JP3269190B2 - Paper coating composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a paper coating composition containing a pigment and an aqueous binder. More specifically, an object of the present invention is to provide a paper coating composition capable of imparting excellent printability and printing effect to paper.

[0002] The term "paper" as used herein has a broad meaning, and includes paper and paperboard in a narrow sense.

[0003]

2. Description of the Related Art Coated paper obtained by applying a coating composition mainly composed of a pigment and an aqueous binder to paper and subjecting it to necessary treatments such as drying and calendering is characterized by its excellent printing effect. Therefore, it is widely used in commercial prints, magazines and books, etc., but with the sophistication of quality requirements and the speeding up of printing, efforts to improve the quality of coated papers are still ongoing. Particularly in offset printing, which accounts for the majority of printing, the improvement and improvement of ink receptivity under the influence of shampoo water, water resistance of wet topics, etc., and blister resistance in rotary printing have become important issues in the industry. .

Conventionally, to solve such problems, a melamine-formaldehyde resin, a urea-formaldehyde resin, or a polyamide polyurea-formaldehyde resin, for example, JP-B-44-11667 and JP-B-59-32597.
There is known a method of adding a water-proofing agent, a printability improving agent, and the like as described in Japanese Patent Application Laid-Open Publication No. H11-163,028.

[0005] However, these conventional water-proofing agents and printability-improving agents all have effective properties, but on the other hand, serious disadvantages or insufficient effects are recognized in some of the properties, so that they are practically used. It was not always satisfactory.

For example, aminoplast resins such as melamine-formaldehyde resin and urea-formaldehyde resin not only generate a large amount of formaldehyde during work or from coated paper, but also have an effect of improving ink receptivity and blister resistance. Is hardly obtained, and when the pH of the coating composition is increased, the water-resistant effect is hardly exhibited.

[0007] Polyamide polyurea-formaldehyde resins are effective for improving ink resistance and blister resistance simultaneously with improving water resistance. However, their degree of improvement is in accordance with recent demands for higher coated paper quality. But it was not necessarily enough. Therefore, efforts have been made to further improve the quality, and further improvements have been attempted, for example, in JP-A-62-104995, JP-A-4-100997, and JP-A-4-263696. However, as the demand for coated paper quality became more sophisticated,
There is a need for higher performance.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to meet the demands for coated paper quality and to provide a paper with higher ink receptivity and water resistance. It is an object of the present invention to provide a paper coating composition which can be used for chemical conversion.

The present inventors have conducted intensive studies to solve such problems, and as a result, have found that a paper coating composition containing a specific amine together with a specific water-soluble resin exhibits excellent performance. Heading, the present invention has been completed.

[0010]

That is, the present invention provides a paper coating composition containing the following components (I), (II), (III) and (IV) as essential components.

(I) pigments, (II) aqueous binders, (III) at least (a) alkylenediamine or polyalkylenepolyamine, (b) ureas, and (c) aldehydes, epihalohydrins, and α, γ-dihalo −β
A water-soluble resin obtained by reacting three components of a compound selected from hydrins, and (IV) amines selected from monoamines, diamines and salts thereof having 4 or more carbon atoms.

Further, the water-soluble resin (III) comprises the above component
In addition to (a), (b) and (c), further components such as a dibasic carboxylic acid compound, an alicyclic amine having at least one active hydrogen and / or an alicyclic epoxy compound are reacted. It may be made to be.

Hereinafter, the present invention will be described in more detail.

In the present invention, the pigment (I) serving as a component of the paper coating composition may be any of those conventionally used in paper coating, and white inorganic pigments and white organic pigments may be used. Examples of the white inorganic pigment include kaolin, talc, calcium carbonate (heavy or light), aluminum hydroxide, satin white, titanium oxide and the like. As the white organic pigment, for example, polystyrene,
Melamine-formaldehyde resin, urea-formaldehyde resin and the like can be mentioned. These pigments can be used alone or in combination of two or more. Still further, a colored inorganic or organic pigment may be used in combination.

Aqueous binder (II) as another component
May also be those conventionally used generally for paper coating, and a water-soluble binder or a water-emulsifying binder may be used. As the water-soluble binder, for example, unmodified or modified starches, including oxidized starch and phosphated starch, polyvinyl alcohol, water-soluble proteins including casein and gelatin, including carboxymethyl cellulose And modified celluloses. Examples of the water-emulsifying binder include, for example, a styrene-butadiene resin, a vinyl acetate resin, an ethylene-vinyl acetate resin, and a methyl methacrylate resin. These aqueous binders can be used alone or in combination of two or more.

In the present invention, in addition to the pigment (I) and the aqueous binder (II), a specific water-soluble resin (III)
And specific amines (IV) in combination.

The water-soluble resin (III) is selected from (a) alkylenediamine or polyalkylenepolyamine, (b) ureas, and (c) aldehydes, epihalohydrins and α, γ-dihalo-β-hydrins. It is obtained by reacting at least three components of a compound.

Examples of the alkylenediamine or polyalkylenepolyamine (a) used herein include aliphatic diamines such as ethylenediamine and propylenediamine, and diethylenetriamine, triethylenetetramine, tetraethylenepentamine, iminobispropylamine, and 3-diamine. Azahexane-1,6-diamine, 4,7
Polyalkylenepolyamines such as -diazadecane-1,10-diamine. Among these,
Diethylenetriamine and triethylenetetramine are industrially advantageous. These alkylenediamines or polyalkylenepolyamines (a) can be used alone or as a mixture of two or more.

The ureas (b) include, for example, urea, thiourea, guanylurea, methylurea and dimethylurea. The ureas (b) can also be used alone or as a mixture of two or more. From an industrial point of view, urea is preferably used.

Examples of the aldehyde constituting the component (c) include alkyl aldehydes such as formaldehyde, acetaldehyde and propyl aldehyde, and alkyl dialdehydes such as glyoxal, propane dial and butane dial. Industrially, formaldehyde and glyoxal are preferred. These aldehydes can be used alone or as a mixture of two or more.

Epihalohydrins are represented by the following general formula.

[0022]

Embedded image

In the formula, X represents a halogen atom, w is 1,
Represents 2 or 3. Preferred examples include epichlorohydrin, epibromohydrin and the like. These epihalohydrins may be used alone or as a mixture of two or more.

Α, γ-dihalo-β-hydrins are represented by the following general formula.

[0025]

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In the formula, X and Z represent a halogen atom.
For example, 1,3-dichloro-2-propanol and the like can be mentioned.

In the present invention, one or more compounds (c) selected from aldehydes, epihalohydrins and α, γ-dihalo-β-hydrins are used. Therefore, of course, these may be used alone or in combination of two or more. For example, aldehydes and epihalohydrins can be used in combination, or aldehydes and α, γ-dihalo-β-
Hydrins can be used in combination.

At least three of the above-mentioned alkylenediamines or polyalkylenepolyamines (a), ureas (b) and compounds (c) selected from aldehydes, epihalohydrins and α, γ-dihalo-β-hydrins. By reacting the components, the water-soluble resin (III) used in the present invention is obtained. The water-soluble resin of the present invention
(III) may be obtained by reacting other components in addition to these three components. Additional reaction components preferably used include dibasic carboxylic acid compounds (d),
And alicyclic compounds (e) selected from alicyclic amines having at least one active hydrogen and alicyclic epoxy compounds.

The dibasic carboxylic acid compound (d) has a carboxyl group or two groups derived therefrom in the molecule, and may be an ester or an acid anhydride in addition to a free acid.

The dibasic carboxylic acids can be aliphatic, aromatic,
It may be any of alicyclic. Examples of the free acid include succinic acid, glutaric acid, adipic acid, sebacic acid,
Aliphatic dicarboxylic acids such as maleic acid, fumaric acid,
Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid, furthermore tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexane-1,3- or 1,4-dicarboxylic acid, cyclopentanedicarboxylic acid,
Alicyclic dicarboxylic acids such as 3- or 4-methyltetrahydrophthalic acid and 3- or 4-methylhexahydrophthalic acid are exemplified. Incidentally, when the alicyclic group has an unsaturated bond, and the position of the unsaturated bond is not specified, it is to be understood that the position of the unsaturated bond is arbitrary, and also in the following description The same is true. Esters of these dibasic carboxylic acids (for example, mono- or di-esters with lower alcohols, polyesters with glycols), acid anhydrides and the like can also be used.

Particularly in the case of an alicyclic dibasic carboxylic acid,
Acid anhydrides are also advantageously used. Specific examples of the acid anhydride include tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3- or 4-methylhexahydrophthalic anhydride, and 3- or 4-methyltetrahydrophthalic anhydride.

In particular, in the case of an alicyclic dibasic carboxylic acid, a polyester which is a reaction product of a dibasic carboxylic acid and a glycol is also advantageously used. Above all,
Those having a free carboxyl group are preferred. Examples of the glycols used here include alkylene glycols such as ethylene glycol, propylene glycol and butanediol, cycloalkylene glycols such as cyclopentanediol and cyclohexanediol, alkenylene glycols such as butenediol and octenediol, and diethylene glycol. And polyalkylene glycols such as dipropylene glycol, triethylene glycol, polyethylene glycol and polytetramethylene glycol, bisphenol A ethylene oxide adducts, hydrogenated bisphenol A ethylene oxide adducts and the like. When a dibasic carboxylic acid, particularly an alicyclic dibasic carboxylic acid, is reacted with a glycol in an excess molar ratio of carboxylic acid, a polyester having a carboxyl group at a molecular terminal can be obtained.

When these dibasic carboxylic acid compounds are used, they may be used alone or in combination of two or more.

Of the alicyclic compounds (e), the alicyclic amine having at least one active hydrogen usually has 5 ring carbon atoms.
A compound having about to 12 alicyclic rings, preferably a cyclohexane ring, and having at least one primary or secondary amino group, wherein the amino group is directly bonded to the alicyclic ring; And may be indirectly bonded to the alicyclic ring via a linking group such as alkylene. Specific examples of the alicyclic amine having at least one active hydrogen include cyclohexylamine, dicyclohexylamine, 1,3-diaminocyclohexane, 1,4
-Diaminocyclohexane, 4,4'-diamino-3,
3'-dimethyldicyclohexylmethane, 4,4'-diamino-3,3'-dimethylbicyclohexane, isophoronediamine, 1,3-, 1,2- or 1,4-bis (aminomethyl) cyclohexane, N-amino Propylcyclohexylamine, 1,5- or 2,6-bis (aminomethyl) octahydro-4,7-methanoindene, 2,2-bis (4-aminocyclohexyl) propane, bis (4-aminocyclohexyl) methane, ,
4'-oxybis (cyclohexylamine), 4,4 '
-Sulfone bis (cyclohexylamine), 1,3,5
-Triaminocyclohexane, 2,4'- or 4,
4'-diamino-3,3 ', 5,5'-tetramethyldicyclohexylmethane and the like. These alicyclic amines can also be used alone or in combination of two or more.

Of the alicyclic compounds (e), the alicyclic epoxy compounds usually have an epoxy group bonded directly or indirectly to an alicyclic ring having about 5 to 12 ring carbon atoms, preferably a cyclohexane ring. A compound, where indirect means that a group having an epoxy group, such as a glycidyl group, is attached to the alicyclic ring. Specific examples of the alicyclic epoxy compound include cyclohexene oxide, vinylcyclohexene dioxide, bis (3,4-epoxycyclohexyl) adipate, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, and 3- (3 , 4-epoxycyclohexyl) -8,9-epoxy-2,4-dioxaspiro [5.5] undecane, diglycidyl hexahydrophthalate, 2,2-bis (4-glycidyloxycyclohexyl) propane, and the like. Also when using these alicyclic epoxy compounds, each alone,
Alternatively, two or more kinds can be used in combination. Of course, an alicyclic amine and an alicyclic epoxy compound can be used in combination.

The water-soluble resin (III) in the present invention includes the above-mentioned alkylenediamine or polyalkylenepolyamine (a), ureas (b), aldehydes, epihalohydrins and α, γ-dihalo-β-hydrin. By reacting three components of a compound (c) selected from the group consisting of a dibasic carboxylic acid compound (d), an alicyclic amine having at least one active hydrogen, It is obtained by reacting an alicyclic compound (e) selected from cyclic epoxy compounds.

For example, a water-soluble resin (III) suitable for use in the present invention can be obtained by reacting the following components.

(A) alkylenediamines or polyalkylenepolyamines, (b) ureas, (c) aldehydes, epihalohydrins and α, γ-dihalo-β-hydrins, and if desired, (e) An alicyclic compound selected from an alicyclic amine having at least one active hydrogen and an alicyclic epoxy compound.

The order of the reaction of each component is arbitrary and is not particularly limited. For example, the following modes can be adopted. The dealkylation reaction of the alkylene diamine or polyalkylene polyamine (a) and the urea (b) is carried out, and then the aldehyde, epihalohydrin and α, γ-
A compound (c) selected from dihalo-β-hydrins is reacted. When an alicyclic amine and / or an alicyclic epoxy compound (e) is used if desired, one or more of these compounds may be reacted during the reaction and / or the reaction. Good.

In the above reaction, the urea (b) may be charged and reacted at a time, or a part of the urea (b) may be charged first to react with the alkylene diamine or polyalkylene polyamine (a). After reacting, the remaining urea
(b) to perform a deammonification reaction,
The reaction can also be performed in two stages. In the reaction of
When an aldehyde is used as the component (c), it is preferable to carry out the reaction under an acidic condition, or to carry out the reaction once under an alkaline condition and then to carry out the reaction under an acidic condition. on the other hand,
Epihalohydrins and / or α, as component (c)
When γ-dihalo-β-hydrins are used, they are weakly acidic to alkaline, for example, pH 5 or more, and furthermore, pH 6 to
It is preferable to carry out the reaction in the range of 9.

These reactions can be carried out according to known methods. For example, the reaction of the above components (a), (b) and (c) is known from JP-A-4-100997, and can be carried out according to the method described therein.
Further, in addition to the above components (a), (b) and (c), the reaction in the case of further using the component (e) is known from JP-A-4-263696 and JP-A-4-333697. Can be carried out according to the method described therein.

Another water-soluble resin suitable for use in the present invention
(III) is obtained by reacting the following components.

(A) alkylene diamine or polyalkylene polyamine, (b) ureas, (c) compounds selected from aldehydes, epihalohydrins and α, γ-dihalo-β-hydrins, (d) dibasic carboxylic acids An acid-based compound and, if desired, (e) an alicyclic compound selected from an alicyclic amine and an alicyclic epoxy compound having at least one active hydrogen.

Also in this case, the order of the reaction of each component is arbitrary and is not particularly limited. For example, the following embodiment can be adopted. Alkylene diamine or polyalkylene polyamine (a), urea (b) and dibasic carboxylic acid compound (d) are subjected to deammonification reaction and dehydration condensation in any order to produce polyamide polyurea, Compounds selected from aldehydes, epihalohydrins and α, γ-dihalo-β-hydrins
(c) is reacted. When an alicyclic amine and / or an alicyclic epoxy compound (e) are used, if desired,
In the reaction and / or the reaction, one or more of these compounds may be reacted.

In the reaction in this case, urea
(b) can be charged at once and reacted.Also, a part of urea (b) can be charged first to carry out deammonification reaction, and the remaining urea (b) can be removed at a later stage. In addition, it is also possible to take a method of performing a deammonification reaction again. For example, alkylene diamine or polyalkylene polyamine (a) and dibasic carboxylic acid compound
(d) is subjected to dehydration condensation, followed by deammonification of ureas (b), after deammonification of a part of ureas (b) with alkylenediamine or polyalkylenepolyamine (a), and then dibasic Method of dehydrating and condensing the reactive carboxylic acid compound (d) and further deammonifying with the remaining urea (b), alkylene diamine or polyalkylene polyamine (a) and dibasic carboxylic acid compound (d)
In addition, a method of adding a part of the urea (b) to perform a dehydration and deammonification reaction and further adding the remaining urea (b) to perform a deammonification reaction can be employed. Also in the case of using an aldehyde as the component (c), it is preferable to carry out the reaction under an acidic condition, or to carry out the reaction once under an alkaline condition and then under an acidic condition. On the other hand, when epihalohydrins and / or α, γ-dihalo-β-hydrins are used as the component (c), the reaction is preferably carried out in a weakly acidic or alkaline state, for example, at a pH of 5 or more, and more preferably at a pH of 6 to 9. .

These reactions can be carried out according to known methods. For example, the components (a), (b),
The reactions of (c) and (d) are described in JP-A-55-31837, JP-A-57-167315, JP-A-62-104995, JP-A-62-125092, It is known from JP-A-62-125093 and others, and can be carried out according to the method described therein. Further, the above components (a), (b), (c) and (d)
In addition to the above, the reaction when the component (e) is further used is known from JP-A-2-216297 and JP-A-2-221498, and can be carried out according to the method described therein.

In the present invention, a specific amine (IV) is used in addition to the water-soluble resin (III) as described above. The amines (IV) used herein are monoamines, diamines or salts thereof having 4 or more carbon atoms, and among them, those having 5 or more carbon atoms are preferable. The amines (IV) can be primary, secondary or tertiary monoamines, diamines or their salts.
Any of aliphatic, aromatic, alicyclic and cyclic ones having at least two carbon atoms may be used.

Examples of the primary monoamine include aliphatic primary monoamines such as butylamine, pentylamine, hexylamine, octylamine, isobutylamine and 2-ethylhexylamine; alicyclic monoamines such as cyclohexylamine and aminomethylcyclohexane. Primary monoamines, and furthermore, aromatic primary amines such as aniline, toluidine, benzylamine, naphthylamine and m-aminophenol are exemplified. Examples of the secondary monoamine include dipropylamine, dicyclohexylamine,
Examples include an aliphatic, aromatic or alicyclic group-containing or cyclic monoamine such as N-methylcyclohexylamine, N-methylaniline, pyrrolidine, and piperidine. Examples of the tertiary monoamine include triethylamine, tributylamine, N, N-dimethyl-n-propylamine, N, N-dimethylcyclohexylamine,
Monocyclic amines containing an aliphatic, aromatic or alicyclic group, or cyclic monoamines such as N, N-dimethylaniline and pyridine are exemplified.

Diamine is a compound having two primary amino groups, a compound having two secondary amino groups, a compound having two tertiary amino groups, and a compound having two different amino groups.
Any compound having a total of two each may be used.
In particular, diamines containing an alicyclic, aromatic or cyclic amino group are preferred. For example, 1,3-diaminocyclohexane, isophoronediamine, 1,3-bis (aminomethyl) cyclohexane, bis (4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, menthanediamine, Alicyclic or aromatic compounds having two primary amino groups, such as 4'-oxybis (cyclohexylamine), 4,4'-sulfonebis (cyclohexylamine), phenylenediamine, tolylenediamine and xylylenediamine; And 3
-Methylaminomethyl-3,5,5-trimethylcyclohexylamine, 1-methylamino-3-aminomethyl-3,5,5-trimethylcyclohexane, 1-aminomethyl-3-methylaminomethylcyclohexane, 1-
A compound having a total of two amino groups of different grades, such as aminomethyl-3-dimethylaminomethylcyclohexane, 1-methylaminomethyl-3-dimethylaminomethylcyclohexane, and 4-aminopyridine;
Compounds having two secondary amino groups, such as N, N'-dimethylisophoronediamine, 1,3-bis (methylaminomethyl) cyclohexane, N, N, N ', N'-
Compounds having two tertiary amino groups such as tetramethylisophoronediamine and 1,3-bis (dimethylaminomethyl) cyclohexane are exemplified.

The amines (IV) may be salts of these monoamines or diamines, and the acids constituting such salts may be either inorganic acids or organic acids. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, and phosphoric acid, and examples of the organic acid include acetic acid, formic acid, and oxalic acid.

These amines (IV) can be used alone or as a mixture of two or more.

The paper coating composition of the present invention contains the above-described pigment (I), aqueous binder (II), water-soluble resin (III) and amines (IV).

In preparing the paper coating composition, the pigment (I)
The composition ratio of each of the aqueous binder (II) and the aqueous binder (II) is determined according to the use and purpose, and there is no particular difference from the composition generally used in the art. A preferred composition ratio of both is about 5 to 200 parts by weight, more preferably 10 to 5 parts by weight of the aqueous binder (II) per 100 parts by weight of the pigment (I).
It is about 0 parts by weight. The water-soluble resin (III) is a pigment (I) 1
It is preferable to add about 0.05 to 5 parts by weight, more preferably about 0.1 to 2 parts by weight, as a solid content with respect to 00 parts by weight. Further, the amines (IV) are water-soluble resins (II
It is preferable to add about 1 to 50% by weight, more preferably about 5 to 20% by weight, based on the weight of the solid content of (I).

The water-soluble resin (III) and the amines (IV)
After pre-mixing, when preparing the paper coating composition, the pigment
It may be added to and mixed with (I) and the aqueous binder (II), or may be individually added to and mixed with the pigment (I) and the aqueous binder (II). Furthermore, these water-soluble resins
The effect of the present invention can also be achieved by adopting a mode in which a mixture of (III) and amines (IV), or each alone, is previously added to and mixed with a pigment slurry or an aqueous binder, and then blended with the remaining components. Can be achieved.

In the paper coating composition of the present invention, other components such as a dispersant, a viscosity / fluidity regulator, an antifoaming agent,
Preservatives, lubricants, water retention agents, coloring agents such as dyes and colored pigments, and the like can be added as necessary.

The paper coating composition of the present invention can be prepared by a conventionally known method, for example, a method using various known coaters such as a blade coater, an air knife coater, a bar coater, a size press coater, a gate roll coater, and a cast coater. , Applied to a paper substrate. Thereafter, necessary drying is performed, and if necessary, a smoothing treatment is performed with a super calender or the like, whereby a coated paper can be manufactured.

Thus, according to the present invention, specific amines
By using (IV) additionally, compared to the case of using a coating composition comprising a pigment (I), an aqueous binder (II) and a specific water-soluble resin (III), further improved performance is obtained. The coated paper shown is obtained.

[0058]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. In the examples, percentages and parts representing the content or the amount of addition are based on weight unless otherwise specified. The viscosity and pH are values measured at 25 ° C. First, a water-soluble resin used in Examples was synthesized in Synthesis Example 1 shown below.
-3.

Synthesis Example 1

In a four-necked flask equipped with a thermometer, a reflux condenser and a stirring rod, 146.2 g of triethylenetetramine was added.
(1.0 mol) and 30.0 g (0.5 mol) of urea were charged and heated at an internal temperature of 140 to 160 ° C. for 3.5 hours to carry out a deammonification reaction. Then, 73.1 g of adipic acid (0.5
Mol), keeping the internal temperature at 150 to 160 ° C.
The dehydration amidation reaction was performed for a time. Then the internal temperature is 130 ° C
And charged with 120.1 g (2.0 mol) of urea.
A deammonification reaction was performed at ~ 130 ° C for 2 hours. Thereafter, 270 g of water was added to obtain a resin aqueous solution. Further 37
% Formalin 60.9g (0.75mol), 70%
The pH of the system was adjusted to 4 to 5 with sulfuric acid and reacted at an internal temperature of 70 ° C for 4 hours. Then, the pH is adjusted to 4 to 5 with aqueous sodium hydroxide solution.
, And reacted at an internal temperature of 70 ° C for 4 hours. The pH was adjusted to 6.5 and the concentration was adjusted to 50% with an aqueous sodium hydroxide solution to obtain 675 g of an aqueous resin solution having a viscosity of 140 cps.

Synthesis Example 2

In the same container as used in Synthesis Example 1, 58.5 g (0.4 mol) of triethylenetetramine and urea 1
2.0 g (0.2 mol) was charged and heated at an internal temperature of 120 to 140 ° C. for 3 hours to carry out a deammonification reaction. Thereafter, 34.4 g (0.2 mol) of hexahydrophthalic acid was charged,
The dehydration amidation reaction was performed at an internal temperature of 150 to 160 ° C. for 5 hours. Next, it is cooled until the internal temperature reaches 130 ° C., and urea 4
8.0 g (0.8 mol) was charged, and a deammonification reaction was performed at a temperature of 120 to 130 ° C. for 2 hours. After the reaction, the mixture was cooled to 100 ° C., and 108 g of water was added to obtain a resin aqueous solution. Then, 32.4 g (0.4 mol) of 37% formalin was added, and
The pH of the system was adjusted to 5.1 with 0% sulfuric acid. This was heated to 60 ° C., reacted for 5 hours, cooled, neutralized with a 28% aqueous sodium hydroxide solution, and had a pH of 7.1, a concentration of 50%, and a viscosity of 45%.
275 g of an aqueous resin solution of cps was obtained.

Synthesis Example 3

In the same container as used in Synthesis Example 1, 146.2 g (1.0 mol) of triethylenetetramine and urea 1
80.2 g (3.0 mol) was charged, and the internal temperature was 120 to 140 ° C.
For 2 hours to carry out a deammonification reaction. afterwards,
150 g of water was added to obtain a resin aqueous solution. Further, 56.8 g (0.7 mol) of 37% formalin was added, and the internal temperature was 70 ° C.
After reacting for an hour, the pH of the system was adjusted to 4.0 with 70% sulfuric acid, and the reaction was continued for 4 hours while maintaining the internal temperature at 70 ° C again. Thereafter, the pH was adjusted to 7.0 with an aqueous solution of caustic soda, and an aqueous resin solution having a concentration of 60% and a viscosity of 350 cps was added to a solution of 515.
g was obtained.

Examples 1 to 6

Preparation of Master Color A master color was prepared according to the formulation shown in Table 1.

[0067]

[Table 1] ^{* 1} Ultra White 90: Clay manufactured by Engel Hard Minerals, Inc. ^{* 2} Carbital 90: Calcium carbonate manufactured by Fuji Kaolin Co., Ltd. ^{* 3} Sumireze Resin DS-10: Polyacrylic acid pigment dispersant manufactured by Sumitomo Chemical Co., Ltd. ^{* 4} SN-307: Styrene butadiene latex manufactured by Sumitomo Dow Co., Ltd. ^{* 5} Oji Ace A: Oxidized starch manufactured by Oji National Co., Ltd. ^{* 6 The} mixing ratio is represented by the weight of solid content.

Preparation of Paper Coating Composition A paper coating composition was prepared by the following method using the above master color, the respective aqueous resin solutions obtained in Synthesis Examples 1 to 3, and amines.

Example 1 225 g of the aqueous resin solution obtained in Synthesis Example 1 was previously mixed with 5.6 g of cyclohexylamine to obtain an aqueous resin solution having a viscosity of 138 cps.
This aqueous resin solution was added to the master color shown in Table 1 at a ratio of 0.5 part solids per 100 parts of pigment.

Example 2 By mixing 22.5 g of 1,3-bis (aminomethyl) cyclohexane in advance with 225 g of the aqueous resin solution obtained in Synthesis Example 1, the viscosity was 1
An aqueous resin solution of 35 cps was added to the master color shown in Table 1 at a ratio of 0.5 part solids per 100 parts of pigment.

Example 3 A resin aqueous solution having a viscosity of 43 cps was prepared by previously mixing 12.5 g of cyclohexylamine with 125 g of the aqueous resin solution obtained in Synthesis Example 2.
This aqueous resin solution was added to the master color shown in Table 1 at a ratio of 0.5 part solids per 100 parts of pigment.

Example 4 A resin aqueous solution having a viscosity of 44 cps was prepared by previously mixing 3.6 g of isophoronediamine with 145 g of the aqueous resin solution obtained in Synthesis Example 2, and this resin aqueous solution was used as a master color as shown in Table 1. And pigment 1
It was added at a rate of 0.5 part solids per 100 parts.

Example 5: To the master color shown in Table 1, 0.4 part of the resin aqueous solution obtained in Synthesis Example 3 and 0.1 part of isophoronediamine were separately added per 100 parts of the pigment as a solid content. did.

Example 6: 172 g of the aqueous resin solution obtained in Synthesis Example 3 was previously mixed with 5.2 g of 1,3-bis (aminomethyl) cyclohexane to give a viscosity of 349 g.
A resin solution of cps was prepared, and this resin solution was added to the master color shown in Table 1 in a solid content of 0.5 per 100 parts of pigment.
Parts.

Each of the coating compositions prepared as described above was adjusted with water and a 10% aqueous solution of sodium hydroxide so that the total solid content was 60% and the pH was about 9.0. Table 2 shows the mixing ratio of the resin and the amine in these examples.
Also summarized.

Measurement of Physical Properties of Coating Composition The physical properties of each coating composition were measured by the following methods, and the results are shown in Table 2.

(1) pH glass electrode type hydrogen ion concentration meter [Toa Denpa Kogyo Co., Ltd.]
The pH of the coating composition immediately after preparation was measured at 25 ° C.

(2) Viscosity Using a B-type viscometer [BL type, manufactured by Tokyo Keiki Co., Ltd.]
The viscosity of the coating composition immediately after preparation was measured at 25 ° C. and rpm.

Preparation of Coated Paper Each of the coating compositions obtained as described above was coated on one side of high-quality paper having a basis weight of 80 g / m ² with a wire rod at a coating weight of 14 g / m ^2. It was applied as a m ^2. Immediately after the application, the resultant was dried with hot air at 120 ° C. for 30 seconds, and then conditioned at a temperature of 20 ° C. and a relative humidity of 65% for 16 hours. To give a coated paper.

Evaluation of Physical Properties of 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.

(3) Water resistance: Wet topic method (WP method) Using a RI tester (manufactured by Meisho Seisakusho), the coated surface was wetted with a water supply roll, and then printed. Judged. The judgment criteria were as follows. Water resistance (poor) 1-5 (excellent)

(4) Ink acceptability (4-1) Method A Using an 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)

(4-2) Method B Using an RI tester, the ink was printed while kneading water, and the ink receptivity was visually observed and judged. The judgment criteria were as follows. Ink acceptability (poor) 1-5 (excellent)

[0084]

[Table 2] ^{* 1} Amine type CYHA: Cyclohexylamine BAMC: 1,3-bis (aminomethyl) cyclohexane IPDA: Isophoronediamine ^{* 2} Addition method of amine A: Add to resin solution beforehand B: Separate from resin solution Addition

Comparative Examples 1-4

A paper coating composition was prepared by the following method using the master color used in the above Examples and the respective resin aqueous solutions obtained in Synthesis Examples 1 to 3.

Comparative Example 1 The aqueous resin solution obtained in Synthesis Example 1 was added to the master color shown in Table 1 at a ratio of 0.5 part solids per 100 parts of pigment.

Comparative Example 2 The aqueous resin solution obtained in Synthesis Example 2 was added to the master color shown in Table 1 at a ratio of 0.5 part solids per 100 parts of pigment.

Comparative Example 3 The aqueous resin solution obtained in Synthesis Example 3 was added to the master color shown in Table 1 at a ratio of 0.5 part solids per 100 parts of pigment.

Comparative Example 4: The master colors shown in Table 1 were used as they were.

The solid content and the pH of each of the coating compositions thus obtained were adjusted in the same manner as in the above Examples, and a coated paper was prepared using each of the coating compositions. A similar test was performed. The test results are shown in Table 3.

[0092]

[Table 3]

[0093]

The coated paper obtained by using the paper coating composition of the present invention has various excellent and effective properties such as excellent ink acceptability and water resistance.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Fujiko Kumei 3-1-198 Kasuganaka, Konohana-ku, Osaka Sumitomo Chemical Co., Ltd. (56) References JP-A-58-126395 (JP, A) JP-A-58-126394 (JP, A) JP-A-61-111328 (JP, A) JP-A-61-281127 (JP, A) JP-A-59-137597 (JP, A) JP-A-59-129229 (JP, A) JP, A) JP-A-2-102226 (JP, A) JP-A-4-209893 (JP, A) JP-A-2-221498 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , (DB name) D21H 11/00-27/42

Claims (7)

(57) [Claims] (I) a pigment, (II) an aqueous binder, (III) at least (a) an alkylenediamine or a polyalkylenepolyamine, (b) ureas, and (c) aldehydes, epihalohydrins and α, γ-
A water-soluble resin obtained by reacting three components of a compound selected from dihalo-β-hydrins, and (IV) an amine selected from monoamines having four or more carbon atoms, diamines and salts thereof. A paper coating composition, characterized in that: 2. The method according to claim 1, wherein the water-soluble resin comprises (a) an alkylenediamine or a polyalkylenepolyamine, (b) a urea, (c) an aldehyde, an epihalohydrin and α, γ-
The composition according to claim 1, which is obtained by reacting a compound selected from dihalo-β-hydrins with (d) a dibasic carboxylic acid compound. 3. The method according to claim 1, wherein the dibasic carboxylic acid compound is a free acid,
The composition according to claim 2, which is an ester or an acid anhydride. 4. A water-soluble resin comprising: (a) an alkylenediamine or a polyalkylenepolyamine, (b) a urea, (c) an aldehyde, an epihalohydrin and α, γ-
The compound according to claim 1, which is obtained by reacting a compound selected from dihalo-β-hydrins with an alicyclic compound selected from (e) an alicyclic amine having at least one active hydrogen and an alicyclic epoxy compound. Composition. 5. The method according to claim 1, wherein the water-soluble resin comprises (a) an alkylenediamine or a polyalkylenepolyamine, (b) a urea, (c) an aldehyde, an epihalohydrin and α, γ-
A compound selected from dihalo-β-hydrins, (d) a dibasic carboxylic acid compound, and (e) an alicyclic compound selected from an alicyclic amine and an alicyclic epoxy compound having at least one active hydrogen The composition according to claim 1, which is obtained by reacting 6. The composition according to claim 1, wherein the amine of component (IV) has 5 or more carbon atoms. 7. An aqueous binder (II) is used in an amount of 5 to 200 parts by weight, and a water-soluble resin (III) is added in an amount of 0.0 to 100 parts by weight of the pigment (I).
The composition according to any one of claims 1 to 6, comprising 5 to 5 parts by weight, and 1 to 50% by weight of the amine (IV) based on the weight of the solid content of the water-soluble resin (III).