth)acrylic acid polyoxyethylene phosphonate salt, allyl allyl group-containing sulfate esters such as oxymethylalkyloxypolyoxyethylene sulfonate salts or salts thereof; allyloxymethylalkoxyethylpolyoxyethylene sulfate ester salts; is not limited to only

Examples of nonionic emulsifiers include polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, condensates of polyethylene glycol and polypropylene glycol, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, fatty acid monoglycerides, ethylene oxide and aliphatic Condensation products with amines, allyloxymethylalkoxyethylhydroxypolyoxyethylenes, polyoxyalkylene alkenyl ethers, etc., but not limited to these examples.

Cationic emulsifiers include, for example, alkylammonium salts such as dodecylammonium chloride, but are not limited to these examples.

Examples of amphoteric emulsifiers include betaine ester emulsifiers, but are not limited to these examples.

Examples of polymer emulsifiers include poly(meth)acrylates such as sodium polyacrylate and ammonium polyacrylate; polyvinyl alcohol; polyvinylpyrrolidone; polyhydroxyalkyl (meth)acrylates such as polyhydroxyethyl acrylate; Copolymers containing one or more of the monomers constituting the coalescence as a copolymerization component may be mentioned, but the invention is not limited to these examples.

As the emulsifier, an emulsifier having a polymerizable group, that is, a so-called reactive emulsifier is preferable from the viewpoint of further improving water resistance and image uniformity, and a non-nonylphenyl emulsifier is preferable from the viewpoint of environmental protection.

Examples of reactive emulsifiers include propenyl-alkylsulfosuccinate ester salts, (meth)acrylic acid polyoxyethylene sulfonate salts, (meth)acrylic acid polyoxyethylene phosphonate salts [for example, manufactured by Sanyo Chemical Industries, Ltd., Product name: Eleminol RS-30, etc.], polyoxyethylene alkylpropenyl phenyl ether sulfonate salt [for example, Daiichi Kogyo Seiyaku Co., Ltd., product name: Aqualon HS-10, etc.], allyloxymethylalkyloxypolyoxyethylene Sulfonate salts [for example, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon KH-10, etc.], sulfonate salts of allyloxymethyl nonylphenoxyethyl hydroxypolyoxyethylene [for example, manufactured by ADEKA Co., Ltd., trade name: ADEKA rear soap SE-10, etc.], allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfate ester salt [for example, manufactured by ADEKA Corporation, trade names: Adeka rear soap SR-10, SR-20, SR-30, etc.], bis (Polyoxyethylene polycyclic phenyl ether) methacrylated sulfonate salt [for example, manufactured by Nippon Nyukazai Co., Ltd., trade name: Antox MS-60, etc.], allyloxymethylalkoxyethyl hydroxypolyoxyethylene [for example, ADEKA Corporation] manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Adekari Soap ER-10, ER-20, etc.], polyoxyethylene alkylpropenyl phenyl ether [for example, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon RN-20, etc.], allyloxymethyl Examples include nonylphenoxyethyl hydroxypolyoxyethylene [eg, manufactured by ADEKA Co., Ltd., trade name: Adekari Soap NE-10, etc.], but are not limited to these examples. Among the above emulsifiers, from the viewpoint of pigment dispersibility, adhesion and scratch resistance, allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfate [for example, manufactured by ADEKA Co., Ltd., trade name: Adekari Soap SR-10, SR] -20, SR-30, etc.] is more preferable.

The amount of the emulsifier per 100 parts by mass of the monomer component constituting the polymer (A) is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and even more preferably, from the viewpoint of improving polymerization stability. is 2 parts by mass or more, particularly preferably 3 parts by mass or more, and from the viewpoint of improving water resistance, scratch resistance, and blocking resistance, it is preferably 10 parts by mass or less, more preferably 6 parts by mass or less.

When the polymer (A) of the present disclosure is an emulsion particle having a multilayer structure, the amount of the emulsifier per 100 parts by mass of the inner layer monomer component is preferably 0.01 mass from the viewpoint of improving the polymerization stability. parts or more, more preferably 0.5 parts by mass or more, still more preferably 1 part by mass or more, and from the viewpoint of improving flexibility, blocking resistance, adhesion to substrates and scratch resistance, preferably 20 parts by mass parts or less, more preferably 15 parts by mass or less, and even more preferably 12 parts by mass or less.

When the polymer (A) of the present disclosure is an emulsion particle having a multilayer structure, the amount of the emulsifier per 100 parts by mass of the outer layer monomer component is preferably 0.01 mass from the viewpoint of improving the polymerization stability. parts or more, more preferably 0.5 parts by mass or more, still more preferably 1 part by mass or more, and from the viewpoint of improving flexibility, blocking resistance, adhesion to substrates and scratch resistance, preferably 20 parts by mass parts or less, more preferably 15 parts by mass or less, and even more preferably 12 parts by mass or less.

Examples of polymerization initiators for polymerizing the polymer (A) of the present disclosure include azobisisobutyronitrile, 2,2-azobis(2-methylbutyronitrile), 2,2-azobis(2, 4-dimethylvaleronitrile), 2,2-azobis (2-diaminopropane) hydrochloride, 4,4-azobis (4-cyanovaleric acid), 2,2-azobis (2-methylpropionamidine) and other azo compounds ; persulfates such as ammonium persulfate and potassium persulfate; hydrogen peroxide, benzoyl peroxide, parachlorobenzoyl peroxide, lauroyl peroxide, and peroxides such as ammonium peroxide; not to be These polymerization initiators may be used alone or in combination of two or more.

The amount of the polymerization initiator per 100 parts by mass of the monomer components constituting the polymer (A) is preferably 0.05 from the viewpoint of increasing the polymerization rate and reducing the residual amount of unreacted monomer components. It is not less than 0.1 part by mass, more preferably not less than 0.1 part by mass, and preferably not more than 1 part by mass, more preferably not more than 0.5 part by mass, from the viewpoint of improving water resistance.

When the polymer (A) of the present disclosure is an emulsion particle having a multi-layered structure, the amount of the polymerization initiator per 100 parts by mass of the inner layer monomer component increases the polymerization rate, and the unreacted inner layer monomer component is From the viewpoint of reducing the residual amount, it is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and still more preferably 0.1 parts by mass or more. From the viewpoint of improving adhesion and scratch resistance, the amount is preferably 1 part by mass or less, more preferably 0.8 parts by mass or less, and even more preferably 0.5 parts by mass or less.

When the polymer (A) of the present disclosure is an emulsion particle having a multilayer structure, the amount of the polymerization initiator per 100 parts by mass of the outer layer monomer component increases the polymerization rate and increases the unreacted inner layer monomer. From the viewpoint of reducing the residual amount of the components, it is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and still more preferably 0.1 parts by mass or more. From the viewpoint of improving adhesion to the material and scratch resistance, the amount is preferably 1 part by mass or less, more preferably 0.8 parts by mass or less, and even more preferably 0.5 parts by mass or less.

The method of adding the polymerization initiator is not particularly limited. Examples of the method of addition include batch charging, divided charging, and continuous dropwise addition. Moreover, from the viewpoint of advancing the completion time of the polymerization reaction, part of the polymerization initiator may be added before or after the completion of adding the monomer components to the reaction system.

In order to accelerate the decomposition of the polymerization initiator, for example, a reducing agent such as sodium bisulfite and a decomposing agent for the polymerization initiator such as a transition metal salt such as ferrous sulfate are added to the reaction system in an appropriate amount. good too.

A chain transfer agent can also be used to adjust the weight average molecular weight of the emulsion particles. Examples of chain transfer agents include 2-ethylhexyl thioglycolate, tert-dodecylmercaptan, n-octylmercaptan, n-dodecylmercaptan, mercaptoacetic acid, mercaptopropionic acid, 2-mercaptoethanol, α-methylstyrene, α-methyl Examples include styrene dimer and the like, but are not limited to these examples. These chain transfer agents may be used alone or in combination of two or more. The amount of the chain transfer agent per 100 parts by weight of the monomer component is preferably 0.01 to 10 parts by weight from the viewpoint of appropriately adjusting the weight average molecular weight of the emulsion particles.

Additives such as a pH buffer, a chelating agent, and a film-forming aid may be added to the reaction system, if necessary. The amount of the additive varies depending on its type and cannot be determined unconditionally. Generally, the amount of the additive per 100 parts by weight of the monomer component is preferably about 0.01 to 5 parts by weight, more preferably about 0.1 to 3 parts by weight.

The atmosphere in which the monomer components are emulsion-polymerized is not particularly limited, but from the viewpoint of increasing the efficiency of the polymerization initiator, an inert gas such as nitrogen gas is preferable.

The polymerization temperature for emulsion polymerization of the monomer components is not particularly limited, but is generally preferably 50 to 100°C, more preferably 60 to 95°C. The polymerization temperature may be constant or may be changed during the polymerization reaction.

The polymerization time for emulsion polymerization of the monomer components is not particularly limited, and may be appropriately set according to the progress of the polymerization reaction, but is usually about 2 to 9 hours.

In addition, when the monomer component is emulsion-polymerized, part or all of the acidic groups possessed by the obtained polymer component may be neutralized with a neutralizing agent. The neutralizing agent may be used after adding the monomer component in the final stage, for example, may be used between the first-stage polymerization reaction and the second-stage polymerization reaction, and may be used during the initial emulsification. It may be used at the end of the polymerization reaction.

Neutralizing agents include, for example, hydroxides of alkali metals and alkaline earth metals such as sodium hydroxide; carbonates of alkali metals and alkaline earth metals such as sodium hydrogen carbonate and calcium carbonate; ammonia, monomethylamine, dimethyl Examples include, but are not limited to, alkaline substances such as organic amines such as aminoethanol. Among these neutralizing agents, a volatile alkaline substance such as ammonia is preferable from the viewpoint of improving water resistance, and sodium hydrogen carbonate is preferable from the viewpoint of improving the storage stability of emulsion particles. Neutralizing agents can be used, for example, as aqueous solutions.

When the outer layer is formed on the emulsion particles obtained above, the monomer component constituting the outer layer after the polymerization reaction rate in producing the emulsion particles reaches 90% or more, preferably 95% or more. is preferably emulsion-polymerized from the viewpoint of forming a layer-separated structure in the emulsion particles.

In addition, after forming the inner layer of the emulsion particles and before forming the outer layer, a layer composed of other polymer components may be formed, if necessary, as long as the object of the present invention is not hindered. Therefore, when producing the emulsion particles contained in the emulsion for water-based ink of the present invention, after forming the inner layer of the emulsion particles and before forming the outer layer, the required may form a layer composed of other polymer components.

The monomer component used for forming the outer layer may be the same as the monomer component used as the starting material for the inner layer of the emulsion particles. The emulsion polymerization method and polymerization conditions for forming the outer layer can be the same as the method and polymerization conditions for producing the inner layer of the emulsion particles.

Emulsion particles having an inner layer and an outer layer can be obtained as described above. If necessary, a surface layer made of other polymer components may be further formed on the surface of the outer layer as long as the object of the present invention is not hindered.

Emulsion particles having an inner layer and an outer layer can be obtained as described above. If necessary, a surface layer made of other polymer components may be further formed on the surface of the outer layer as long as the object of the present invention is not hindered.

Crosslinkability can be imparted to the above emulsion by further containing a crosslinking agent. The cross-linking agent may be one that initiates the cross-linking reaction at room temperature, or one that initiates the cross-linking reaction by heat. In the aqueous ink emulsion of the present invention, blocking resistance and adhesion can be further improved by incorporating a cross-linking agent into the emulsion particles.

Suitable cross-linking agents include, for example, oxazoline group-containing compounds, isocyanate group-containing compounds, aminoplast resins, epoxy group-containing compounds, carbodiimide group-containing compounds, and silane group-containing compounds. These cross-linking agents may be used alone or in combination of two or more. Among these cross-linking agents, oxazoline group-containing compounds and carbodiimide group-containing compounds are preferable from the viewpoint of improving the storage stability of the aqueous ink emulsion of the present invention. A carbodiimide group-containing compound is also preferable from the viewpoint of improving the storage stability of the aqueous ink emulsion of the present invention and improving the strength of the coating film when dried at a low temperature. The low temperature used herein may be 120° C. or lower, 110° C. or lower, or 100° C. or lower.

Specific examples of the cross-linking agent of the present disclosure include oxazoline group-containing compounds, epoxy group-containing compounds, carbodiimide group-containing compounds, isocyanate group-containing compounds, silane group-containing compounds, and the like. These cross-linking agents may be used alone or in combination of two or more. Among these cross-linking agents, oxazoline group-containing compounds, epoxy group-containing compounds, and carbodiimide group-containing compounds are preferable from the viewpoint of improving the storage stability of the aqueous ink emulsion of the present invention. Compounds are more preferable, and carbodiimide group-containing compounds are even more preferable from the viewpoint of storage stability and crosslinkability at low temperatures. The cross-linking agents of the present disclosure may be used alone or in combination of two or more.

Examples of oxazoline group-containing compounds of the present disclosure include 2,2′-bis(2-oxazoline), 2,2′-methylene-bis(2-oxazoline), 2,2′-ethylene-bis(2-oxazoline ), 2,2′-trimethylene-bis(2-oxazoline), 2,2′-tetramethylene-bis(2-oxazoline), 2,2′-hexamethylene-bis(2-oxazoline), 2,2′ -octamethylene-bis(2-oxazoline), 2,2'-ethylene-bis(4,4'-dimethyl-2-oxazoline), 2,2'-p-phenylene-bis(2-oxazoline), 2, 2′-m-phenylene-bis(2-oxazoline), 2,2′-m-phenylene-bis(4,4′-dimethyl-2-oxazoline), bis(2-oxazolinylcyclohexane) sulfide, bis( 2-oxazolinylnorbornane) sulfide, oxazoline ring-containing polymers, and the like. Examples of oxazoline group-containing compounds include those manufactured by Nippon Shokubai Co., Ltd., trade names: Epocross WS-300, Epocross WS-500, Epocross WS-700, Epocross K-2010, Epocross K-2020, Epocross K-2030, and the like. A commercial item is mentioned.
Examples of epoxy group-containing compounds of the present disclosure include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerin triglycidyl ether, glycerol polyglycidyl ether, polyglycerol polyglycidyl ether, trimethylolpropane poly Examples include polyglycidyl ethers such as glycidyl ether, sorbitol polyglycidyl ether, pentaerythritol polyglycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, and hydrogenated bisphenol A diglycidyl ether.

Examples of the carbodiimide group-containing compound of the present disclosure include aromatic carbodiimide compounds, aliphatic carbodiimide compounds, and the like. Examples of the carbodiimide group-containing compounds of the present disclosure include carbodilite SV-02, carbodilite V-02, carbodilite V-02-L2, carbodilite V-04, carbodilite V-06, carbodilite V-10, carbodilite SW-12G, and carbodilite E-. 02 and Carbodilite E-05 (both are trade names).
Examples of isocyanate group-containing compounds of the present disclosure include aromatic polyisocyanates such as xylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and hydrogenated products of the above aromatic polyisocyanates. , dimers or trimers of these polyisocyanates, and adducts of these polyisocyanates and polyols such as trimethylolpropane. These isocyanate group-containing compounds may be used alone or in combination of two or more. As the isocyanate group-containing compound, a blocked isocyanate compound in which the active isocyanate group in the polyisocyanate compound is previously reacted with a blocking agent such as phenol to be inactivated may be used. The use of a blocked isocyanate compound can improve the storage stability of the aqueous dispersion of the present invention and the ink using it.

Silane group-containing compounds of the present disclosure include, for example, bis-(3-triethoxysilylpropyl)-tetrasulfane, bis-(3-triethoxysilylpropyl)-disulfane, alkoxysilane compounds such as ethoxysiloxane oligomers, Hydrolysates of these alkoxysilane compounds and the like are included.
The isocyanate group-containing compounds of the present disclosure include, for example, "Coronate L", "Coronate HX", "Coronate HL", "Coronate HL-S", "Coronate 2234", "Aquanate 105", "Aquanate 130", "Aquanate 140", "Aquanate 200", "Aquanate 210" [manufactured by Tosoh Corporation, "Coronate" and "Aquanate" are registered trademarks], "Desmodur N3400" [Sumitomo Bayer Urethane Co., Ltd. ) (now Bayer AG), "Desmodur" is a registered trademark), "Duranate D-201", "Duranate TSE-100", "Duranate TSS-100", "Duranate 24A-100", " Duranate E-405-80T", "Duranate WB40-100", "Duranate WB40-80D", "Duranate WT20-100", "Duranate WT30-100", "Duranate WT31-100", "Duranate WL70-100", " Duranate WR80-70P", "Duranate WE50-100", "Duranate WM44-L70G", [manufactured by Asahi Kasei Chemicals Co., Ltd., "Duranate" is a registered trademark], "Takenate D-110N", "Takenate D-120N ”, “Takenate M-631N”, “MTERT-Olestar NP1200” (manufactured by Mitsui Chemicals Polyurethanes, Ltd., “Takenate” and “Olestar” are registered trademarks).

A plurality of functional groups may be included in the cross-linking agent of the present disclosure. The amount of functional groups contained in the cross-linking agent of the present disclosure is preferably 100 g/mol or more, more preferably 150 g/mol or more, still more preferably 200 g/mol or more, preferably 700 g/mol or less, and 650 g/mol or less. More preferably, it is 600 g/mol or less.
Functional groups included in the cross-linking agents of the present disclosure include oxazoline groups, epoxy groups, carbodiimide groups, isocyanate groups, silane groups, and the like.

The functional group contained in the cross-linking agent of the present disclosure reacts with the reactive group that reacts with the functional group contained in the cross-linking agent of the main agent (polymer (A) and wax component (B)) to form a crosslinked structure. be able to.
Reactive groups that react with the functional groups of the crosslinkers of the present disclosure include acid groups, hydroxyl groups, amino groups, and the like. The acid group includes a carboxyl group, a sulfonic acid group, a phosphoric acid group and the like, and a carboxyl group is more preferable.
The 1:1 equivalent number of the functional group of the cross-linking agent of the present disclosure and the main agent (polymer (A) and/or wax component (B)) is calculated, for example, from the following formula.
Amount of cross-linking agent = Reactive group of main agent/(56.1 x 1000) x Equivalent weight of cross-linking agent x Amount of main agent It is preferable from the viewpoint of improving adhesion, blocking resistance, and cellophane tape peeling resistance.
The amount of functional groups contained in the cross-linking agent can be measured by a known method according to the type of functional group, catalog values may be used as a reference, the polymer solution is lyophilized, and this is subjected to 1H-NMR. , and the amount of each functional group may be calculated from the absorption peak intensity derived from each functional group and the absorption peak intensity derived from other monomers.

<Wax component (B)>
Aqueous dispersions of the present disclosure contain a wax component (B).

The wax component (B) of the present disclosure can include natural waxes and synthetic waxes.

Natural waxes include petroleum waxes, vegetable waxes, animal and plant waxes, and the like. Examples of petroleum wax include paraffin wax, microcrystalline wax, petrolatum, and the like. Plant-based waxes include carnauba wax, candelilla wax, rice wax, Japan wax, and the like. Examples of animal and plant waxes include lanolin and beeswax.

Synthetic waxes include synthetic hydrocarbon waxes and modified waxes. Synthetic hydrocarbon waxes include polyolefin waxes, (meth)acrylic waxes, Fischer-Tropsch waxes, and the like. Modified waxes include paraffin wax derivatives, montan wax derivatives, microcrystalline wax derivatives and the like. Polyolefin waxes and (meth)acrylic waxes are preferred from the viewpoint of improving adhesion and scratch resistance.

The (meth)acrylic wax is not particularly limited. ) As acrylic monomers, polymers produced from lauryl (meth)acrylate, tridecyl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate, or derivatives thereof, etc. mentioned.

A commercially available product can also be used as the (meth)acrylic wax. Preferred commercial products include ST100 and ST200 manufactured by Nippon Shokubai Co., Ltd.

The polyolefin wax is not particularly limited, and examples thereof include waxes produced from olefins such as ethylene, propylene and butylene or derivatives thereof, and copolymers thereof, specifically polyethylene waxes, polypropylene waxes and polybutylene. wax, a copolymer wax composed of ethylene and a monomer having a carboxylic acid group such as methacrylic acid or acrylic acid, and an oxidized polyethylene wax. Among these, polyethylene waxes, polypropylene waxes, copolymer waxes composed of ethylene and a monomer having a carboxylic acid group such as methacrylic acid or acrylic acid, and oxidized polyethylene waxes are preferred from the viewpoint of improving adhesion and scratch resistance. .

The oxidized polyethylene wax of the present disclosure is obtained by oxidizing polyethylene wax and has a skeleton derived from polyethylene (polyethylene skeleton). The polyethylene skeleton mainly has structural units derived from ethylene. The polyethylene skeleton may be a homopolyethylene (ethylene homopolymer) skeleton, a block polyethylene (a block copolymer of ethylene and another olefin) skeleton, or a random polyethylene (ethylene and another olefin random copolymer) skeleton. Other olefins include alkenes such as propylene, isobutylene, 1-butene, 1-pentene and 1-hexene. These components may be linear or branched. Other olefin components have, for example, 2 to 6 carbon atoms.

The content of the ethylene component in the polyethylene skeleton (content of structural units derived from ethylene) is, for example, 60 mol% or more, and may be 70 mol% or more. When the polyethylene skeleton is a block polyethylene skeleton or a random polyethylene skeleton, the content of the ethylene component in the polyethylene skeleton (the content of structural units derived from ethylene) is, for example, 95 mol% or less, and 90 mol% or less. good too.

The oxidized polyethylene wax preferably contains a high-density oxidized polyethylene wax from the viewpoint of obtaining better adhesion and scratch resistance.

A commercially available product can also be used as the oxidized polyethylene wax. Preferred commercially available products include BYK AQUACER497, AQUACER515, AQUACER531, AQUACER1547, and the like.

The wax component (B) can be used singly or in combination of two or more.

The wax component (B) of the present disclosure is preferably in the form of solid wax particles dissolved or dispersed in a solvent, more preferably in the form of an emulsion dispersed in the solvent. The solvent is preferably an aqueous medium, more preferably the same aqueous medium as the aqueous medium used for the solvent of the aqueous ink composition.

The volume average particle diameter (nm) of the wax particles of the present disclosure is preferably 25 nm or more and 500 nm or less, more preferably 30 nm or more and 400 nm or less. The volume average particle size of wax particles is
Although not particularly limited, it can be measured by a dynamic light scattering method, a laser diffraction/scattering method, a Coulter counter, a microscope method, or the like.

The average particle size described in this example was determined by the photon correlation method using a multi-sample nanoparticle size measurement system [manufactured by Otsuka Electronics Co., Ltd., trade name: nanoSAQLA], which is a particle size measurement device based on the dynamic light scattering method. It is the average particle diameter (hydrodynamic diameter) obtained by obtaining the correlation function and performing cumulant analysis.

From the viewpoint of adhesion, the melting point of the wax component (B) of the present disclosure is preferably 20° C. or higher, more preferably 25° C. or higher, even more preferably 30° C. or higher, preferably 150° C. or lower, and more preferably 140° C. or lower. , 130° C. or less is more preferable. The melting point (Tm ₂ ) of the wax component (B) can be measured with a melting point measuring device conforming to JIS K 0064.

The acid value (mgKOH/g) of the wax component of the present disclosure may or may not match from the viewpoint of adhesion, preferably 0 mgKOH/g, preferably 100 mgKOH/g or less, more preferably 90 mgKOH/g or less, 80 mgKOH/g or less is more preferable.
<Aqueous dispersion>
The content of the polymer (A) in 100 parts by mass of the non-volatile content of the aqueous dispersion of the present disclosure may be 80 parts by mass or more from the viewpoint of adhesion, scratch resistance, and blocking resistance. It is preferably 85 parts by mass or more, and may be 99 parts by mass or less, preferably 98 parts by mass or less, and more preferably 95 parts by mass or less.

The non-volatile content of the aqueous dispersion of the present disclosure may be calculated as a mass excluding the mass of volatile components contained in the resin and various additives from the total mass of the aqueous dispersion. Dry in a dryer at a temperature of 110 ° C. for 1 hour, and use the resulting residue as a non-volatile matter, formula:
[Non-volatile content (mass%) in aqueous resin dispersion]
= ([mass of residue] ÷ [water-based resin dispersion 1 g]) × 100
can be determined based on

The total content of the polymer (A) and the wax component (B) in 100 parts by mass of the nonvolatile content of the aqueous dispersion of the present disclosure is 1 part by mass or more from the viewpoint of adhesion, scratch resistance, and blocking resistance. It is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and may be 25 parts by mass or less, preferably 20 parts by mass or less, and more preferably 15 parts by mass or less.

The content of the wax component (B) in 100 parts by mass of the nonvolatile content of the aqueous dispersion of the present disclosure may be 1 part by mass or more from the viewpoint of adhesion, scratch resistance, and blocking resistance. It is preferably 5 parts by mass or more, and may be 25 parts by mass or less, preferably 20 parts by mass or less, and more preferably 15 parts by mass or less.

The mass ratio of the polymer (A) and the wax component (B) of the present disclosure may be 99/1 to 80/20, 99/1 to 82, from the viewpoint of adhesion, scratch resistance, and blocking resistance. /18 is preferred, and 99/1 to 85/15 are more preferred.

The mass ratio of the structural unit derived from the cycloaliphatic group-containing monomer of the present disclosure and the wax component (B) is 99/1 to 55/45 from the viewpoint of adhesion, scratch resistance, and blocking resistance. Well, 99/1 to 60/40 are preferred, and 99/1 to 65/35 are more preferred.

The content of the polymer (A) in 100 parts by mass of the aqueous dispersion of the present disclosure may be 20 parts by mass or more, preferably 30 parts by mass or more, from the viewpoint of adhesion, scratch resistance, and blocking resistance. It is more preferably 70 parts by mass or less, preferably 60 parts by mass or less, and more preferably 50 parts by mass or less.

The content of the wax component (B) in 100 parts by mass of the aqueous dispersion of the present disclosure may be 0.1 parts by mass or more from the viewpoint of adhesion, scratch resistance, and blocking resistance, and may be 0.5 parts by mass or more. , more preferably 1 part by mass or more, may be 20 parts by mass or less, preferably 15 parts by mass or less, and more preferably 10 parts by mass or less.

The content of the polymer (A) in the total 100 parts by mass of the polymer (A) and the wax component (B) in the nonvolatile matter of the aqueous dispersion of the present disclosure is preferably 80 parts by mass or more, more preferably 85 parts by mass or more. It is preferably 90 parts by mass or more, more preferably 99 parts by mass or less, more preferably 97 parts by mass or less, and even more preferably 95 parts by mass or less.

The content of the wax component (B) in the total 100 parts by mass of the polymer (A) and the wax component (B) in the nonvolatile matter of the aqueous dispersion of the present disclosure is preferably 1 part by mass or more, and more preferably 3 parts by mass or more. It is preferably 5 parts by mass or more, more preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less.

The aqueous dispersion of the present disclosure contains resins other than the polymer (A) or the wax component (B), such as resin emulsions, water-soluble resins, and water-dispersible resins, to the extent that the object of the present invention is not hindered. may
In addition, the aqueous dispersion of the present disclosure contains, for example, surfactants, film-forming aids, UV absorbers, UV inhibitors, fillers, leveling agents, dispersants, Additives such as thickeners, wetting agents, plasticizers, stabilizers, antioxidants, preservatives and the like may be included in appropriate amounts.

When the aqueous dispersion of the present disclosure contains a cross-linking agent, the total content of the polymer (A) and/or wax component (B) and the cross-linking agent in 100 parts by mass of the aqueous dispersion of the present disclosure is From the viewpoint of properties, scratch resistance, and blocking resistance, the amount may be 1 part by mass or more, preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and may be 60 parts by mass or less, and 55 parts by mass or less. Preferably, 50 parts by mass or less is more preferable.
The content of the cross-linking agent in 100 parts by mass of the nonvolatile content of the aqueous dispersion of the present disclosure may be 1 part by mass or more, preferably 3 parts by mass or more, from the viewpoint of adhesion, scratch resistance, and blocking resistance. It is more preferably 25 parts by mass or less, preferably 20 parts by mass or less, and more preferably 15 parts by mass or less.
The mass ratio of (the polymer (A) and the wax component (B)) and the cross-linking agent of the present disclosure may be 99/1 to 80/20 from the viewpoint of adhesion, scratch resistance, and blocking resistance. 99/1 to 82/18 are preferred, and 99/1 to 85/15 are more preferred.
It is preferred that the (polymer (A) and/or wax component (B)) of the present disclosure have structural units derived from reactive group-containing monomers that react with the functional groups of the crosslinker.
Reactive groups that react with the functional groups of the crosslinkers of the present disclosure include acid groups, hydroxyl groups, amino groups, and the like. The acid group includes a carboxyl group, a sulfonic acid group, a phosphoric acid group and the like, and a carboxyl group is more preferable.

When the (polymer (A) and/or wax component (B)) of the present disclosure has a structural unit derived from a reactive group-containing monomer that reacts with the functional group of the cross-linking agent, the functional group of the cross-linking agent and The mass ratio of the structural unit derived from the reacting reactive group-containing monomer and the cross-linking agent may be 99/1 to 55/45 from the viewpoint of adhesion, scratch resistance, and blocking resistance, and 99/1. ~60/40 is preferred, and 99/1 to 65/35 is more preferred. When both the polymer (A) and the wax component (B) contain structural units derived from a reactive group-containing monomer that reacts with the functional group of the cross-linking agent, these mass ratios are Using the mass of the structural unit derived from the reactive group-containing monomer that reacts with the functional group of the cross-linking agent in the component (B), only the polymer (A) or only the wax component (B) reacts with the functional group of the cross-linking agent. When a structural unit derived from a reactive group-containing monomer that calculated as
When the (polymer (A) and/or wax component (B)) of the present disclosure has a structural unit derived from an acid group-containing monomer, the mass of the structural unit derived from the acid group-containing monomer and the cross-linking agent The ratio may be 99/1 to 55/45, preferably 99/1 to 60/40, more preferably 99/1 to 65/35, from the viewpoint of adhesion, scratch resistance and blocking resistance. When both the polymer (A) and the wax component (B) contain structural units derived from the acid group-containing monomer, these mass ratios are Using the mass of the structural unit derived from the polymer, when only the polymer (A) or only the wax component (B) contains the structural unit derived from the acid group-containing monomer, It is calculated using the mass containing the derived structural unit.

When the (polymer (A) and/or wax component (B)) of the present disclosure has a structural unit derived from a hydroxyl group-containing monomer, the mass ratio of the structural unit derived from the hydroxyl group-containing monomer and the cross-linking agent is , from the viewpoint of adhesion, scratch resistance and blocking resistance, it may be 99/1 to 55/45, preferably 99/1 to 60/40, more preferably 99/1 to 65/35. When the structural unit derived from the hydroxyl group-containing monomer is contained in both the polymer (A) and the wax component (B), these mass ratios are the hydroxyl group-containing monomers in the polymer (A) and the wax component (B). Using the mass of the structural unit derived from, when only the polymer (A) or only the wax component (B) contains the structural unit derived from the hydroxyl group-containing monomer, the structural unit derived from the hydroxyl group-containing monomer is calculated using the mass containing
The content of the polymer (A) in the total 100 parts by mass of (the polymer (A) and the wax component (B)) and the cross-linking agent in the non-volatile content of the aqueous dispersion of the present disclosure is preferably 50 parts by mass or more, and 55 parts by mass. It is more preferably 60 parts by mass or more, preferably 99 parts by mass or less, more preferably 97 parts by mass or less, and even more preferably 95 parts by mass or less.
In the non-volatile content of the aqueous dispersion of the present disclosure (the polymer (A) and the wax component (B)) and a total of 100 parts by mass of the cross-linking agent, the content of the cross-linking agent is preferably 1 part by mass or more, and 3 parts by mass or more. is more preferably 5 parts by mass or more, preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and even more preferably 40 parts by mass or less.
The volume average particle diameter (nm) of the aqueous dispersion of the present disclosure is preferably 25 nm or more and 500 nm or less, and 50 nm, from the viewpoint of blocking resistance, adhesion to substrates and scratch resistance, ejection stability, and image quality improvement. It is more preferably 400 nm or less, and most preferably 100 nm or more and 300 nm or less.
The volume average particle size of the aqueous dispersion is not particularly limited, but can be measured by a dynamic light scattering method, a laser diffraction/scattering method, a Coulter counter, a microscope method, or the like.
The average particle size of the present disclosure is determined by the photon correlation method using a multi-sample nanoparticle size measurement system [manufactured by Otsuka Electronics Co., Ltd., trade name: nanoSAQLA], which is a particle size measurement device based on the dynamic light scattering method. is the average particle diameter (hydrodynamic diameter) obtained by cumulant analysis.

<Aqueous ink>
The aqueous dispersion of the present disclosure can be suitably used for aqueous ink.

The content of the polymer (A) in 100 parts by mass of the water-based ink of the present disclosure may be 1 part by mass or more from the viewpoint of ejection stability, storage stability, and dispersion stability when used for white ink, and may be 3 parts by mass. It is preferably at least 5 parts by mass, more preferably at least 5 parts by mass, may be at most 50 parts by mass, preferably at most 40 parts by mass, more preferably at most 30 parts by mass, and even more preferably at most 20 parts by mass. On the other hand, when used for color inks other than white ink, from the viewpoint of ejection stability and storage stability, the amount may be 1 part by mass or more, preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and 40 parts by mass. 30 parts by mass or less is preferable, 25 parts by mass or less is more preferable, and 20 parts by mass or less is even more preferable.

The content of the wax component (B) in 100 parts by mass of the aqueous ink of the present disclosure may be 0.01 parts by mass or more, preferably 0.05 parts by mass or more, from the viewpoint of ejection stability and storage stability. It is more preferably 1 part by mass or more, may be 8 parts by mass or less, preferably 6 parts by mass or less, and more preferably 4 parts by mass or less.

The mass ratio of the polymer (A) and the wax component (B) of the present disclosure may be 99/1 to 80/20, 99/1 to 82, from the viewpoint of adhesion, scratch resistance, and blocking resistance. /18 is preferred, and 99/1 to 85/15 are more preferred. The mass ratio of the structural unit derived from the cycloaliphatic group-containing monomer and the wax component (B) in the water-based ink of the present disclosure is 99/1 to 55/45 from the viewpoint of adhesion, scratch resistance, and blocking resistance. , preferably 99/1 to 60/40, more preferably 99/1 to 65/35.
When the water-based ink of the present disclosure contains a cross-linking agent, the content of the cross-linking agent in 100 parts by mass of the water-based ink of the present disclosure is 0.01 parts by mass or more from the viewpoint of ejection stability and storage stability. preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, may be 8 parts by mass or less, preferably 6 parts by mass or less, and more preferably 4 parts by mass or less.
The mass ratio of the polymer (A) of the present disclosure and the cross-linking agent may be 99/1 to 80/20 from the viewpoint of adhesion, scratch resistance, and blocking resistance, and 99/1 to 82/18. Preferably, 99/1 to 85/15 are more preferable.
The mass ratio of the structural unit derived from the cycloaliphatic group-containing monomer and the cross-linking agent in the water-based ink of the present disclosure is 99/1 to 55/45 from the viewpoint of adhesion, scratch resistance, and blocking resistance. Well, 99/1 to 60/40 are preferred, and 99/1 to 65/35 are more preferred.

Aqueous inks of the present disclosure contain a colorant. Colorant hues include, for example, achromatic colors such as white, black, and gray, and chromatic colors such as yellow, magenta, cyan, blue, red, orange, and green. is not limited to only

Colorants of the present disclosure include pigments and dyes. Among these, pigments are preferred because of their excellent weather resistance. When a pigment is used, the pigment may be used in the form of a pigment dispersion such as a paste. Examples of pigments include organic pigments and inorganic pigments, and these may be used alone or in combination.

Examples of dyes include C.I. I. solvent black, C.I. I. Solvent Red, C.I. I. Solvent Yellow, C.I. I. solvent blue, C.I. I. solvent green, C.I. I. solvent orange, C.I. I. Examples include solvent violet and the like, but the present invention is not limited only to such examples.

Examples of organic pigments include azo pigments such as benzidine and Hansa yellow; azomethine pigments; methine pigments; anthraquinone pigments; phthalocyanine pigments such as phthalocyanine blue; perinone pigments; pigments, iminoisoindolinone pigments, quinacridone pigments such as quinacridone red and quinacridone violet, flavanthrone pigments, indanthrone pigments, anthrapyrimidine pigments, carbazole pigments, monoarylide yellow, diarylide yellow, benzimidazolone yellow, tolyl orange , naphthol orange, and quinophthalone pigments, but the present invention is not limited to these examples. These organic pigments may be used alone or in combination of two or more. Preferred organic pigments include, for example, C.I. I. Pigment Yellow, C.I. I. Pigment Red, C.I. I. pigment orange, C.I. I. pigment violet, C.I. I. pigment blue, C.I. I. pigment green and the like.

Examples of inorganic pigments include titanium dioxide, antimony trioxide, zinc white, lithopone, lead white, red iron oxide, black iron oxide, iron oxide, chromium oxide green, carbon black, yellow lead, molybdenum red, ferrocyanide Ferrous (Prussian blue), ultramarine, lead chromate, etc., mica, clay, aluminum powder, talc, flat-shaped pigments such as aluminum silicate, calcium carbonate, magnesium hydroxide, aluminum hydroxide , barium sulfate, and magnesium carbonate, but the present invention is not limited to these examples. These inorganic pigments may be used alone or in combination of two or more.

The colorant used in the water-based ink of the present disclosure is preferably any one colorant selected from white pigments, yellow, magenta, cyan, black, red, blue and green.

A known inorganic white pigment can be used without any particular limitation as the white pigment. Examples include silicas such as alkaline earth metal sulfates, carbonates, finely divided silicic acid and synthetic silicates, calcium silicate, alumina, alumina hydrate, titanium oxide, zinc oxide, talc and clay. . Moreover, the inorganic white pigment may be surface-treated by various surface treatment methods. Among them, surface-treated titanium oxide is preferable because it exhibits relatively good dispersibility in an aqueous medium. For example, in order to avoid photocatalytic effects, titanium oxide surface-treated with an inorganic substance is preferred, and titanium oxide surface-treated with silica and alumina is preferred. Furthermore, it is also possible to use titanium oxide which has been surface-treated with the silica and alumina and then further surface-treated with a silane coupling agent. In titanium oxide surface-treated with silica and alumina, known rutile-type or anatase-type titanium dioxide can be used as titanium oxide, and rutile-type titanium dioxide is more preferable.

The average particle size of the titanium oxide is preferably 100-500 nm, more preferably 150-400 nm. When the average particle size is 100 nm or less, non-settling property and dispersion stability in an aqueous medium are more likely to be achieved, but the whiteness and opacity are inferior, and there is a possibility that the practicality as an original white ink is reduced. On the other hand, if the average particle diameter is 500 nm or more, there is no problem in terms of whiteness and hiding power, but ejection stability tends to be insufficient. Practically, the particle size is more preferably 200 to 300 nm. The average particle size of titanium oxide used as a raw material is obtained by measuring the particle size of 20 particles using an electron micrograph and taking the average.

In the present invention, the average of aqueous inks using the polymer (A) and the wax component (B), the aqueous dispersion containing (A) and (B), and the aqueous dispersion containing (A) and (B) Although the particle size is not particularly limited, it can be measured by a dynamic light scattering method, a laser diffraction/scattering method, a Coulter counter, a microscope method, or the like.

The average particle size described in this example was determined by the photon correlation method using a multi-sample nanoparticle size measurement system [manufactured by Otsuka Electronics Co., Ltd., trade name: nanoSAQLA], which is a particle size measurement device based on the dynamic light scattering method. It is the average particle diameter (hydrodynamic diameter) obtained by obtaining the correlation function and performing cumulant analysis.

Organic pigments for yellow include C.I. I. Pigment Yellow 1 (Hansa Yellow G), 2, 3 (Hansa Yellow 10G), 4, 5 (Hansa Yellow 5G), 6, 7, 10, 11, 12 (Disazo Yellow AAA), 13, 14, 16, 17, 24 (flavanthrone yellow), 55 (disazo yellow AAPT), 61, 61:1, 65, 73, 74 (fast yellow 5GX), 75, 81, 83 (disazo yellow HR), 93 (condensed azo yellow 3G), 94 (condensed azo yellow 6G), 95 (condensed azo yellow GR), 97 (fast yellow FGL), 98, 99 (anthraquinone), 100, 108 (anthrapyrimidine yellow), 109 (isoindolinone yellow 2GLT), 110 ( isoindolinone yellow 3RLT), 113, 117, 120 (benzimidazolone yellow H2G), 123 (anthraquinone yellow), 124, 128 (condensed azo yellow 8G), 129, 133, 138 (quinophthalone yellow), 139 (isoind Linon Yellow), 147, 151 (Benzimidazolone Yellow H4G), 153 (Nickel Nitroso Yellow), 154 (Benzimidazolone Yellow H3G), 155, 156 (Benzimidazolone Yellow HLR), 167, 168, 172, 173 ( isoindolinone yellow 6GL), 180 (benzimidazolone yellow), and the like.

Organic pigments for magenta water-based ink include C.I. I. Pigment Red 1 (Para Red), 2, 3 (Toluidine Red), 4, 5 (lTR Red), 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21 , 22, 23, 30, 31, 32, 37, 38 (pyrazolone red B), 40, 41, 42, 88 (thioindigo Bordeaux), 112 (naphthol red FGR), 114 (brilliant carmine BS), 122 (dimethyl quinacridone), 123 (perylene vermillion), 144, 146, 149 (perylene scarred), 150, 166, 168 (anthanthrone orange), 170 (naphthol red F3RK), 171 (benzimidazolone maroon HFM), 175 ( benzimidazolone red HFT), 176 (benzimidazolone carmine HF3C), 177, 178 (perylene red), 179 (perylene maroon), 185 (benzimidazolone carmine HF4C), 187, 188, 189 (perylene red), 190 (perylene red), 194 (perinone red), 202 (quinacridone magenta), 209 (dichloroquinacridone red), 214 (condensed azo red), 216, 219, 220 (condensed azo), 224 (perylene red), 242 (condensed azo scarlet) ), 245 (naphthol red), or C.I. I. Pigment Violet 19 (quinacridone), 23 (dioxazine violet), 31, 32, 33, 36, 38, 43, 50 and the like.

Organic pigments for cyan include C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6 (all of these are phthalocyanine blue), 16 (metal-free phthalocyanine blue), 17:1, 18 (alkali blue toner), 19, 21, 22, 25, 56, 60 (thren blue), 64 (dichloroindanthrone blue), 65 (violanthrone), 66 (indigo) and the like.

As the organic pigment for black, a black organic pigment such as aniline black (C.I. Pigment Black 1) can be used.

Organic pigments used in color water-based inks other than white pigments, yellow, cyan, or magenta water-based inks include C.I. I. Pigment Orange 1, 2, 5, 7, 13, 14, 15, 16 (Vulcan Orange), 24, 31 (Condensed Azo Orange 4R), 34, 36 (Benzimidazolone Orange HL), 38, 40 (Pyrantrone Orange ), 42 (isoindolinone orange RLT), 43, 51, 60 (benzimidazolone-based insoluble monoazo pigment), 62 (benzimidazolone-based insoluble monoazo pigment), 63; I. Pigment Green 7 (phthalocyanine green), 10 (green gold), 36 (chlorobrominated phthalocyanine green), 37, 47 (violanthrone green); or C.I. I. Pigment Brown 1, 2, 3, 5, 23 (Condensed Azo Brown 5R), 25 (Benzimidazolone Brown HFR), 26 (Perylene Bordeaux), 32 (Benzimidazolone Brown HFL) and the like.

The amount of the coloring agent per 100 parts by mass of the non-volatile content of the resin emulsion for aqueous ink used in the aqueous ink of the present disclosure is preferably 30 parts by mass or more from the viewpoint of sufficiently coloring the print or image formed with the aqueous ink. , more preferably 50 parts by mass or more, and from the viewpoint of forming a uniform coating film, it is preferably 300 parts by mass or less, more preferably 200 parts by mass or less.

When a white pigment is used, the amount of the white pigment per 100 parts by mass of the non-volatile matter of the resin emulsion for water-based ink is preferably from the viewpoint of sufficiently coloring the print or image formed with the water-based ink and improving the color development. It is 50 parts by mass or more, more preferably 60 parts by mass or more, and preferably 500 parts by mass or less, more preferably 400 parts by mass or less from the viewpoint of forming a uniform coating film and/or improving gloss.

The water-based ink of the present disclosure contains water and other water-soluble organic solvents from the viewpoints of the ink viscosity of the water-based ink, the control of the wetting and spreading on the recording medium to be printed, the improvement of the image quality, and the ejection stability. may be included. Examples of water-soluble organic solvents include glycols such as propylene glycol, 1,3-propanediol, glycerin, dipropylene glycol, tripropylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol; monoethylene glycol monomethyl ether, monoethylene glycol; Ethers of monoethylene glycol such as monoethyl ether, monoethylene glycol monopropyl ether, monoethylene glycol monoisopropyl ether, monoethylene glycol monobutyl ether, monoethylene glycol monoisobutyl ether; monopropylene glycol monomethyl ether, monopropylene glycol monoethyl ether , Monopropylene Glycol Monopropyl Ether, Monopropylene Glycol Monoisopropyl Ether, Monopropylene Glycol Monobutyl Ether, Monopropylene Glycol Monoisobutyl Ether, etc.; to 4), monomethyl ether of polyethylene glycol (number of EO addition moles = 2 to 10, preferably 2 to 4), monoethyl ether of polyethylene glycol (number of EO addition moles = 2 to 10, preferably 2 to 4) Propyl ether, monoisopropyl ether of polyethylene glycol (number of EO addition moles = 2 to 10, preferably 2 to 4), monobutyl ether of polyethylene glycol (number of EO addition moles = 2 to 10, preferably 2 to 4), polyethylene glycol Ether of polyethylene glycol such as monoisobutyl ether (number of EO addition moles = 2 to 10, preferably 2 to 4); Monomethyl ether of polypropylene glycol (number of EO addition moles = 2 to 10, preferably 2 to 4), polypropylene Monoethyl ether of glycol (number of EO addition moles = 2 to 10, preferably 2 to 4), monopropyl ether of polypropylene glycol (number of EO addition moles = 2 to 10, preferably 2 to 4), polypropylene glycol (EO addition Monoisopropyl ether with mole number = 2 to 10, preferably 2 to 4), monobutyl ether of polypropylene glycol (EO addition mole number = 2 to 10, preferably 2 to 4), polypropylene glycol (EO addition mole number = 2 to 10, preferably 2 to 4) polyprop such as monoisobutyl ether Ethers of propylene glycol may be mentioned. Among these, propylene glycol, diethylene glycol, triethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, tripropylene glycol monomethyl ether, monoethylene glycol monoisopropyl ether, mono Propylene glycol monopropyl ether is preferred. These organic solvents may be used alone or in combination of two or more.

Since the amount of the water-soluble organic solvent varies depending on the type and amount of the colorant contained in the water-based ink, it cannot be determined unconditionally. It is preferable to determine it as appropriate.

For example, if the colorant contains a white pigment, the amount of the organic solvent in 100 mass of the water-based ink may be 5 parts by mass or more from the viewpoint of controlling the wetting and spreading on the recording medium to be printed and improving the image quality. , preferably 8 parts by mass or more, more preferably 10 parts by mass or more, may be 50 parts by mass or less, preferably 45 parts by mass or less, and more preferably 40 parts by mass or less.

The water-based ink of the present disclosure contains the resin emulsion for water-based ink and a colorant. A resin such as a water-dispersible resin may also be included. The water-based ink of the present invention may contain, for example, surfactants, film-forming aids, UV absorbers, UV inhibitors, fillers, leveling agents, dispersants, and thickening agents, as long as the objects of the present invention are not hindered. Additives such as thickeners, wetting agents, plasticizers, stabilizers and antioxidants may be included in appropriate amounts.

An ionic dispersant is preferable as the dispersant used in the water-based ink of the present disclosure. The content of the dispersant is preferably 0.1% by mass or more and 2.0% by mass or less, more preferably 0.2% by mass or more and 1.0% by mass or less, relative to 100 parts by mass of the inkjet ink of the present invention. .

A polymer dispersant is preferred as the dispersant used in the aqueous ink of the present disclosure.

A dispersant used in the water-based ink of the present disclosure may have an acid value. From the viewpoint of redispersibility, the acid value of the dispersant is preferably 350 mgKOH/g or more, more preferably 450 mgKOH/g or more, more preferably 550 mgKOH/g or more, 650 mgKOH/g or more, 720 mgKOH/g or more in that order, and 1000 mgKOH/g. g or less is preferable, 900 mgKOH/g or less is more preferable, and 850 mgKOH/g or less and 800 mgKOH/g or less are more preferable in that order. On the other hand, it is preferably 100 mgKOH/g or less, more preferably 50 mgKOH/g or less, even more preferably 30 mgKOH/g or less from the viewpoint of lowering the viscosity and conductivity of the aqueous ink, and does not need to have an acid value. It may be 1 mgKOH/g or more, or 5 mgKOH/g or more.
The volume average particle diameter (nm) of the water-based ink of the present disclosure is preferably 25 nm or more and 500 nm or less, and 50 nm or more, from the viewpoint of blocking resistance, adhesion and scratch resistance to substrates, ejection stability, and image quality improvement. It is more preferably 400 nm or less, and most preferably 100 nm or more and 300 nm or less.
The volume average particle size of the water-based ink is not particularly limited, but can be measured by a dynamic light scattering method, a laser diffraction/scattering method, a Coulter counter, a microscope method, or the like.
The average particle size of the present disclosure is determined by the photon correlation method using a multi-sample nanoparticle size measurement system [manufactured by Otsuka Electronics Co., Ltd., trade name: nanoSAQLA], which is a particle size measurement device based on the dynamic light scattering method. is the average particle diameter (hydrodynamic diameter) obtained by cumulant analysis.

The water-based ink of the present disclosure obtained as described above has excellent adhesion and excellent scratch resistance. It can be suitably used as an ink such as an ink, gravure printing ink, or screen printing ink, especially as an aqueous inkjet ink.

The water-based ink of the present disclosure can form prints or images having a predetermined pattern by ejecting the water-based ink onto a recording medium in a predetermined pattern using an inkjet recording apparatus, for example.

Examples of recording media include paper, paper laminated with resin films such as polyethylene, polypropylene, and polystyrene (coated paper, etc.), metal plates such as aluminum, zinc, and copper, cellulose, polyethylene terephthalate, polystyrene, and olefin-based media. Examples include resin films such as resins, polycarbonate, polyvinyl acetal, polyvinyl chloride, polyamide, nylon, and acrylic resins, paper having a metal coating, and resin films having a metal coating. As a recording medium on which the water-based ink of the present disclosure is printed, resin films are preferable, and polyethylene terephthalate and olefin-based resins are particularly preferable.

Examples of olefinic resins include polyethylene and polypropylene, and application to polypropylene such as biaxially oriented polypropylene film (OPP) and non-oriented polypropylene film (CPP) is particularly preferred.

The water-based ink of the present disclosure is preferably formed on a resin film, and its embodiment is a laminate having a printed layer formed from the water-based ink on the resin film.

The laminate of the present disclosure may or may not have a primer layer between the resin film and the printed layer, but it is preferable not to have it from the viewpoint of productivity, and the resin film is printed directly. Layer formation is preferred. The laminate of the present disclosure is laminated in the order of a resin film and a printed layer, and may or may not have a protective film (laminate layer) on the printed layer, but does not have it from the viewpoint of productivity. By using the water-based ink of the present disclosure, it is possible to obtain a laminate that has excellent adhesion to a substrate and good scratch resistance even without a primer layer or a protective film (laminate layer). can be expected.

The laminate of the present disclosure can be suitably used for various printed matter.

EXAMPLES Next, the present invention will be described in more detail based on examples, but the present invention is not limited only to these examples. In the following examples, "parts" means "parts by mass" and "%" means "% by mass" unless otherwise specified.
<Glass transition temperature of polymer component>
The glass transition temperature (Tg) of the polymer component is expressed by the formula:
1/Tg=Σ(Wm/Tgm)/100
[Wherein, Wm is the content (% by mass) of the monomer m in the monomer component constituting the polymer component, and Tgm is the glass transition temperature (absolute temperature: K) of the homopolymer of the monomer m. ]
It was obtained by calculation based on the Fox equation represented by:

<Acid value derived from carboxyl group of resin emulsion particles>
The acid value derived from the carboxyl groups of the resin emulsion particles was obtained by approximating the number of mg of potassium hydroxide required to neutralize the carboxyl groups present in 1 g of the monomer component used as an acid value.
<Minimum film-forming temperature>
The minimum film-forming temperature is a value measured according to JISK6828-2:2003.
<Average particle size>
Measurement temperature 25 ± 0.5 ° C., using a multi-sample nanoparticle size measurement system [manufactured by Otsuka Electronics Co., Ltd., product name: nanoSAQLA], which is a particle size measurement device by the dynamic light scattering method, autocorrelation by the photon correlation method A function was determined, and an average particle diameter (hydrodynamic diameter) determined by cumulant analysis was determined.
<Non-volatile content (NV)>
The non-volatile content of the aqueous dispersion of the present disclosure was obtained by weighing 1 g of the aqueous dispersion from the total mass of the aqueous dispersion, drying it with a hot air dryer at a temperature of 110° C. for 1 hour, and using the resulting residue as the non-volatile content.
formula:
[Non-volatile content (mass%) in aqueous resin dispersion]
= ([mass of residue] ÷ [water-based resin dispersion 1 g]) × 100

[Production Example 1] Core-Shell Emulsion A flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser was charged with 520 parts of deionized water. In a dropping funnel, 163 parts of deionized water, 80 parts of a 25% aqueous solution of emulsifier [manufactured by ADEKA Co., Ltd., trade name: Adekari Sorb SR-10], 322 parts of cyclohexyl methacrylate, 103 parts of 2-ethylhexyl acrylate, 2-hydroxyethyl methacrylate. 75 parts of a pre-emulsion for first-stage dropping was prepared, of which 74 parts corresponding to 5% of the total amount of all monomer components was added into the flask, and the temperature was raised to 70°C while gently blowing nitrogen gas, 30 parts of a 5% aqueous ammonium persulfate solution was added to initiate polymerization. Thereafter, the remainder of the pre-emulsion for dropping was uniformly dropped into the flask over 120 minutes.

After completion of dropping, the contents of the flask were maintained at 70° C. for 60 minutes, followed by 163 parts of deionized water, 80 parts of a 25% aqueous solution of an emulsifier [manufactured by ADEKA Co., Ltd., trade name: Adekari Sorb SR-10], and cyclohexyl. 310 parts of methacrylate, 105 parts of 2-ethylhexyl acrylate, 75 parts of 2-hydroxyethyl methacrylate and 4-(meth)acryloyloxy-1,2,2,6,6-pentamethylpiperidine [manufactured by ADEKA Corporation, trade name: Adekastab LA-82] 10 parts of pre-emulsion for second stage dropping and 30 parts of 5% ammonium persulfate aqueous solution were uniformly dropped into the flask over 120 minutes.

After the dropwise addition was completed, the contents of the flask were maintained at 70° C. for 60 minutes, and the pH was adjusted to 8 by adding 25% aqueous ammonia to complete the polymerization. After cooling the obtained reaction solution to room temperature, an aqueous dispersion was prepared by filtering through a 300-mesh wire mesh. The obtained aqueous dispersion contains a polymer, and the obtained polymer is a resin emulsion, which is a two-layered emulsion particle having an inner layer and an outer layer. The content of non-volatile matter in this aqueous dispersion was 50%, the acid value derived from the carboxyl groups of the polymer was 0 mgKOH/g, and the glass transition of the inner layer resin constituting the resin emulsion particles contained in the emulsion was The temperature was 32°C and the glass transition temperature of the outer layer resin was 32°C. The minimum film-forming temperature was 40° C. and the average particle size was 150 nm.

[Production Examples 2, 3, 6-8, 10-12, 14-18, Comparative Production Examples 1 and 2]
In Production Example 1, polymers were prepared in the same manner as in Production Example 1, except that the monomer components shown in Tables 1 and 2 were used for polymerization. -12, 14-18, and the polymers of Comparative Production Examples 1 and 2 were obtained.

[Production Example 4] Single Emulsion A flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser was charged with 536 parts of deionized water. In a dropping funnel, 326 parts of deionized water, 160 parts of a 25% aqueous solution of an emulsifier [manufactured by ADEKA Co., Ltd., trade name: Adekari Sorb SR-10], 632 parts of cyclohexyl methacrylate, 208 parts of 2-ethylhexyl acrylate, and 2-hydroxyethyl methacrylate. 150 parts of 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine [manufactured by ADEKA Co., Ltd., trade name: ADEKA STAB LA-87] was prepared as a pre-emulsion for the first dropwise addition of 10 parts. 74 parts corresponding to 5% of the total amount of all monomer components were added into the flask, the temperature was raised to 70°C while gently blowing nitrogen gas, and 30 parts of a 5% aqueous ammonium persulfate solution was added to initiate polymerization. Thereafter, the remainder of the pre-emulsion for dropping and 30 parts of a 5% aqueous ammonium persulfate solution were uniformly dropped into the flask over 180 minutes.

After the dropwise addition was completed, the contents of the flask were maintained at 70° C. for 60 minutes, and the pH was adjusted to 8 by adding 25% aqueous ammonia to complete the polymerization. After cooling the obtained reaction solution to room temperature, an emulsion was prepared by filtering through a 300-mesh wire mesh. The content of non-volatile matter in this emulsion was 50%, the acid value derived from the carboxyl groups of the resin emulsion particles was 0 mgKOH/g, and the resin constituting the resin emulsion particles contained in the emulsion had a glass transition temperature of 32. °C. The minimum film-forming temperature was 40° C. and the average particle size was 150 nm.

[Production Examples 5, 9, 13]
In Production Example 4, polymers were prepared in the same manner as in Production Example 4, except that the monomer components shown in Tables 1 and 2 were used for polymerization. Obtained.

The abbreviations in each table mean the following.
IBOA: isobornyl acrylate CHMA: cyclohexyl methacrylate St: styrene MMA: methyl methacrylate 2EHA: 2-ethylhexyl acrylate AA: acrylic acid HEMA: hydroxyethyl methacrylate LA-87: 4-methacryloyloxy-2,2,6,6-tetra Methylpiperidine LA-82: 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine AC-10SL: manufactured by Toagosei Co., Ltd., polyacrylic acid-based dispersant, Mw 3000
DESCOAT N14: Daiichi Kogyo Seiyaku Co., Ltd., dispersing agent (anionic surfactant, polycarboxylic acid ammonium salt (containing a phenyl group as a hydrophobic group and a carboxyl group as a hydrophilic group), Mw: 7000)
BYK-190: manufactured by BYK-Chemie Japan, dispersant (acid value 10 mgKOH/g)
PG: manufactured by ADEKA, propylene glycol CR-95: manufactured by Ishihara Sangyo Co., Ltd., titanium oxide (rutile type)
ST-200: Nippon Shokubai Co., Ltd., (meth)acrylic WAX emulsion KF-6011: Polyether-modified silicone surfactant Aquacer531: BYK Chemie Japan Co., Ltd., oxidized high-density polyethylene WAX emulsion BDG: Nippon Emulsifier Co., Ltd., diethylene glycol Monobutyl ether KF-6011: Shin-Etsu Chemical Co., Ltd., PEG-11 methyl ether dimethicone (polyether-modified silicone surfactant)
PET: manufactured by Futamura Chemical Co., Ltd., trade name: Taiko polyester film FE2001
OPP: manufactured by Futamura Chemical Co., Ltd., trade name: FOR-AQ
Cross-linking agent A: oxazoline group-containing polymer (oxazoline group equivalent: 220 g/mol, weight average molecular weight: 40,000, glass transition temperature: 50°C)
Cross-linking agent B: Polyisocyanate group-containing cross-linking agent (isocyanate group equivalent: 255 g/mol, viscosity: 2,000 mPa s)
Crosslinking agent C: polycarbodiimide resin (carbodiimide group equivalent 430 g/mol, viscosity 100 mPa s)

[White paste A]
411 parts of deionized water, dispersant [manufactured by Toagosei Co., Ltd., Jurimar AC-10SL] 67 parts, 25% aqueous ammonia 25 parts, propylene glycol 60 parts, titanium oxide [manufactured by Ishihara Sangyo Co., Ltd., CR-95] 1000 parts and 200 parts of glass beads (1 mm in diameter) were dispersed with a disper at a rotation speed of 3000 min ⁻¹ for 120 minutes, and then filtered through a 300-mesh wire mesh.
[White paste B, C]
White pastes B and C were prepared in the same manner as white paste A, except that white paste A was adjusted using the components shown in Table 3.

[Example 1]
2.8 parts of ST200 (manufactured by Nippon Shokubai Co., Ltd.) as a WAX emulsion was added to 19.8 parts of the emulsion obtained in Production Example 1, and while stirring with a homodisper at a rotation speed of 1000 min ^-1 , white paste A 30 parts, propylene Glycol 20 parts, diethylene glycol monobutyl ether (BDG, SP value 9.5) 10 parts, surfactant [manufactured by Shin-Etsu Chemical Co., Ltd., KF-6011] 0.4 parts, and ion exchange so that the total is 100 parts After adding water and stirring for 30 minutes, the mixture was filtered through a 3 μm filter [MCP-3-C10S, manufactured by Advantech] to prepare an aqueous ink.

[Examples 2-18, Comparative Examples 1 and 2]
In Example 1, water-based inks were prepared with the compositions shown in Tables 4 and 5, and water-based inks of Examples 2-18 and Comparative Examples 1 and 2 were obtained.
<Production of inkjet printed matter>
Water-based ink is applied to a print evaluation device [manufactured by Genesis Co., Ltd.] equipped with an inkjet print head [manufactured by Kyocera Corporation, product number: KJ4B-YH06WST-STDV] in air at a temperature of 25 ± 1 ° C and a relative humidity of 30 ± 5%. was filled.

Next, in the print evaluation device, the head voltage was set to 26 V, the frequency was set to 4 kHz, the ejected droplet volume was set to 12 pL (picoliters), the head temperature was set to 32° C., the resolution was set to 600 dpi, and the negative pressure was set to −4.0 kPa. set to A corona-treated polyester film [manufactured by Futamura Chemical Co., Ltd., trade name: Taiko polyester film FE2001] was used as a recording medium, and the longitudinal direction of the corona-treated polyester film and the conveying direction were aligned in the same direction and fixed to the conveying table. bottom. A print command is transferred to the print evaluation device, and a solid image is printed on a corona-treated polyester film with an ink-jet recording method at a printing amount of 100% (12 pL, 600 x 600 dpi). A test sheet was obtained by drying the corona-treated polyester film at for 10 seconds.

-Evaluation method-
<Scratch resistance>
The printed image on the test sheet was rubbed with a nylon nonwoven fabric, and the adhesion to the substrate was evaluated based on the following evaluation criteria. Tables 4 and 5 show the evaluation results of each example and comparative example.
〔Evaluation criteria〕
5: Even if the printed image is rubbed, the image is not peeled off at all.
4: The image peels off only slightly when the printed image is rubbed.
3: The image is slightly peeled off when the printed image is rubbed.
2: When the printed image is rubbed, the image is slightly peeled off.
1: When the printed image is rubbed, the image is clearly peeled off.
0: The image is easily peeled off when the printed image is rubbed.

<Adhesion (PET)>
The printed image on the test sheet was rubbed with a fingernail, and the adhesion to the substrate was evaluated based on the following evaluation criteria. Tables 4 and 5 show the evaluation results of each example and comparative example.
〔Evaluation criteria〕
5: Even if the printed image is rubbed with a fingernail, the image is not peeled off at all.
4: When the printed image is rubbed with a fingernail, the image is very slightly peeled off.
3: The image is slightly peeled off when the printed image is rubbed with a fingernail.
2: When the printed image is rubbed with a fingernail, the image is slightly peeled off.
1: When the printed image is rubbed with a fingernail, the image is clearly peeled off.
0: The image is easily peeled off when the printed image is rubbed with a fingernail.

<Adhesion (OPP)>
A corona-treated polyester film [manufactured by Futamura Chemical Co., Ltd., trade name: Taiko polyester film FE2001] as a recording medium was changed to a corona-treated OPP film [manufactured by Futamura Chemical Co., Ltd., trade name: FOR-AQ], and used as a test sheet. Evaluation was performed under the same conditions as ◇adhesion (PET) except that Tables 4 and 5 show the evaluation results of each example and comparative example.
<Blocking resistance>
A polyester film that has not been subjected to corona treatment is superimposed on the printed surface of the test sheet, and a load of 2 N/cm ² is applied to the polyester film in the air at 25 ° C. for 1 hour, and then the polyester film is quickly removed. The film was peeled off, resistance was observed at that time, and blocking resistance was evaluated based on the following evaluation criteria. Tables 4 and 5 show the evaluation results of each example and comparative example.
〔Evaluation criteria〕
5: No resistance is felt when the polyester film is peeled off.
4: Very little resistance is felt when the polyester film is peeled off.
3: Only a little resistance is felt when the polyester film is peeled off.
2: Resistance is clearly felt when the polyester film is peeled off.
1: Strong resistance is felt when the polyester film is peeled off.
0: Very strong resistance is felt when the polyester film is peeled off.

<Scotch tape peel resistance>
A corona-treated polyester film [manufactured by Futamura Chemical Co., Ltd., trade name: Taiko polyester film FE2001] as a recording medium was changed to a corona-treated OPP film [manufactured by Futamura Chemical Co., Ltd., trade name: FOR-AQ], and a test sheet was used. made. An adhesive tape (Cellotape (registered trademark) No. 405, 24 mm width, manufactured by Nichiban Co., Ltd.) was attached to the obtained test sheet under a normal temperature environment, and left to stand for 1 minute. After that, it was peeled off in the direction of 180°, and the cellophane tape peel resistance was evaluated based on the following evaluation criteria. Tables 4 and 5 show the evaluation results of each example and comparative example.
〔Evaluation criteria〕
5: The printed image is not peeled off at all.
4: 1 to 20% of the printed image is peeled off.
3: 21 to 50% of the printed image is peeled off.
2: 51 to 75% of the printed image is peeled off.
1: 76 to 100% of the printed image is peeled off.

［製造例１９－２２、２５、２６］
製造例１において、表８に示す単量体成分を用いて重合させたことを除き、製造例１と同様にして重合体を調製し、製造例１９－２２、２５、２６の重合体を得た。
［製造例２３、２４］
製造例４において、表８に示す単量体成分を用いて重合させたことを除き、製造例４と同様にして重合体を調製し、製造例２３、２４の重合体を得た。

[Production Examples 19-22, 25, 26]
Polymers were prepared in the same manner as in Production Example 1, except that the monomer components shown in Table 8 were polymerized in Production Example 1 to obtain the polymers of Production Examples 19-22, 25, and 26. rice field.
[Production Examples 23 and 24]
In Production Example 4, polymers were prepared in the same manner as in Production Example 4, except that the monomer components shown in Table 8 were used for polymerization, and polymers of Production Examples 23 and 24 were obtained.

［実施例１９－２６］
実施例１において表９に示す組成にて水性インクを調製し、実施例１９－２６の水性インクを得た。上述の評価方法にて評価した結果を表９に記載する。

[Examples 19-26]
In Example 1, water-based inks were prepared according to the compositions shown in Table 9 to obtain water-based inks of Examples 19-26. Table 9 shows the results of evaluation by the evaluation method described above.

Claims (8)

An aqueous dispersion containing a polymer (A) having a structural unit derived from a cycloaliphatic group-containing monomer and a wax component (B). 2. The aqueous dispersion according to claim 1, wherein the polymer (A) contains 30 parts by mass or more and 95 parts by mass or less of the cycloaliphatic group-containing monomer relative to 100 parts by mass of the polymer (A). 3. The aqueous dispersion according to claim 1, wherein the polymer (A) has an acid value of 20 mgKOH/g or less. 4. The aqueous dispersion according to any one of claims 1 to 3, wherein the mass ratio of polymer (A) and wax component (B) is 99/1 to 80/20. An aqueous ink comprising the aqueous dispersion according to any one of claims 1 to 4 and a colorant. A water-based ink according to claim 5, wherein the colorant is a white pigment. A water-based ink according to claim 5, wherein the coloring agent is any one selected from yellow, magenta, cyan, black, red, blue and green. A printed matter comprising a printed layer formed from the water-based ink according to any one of claims 5 to 7.