JP2009024280A - Resin composition for paper coating - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for paper coating, which does not emit formaldehyde, has excellent storage stability at a low temperature and imparts high water resistance. <P>SOLUTION: The resin composition for paper coating is obtained by reacting four or five components of polyamines, alicyclic dibasic carboxylic acids and/or a reaction product obtained by reacting glycols of 1 mol with the alicyclic dibasic carboxylic acids of >1 mol, ureas and a crosslinkable compound, and contains <1.5 wt.% of the total of compounds (I) and (II). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to a paper coating resin composition useful for coating paper, in particular, a paper and a pigment and an aqueous binder, and its application to paper coating. More specifically, an object of the present invention is to provide a paper coating composition that does not generate formaldehyde and can impart excellent water resistance to paper, and a paper coating resin composition useful for it. . The term “paper” used in the present specification has a broad meaning, and includes paper and paperboard in a narrow sense.

A coated paper obtained by applying a coating composition mainly composed of a pigment and a water-based binder to paper and performing necessary treatments such as drying and calendering is used for commercial printed matter and Although it is widely used in magazines and books, efforts to improve the quality of coated paper are still ongoing as quality requirements become higher and printing speeds increase. Especially in offset printing, which accounts for a large part of printing, improvement of and improvement in ink acceptability under the influence of dampening water, water resistance such as wet topics, and blister resistance in rotary printing are important issues in the industry. It has become.

Conventionally, in response to such problems, melamine-formaldehyde resin, urea-formaldehyde resin, polyamide polyurea-formaldehyde resin (Patent Document 1), block glyoxal resin (Patent Document 2), amine-epihalohydrin resin (Patent Document 3), polyamide A technique of adding as a water resistance agent or an additive for a binder such as polyurea-epihalohydrin-formaldehyde resin (Patent Document 4) is disclosed. However, these conventional water-proofing agents and additives for binders currently have serious defects or insufficient effects in some properties due to recent sophistication of quality requirements and accompanying changes in formulation composition. Therefore, it is not always satisfactory in practical use.

For example, so-called aminoplast resins such as melamine-formaldehyde resin and urea-formaldehyde resin not only generate a lot of formaldehyde during work or from coated paper, but also have an effect of improving ink acceptability and blister resistance. There are problems that it cannot be obtained, and that when the pH of the coating composition is increased, the water resistance effect is hardly exhibited. Polyamide polyurea-formaldehyde resins, like aminoplast resins, have the problem of formaldehyde generation during work or from coated paper. On the other hand, block glyoxal resin, which is known as an additive for formaldehyde-free binder, can give water resistance to fountain solution to some extent, but it is almost impossible to improve coated paper quality such as ink acceptability and blister resistance. has no effect. In addition, amine-epihalohydrin resins are not very effective in improving the quality of coated paper such as water resistance and ink acceptability, and use of epihalohydrin-derived adsorptive organic halogen compounds tends to be withheld.

In recent years, quality requirements have become more sophisticated and printing speed has been increased, and efforts to improve the quality of coated paper are still ongoing. Especially in offset printing, which accounts for a large part of printing, improvement and improvement of water resistance such as wet topic under the influence of dampening water is an important issue in the industry.

  In response to these problems, the present inventors have previously proposed polyamines, alicyclic dibasic carboxylic acids, urea as a resin composition for paper coating that gives coated paper excellent in ink acceptability and water resistance. In addition, a resin composition (Patent Document 5) obtained by reacting an alkylating agent was proposed. Although the resin composition has improved ink acceptability and water resistance as compared to conventional coating compositions, further improvement is desired in terms of water resistance and product storage stability at low temperatures (10 ° C or lower). It was.

Japanese Patent Publication No. 44-11667

Japanese Unexamined Patent Publication No. Sho 63-120197

Japanese Patent Publication No.53-44567

JP 58-180529 A

JP 2003-227096 A

  An object of the present invention is to provide a resin composition for paper coating which gives coated paper having no formaldehyde generation, excellent product storage stability at a low temperature (10 ° C. or less), and having excellent water resistance. It is.

（Ｒ_１はそれぞれ独立して水素またはメチル基をあらわす） As a result of intensive studies on a resin composition that does not contain formaldehyde and a compound that generates formaldehyde in order to solve the above problems, the present inventors have found that (A) polyamines, (B) (B-1) alicyclic dibases. Free carboxyl groups at the molecular ends, obtained by reacting more than 1 mol of alicyclic dibasic carboxylic acid with respect to 1 mol of functional carboxylic acids and / or (B-2) glycols A resin composition obtained by reacting 4 or 5 components of a reaction product, (C) ureas, and (D) a crosslinkable compound, and a total of compounds (I) and (II) having the following structures The resin composition for paper coating, characterized by having a water content of less than 1.5% by weight, has a water resistance equivalent to that of a conventional resin composition for paper coating, and is a product at a low temperature (10 ° C. or lower) Excellent storage stability Heading the Rukoto, it has led to the completion of the present invention.

(R ₁ independently represents hydrogen or a methyl group)

The resin composition for paper coating of the present invention has water resistance equivalent to that of a conventional resin composition for paper coating, and excellent low temperature (10 ° C. or lower) storage stability. The resin composition for paper coating of the present invention can also be used as a printability improver and a water-proofing agent.

Hereinafter, the present invention will be described in detail.
The (A) polyamines in the present invention are aliphatic polyamines, alicyclic polyamines, and heterocyclic polyamines having at least two primary or secondary amino groups in the molecule, and are obtained, for example, by polymerizing ethyleneimine. Polyethyleneimine; alkylenediamine containing an alkylene group having 1 to 10 carbon atoms such as ethylenediamine, propylenediamine, hexamethylenediamine; diethylenetriamine, triethylenetetramine, pentaethylenehexamine, tetraethylenepentamine, iminobispropylamine, 3- Examples include polyalkylene polyamines such as azahexane-1,6-diamine and 4,7-diazadecane-1,10-diamine; and alicyclic polyamines such as isophorone diamine and bis (aminomethyl) cyclohexane.

  Here, the heterocyclic polyamine is a polyamine having a heterocyclic ring containing at least one heteroatom such as a nitrogen atom, an oxygen atom or a sulfur atom in the molecule and having at least two primary or secondary amino groups. is there. Of these, heterocyclic polyamines containing a nitrogen atom in the heterocyclic ring are preferred. Specific examples include heterocyclic diamines such as piperazine and homopiperazine; N-aminoethylpiperazine, N-aminopropylpiperazine, and 1,4 -The heterocyclic polyamine which consists of heterocyclic amines, such as bis (aminopropyl) piperazine, and an aminoalkyl group, etc. are mentioned.

(A) Two or more different polyamines may be used as the polyamines. Of these, polyalkylene polyamines are preferred as polyamines, with diethylenetriamine and triethylenetetramine being particularly preferred.

The (B-1) alicyclic dibasic carboxylic acids in the present invention have two or more carboxyl groups in the molecule, and may have a double bond in the molecule. Carboxylic acid, an ester composed of the carboxylic acid and an alcohol having 1 to 4 carbon atoms, or an anhydride of the carboxylic acid.

(B-1) Among the alicyclic dibasic carboxylic acids, examples of the free acid include tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexane-1,4-dicarboxylic acid, 3-methyltetrahydrophthalic acid, 4- And methyl tetrahydrophthalic acid. Of these, tetrahydrophthalic acid, hexahydrophthalic acid, 3-methyltetrahydrophthalic acid and 4-methyltetrahydrophthalic acid are preferred.

(B-1) Among the alicyclic dibasic carboxylic acids, the esters include, for example, lower esters comprising the alicyclic dibasic carboxylic acid and a lower alcohol such as methanol and ethanol, and the above free Examples thereof include polyesters of acids and glycols.

(B-1) Among the alicyclic dibasic carboxylic acids, examples of the acid anhydride include tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, and the like. Is mentioned. Of these, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, and 4-methyltetrahydrophthalic anhydride are preferable.

(B-2) Reaction product having a free carboxyl group at the molecular end, obtained by reacting more than 1 mol of alicyclic dibasic carboxylic acid with 1 mol of glycol of (B-2) glycol of the present invention Examples of glycols used in the products include alkylene glycols such as ethylene glycol, propylene glycol, butanediol, glycerin and pentaerythritol, alkenylene glycols such as butenediol and octenediol, diethylene glycol, dipropylene glycol and triethylene glycol. And polyalkylene glycols such as polyethylene glycol and polytetramethylene glycol are exemplified. Among them, ethylene glycol, diethylene glycol, and glycerin are preferably used. These glycols may be used alone or in combination of two or more different types.

(B-2) As a reaction product having a free carboxyl group at the molecular end, obtained by reacting more than 1 mol of alicyclic dibasic carboxylic acid with respect to 1 mol of glycols , Tetrahydrophthalic acid, hexahydrophthalic acid, 3-methyltetrahydrophthalic acid and 4-methyltetrahydrophthalic acid, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, and 4-methyltetrahydrophthalic anhydride A reaction product of a kind of alicyclic dibasic carboxylic acid and at least one kind of glycol selected from ethylene glycol, diethylene glycol or glycerin is preferable. Tetrahydrophthalic anhydride and ethylene glycol, tetrahydrophthalic anhydride, 3-methyl Tetrahydro anhydride phthalate , And the reaction product of 4-methyl tetrahydrophthalic anhydride and ethylene glycol are more preferable.

(B-2) A reaction product having a free carboxyl group at the molecular end, obtained by reacting more than 1 mole of an alicyclic dibasic carboxylic acid with respect to 1 mole of glycols, Obtained by reacting more than 1 mole of alicyclic dibasic carboxylic acid with respect to 1 mole of glycols, the molar amount of alicyclic dibasic carboxylic acids relative to 1 mole of glycols is: If the amount of the alicyclic dibasic carboxylic acid is less than 1 mole per mole of glycols, the water resistance tends to decrease. (B-2) Reaction of a reaction product having a free carboxyl group at the molecular end obtained by reacting more than 1 mole of alicyclic dibasic carboxylic acid with respect to 1 mole of glycols As conditions, it is usually obtained by stirring at a temperature of 100 to 200 ° C., preferably 120 to 180 ° C. for 2 to 10 hours, preferably 3 to 8 hours, while distilling off generated water as necessary. it can.

These (B-1) alicyclic dibasic carboxylic acids and (B-2) glycols are reacted with 1 mol of alicyclic dibasic carboxylic acid having a mole number greater than 1 mole. The obtained reaction product having a free carboxyl group at the molecular end may be used alone or in combination of two or more. (B-1) Alicyclic dibasic carboxylic acids and (B-2) reaction products having a free carboxyl group at the molecular end are generally 0.05 per mol of (A) polyamines. It is used in the range of -0.7 mol, preferably in the range of 0.1-0.6 mol, more preferably in the range of 0.2-0.5 mol. (B-1) Obtained by reacting more than 1 mole of alicyclic dibasic carboxylic acid with respect to 1 mole of mole of alicyclic dibasic carboxylic acid or (B-2) glycol. When the reaction product having a free carboxyl group at the molecular end is less than 0.05 mol with respect to 1 mol of the polyamines (A), the water resistance tends to decrease, and when it exceeds 0.7 mol, the reaction temperature is low (10 ℃ or less) Storage stability tends to deteriorate.

Examples of (C) ureas in the present invention include urea, methylurea, dimethylurea, thiourea, 4,5-dihydroxy-2-imidazolidinone, and 1- (2-aminoethyl) -2-imidazolidinone. Among them, urea is preferable.

These (C) ureas may be used alone or in combination of two or more. (C) Ureas are derived from (B-1) alicyclic dibasic carboxylic acids and (B-2) from the total number of moles (x) of primary and secondary amino groups contained in (A) polyamines. ) Carboxyl group contained in the reaction product having a free carboxyl group at the molecular end, obtained by reacting more than 1 mole of alicyclic dibasic carboxylic acid with 1 mole of glycols When the number of moles obtained by subtracting the number of moles (y) is defined as the number of moles (z) ((z) = (x) − (y)), the (number of moles of urea) / (z) is generally Is in the range of 0.05 to 1.5 molar ratio, preferably in the range of 0.05 to 1.2 molar ratio, more preferably in the range of 0.05 to 1.0 molar ratio, most preferably 0. It is used in the range of 0.05 to 0.8 mol. When (the number of moles of ureas) / (z) is less than 0.05 mole ratio or greater than 1.2 mole ratio, the water resistance tends to decrease.

Examples of the crosslinkable compound (D) in the present invention include epihalohydrins, monohalohydrins, α, γ-dihalo-β-hydrins, glycidyl compounds or isocyanates. (D) Epihalohydrins among the crosslinkable compounds are represented by the following formula (1).

（式中、Ｘはハロゲン原子を表し、ｗは１〜３の整数を表す。）で示される。

(Wherein X represents a halogen atom and w represents an integer of 1 to 3).

Preferable examples of epihalohydrins include epichlorohydrin and epibromohydrin.
(D) Monohalohydrins among the crosslinkable compounds have the formula (2)

（式中、Ｘはハロゲン原子を表し、ｗは１〜３の整数を表す。）で示される。

(Wherein X represents a halogen atom and w represents an integer of 1 to 3).

Examples of the monohalohydrin include ethylene chlorohydrin and ethylene bromohydrin.

(D) Of the crosslinkable compounds, α, γ-dihalo-β-hydrins have the formula (3)

（式中、Ｘはハロゲン原子等を表し、Ｙはハロゲン原子又は水酸基を表し、Ｚは前記Ｙがハロゲン原子のとき水酸基を表し、前記Ｙが水酸基のときハロゲン原子を表す。）で示される。

(Wherein X represents a halogen atom, Y represents a halogen atom or a hydroxyl group, Z represents a hydroxyl group when Y is a halogen atom, and represents a halogen atom when Y is a hydroxyl group).

Examples of such α, γ-dihalo-β-hydrins include 1,3-dichloro-2-propanol.

(D) Of the crosslinkable compounds, the glycidyl compound usually has at least two glycidyl groups in the molecule. Specific examples thereof include alkylene glycol diglycidyl ethers such as ethylene glycol diglycidyl ether and propylene glycol diglycidyl ether, polyoxyalkylene glycol diglycidyl ethers such as polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether, Aromatic diglycidyl ethers such as resorcin diglycidyl ether and bisphenol A diglycidyl ether, trimethylolpropane di- or tri-glycidyl ether, sorbitol di-, tri-, tetra-, penta- or hexa-glycidyl ether, penta And erythritol di-, tri- or tetra-glycidyl ether.

(D) Isocyanates among the crosslinkable compounds usually have at least two isocyanato groups in the molecule. Specific examples thereof include isophorone diisocyanate, 3- (2-isocyanatocyclohexyl) propyl isocyanate, bis (isocyanatomethyl) cyclohexane, isopropylidenebis (cyclohexyl isocyanate), transcyclohexane-1,4-diisocyanate, bicycloheptane triisocyanate. Aliphatic isocyanates such as hexamethylene diisocyanate, trimethylhexane-1,6-diisocyanate, aliphatic isocyanates such as methyl 2,6-diisocyanatohexanoate (also called lysine diisocyanate), and tolylene diisocyanate , Triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, phenylene diisocyanate, dianisidi Diisocyanate, aromatic isocyanates such as diphenyl ether diisocyanate.

These (D) crosslinkable compounds can be used alone or in combination of two or more. Of course, among epihalohydrins, α, γ-dihalo-β-hydrins, glycidyl compounds and isocyanates, two or more of those belonging to different types can be used in combination. Among these, epihalohydrins and α, γ-dihalo-β-hydrins are industrially preferable, and epihalohydrins are particularly preferable. When (D) the crosslinkable compound is reacted, the (D) crosslinkable compound is usually in the range of 0.1 mol or more and less than 1 mol, preferably 0.2 mol, per mol of (A) polyamines. It is used in the range of not less than mol and not more than 0.8 mol.

(A) Polyamines, (B-1) Alicyclic dibasic carboxylic acids having a mole number greater than 1 mole per mole of the alicyclic dibasic carboxylic acids and (B-2) glycols When reacting 4 or 5 components of a reaction product having a free carboxyl group at the molecular end, (C) ureas, and (D) a crosslinkable compound, obtained by reacting, for example, (a): (A The number of moles of alicyclic dibasic carboxylic acid greater than 1 mole per mole of polyamines and (B-1) alicyclic dibasic carboxylic acids and / or (B-2) glycols Is reacted with a reaction product having a free carboxyl group at the molecular end, followed by (A) deammonia reaction with (C) urea, and (D) further reacting with a crosslinkable compound. Method (a): (A) Polya And (B-1) alicyclic dibasic carboxylic acid and / or (B-2) glycol having 1 mole per mole of alicyclic dibasic carboxylic acid of more than 1 mole. A reaction product obtained by reacting with a reaction product having a free carboxyl group at the molecular end, then (D) a crosslinkable compound is reacted, and (C) a deammonia reaction with ureas , (U): (A) polyamines and (D) crosslinkable compounds are reacted, and then (B-1) alicyclic dibasic carboxylic acids and / or (B-2) glycols are reacted. A reaction product having a free carboxyl group at the molecular end obtained by reacting an alicyclic dibasic carboxylic acid having a mole number greater than 1 mole with respect to 1 mole is further subjected to an amidation reaction, and (C ) Ureas and deammonia (D): More than 1 mole per mole of moles of (A) polyamines and (B-1) alicyclic dibasic carboxylic acids and / or (B-2) glycols A reaction product obtained by reacting several alicyclic dibasic carboxylic acids with a free carboxyl group at the molecular end, (C) ureas and (D) a crosslinkable compound, Examples include a method in which a deammonification reaction and a crosslinking reaction are performed simultaneously, but it is preferable to react a urea compound (C) after reacting with a crosslinkable compound (D) because water resistance becomes higher. .

(A) Polyamines and (B-1) alicyclic dibasic carboxylic acids and / or (B-2) glycols having 1 mole per mole of alicyclic dibasic than 1 mole The reaction with a reaction product having a free carboxyl group at the molecular end obtained by reacting a carboxylic acid is (B-1) alicyclic dibasic carboxylic acid or (B-2) glycol having 1 mole number. On the other hand, the reaction temperature and reaction time differ depending on the type of reaction product having a free carboxyl group at the molecular end, obtained by reacting more than 1 mol of alicyclic dibasic carboxylic acid. When (B-1) an alicyclic dibasic carboxylic acid and / or (B-2) a reaction product having a free carboxyl group at the molecular end and a polyamine (A) are subjected to an amidation reaction, 130-25 A method of reacting for 2 to 10 hours while distilling off water and the like at ° C; (B-1) an alicyclic dibasic carboxylic acid anhydride of an alicyclic dibasic carboxylic acid and a polyamine (A); In the case of amidation reaction, the reaction is usually performed at about 50 to 200 ° C. while distilling off water and the like for about 1 to 10 hours; (B-1) alicyclic dibasic carboxylic acid alicyclic When an amidation reaction of a dibasic carboxylic acid ester and (A) polyamine is performed, a method of reacting for 2 to 10 hours while distilling off water or alcohol at about 80 to 250 ° C. is usually mentioned. .

(A) The deammonia reaction between the amino group of polyamines and (C) ureas is usually 80 to 180 ° C., preferably 90 to 160 ° C., preferably 4 to 30 hours while distilling off the generated ammonia. Includes a method of reacting for 5 to 20 hours.

(A) Reaction of amino group of polyamines and (D) crosslinkable compound is usually 30-120 ° C, preferably 50-100 ° C for 1-20 hours, preferably 2-10 hours, etc. Is mentioned.

The resin composition for paper coating thus obtained uses an inorganic acid such as phosphoric acid, sulfuric acid, hydrochloric acid, or nitric acid, or an organic acid such as formic acid, acetic acid, propionic acid, or adipic acid, if necessary. And may be adjusted to pH 6-10.

（Ｒ_１はそれぞれ独立して水素またはメチル基をあらわす） This resin composition for paper coating has a low temperature (10%) by making the total of compounds (I) and (II) having the structure shown below less than 1.5% by weight, more preferably less than 1.3%. Excellent storage stability at temperatures below ℃) is achieved. Examples of the compound (I) include N, N′-bis (N ″-(1,2,3,6-tetrahydrophthalimido) ethyl) -2-imidazolidinone, N- (N ″-(1 , 2,3,6-tetrahydrophthalimido) ethyl) -N ′-(N ′ ″-(3-methyl-1,2,3,6-tetrahydrophthalimido) ethyl) -2-imidazolidinone and the like. As the compound (II), for example, N, N′-bis (N ″-(1,2,3,6-tetrahydrophthalimido) ethyl) -N, N′-dicarbamoylethylenediamine, N- (N ′ '-(1,2,3,6-tetrahydrophthalimide) ethyl) -N ″-(N ′ ″-(3-methyl-1,2,3,6-tetrahydrophthalimide) ethyl) -N, N ′ -Dicarbamoyl ethylenediamine etc. are mentioned. When the total of these compounds (I) and (II) is 1.5% by weight or more, the storage stability at a low temperature (10 ° C. or less) is deteriorated.

(R ₁ independently represents hydrogen or a methyl group)

The resin composition for paper coating thus obtained is prepared as a paper coating composition together with a pigment and an aqueous binder. Here, examples of the pigment include white inorganic pigments and white organic pigments. Specific examples of the white inorganic pigment include kaolin, talc, calcium carbonate (heavy or light), aluminum hydroxide, satin white, titanium oxide, and the like. Specific examples of the white organic pigment include polystyrene, melamine-formaldehyde resin, urea-formaldehyde resin, and the like. Two or more types of pigments may be used as the pigment.

Examples of the aqueous binder include a water-soluble binder and a water-emulsified binder. Specific examples of the water-soluble binder include starches such as starch modified with oxidized starch, non-denatured starch and phosphate ester; water-soluble proteins such as casein and gelatin; modified celluloses such as carboxymethyl cellulose; partial or complete Examples thereof include saponified polyvinyl alcohol and modified polyvinyl alcohol. Specific examples of water-emulsifying binders include styrene-butadiene resins (SBR latex), acrylonitrile-butadiene resins (NBR latex), chloroprene resins (CR latex), and methyl methacrylate, which may have carboxyl groups or nitrile groups. -Butadiene resin (MBR latex), copolymer resin of two or more acrylic monomers, copolymer resin of acrylic monomers and vinyl acetate, copolymer resin of acrylic monomers and styrene, vinyl acetate resin, styrene-acetic acid Examples thereof include vinyl resins and ethylene-vinyl acetate resins. Two or more different aqueous binders may be used as the aqueous binder.

The weight ratio of the pigment, the aqueous binder (solid content) and the paper coating resin (solid content) in the paper coating composition of the present invention is usually 1 to 200 based on 100 parts by weight of the pigment. Part by weight, particularly preferably 5 to 50 parts by weight, and the resin composition for paper coating is 0.01 to 5 parts by weight, particularly preferably 0.05 to 2 parts by weight.

In preparing the paper coating composition, the order of addition and mixing of the pigment, the aqueous binder and the resin composition is arbitrary and is not particularly limited. For example, a method of adding and mixing a resin composition to a mixture of a pigment and an aqueous binder, a method of adding and mixing a resin composition in advance to a pigment or an aqueous binder, and blending it with the remaining components can be employed.

Furthermore, the coating composition includes, for example, a dispersant such as Aron T-40 (manufactured by Toagosei Co., Ltd.), Sumirez Resin DS-10 (manufactured by Sumitomo Chemical Co., Ltd.), viscosity / fluidity modifier, antifoaming agent, antiseptic A colorant such as an agent, a lubricant, a water retention agent, a dye or a colored pigment, and a printability improver and a water resistance agent different from the paper coating resin of the present invention may be contained.

The coated paper of the present invention is a paper containing the paper coating composition on one side or both sides. Examples of paper manufacturing methods include papermaking science (published by Chugai Industry Research Council (1982)), Pulp and Paper: Chemistry and Chemical Technology, Vol. II, John Wiley &amp; Sons (1980) and the like, and methods such as chemical pulping, mechanical pulping, waste paper pulping, and the like. The paper used in the present invention may be paper in which additives such as a filler, a sizing agent, a banding agent, a paper strength enhancer, and a dye are added as necessary. In addition, the paper of the present invention has a broad meaning, and includes so-called paperboard in addition to paper in a narrow sense.

Examples of the method for producing the coated paper of the present invention include, for example, a method in which a coating composition is applied to paper once, and a method in which a coating composition having the same or different blending ratio is applied multiple times. Etc. Here, as a coating method, for example, a coating composition is applied to a coating base paper using a coater such as a blade coater, an air knife coater, a bar coater, a size press coater, a gate roll coater, or a cast coater, and then And a method of performing necessary drying and further performing a smoothing treatment with a super calender or the like, if necessary.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not a thing limited by these. In the examples, parts and% are based on weight unless otherwise specified. Moreover, solid content is the evaporation residue calculated | required by drying according to 4.9 of JISK6828, pH uses a glass electrode type hydrogen ion concentration meter (made by Toa Denpa Kogyo Co., Ltd.), and immediately after preparation. The pH of the sample was measured at 25 ° C., and the viscosity was measured using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd., BL type) at 60 rpm and 25 ° C. to measure the viscosity of the coating composition immediately after preparation. It is the value.

(Synthesis Example 1)
<Production Example (B-2) Component 1: Synthesis of Resin 1-1>
A reactor equipped with a thermometer, a reflux condenser and a stir bar was charged with 220.6 parts of a mixture of (B-1) 3-methyltetrahydrophthalic anhydride and 4-methyltetrahydrophthalic anhydride (1.33 molar ratio, HN -2000 Hitachi Chemical Co., Ltd.) and (B-1) tetrahydrophthalic anhydride 532.5 parts (3.50 mole ratio) were charged, and the internal temperature was raised to 120 ° C. Next, while maintaining the internal temperature at 120 to 140 ° C., 149.8 parts (2.41 mole ratio) of ethylene glycol was slowly added dropwise, and after completion of the dropwise addition, the mixture was further stirred at an internal temperature of 140 to 155 ° C. for 1 hour, 902.7 parts of a reaction product having a free carboxyl group at the end was obtained. The reaction product was considered a 2.41 molar ratio, assuming all the ethylene glycol had reacted. Thereafter, this polyester was recovered in a stainless steel tray without cooling, and solidified by cooling to obtain a resin composition (1-1).

<Production Example 1: Product of Component (A) and Component (B-2) 1: Synthesis of Resin 1-2>
To a reactor equipped with a thermometer, a reflux condenser and a stirring rod, 101.1 parts (0.27 mole ratio, 0.33 mole ratio with respect to polyamine) of the resin composition (1-1) was added. After raising the temperature to 110 ° C, 118.6 parts of (A) triethylenetetramine (0.81 molar ratio, 3.25 molar ratio as an amino group) was slowly added dropwise at 110-135 ° C. Next, the internal temperature was raised to 145 ° C. while distilling off the generated water, and the reaction was further carried out for 4 hours at an internal temperature of 145 to 155 ° C. while distilling off the generated water. At this time, the weight of distilled water was 1.4 parts. Thereafter, 99.4 parts of water was added to the aqueous polyester polyamide resin composition aqueous solution (resin composition 1-2) having a solid content of 70%, 299.6 parts (0.81 molar ratio based on triethylenetetramine, 2 amino groups) .70 molar ratio).

<Production Example 1: Product of Component (A), Component (B-2), and Component (D) 1: Synthesis of Resin 1-3>
In a reactor equipped with a thermometer, a reflux condenser, and a stirring rod, 299.6 parts of resin composition (1-2) (0.81 mole ratio based on triethylenetetramine, 2.70 mole ratio as amino group) And water (16.1 parts), while maintaining the internal temperature at 65 to 75 ° C., (D) 37.5 parts of epichlorohydrin (0.41 mole ratio, 0.50 mole ratio to polyamine) was added for 2 hours. The mixture was added dropwise and stirred at an internal temperature of 65 to 75 ° C. for 4 hours. Thereafter, the mixture was cooled to room temperature, and 352.2 parts (resin composition 1-3) of an epichlorohydrin-modified polyester polyamide resin composition having a solid content concentration of 70% (0.81 molar ratio based on triethylenetetramine, 2. as amino groups). 70 molar ratio).

<Production Example 1: Resin Composition for Paper Coating 1: Preparation of Resin Composition 1 for Paper Coating>
In a reactor equipped with a thermometer, a reflux condenser and a stirring rod, 171.0 parts of resin (1-3) (0.39 molar ratio based on triethylenetetramine, 1.31 molar ratio as amino group), and 20.3 parts of water was added, and the internal temperature was raised to 80 ° C. Next, 47.3 parts of urea (C) (0.79 molar ratio, 0.60 molar ratio to amino group) was added, and the internal temperature was raised to 90 ° C. Subsequently, while the generated ammonia is distilled out of the system, the temperature is raised to an internal temperature of 104 ° C. over 2 hours, and further, the generated ammonia is distilled from the reactor at an internal temperature of 104 to 106 ° C. for 8 hours. Reacted for hours. Thereafter, the mixture was cooled while gradually adding 76.0 parts of water to obtain 301.0 parts of an aqueous solution (resin composition 1 for paper coating) having a non-volatile content of 51.0%, a pH of 8.42, and a viscosity of 41 mPa · s. .

(Synthesis Example 2)
<Production Example 2 of Component (B-2): Synthesis of Resin 2-1>
A reactor equipped with a thermometer, a reflux condenser and a stir bar was charged with 458.0 parts of a mixture of (B-1) 3-methyltetrahydrophthalic anhydride and 4-methyltetrahydrophthalic anhydride (2.76 molar ratio, HN -2000 Hitachi Chemical Co., Ltd.) and (B-1) Tetrahydrophthalic anhydride 1677.5 parts (11.03 molar ratio) were charged, and the internal temperature was raised to 120 ° C. Next, while maintaining the internal temperature at 120 to 140 ° C., 427.7 parts (6.89 mole ratio) of ethylene glycol was slowly added dropwise, and after completion of the dropwise addition, the mixture was further stirred at an internal temperature of 140 to 155 ° C. for 1 hour, 2563.0 parts of a reaction product having a free carboxyl group at the end was obtained. The reaction product was regarded as a 6.89 molar ratio, assuming all the ethylene glycol had reacted. Thereafter, this polyester was recovered in a stainless steel tray without cooling, and solidified by cooling to obtain a resin composition (1-1).

<Production Example 2 of Product of Component (A) and Component (B-2): Synthesis of Resin 2-2>
1208.4 parts (3.25 mole ratio, 0.50 mole ratio to polyamine) of the resin composition (2-1) was added to a reactor equipped with a thermometer, a reflux condenser, and a stirring rod, and 85 % Ε-caprolactam 22.9 parts (0.17 mole ratio, 0.026 mole ratio with respect to polyamine) was added dropwise, and the internal temperature was raised to 110 ° C., and (A) triethylenetetramine 950. 2 parts (6.50 molar ratio, 26.0 molar ratio as an amino group) were slowly added dropwise at 110 to 135 ° C. Next, the internal temperature was raised to 145 ° C. while distilling off the generated water, and the reaction was further carried out for 4 hours at an internal temperature of 145 to 155 ° C. while distilling off the generated water. At this time, the weight of distilled water was 39.0 parts. Thereafter, 634.6 parts of water was added and 2766.4 parts of a polyester polyamide resin composition aqueous solution (resin composition 2-2) having a solid content concentration of 73.6% (6.50 molar ratio based on triethylenetetramine, amino group) As 19.5 molar ratio).

<Production Example 2 of Product of (A) Component, (B-2) Component, (B-1) Component, and (D) Component: Synthesis of Resin 2-3>
In a reactor equipped with a thermometer, a reflux condenser and a stirring rod, 145.0 parts of resin composition (2-2) (0.34 molar ratio based on triethylenetetramine, 1.02 molar ratio as amino group) And 14.0 parts of water were added and while maintaining the internal temperature at 65 to 75 ° C., 2.6 parts of (B-1) tetrahydrophthalic anhydride (0.017 mole ratio, 0.05 moles relative to polyamine) The mixture was stirred at an internal temperature of 65 to 75 ° C. for 2 hours. After completion of stirring, 12.6 parts of (D) epichlorohydrin (0.14 mole ratio, 0.40 mole ratio with respect to polyamine) was added dropwise over 2 hours, and the mixture was further stirred at an internal temperature of 65 to 75 ° C. for 4 hours. Thereafter, the mixture was cooled to room temperature, and 173.8 parts of an aqueous solution of an epichlorohydrin-modified polyester polyamide resin composition having a solid content concentration of 70% (resin composition 2-3) (0.34 molar ratio based on triethylenetetramine, 1. 00 molar ratio).

<Production Example 2 of Paper Coating Resin Composition: Preparation of Resin Composition 2 for Paper Coating>
Add 173.8 parts of resin (2-3) (0.34 mole ratio based on triethylenetetramine, 1.00 mole ratio as amino group) to a reactor equipped with a thermometer, reflux condenser and stir bar. The internal temperature was raised to 80 ° C. Next, 25.6 parts of (C) urea (0.43 molar ratio, 0.42 molar ratio with respect to amino groups) was added, and then the internal temperature was raised to 90 ° C. Subsequently, while the generated ammonia is distilled out of the system, the temperature is raised to an internal temperature of 104 ° C. over 2 hours, and further, the generated ammonia is distilled from the reactor at an internal temperature of 104 to 106 ° C. for 8 hours. Reacted for hours. Thereafter, the mixture was cooled while gradually adding 82.4 parts of water to obtain 274.1 parts of an aqueous solution (resin composition 2 for paper coating) having a non-volatile content of 51.2%, a pH of 8.39, and a viscosity of 64 mPa · s. .

<Production Example 3 of Product of (A) Component, (B-2) Component, (B-1) Component, and (D) Component: Synthesis of Resin 3-3>
In a reactor equipped with a thermometer, a reflux condenser, and a stirring rod, 110.4 parts of resin composition (2-2) (0.26 molar ratio based on triethylenetetramine, 0.78 molar ratio as amino group) And 12.4 parts of water and (B-1) 5.9 parts of tetrahydrophthalic anhydride (0.039 mole ratio, 0.15 moles relative to polyamine) while maintaining the internal temperature at 65 to 75 ° C The mixture was stirred at an internal temperature of 65 to 75 ° C. for 2 hours. After completion of the stirring, 9.6 parts of (D) epichlorohydrin (0.10 molar ratio, 0.40 molar ratio with respect to polyamine) was added dropwise over 2 hours, and further stirred at an internal temperature of 65 to 75 ° C. for 4 hours. Thereafter, the mixture was cooled to room temperature, and 137.9 parts of an aqueous solution of an epichlorohydrin-modified polyester polyamide resin composition (resin composition 3-3) having a solid content concentration of 70% (0.26 molar ratio based on triethylenetetramine, and 0.1% as an amino group). 74 molar ratio) was obtained.

<Production Example 3 of Paper Coating Resin Composition: Preparation of Resin Composition 3 for Paper Coating>
137.9 parts of resin (3-3) (0.26 molar ratio based on triethylenetetramine, 0.74 molar ratio as amino group) was added to a reactor equipped with a thermometer, a reflux condenser and a stirring rod. The internal temperature was raised to 80 ° C. Next, (C) 19.5 parts of urea (0.32 mole ratio, 0.44 mole ratio with respect to amino groups) was added, and the internal temperature was raised to 90 ° C. Subsequently, while the generated ammonia is distilled out of the system, the temperature is raised to an internal temperature of 104 ° C. over 2 hours, and further, the generated ammonia is distilled from the reactor at an internal temperature of 104 to 106 ° C. for 8 hours. Reacted for hours. Thereafter, the mixture was cooled while gradually adding 64.8 parts of water to obtain 217.1 parts of an aqueous solution (resin composition 3 for paper coating) having a non-volatile content of 51.6%, a pH of 8.26, and a viscosity of 65 mPa · s. .

(Comparative Synthesis Example 1)
<Production Example 4 of Component (B-2): Synthesis of Resin 4-1>
A reactor equipped with a thermometer, reflux condenser and stir bar was charged with 373.9 parts of a mixture of (B-1) 3-methyltetrahydrophthalic anhydride and 4-methyltetrahydrophthalic anhydride (2.25 molar ratio, HN -2000 Hitachi Chemical Co., Ltd.) and (B-1) 1369.3 parts of tetrahydrophthalic anhydride (9.00 molar ratio) were charged, and the internal temperature was raised to 120 ° C. Next, while maintaining the internal temperature at 120 to 140 ° C., 349.1 parts (5.63 molar ratio) of ethylene glycol was slowly added dropwise, and after completion of the dropwise addition, the mixture was further stirred at an internal temperature of 140 to 155 ° C. for 1 hour, 2091.7 parts of a reaction product having a free carboxyl group at the end was obtained. The reaction product was considered to be a 5.63 molar ratio, assuming all the ethylene glycol had reacted. Then, this polyester was collect | recovered to the stainless steel tray, without cooling, and it was made to cool and solidify and the resin composition (4-1) was obtained.

<Production Example 4 of Product of Component (A) and Component (B-2): Synthesis of Resin 4-2>
361.1 parts (0.97 mole ratio, 0.50 mole ratio to polyamine) of the resin composition (4-1) was added to a reactor equipped with a thermometer, a reflux condenser, and a stirring rod, and 85 6.8 parts of% ε-caprolactam (0.051 molar ratio, 0.026 molar ratio with respect to polyamine) was added dropwise, and then the internal temperature was raised to 110 ° C., and (A) triethylenetetramine 284. 0 parts (1.94 molar ratio, 7.77 molar ratio as an amino group) were slowly added dropwise at 110 to 135 ° C. Next, the internal temperature was raised to 145 ° C. while distilling off the generated water, and the reaction was further carried out for 4 hours at an internal temperature of 145 to 155 ° C. while distilling off the generated water. At this time, the weight of distilled water was 18.6 parts. Thereafter, 239.3 parts of water was added to 892.1 parts of a polyester polyamide resin composition aqueous solution (resin composition 4-2) having a solid content concentration of 70% (1.94 molar ratio based on triethylenetetramine, 5 as amino groups). .83 molar ratio).

<Production Example 4 of Product of (A) Component, (B-2) Component, (B-1) Component, and (D) Component: Synthesis of Resin 4-3>
In a reactor equipped with a thermometer, a reflux condenser, and a stirring rod, 164.8 parts of resin composition (4-2) (0.36 mole ratio based on triethylenetetramine, 1.08 mole ratio as amino group) 11.5 parts of water and 11.5 parts of water, while maintaining the internal temperature at 65-75 ° C., (B-1) 13.6 parts of tetrahydrophthalic anhydride (0.090 mole ratio, 0.25 moles relative to polyamine) The mixture was stirred at an internal temperature of 65 to 75 ° C. for 2 hours. After the completion of stirring, 13.3 parts of (D) epichlorohydrin (0.14 mole ratio, 0.40 mole ratio with respect to polyamine) was added dropwise over 2 hours, followed by stirring at an internal temperature of 65 to 75 ° C. for 4 hours. Thereafter, the mixture was cooled to room temperature, and 202.9 parts of an aqueous solution of an epichlorohydrin-modified polyester polyamide resin composition (resin composition 4-3) having a solid content concentration of 70% (0.36 molar ratio based on triethylenetetramine, and 0.2 as an amino group). 99 molar ratio).

<Production Example 4 of Paper Coating Resin Composition: Preparation of Resin Composition 4 for Paper Coating>
To a reactor equipped with a thermometer, a reflux condenser, and a stirring rod, 202.9 parts of resin (4-3) (0.36 mole ratio based on triethylenetetramine, 0.99 mole ratio as amino group) was added. The internal temperature was raised to 80 ° C. Next, (C) 26.9 parts of urea (0.45 mole ratio, 0.45 mole ratio with respect to amino groups) was added, and then the internal temperature was raised to 90 ° C. Subsequently, while the generated ammonia is distilled out of the system, the temperature is raised to an internal temperature of 104 ° C. over 2 hours, and further, the generated ammonia is distilled from the reactor at an internal temperature of 104 to 106 ° C. for 8 hours. Reacted for hours. Then, it cooled, adding 101.5 parts of water gradually, and obtained 325.2 parts of aqueous solution (resin composition 4 for paper coating) of 48.9% of non volatile matter, pH 7.86, and a viscosity of 46 mPa * s. .

<Production example of coating composition>
Ultra white 90 (pigment, clay manufactured by Engelhard Minerals, USA) 60 parts by weight Carbital 90 (pigment, calcium carbonate manufactured by Fuji Kaolin Co., Ltd.) 40 parts by weight, polyacrylic acid pigment dispersant 0.2 weight Part, 9 parts by weight of styrene-butadiene latex (aqueous binder) and 2 parts by weight of commercially available oxidized starch were mixed, and water was added to prepare a master color so that the solid content was 64.5%. Subsequently, the solid content of the resin composition 1 for paper coating obtained in <Preparation Example 1 for Resin Composition for Paper Coating> is added to 100 parts by weight of the pigment of the master color at a ratio of 0.6 parts by weight. The solid content was adjusted to 64%.
The obtained coating composition had a pH of 9.2 and a viscosity of 1950 mPa · s.

<Examples of coated paper production>
The coating composition was applied to one side of a high-quality paper having a basis weight of 80 g / m 2 using a wire rod so that the coating amount was 15 g / m 2. Immediately after the application, it is dried with hot air at 130 ° C. for 10 seconds, then conditioned for 16 hours at a temperature of 20 ° C. and a relative humidity of 65%, and further subjected to supercalender treatment twice under the conditions of a temperature of 60 ° C. and a linear pressure of 60 kN / m. And coated paper was obtained. The coated paper thus obtained was subjected to a water resistance test, and the test results are shown in Table 1. The test method is as follows.

<Water resistance: Wet pick method (WP method)>
Using an RI testing machine (manufactured by Meisei Seisakusho), the coated surface was wetted with a water supply roll and then printed, and the peeled state was visually observed and judged. The judgment criteria were as follows.
Water resistance (poor) 1-5 (excellent)

<Refrigerated storage stability>
The paper coating resin was stored in a refrigerated showcase at 5 ° C. for 1 week, and the state was determined by visual observation. The judgment criteria were as follows.
Refrigerated storage stability ○: Clear and no problem in appearance
×: Solid is generated

<Quantification of Compound (I)>
Compound (I) was quantified by gas chromatography (GC-14B, manufactured by Shimadzu Corporation) using the resin composition for paper coating as it was.

<Quantification of Compound (II)>
Compound (II) was quantified by liquid chromatography (LC-20A, manufactured by Shimadzu Corporation) using the resin composition for paper coating as it was.

(Examples 2-3, Comparative Example 1)
A coating composition and coated paper are produced in the same manner as in Example 1 except that the paper coating resin shown in Table 1 is used. The physical properties of the resin composition for paper coating and the physical properties of the coated paper are as follows. It was measured. The results are shown in Table 1 together with the results of Example 1.

*1：紙塗工樹脂の製造に用いられた（Ａ）ポリアミン類１モルに対する、用いられた（Ｂ）脂環式二塩基性カルボン酸類のモル比
*2： ポリアミン類に含有される１級および２級アミノ基の合計モル数（ｘ）から脂環式二塩基性カルボン酸類に含有されるカルボキシル基のモル数（ｙ）を差し引いたモル数（ｚ）１モルに対する、（Ｃ）尿素のモル比
*3：紙塗工樹脂の製造に用いられた（Ａ）ポリアミン類１モルに対する、用いられた（Ｄ）架橋性化合物のモル比

* 1: Molar ratio of (B) alicyclic dibasic carboxylic acids used to 1 mol of (A) polyamines used in the production of paper coating resin
* 2: Number of moles obtained by subtracting the number of moles of carboxyl groups (y) contained in alicyclic dibasic carboxylic acids from the total number of moles (x) of primary and secondary amino groups contained in polyamines ( z) mole ratio of (C) urea to 1 mole
* 3: Molar ratio of (D) crosslinkable compound used to 1 mol of (A) polyamines used in the production of paper coating resin.

Claims (4)

(A) polyamines, (B) (B-1) alicyclic dibasic carboxylic acids and / or (B-2) alicyclics having a mole number of more than 1 mole per mole of glycols A resin composition obtained by reacting dibasic carboxylic acids with a reaction product having a free carboxyl group at the molecular end, (C) ureas, and (D) crosslinkable compounds. A total of the compounds (I) and (II) having the structure shown below is less than 1.5% by weight.

(R ₁ independently represents hydrogen or a methyl group) (B) (B-1) is tetrahydrophthalic anhydride and / or 3-methyltetrahydrophthalic anhydride and / or 4-methyltetrahydrophthalic anhydride, and (B-2) is 1 mole of glycols, A reaction product having a free carboxyl group at the molecular end, obtained by reacting more than 1 mole of tetrahydrophthalic anhydride and / or 3-methyltetrahydrophthalic anhydride and / or 4-methyltetrahydrophthalic anhydride. The resin composition for paper coating according to claim 1, wherein the resin composition is for paper coating. A paper coating composition comprising the resin composition for paper coating according to claim 1, a pigment, and an aqueous binder.   A coated paper obtained by coating the paper coating composition according to claim 3 on paper.