JP2002235296A - Water-soluble resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-soluble resin composition contained in resin compositions which are used for coating paper and can impart excellent ink receivability and excellent water resistance. SOLUTION: This water-soluble resin composition comprises the following components (I) and (II). (I): A reaction product comprising an aliphatic amine and a glycidyl compound having at least two glycidyl ether groups in the molecule. (II): A reaction product comprising an aliphatic amine and an epihalohydrin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a resin composition for paper coating. More specifically, a reaction product comprising an aliphatic amine and a glycidyl compound, and a water-soluble resin composition containing a reaction product comprising an aliphatic amine and epihalohydrin, and excellent ink receptivity and water resistance to paper The present invention relates to a paper coating resin composition containing the water-soluble resin composition, which can impart properties.

[0002]

2. Description of the Related Art Coated paper obtained by applying a paper coating resin composition containing a pigment, an aqueous binder and a water-soluble resin composition to paper, followed by drying, calendering, etc. is used for magazines, books, etc. Used in printed materials. Various water-soluble resin compositions have been proposed as a water-soluble resin composition contained in a paper coating resin composition that imparts excellent ink receptivity and water resistance, for example, aliphatic amines and The present inventors have already proposed a reaction product comprising a glycidyl compound (JP-A-10-77599).

[0003]

By the way, recently, with the sophistication of quality requirements of coated papers and the speeding up of printing, coated papers having further excellent ink acceptability and water resistance have been demanded. I have. Under such circumstances, an object of the present invention is to provide a water-soluble resin composition contained in a paper coating resin composition that imparts even better ink acceptability and water resistance.

[0004]

Means for Solving the Problems In order to solve the above problems, as a result of intensive studies on a reaction product comprising an aliphatic amine and a glycidyl compound,
The present inventors have found that a water-soluble resin composition containing a reaction product consisting of an aliphatic amine and epihalohydrin can be contained in a resin composition for paper coating that imparts excellent ink receptivity and water resistance. Completed the invention.

That is, the present invention is a water-soluble resin composition containing the following components (I) and (II). (I): a reaction product comprising an aliphatic amine and a glycidyl compound having at least two glycidyl ether groups in the molecule. (II): a reaction product comprising an aliphatic amine and epihalohydrin.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. Examples of the aliphatic amine used in the components (I) and (II) of the present invention include an aliphatic hydrocarbon containing at least one primary and / or secondary amino group in the molecule. Can be Specifically, monoalkylamines comprising an alkyl group having about 1 to 10 carbon atoms such as methylamine, ethylamine and propylamine and a primary amino group; dimethylamine, diethylamine, dipropylamine, dibutylamine, methylethylamine, etc. Dialkylamines obtained by bonding an alkyl group having about 1 to 10 carbon atoms with a secondary amino group; (poly) alkylenepolyamines such as ethylenediamine, diethylenetriamine and triethylenetetramine; and fats such as isophoronediamine and bis (aminomethyl) cyclohexane. Aliphatic amines containing a cyclic hydrocarbon group; aliphatic amines containing an alkylene group such as xylylenediamine; and heterocyclic amines.

Here, the heterocyclic amine is usually an amine containing a heterocyclic ring which is an alicyclic hydrocarbon group containing at least one hetero atom such as a nitrogen atom, an oxygen atom and a sulfur atom. Specifically, pyrrolidine, piperidine, 2-
Pipecoline, 3-Pipecoline, 4-Pipecoline, 2,4
-Pipecoline, 2,6-pipecholine, 3,5-lupetidine, piperazine, homopiperazine, N-methylpiperazine, N-ethylpiperazine, N-propylpiperazine,
N-methylhomopiperazine, N-acetylpiperazine,
N-acetylhomopiperazine, 1- (chlorophenyl)
A heterocyclic amine containing at least one nitrogen atom in a heterocyclic ring such as piperazine; N-aminoethylpiperidine;
N-aminopropylpiperidine, N-aminoethylpiperazine, N-aminopropylpiperazine, N-aminoethylmorpholine, N-aminopropylmorpholine, N-
Heterocyclic amines containing an aminoalkyl group such as aminopropyl-2-pipecholine, N-aminopropyl-4-pipecholine, 1,4-bis (aminopropyl) piperazine and a heterocycle containing at least one nitrogen atom, and the like Is mentioned.

As the aliphatic amine, two or more kinds of aliphatic amines may be mixed and used. As an aliphatic amine,
Among them, monoalkylamine, dialkylamine, (poly) alkylenepolyamine, and heterocyclic amine are preferable,
Particularly, a heterocyclic amine containing at least one nitrogen atom in the heterocyclic ring is preferable, and more preferably pyrrolidine, piperidine, piperazine, N-aminoethylpiperazine, N-aminopropylpiperazine, 1,4-bis (aminoethyl ) Piperazine, 1,4-bis (aminopropyl) piperazine.

The glycidyl compound having at least two glycidyl ether groups in the molecule (hereinafter referred to as glycidyl compound) used in the component (I) of the present invention includes:
For example, epoxidized allyl groups of allyl ethers of polyhydric alcohols and / or polyhydric phenols, condensation products of polyhydric alcohols and / or polyhydric phenols with epihalohydrins such as epichlorohydrin Specific examples of the condensation product of bisphenol A, which is a polyhydric phenol, with epihalohydrin are described in detail by the following formula (1). (Wherein, n represents an integer of about 0 to 20), such as diglycidyl ethers and oligomers thereof. The glycidyl compound of the present invention is usually a glycidyl ether compound having a minimum repeating unit represented by 0 (for example, n = 0 in the general formula (1));
Alternatively, an oligomer containing a minimum unit of a glycidyl ether compound as a main component (for example, n = 0 to 0 in the general formula (1))
A mixture of glycidyl ether compounds represented by about 20).

As the glycidyl compound, a glycidyl ether compound having a minimum unit is exemplified as a representative name. Examples thereof include alkylene glycol diglycidyl ethers such as ethylene glycol diglycidyl ether and propylene glycol diglycidyl ether; polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl. Polyoxyalkylene glycol diglycidyl ethers such as ethers; aromatic polyvalent glycidyl ethers such as resorcin diglycidyl ether and bisphenol A diglycidyl ether; trimethylolpropane such as trimethylolpropane diglycidyl ether and trimethylolpropane triglycidyl ether Polyvalent glycidyl ethers; sorbitol diglycidyl ether, sorbitol Glycidyl ether, sorbitol tetraglycidyl ether, sorbitol penta glycidyl ether, sorbitol hexaglycidyl ether, pentaerythritol diglycidyl ether, pentaerythritol triglycidyl ether, fatty polyglycidyl ethers such as pentaerythritol tetraglycidyl ether, and the like. As the glycidyl compound, an oligomer of the glycidyl ether compound exemplified above may be used, or two or more glycidyl compounds may be used as a mixture. Among the glycidyl compounds, aromatic polyvalent glycidyl ethers and oligomers thereof are preferred.

The component (I) of the present invention is a reaction product comprising an aliphatic amine and a glycidyl compound. The amount of the glycidyl compound used in the component (I) is usually about 0.1 to 1.5 mol, preferably 0.3 to 1.2 mol of the glycidyl ether group of the glycidyl compound per 1 mol of the aliphatic amine. About molar, more preferably 0.5
It is preferable to use about 1 mol. When the glycidyl ether group is 1.5 mol or more with respect to the aliphatic amine, the component (I) tends to gel, which is not preferable.

As a raw material of the component (I), in addition to an aliphatic amine and a glycidyl compound, at least one kind selected from α, β-unsaturated carbonyl compounds, α, β-unsaturated nitrile compounds, α-halocarboxylic acids and the like is used. (Hereinafter, referred to as component (a)) may be used. Here, examples of the α, β-unsaturated carbonyl compound include α, β-unsaturated carboxylic acids such as acrylic acid, crotonic acid, isocrotonic acid, methacrylic acid, sorbic acid, and cinnamic acid; methyl group, ethyl group, Α, β with butyl group etc.
Esters with unsaturated carboxylic acids; α, β-unsaturated aldehydes such as acrolein kilotonaldehyde and cinnamaldehyde; α such as methyl vinyl ketone, mesityl oxide, benzalacetone, dibenzalacetone, benzalacetophenone, and dipnone. , Β-unsaturated ketones;
Α, β-unsaturated dicarboxylic acids such as fumaric acid and maleic acid and esters thereof; α, β-unsaturated dicarboxylic acids such as maleic anhydride
And unsaturated carboxylic anhydrides.

As the α, β-unsaturated nitrile compound,
For example, acrylonitrile, methacrylonitrile and the like can be mentioned. As the α-halocarboxylic acids, for example,
Α-halocarboxylic acids such as chloroacetic acid, bromoacetic acid, dichloroacetic acid, dibromoacetic acid, trichloroacetic acid, α-chloropropionic acid, α-chlorobutyric acid, α-bromoisovaleric acid; methyl group, ethyl group, butyl group, etc. and α- Esters with halocarboxylic acids; α-halocarboxylates of alkali (earth) metals such as potassium, sodium and calcium.

Component (a) includes, among others, α, β-unsaturated carboxylic acid, α, β-unsaturated carboxylic acid ester,
And α-chlorocarboxylic acids are preferred, and acrylic acid and chloroacetic acid are particularly preferred.

The number of moles of the component (a) is usually calculated by subtracting the number of moles of glycidyl ether groups of the glycidyl compound from the total number of moles of primary and / or secondary amino groups contained in the aliphatic amine. Is also a small number of moles. Specifically, the number of moles of the component (a) is about 0.02 to 1.5 moles relative to 1 mole of the primary and / or secondary amino groups contained in the aliphatic amine, and preferably,
0.05 to 1 mol, particularly preferably 0.1 to 0.5
Is a mole.

As a reaction method for obtaining the component (I), for example, a reaction temperature of about 30 to 100 ° C. in a solvent, preferably 40 ° C. when the solvent is a mixture of water and an organic solvent.
A method of reacting an aliphatic amine with a glycidyl compound for about 1 to 20 hours at about 40 to 70 ° C. when the solvent is an organic solvent containing no water, and then diluting with water. Is mentioned. At that time, if an organic solvent is contained, the solvent may be distilled off under reduced pressure before dilution with water or after dilution with water when the solvent has a boiling point lower than that of water. The reaction between the aliphatic amine and the glycidyl compound is usually carried out without a catalyst, but a basic catalyst such as ammonia or caustic soda, or a Lewis acid catalyst such as aluminum chloride may be used.

The solvent used for the reaction for obtaining the component (I) is, for example, water; methanol, ethanol, 1- or 2-propanol, 1- or 2-butanol, 1-pentanol, 3- Methyl-1-butanol,
1-hexanol, 4-methyl-2-pentanol,
2,4-dimethyl-3-pentanol, 2,6-dimethyl-4-heptanol, 2-ethyl-1-hexanol, 1- or 2-octanol, lauryl alcohol,
Alcohols such as cyclohexanol and benzyl alcohol; furfuryl alcohol, tetrahydrofurfuryl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether;
Ethers such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, β, β'-dichlorodiethyl ether, 1,4-dioxane, diethylcellosolve, dibutyl carbitol; aldehydes such as butyraldehyde; cyclohexane, hexane , Heptane, toluene, o-, m- or p-xylene and other hydrocarbons; 1,1,1-trichloroethane,
Trichloroethylene, 1- or 2-bromopropane, 1
Organic halogen compounds such as -bromobutane, lauryl bromide, 1-bromo-3-chloropropane, 1,3-dibromopropane, 1,4-dibromobutane, 1,5-dibromopentane, and 2,3-dibromo-1-propanol Acetone, 2,4-pentanedione, methyl ethyl ketone, 2- or 3-pentanone, 3-methyl-2-butanone, methyl isobutyl ketone, 2-heptanone, 2,6
-Dimethyl-4-heptanone, 2,4-dimethyl-3-
Ketones such as pentanone, cyclohexanone, mesityl oxide, isophorone, 4-hydroxy-4-methyl-2-pentanone; methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, sec-butyl acetate, isobutyl acetate, acetic acid Esters such as amyl, benzyl acetate, ethyl propionate, butyl propionate, amyl propionate, methyl benzoate, ethyl benzoate, diethyl malonate, diethyl oxalate, butyl phosphate, and ethyl acetoacetate.

As a solvent for the reaction for obtaining the component (I), a mixture of two or more solvents may be used. When a mixture of water and an organic solvent is used as a solvent in the reaction solution for obtaining the component (I), the content of water is usually about 20% by weight or less based on the solution. Especially, 10% by weight or less is preferable. Among the reaction methods for obtaining the component (I), a method in which a solution in which a glycidyl compound is dissolved or dispersed in a ketone is added to a solution in which an aliphatic amine is dissolved in an alcohol.

As a reaction method for obtaining the component (I) composed of the aliphatic amine, the glycidyl compound and the component (a), for example, the aliphatic amine is reacted with the glycidyl compound, and then the component (a) is reacted. Method, reaction of component (a) with aliphatic amine, reaction of glycidyl compound, reaction of component (a) with aliphatic amine, reaction of glycidyl compound, and further component (a)
And a method of reacting an aliphatic amine with a glycidyl compound, then reacting the component (a), and further reacting the glycidyl compound.

The component (II) in the present invention is a reaction product comprising an aliphatic amine and epihalohydrin. Here, the epihalohydrin includes, for example, epichlorohydrin and epibromohydrin, among which epichlorohydrin is preferable. Ingredient (I
The amount of the epihalohydrin used in I) is usually in the range of 1 mole of the aliphatic amine used in the component (II).
The amount is about 0.05 to 2 mol, preferably 0.05 to 1.5 mol, particularly preferably 0.1 to 1 mol.

As described above, the aliphatic amine used in the component (II) may be the same as or different from that of the component (I). Two or more aliphatic amines may be used as the amine.

As a raw material for the component (II), an alkylating agent can be used in addition to the aliphatic amine and epihalohydrin. Here, as the alkylating agent, for example,
Methyl chloride, methyl bromide, methyl iodide, ethyl chloride,
Halogenated hydrocarbons such as ethyl bromide, propyl iodide, isopropyl iodide, butyl bromide, benzyl chloride and benzyl bromide; halogenated acetates such as methyl chloroacetate, ethyl chloroacetate, methyl bromoacetate and ethyl bromoacetate And halogen-free epoxy compounds such as ethylene oxide and propylene oxide; and alkyl sulfates such as dimethyl sulfate and diethyl sulfate.

As the alkylating agent, two or more alkylating agents may be used. Among the alkylating agents, halogenated hydrocarbons and alkyl sulfates are preferable, and alkyl sulfates are particularly preferable.
The amount of the alkylating agent to be used is generally about 0 to 1 mol, per 1 mol of the amino group contained in the component (II),
It is preferably from 0.03 to 0.9 mol, particularly preferably from 0.1 to 0.7 mol. The alkylating agent reacts with the amino group to alkylate the active hydrogen of the amino group, or alkylates the tertiary amino group to form a quaternary ammonium salt.

The method for producing the component (II) includes, for example,
The aliphatic amine is dissolved in the solvent exemplified above as the solvent used in the component (I), preferably water, and 30 to 1
A method in which epihalohydrin is added at a temperature of about 00 ° C., preferably about 40 to 90 ° C. and reacted for about 1 to 20 hours, and if necessary, an alkylating agent is added and reacted. The reaction between the aliphatic amine and epihalohydrin may be carried out without a catalyst, or a basic catalyst such as ammonia or caustic soda, or a Lewis acid catalyst such as aluminum chloride may be used.

The water-soluble resin composition of the present invention contains the component (I) and the component (II) thus obtained,
Component (I) and component (II) may be reacted or mixed. Component (I) and component (I) in the water-soluble resin composition
As the weight ratio (solid content) to (I), the component (I) is usually used.
/ Component (II) = about 1/99 to 99/1, preferably 5
/ 95 to 95/5.

The water-soluble resin composition comprises component (I) and component (I)
In the case of the reaction product of I), the water-soluble resin composition of the present invention may be produced, for example, by the following method for producing component (II) in the presence of (A): component (I). Method (A): The above-mentioned component (I) in the presence of component (II)
(C): Component (I)
And producing the component (II) and then using them without a solvent or in a solvent exemplified above as the solvent used in the component (I), preferably in water, at a temperature of about 40 to 100 ° C., without using a catalyst. Or, in the presence of a catalyst, usually 1-2
For example, a method of stirring for about 0 hours is exemplified. Among them, the method (c) is preferred. Here, examples of the catalyst include a basic catalyst such as ammonia and sodium hydroxide, and a Lewis catalyst such as aluminum chloride.

The water-soluble resin composition comprises the component (I) and the component (I
In the case of the mixture of I), examples of the method for producing the water-soluble resin composition of the present invention include a method of mixing the component (II) with the component (I) and a method of mixing the component (I) with the component (II). A method, a method of collectively mixing the component (I) and the component (II), and any one of the component (I) and the component (II) in a pigment, an aqueous binder, and the like used in a resin composition for paper coating described below. A method of mixing one in advance and then mixing the other is exemplified.

For an aqueous solution prepared by adjusting the reaction product or mixture of the component (I) and the component (II) to have a solid content of 30%, the viscosity of the aqueous solution is usually from 1 to 2000 mPa · s.
And preferably about 2 to 1000 mPa · s.

A nonvolatile substance may be mixed with the water-soluble resin composition of the present invention. As the non-volatile substance, for example, inorganic salts such as ammonium chloride, sodium chloride, calcium chloride, magnesium chloride, aluminum chloride, ammonium sulfate, sodium sulfate, and ammonium phosphate; urea, methyl urea, dimethyl urea, thiourea,
4,5-dihydroxy-2-imidazolidinone, 1-
(2-aminoethyl) -2-imidazolidinone, the following general formula (1) such as a mixture containing 1- (2-aminoethyl) -2-imidazolidinone as a main component obtained by a deammonification reaction between diethylenetriamine and urea: 2) (In the formula, Q represents, for example, an oxygen atom or a sulfur atom, and X ¹ , X ² , X ³ and X ⁴ are each independently a hydrogen atom,
A linear alkyl group, a branched alkyl group, an alkylene group in which X ¹ or X ² is bonded to X ³ or X ⁴ or the like. However, the alkyl group and the alkylene group may be substituted with a hydroxyl group. ), And ureas; saccharides such as glucose and fructose.
Among these non-volatile substances, ureas and saccharides are preferable, and urea and imidazolidinones are particularly preferable.

When mixing the non-volatile substance, the component (I)
The mixing ratio of the solid content weight of the component (II) and the non-volatile substance (solid content weight) is [Component (I) + Component (II)]
/ [Non-volatile substance] = 1/99 to 90/10,
Preferably, it is about 5/95 to 70/30.

With respect to the aqueous solution obtained by adjusting the solid content of the water-soluble resin composition thus obtained to 50%, the viscosity of the aqueous solution is usually about 1 to 5000 mPa · s, preferably 5 to 1000 mPa · s. It is about mPa · s.

The composition comprising the water-soluble resin composition, the pigment and the aqueous binder of the present invention is the resin composition for paper coating of the present invention. The viscosity of the resin composition for paper coating is usually from 1 to
It has a viscosity of about 10,000 mPa · s, that is, a level that can be easily applied to paper. Examples of the pigment include white inorganic pigments such as kaolin, talc, calcium carbonate (heavy or light), aluminum hydroxide, satin white, and titanium oxide; white pigments such as polystyrene, melamine-formaldehyde resin, and urea-formaldehyde resin. And organic pigments. Two or more pigments may be used as the pigment. As the pigment, kaolin, calcium carbonate, and satin white are particularly preferable.

Examples of the aqueous binder include unmodified or modified starches such as oxidized starch and phosphorylated ester; partially or completely saponified polyvinyl alcohol; water-soluble proteins such as casein and gelatin;
Modified celluloses such as carboxymethyl cellulose;
Styrene-butadiene-based resin (SBR latex) which may have a carboxyl group or a nitrile group; acrylonitrile-butadiene-based resin (NBR latex); chloroprene-based resin (CR latex); methyl methacrylate-butadiene-based resin (MBR latex); Copolymer resin of two or more acrylic monomers selected from acid, methacrylic acid and their esters such as methyl, ethyl and butyl, copolymer resin of acrylic monomer and vinyl acetate, copolymer of acrylic monomer and styrene Resin; vinyl acetate resin; styrene-vinyl acetate resin;
Ethylene-vinyl acetate resin and the like can be mentioned. As the aqueous binder, two or more types of aqueous binders may be used.

The weight ratio (solid content) of the pigment, the aqueous binder and the water-soluble resin composition in the paper coating resin composition of the present invention is usually 1 to 200 parts of the aqueous binder with respect to 100 parts of the pigment. Degree, preferably 5-50
Parts, and the water-soluble resin composition is about 0.05 to 5 parts, preferably about 0.1 to 2 parts. As a method of mixing the pigment, the aqueous binder and the water-soluble resin composition,
For example, a method in which a water-soluble resin composition dissolved or dispersed in a liquid medium is mixed with a mixture of a pigment and an aqueous binder, and a water-soluble resin composition dissolved or dispersed in a solvent is previously mixed with an aqueous binder or a pigment such as SBR latex. For example, there is a method in which the components are mixed and then mixed with the remaining components.

The resin composition for paper coating includes, for example, a water-proofing agent, a printability improving agent, a dispersant, a viscosity / fluidity adjusting agent, an antifoaming agent, a preservative, a lubricant, a water-retaining agent, a dye and a coloring agent. A compounding agent such as a coloring agent such as a pigment may be included.

The thus obtained paper coating resin composition is
For example, it is applied to paper by a method such as a blade coater, an air knife coater, a bar coater, a size press coater, a gate roll coater, a cast coater, and then dried as necessary, and further subjected to a smoothing process using a super calender if necessary. By applying, the coated paper of the present invention can be manufactured. Here, as the paper used in the present invention, for example, paper made of plant fibers such as paper, Japanese paper, paperboard, synthetic fiber paper, inorganic fiber paper,
Examples include plastic paper made of synthetic resin film, synthetic fiber made of synthetic pulp made of synthetic resin, and synthetic paper such as non-woven sheet.

[0037]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. In Examples,% and parts are by weight unless otherwise specified. The viscosity and pH are values measured at 25 ° C., and the nonvolatile content is a value measured according to JIS K00674.1. The solid content indicates the weight of each component excluding a solvent such as water in each component, and the concentration indicates the weight ratio (%) of the solid content in the solution.

<Production Example of Component (I)> N- (2-aminoethyl) piperazine (594.3 parts, 4.6 mol ratio) was contained in a container equipped with a thermometer, a reflux condenser, and a stirring rod. To 865.1 parts of a methanol solution, an epoxy equivalent of 18 was added.
940.2 parts of an acetone solution containing 669.4 parts of 1.9 g / eq of bisphenol A diglycidyl ether (3.7 mol ratio as glycidyl group) was heated at an internal temperature of 45 to 55 ° C.
The mixture was added dropwise over 5 hours while stirring at, followed by stirring for 4 hours. Next, after replacing the reflux condenser with a Liebig condenser, the internal temperature was raised to 80 ° C. while distilling off acetone and methanol, and then the pressure in the reaction system was maintained while maintaining the internal temperature at 75 to 85 ° C. After reducing the pressure to 35 kPa, the mixture was kept warm and stirred for 30 minutes. Then, 935.3 g of water
Was added, the non-volatile content was 49.3%, the viscosity was 4050 mPa · s, p
2291.7 parts (component (I)) of an aqueous solution of H12.1 were obtained.

<Production Example 1 of Component (II)> An aqueous solution containing 33.6 parts (0.23 mol ratio) of triethylenetetramine was placed in the same reactor as used in the production example of Component (I).
To 68 parts, 128 parts (1.38 molar ratio) of epichlorohydrin was added dropwise at an internal temperature of 25 to 50 ° C over 5 hours. 295 parts of an aqueous solution having a concentration of 54.5% (aqueous solution of component (II) -1) were obtained.

<Production Example 2 of Component (II)> An aqueous solution containing 77.0 parts (0.75 mol ratio) of diethylenetriamine was placed in the same reactor as used in the production example of Component (I).
To 00 parts, 55.2 parts (0.60 mole ratio) of epichlorohydrin was added dropwise at an internal temperature of 45 to 55 ° C over 6 hours.
Next, keep the temperature for 1 hour while keeping the internal temperature at 45 to 55 ° C,
28% NaOH aqueous solution 4 while cooling to 40-45 ° C
8.0 parts were charged. Thereafter, 138.0 parts of diethyl sulfate (0.89 mole ratio) while maintaining the internal temperature at 40 to 45 ° C.
Is dropped over 5 hours, and after completion of the dropping, the internal temperature is reduced to 40 to 45.
After keeping the temperature for 1 hour while keeping the temperature at 35 ° C, 5.0 parts of a 28% NaOH aqueous solution was added while cooling the internal temperature to about 35 ° C. Further, the mixture was diluted by adding water to a concentration of 51.5.
%, Aqueous solution of pH 8.8 (component (II) -2 aqueous solution) was obtained.

<Example 1: Production example of water-soluble resin composition>
Aqueous solution 1 of component (I) obtained in <Production example of component (I)>
66.4 parts, 16.8 parts of the aqueous solution of component (II) -1 obtained in <Production Example 1 of component (II)> and 28.9 parts of water were mixed, and the mixture was heated at an internal temperature of 65 to 75 ° C. By stirring for hours, a concentration of 46.5%, a pH of 10.3, and a viscosity of 3450 mPa
211.5 parts of an aqueous solution of s were obtained. 82.8 parts of the aqueous solution,
After mixing 89.8 parts of urea and 106.3 parts of water, the mixture is sufficiently stirred to obtain an aqueous solution having a concentration of 46.0%, a pH of 11.8 and a viscosity of 6.4 mPa · s, ie, a water-soluble resin composition. (A) 279 parts were obtained.

<Example 2: Production example of water-soluble resin composition>
201.0 parts of the aqueous solution of the component (I), 32.1 parts of the aqueous solution of the component (II) -1 and 38.0 parts of water were mixed, and the internal temperature was adjusted to 65%.
Stir at ~ 75 ° C for 4 hours, concentration 47.5%, pH1
0.00.3 and 270.3 parts of an aqueous solution having a viscosity of 4790 mPa · s were obtained. 82.2 parts of the aqueous solution, 91.1 parts of urea and 10 parts of water
After mixing 9.6 parts, the mixture was thoroughly stirred to obtain a concentration of 46.0.
%, PH 10.0, and a viscosity of 6.2 mPa · s, that is, 283 parts of a water-soluble resin composition (B) was obtained.

<Example 3: Production example of water-soluble resin composition>
203.5 parts of the aqueous solution of the component (I), 10.0 parts of the aqueous solution of the component (II) -1 and 32.5 parts of water were mixed, and the internal temperature was 65 to 65 parts.
The mixture was stirred at 75 ° C for 4 hours, and had a concentration of 45.4% and a pH of 10.
7. 245 parts of an aqueous solution having a viscosity of 2575 mPa · s were obtained.
79.6 parts of the aqueous solution, 84.3 parts of urea, and 97.9 parts of water
After mixing, the mixture was thoroughly stirred to obtain a concentration of 46.0%, p
An aqueous solution having an H of 9.4 and a viscosity of 6.2 mPa · s, that is, 262 parts of a water-soluble resin composition (C) was obtained.

<Example 4: Production example of water-soluble resin composition>
20.0 parts of the aqueous solution of the component (I), 95.7 parts of the aqueous solution of the component (II) -2, and 32.2 parts of water are sufficiently stirred and mixed to give a water-soluble resin composition (D) 148 having a concentration of 40.0%. Got a part.

Comparative Example 1 Aqueous solution of component (I) 20.0
Parts, 39.4 parts of urea and 74.0 parts of water,
The mixture was sufficiently stirred to obtain 133 parts of a water-soluble resin composition (E) having a concentration of 40.0%.

<Comparative Example 2> An aqueous solution of the component (I) was used as it was as the water-soluble resin composition (F).

<Production Example of Resin Composition for Paper Coating><Examples 1 to 4, Comparative Examples 1 and 2> A pigment, an aqueous binder, a dispersant, and a water retention agent were mixed with a solid content (water) as shown in Table 1. And the pH is about 9.
The mixture was adjusted with caustic soda to 5 and with water so as to have a concentration of 64% to obtain a color 1. Similarly, pH
Was adjusted to approximately 11.5 with aqueous ammonia, and adjusted to a concentration of 55% with water to obtain color 2.
The solids of the water-soluble resin compositions (A) to (F) were mixed at a weight ratio shown in Table 2 with respect to 100 parts (solids) of the pigments contained in the colors 1 and 2, and paper coating was performed. A resin composition for use was obtained. The respective pH and viscosity were measured as follows, and the results are shown in Table 2.

<PH>: The pH of the resin composition for paper coating immediately after preparation was measured at 25 ° C. using a glass electrode type hydrogen ion concentration meter (manufactured by Toa Denpa Kogyo KK).

<Viscosity> The viscosity of the paper coating resin composition immediately after preparation was measured at 60 rpm and 25 ° C. using a B-type viscometer (BL type, manufactured by Tokyo Keiki Co., Ltd.).

[0050]

[Table 1]

[0051] Ultra White 90 ^{* 1} : First-class clay manufactured by Engelhard Minerals. Class 2 kaolin ^{* 2} : Class 2 clay made by Drive Rank Kaolin. Sachin White BL ^{* 3} : Sachin manufactured by Shiraishi Industry Co., Ltd. Heavy calcium carbonate ^{* 4} : Heavy calcium carbonate manufactured by Fimatec. Light calcium carbonate ^{* 5} : Light calcium carbonate manufactured by Okutama Industry Co., Ltd. Alon T-40 ^{* 6} : Polyacrylic acid pigment dispersant manufactured by Toagosei Co., Ltd. MS-4600 ^{* 7} : Urea phosphate esterified resin manufactured by Nippon Shokuhin Kako Co., Ltd. Latex for SO ^{* 8} : Latex binder for sheet-fed offset printing paper manufactured by A & L Japan. WO latex ^{* 9:} Nippon A & L Inc. of web offset printing paper for latex binder. Synthetic water retention agent ^{* 10} : A synthetic water retention agent manufactured by San Nopco. SH-3 ^{* 11} : Water retention agent manufactured by Sumitomo Chemical Co., Ltd.

<Production Example of Coated Paper><Examples 1 to 4, Comparative Examples 1 and 2> A resin composition for paper coating was prepared by using a rice basis weight of 80 g /
on one surface of woodfree paper having m ^2, the coated amount was coated to a 15 g / m ² using a wire rod. Immediately after application, 1
Dry with hot air at 20 ° C for 30 seconds, and then humidify at a temperature of 20 ° C and a relative humidity of 65% for 16 hours.
Supercalendering was performed twice under the conditions of a linear pressure of 60 kN / cm (60 kg / cm) to obtain a coated paper. The coated paper thus obtained was subjected to tests for water resistance and ink acceptability, and the test results are shown in Table 2. The test method is as follows.

<Water resistance: wet pick method (WP method)>
Using a RI tester (manufactured by Akira Seisakusho), printing was performed after the coated surface was wetted with a water supply roll, and the paper peeling state was visually observed and judged. The judgment criteria were as follows. Water resistance (poor) 1-5 (excellent)

<Ink Acceptability> (1) Method A Using a RI tester, the coated surface was wetted with a water supply roll and then printed, and the ink acceptability was visually observed and judged. The judgment criteria were as follows. Ink acceptability (poor) 1-5 (excellent)

(2) Method B Using a RI tester, make a slight gap between the metal roll and the rubber roll, pour water into the gap, print immediately, and visually observe the ink acceptability with the naked eye. Was determined. The judgment criteria were as follows. Ink acceptability (poor) 1-5 (excellent)

[0056]

[Table 2] Addition amount ^{* 1} : Solid content of water-soluble resin composition to be added to 100 parts of pigment

[0057]

As is apparent from Table 2, the resin composition for paper coating containing the water-soluble resin composition of the present invention has been conventionally known to impart excellent ink receptivity and water resistance. More excellent ink receptivity and water resistance can be imparted to paper than a paper coating resin composition containing a water-soluble resin composed of an aliphatic amine and a glycidyl compound (Comparative Examples 1 and 2). . Coated paper using the resin composition for paper coating of the present invention is excellent in ink receptivity, water resistance, high-speed printing, and suitable for very clean and clear printed matter, for example, It can be used for product catalogs, calendars, brochures, advertisements, posters, photo magazines, pictorial books, packages, etc.

────────────────────────────────────────────────── ─── front page continued (51) Int.Cl. ⁷ identifications FI theme coat Bu (reference) C08L 63/00 C08L 63/00 C C09D 5/00 C09D 5/00 Z 163/00 163/00 (72) Inventor Akira Tanigawa 3-1-198 Kasuganaka, Konohana-ku, Osaka F-term (reference) in Sumitomo Chemical Co., Ltd. EL147 EN016 EN026 EN036 ES007 ET018 EU118 EV128 FD090 FD146 FD147 FD202 FD208 GH00 4J036 AD01 AD08 AJ01 AJ05 DB14 DB17 DB28 DC01 DC02 DC03 DC04 DC06 DC09 DC22 DC30 DC38 FA01 FA02 FA03 FA04 FA08 FA09 FA10 FB01 BA1 FB01 BA1 FB03 BA01 FB01 BA1 CE021 CF021 CG141 DB032 DB052 DB062 DB392 EA011 HA116 HA126 HA306 HA376 HA416 JB08 JB24 JB26 JB31 JB32 JC05 JC43 KA0 8 MA09 NA04 PC10 4L055 AG11 AG12 AG27 AG39 AG80 AG87 AG93 AH02 AH37 AJ04 BE02 BE08 FA15 FA19 GA19

Claims (12)

[Claims] 1. A water-soluble resin composition containing the following components (I) and (II). (I): a reaction product comprising an aliphatic amine and a glycidyl compound having at least two glycidyl ether groups in the molecule. (II): a reaction product comprising an aliphatic amine and epihalohydrin. 2. The method according to claim 1, wherein the water-soluble resin composition comprises the components (I) and (I).
The resin composition according to claim 1, which is a reaction product of I). (3) The water-soluble resin composition comprises the components (I) and (I)
The resin composition according to claim 1, which is a mixture of I). 4. The resin composition according to claim 1, wherein the aliphatic amine is a heterocyclic amine. 5. The resin composition according to claim 1, wherein the glycidyl compound is an aromatic polyvalent glycidyl ether or an oligomer thereof. 6. The resin composition according to claim 1, wherein the component (I) is obtained by reacting an aliphatic amine, a glycidyl compound and the following component (a). (A): at least one compound selected from α, β-unsaturated carbonyl compounds, α, β-unsaturated nitrile compounds, and α-halocarboxylic acids. 7. The resin composition according to claim 1, wherein the component (II) is obtained by reacting an aliphatic amine, epihalohydrin, and an alkylating agent. 8. The resin composition according to claim 1, wherein the resin composition contains a non-volatile substance. 9. The resin composition according to claim 8, wherein the non-volatile substance is at least one non-volatile substance selected from inorganic salts, ureas, and saccharides. 10. A pigment, an aqueous binder and a composition according to claim 1.
A resin composition for paper coating, comprising the resin composition according to any one of claims 9 to 10. 11. Coated paper obtained by applying the paper coating resin composition according to claim 10 to paper. 12. A method for improving the ink receptivity and water resistance of a coated paper, comprising using the resin composition for paper coating according to claim 10.