JP3351096B2 - Coating composition for paper - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a coating composition for paper containing a pigment and an aqueous binder. More specifically, an object of the present invention is to provide a paper coating composition that can impart 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 coating.

The present inventors have conducted intensive studies to solve such problems, and as a result, have found that a composition containing a specific compound together with a specific water-soluble resin gives excellent performance to paper. 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) a polyamide obtained by reacting a dibasic carboxylic acid compound with a polyamine.

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.

The pigment (I) which is a component of the paper coating composition is
What has been conventionally used for paper coating may be used.
White inorganic pigments and white organic pigments can be used. Examples of white inorganic pigments include kaolin, talc,
Examples include calcium carbonate (heavy or light), aluminum hydroxide, satin white, and titanium oxide. Examples of the white organic pigment include polystyrene, melamine-formaldehyde resin, and urea-formaldehyde resin. 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.

The aqueous binder (II) may be any of those generally used for coating paper, and a water-soluble binder or a water-emulsifying binder can be used. As the water-soluble binder, for example, unmodified or modified starches such as 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 styrene-butadiene-based resin, vinyl acetate resin, ethylene-vinyl acetate resin, and 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 a specific polyamide (IV).

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

The alkylenediamine or polyalkylenepolyamine (a) used herein includes, for example, aliphatic diamines such as ethylenediamine, propylenediamine, 1,3-propanediamine, hexamethylenediamine, and diethylenetriamine, triethylenetetramine, tetraethylenediamine. Ethylenepentamine, iminobispropylamine, 3-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, dimethylurea and the like. 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.

The aldehyde constituting the component (c) includes, for example, 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]

In the formula, X represents a halogen atom, w is 1,
Represents 2 or 3. Preferred examples of epihalohydrins 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]

In the formula, Y and Z represent a halogen atom.
Examples of such α, γ-dihalo-β-hydrins include 1,3-dichloro-2-propanol.

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, and aldehydes, epihalohydrins and α, γ-
Dihalo-β-hydrins can also 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. As an additional reaction component preferably used, a dibasic carboxylic acid compound (d)
Alicyclic compound selected from alicyclic amine and alicyclic epoxy compound having at least one active hydrogen (e)
Is mentioned.

The dibasic carboxylic acid compound (d) is a compound having two carboxyl groups in the molecule or a compound derived therefrom, for example, free acids, esters,
Acid anhydride and the like.

The dibasic carboxylic acids can be aliphatic, aromatic,
Any of alicyclic compounds may be used. In the case of an aliphatic compound, one having 4 or more carbon atoms is usually used, and the upper limit of the number of carbon atoms is 3
It is about 6. Examples of the dibasic carboxylic acid used include succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, fumaric acid, aliphatic dicarboxylic acids such as dimer acid of linoleic acid, phthalic acid, isophthalic acid, and terephthalic acid. Aromatic dicarboxylic acids such as tetrahydrophthalic acid, hexahydrophthalic acid,
Cycloaliphatic dicarboxylic acids such as cyclohexane-1,3- or -1,4-dicarboxylic acid, cyclopentanedicarboxylic acid, 3- or 4-methyltetrahydrophthalic acid, 3- or 4-methylhexahydrophthalic acid No. 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.

The dibasic carboxylic acid compounds (d) include, in addition to these dibasic carboxylic acids which are free acids,
Esters (eg, mono- or di-esters with lower alcohols, polyesters with glycols), acid anhydrides, and the like can also be used.

In particular, as the alicyclic dibasic carboxylic acid-based compound, in addition to alicyclic dicarboxylic acids, acid anhydrides of the dicarboxylic acids and polyesters which are reaction products of the dicarboxylic acids with glycols are advantageously used. used. Specific examples of the acid anhydride include tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3- or 4-methylhexahydrophthalic anhydride, and 3- or 4-methyltetrahydrophthalic anhydride.

As the polyester, those having a free carboxyl group are preferable, and the glycols used in the production thereof include alkylene glycols such as ethylene glycol, propylene glycol and butanediol, and cyclopentanediol and cyclohexanediol. Cycloalkylene glycols, butenediol, alkenylene glycols such as octenediol, diethylene glycol, dipropylene glycol,
Examples thereof include polyalkylene glycols such as triethylene glycol, polyethylene glycol, and polytetramethylene glycol, ethylene oxide adduct of bisphenol A, and ethylene oxide adduct of hydrogenated bisphenol A. When a dibasic carboxylic acid, particularly an alicyclic dicarboxylic acid, is reacted with a glycol in an excess molar ratio of carboxylic acid, a polyester having a free 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, menthanediamine 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 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 at once and reacted, 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.

Each of these reactions can be carried out according to a known method. 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 embodiments can be employed. 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 polyamide (IV) is further used in addition to the water-soluble resin (III) described above. The polyamide (IV) used here is obtained by reacting a dibasic carboxylic acid compound with a polyamine.

The dibasic carboxylic acid compound serving as one raw material of the polyamide (IV) is a compound having two carboxyl groups in the molecule or a compound derived therefrom. And acid anhydrides can be used. Specifically, those exemplified above as the optional component (d) when producing the water-soluble resin (III), that is, aliphatic,
Aromatic or alicyclic dicarboxylic acids, mono- or di-esters of any of these with lower alcohols, acid anhydrides thereof, polyesters of any of these with glycols, especially polyesters having a free carboxyl group Can be used. When polyesters are used, those having a polymerization degree of 20 or less are preferred.
These dibasic carboxylic acid compounds can be used alone or in combination of two or more.

Examples of the polyamine serving as the other raw material of the polyamide (IV) include, for example, alkylenediamine and aliphatic polyamine similar to polyalkylenepolyamine (a) used for obtaining the water-soluble resin (III), Amines having a total of two or more primary and / or secondary amino groups in one molecule, such as cyclic polyamines and aromatic polyamines, are widely used, and among them, alicyclic diamines are preferably used. These polyamines can be used alone or in combination of two or more.

The alicyclic diamine is usually a compound having an alicyclic ring having about 5 to 12 ring carbon atoms, preferably a cyclohexane ring, and having a total of two primary and / or secondary amino groups. Is mentioned. Here, the amino group may be directly bonded to the alicyclic ring, or may be indirectly bonded to the alicyclic ring via a linking group such as alkylene. Further, a diamine may be formed in such a manner that one amino group is directly or indirectly bonded to an alicyclic ring and an aminoalkyl group is bonded to the amino group.

Specific examples of the alicyclic diamine include diaminocyclohexane, isophoronediamine, bis (aminomethyl) cyclohexane, bis (4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, and menthanediamine. 4,4'-oxybis (cyclohexylamine), 4,4'-sulfonebis (cyclohexylamine), 4,4'-diamino-3,
3'-dimethyldicyclohexylmethane, 4,4'-diamino-3,3'-dimethylbicyclohexane, N-aminopropylcyclohexylamine, 1,5- or 2,6-bis (aminomethyl) octahydro-4,7
-Methanoindene, 2,4'- or 4,4'-diamino-3,3 ', 5,5'-tetramethyldicyclohexylmethane and the like.

The aromatic diamine is a compound having at least one aromatic ring and having a total of two primary and / or secondary amino groups.
Xylylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, N-aminopropylaniline, 2,4'-
Or 4,4'-diamino-3,3 ', 5,5'-tetramethyldiphenylmethane and the like can be mentioned.

The physical properties of the polyamide (IV), such as solubility in water and other solvents and crystallinity, can be arbitrarily adjusted by selecting a dibasic carboxylic compound and a polyamine. Can be changed according to the purpose.

In the reaction for obtaining the polyamide (IV), the dibasic carboxylic acid compound and the polyamine are reacted at 100 to 250 ° C.
The reaction is preferably performed at 130 to 200 ° C. for 2 to 12 hours while removing generated water outside the system. The amount of the dibasic carboxylic acid compound to be used is 0.5 to 1 mol of the polyamine.
One mole is preferred. This reaction proceeds without a catalyst,
It may be carried out in the presence of a catalyst, for example an acid catalyst such as hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid. Polyamide (IV) has a viscosity at 25 ° C. of a 60% aqueous solution of 20 to 10,000 c.
Ps is preferred, and particularly preferred is 50-5,000 cps.

The polyamide (IV) obtained by reacting such a dibasic carboxylic acid compound with a polyamine is 1
The species alone may be used alone, or, of course, two or more species may be used as a mixture.

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

In preparing the paper coating composition, a pigment
The composition ratio of each of (I) and the aqueous binder (II) is determined according to the use and purpose, and there is no particular difference from compositions generally used in the art. The preferred composition ratio of both is about 5 to 200 parts by weight, more preferably about 10 parts by weight of the aqueous binder (II) per 100 parts by weight of the pigment (I).
It is about 50 parts by weight. Water-soluble resin (III) is a pigment
(I) It is preferable to add about 0.05 to 5 parts by weight, more preferably 0.1 to 2 parts by weight, as a solid content with respect to 100 parts by weight.
It is blended in about parts by weight. The polyamide (IV) is 1 to 90% by weight based on the weight of the solid content of the water-soluble resin (III).
It is preferable to mix in a range of about 3 to 80.
It is more preferable to mix in the range of about weight%.

Water-soluble resin (III) and polyamide (IV)
After pre-mixing, when preparing a paper coating composition,
The pigment (I) and the aqueous binder (II) may be added and mixed, or each alone, the pigment (I) and the aqueous binder (II)
May be added and mixed. Still further, a mixture of these water-soluble resins (III) and polyamides (IV), or each alone, is previously added to and mixed with a pigment slurry or an aqueous binder, and then mixed with the remaining components. Also, the effect of the present invention 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, a preservative, a lubricant, a water retention agent, and a dye / colored pigment may be used. Such coloring agents and the like can be blended as necessary.

The paper coating composition of the present invention can be prepared by a conventionally known method, for example, by 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. Is 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, a coating composition comprising a pigment (I) and an aqueous binder (II) can be obtained by additionally using a specific water-soluble resin (III) and a specific polyamide (IV). As a result, a coated paper showing significantly improved performance is obtained as compared with the case of using a coated paper. Further, by simultaneously using the water-soluble resin (III) and the polyamide (IV), a coating composition obtained by adding only the water-soluble resin (III) to the pigment (I) and the aqueous binder (II) Thus, a coated paper showing further improved performance as compared with the case where is used is obtained.

[0063]

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. In addition, polyamides are synthesized in Synthesis Examples 4 to
Synthesized according to No. 10.

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. 37% more
60.9 g (0.75 mol) of formalin was charged, the pH of the system was adjusted to 4 to 5 with 70% sulfuric acid, and the mixture was reacted at an internal temperature of 70 ° C. for 4 hours. Thereafter, the pH was adjusted to 4 to 5 with a sodium hydroxide aqueous solution, and the reaction was performed 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.

Synthesis Example 4

In a four-necked flask equipped with a thermometer, a Liebig condenser and a stirring rod, 142 g (1.0 mol) of 1,3-bis (aminomethyl) cyclohexane and 73.0 g (0.5 mol) of adipic acid were added. And the internal temperature is 150 ~
The dehydration amidation reaction was performed at 160 ° C. for 5 hours. After the reaction was completed, water was added to obtain 338 g of an aqueous polyamide solution having a concentration of 60% and a viscosity of 400 cps.

Synthesis Example 5

In the same container as used in Synthesis Example 4, 170.2 g (1.0 mol) of isophoronediamine and 50 g (0.5 mol) of succinic anhydride were charged, and the internal temperature was raised to 150 to 16%.
The dehydration amidation reaction was carried out at 0 ° C. for 5 hours. After the reaction was completed, water was added to obtain 357 g of an aqueous polyamide solution having a concentration of 60% and a viscosity of 450 cps.

Synthesis Example 6

In the same container as used in Synthesis Example 4, 1
74.2 g (1.0 mol) of 3-propanediamine and 3
-Or 4-methyl-1,2,3,6-tetrahydrophthalic anhydride (mixture of 3-methyl and 4-methyl forms)
83.1 g (0.5 mol) was charged and the internal temperature was adjusted to 150 to 155.
Dehydration amidation reaction was carried out for 5 hours while maintaining the temperature. After the completion of the reaction, water was added, and a 60% -concentration polyamide aqueous solution 247.2 was added.
g was obtained.

Synthesis Example 7

In the same container as used in Synthesis Example 4, 116.2 g (1.0 mol) of hexamethylenediamine and 3
-Or 4-methyl-1,2,3,6-tetrahydrophthalic anhydride (mixture of 3-methyl and 4-methyl forms)
83.1 g (0.5 mol) was charged and the internal temperature was adjusted to 150 to 155.
Dehydration amidation reaction was carried out for 5 hours while maintaining the temperature. After the completion of the reaction, water was added, and a polyamide aqueous solution having a concentration of 60% 317.2 was added.
g was obtained.

Synthesis Example 8

To the same container as used in Synthesis Example 4, 103.2 g (1.0 mol) of diethylenetriamine and 73.1 g (0.5 mol) of adipic acid were added, and the mixture was kept at 150 to 155 ° C. for 5 hours. A dehydration amidation reaction was performed. One more
152.1 g of 2,3,6-tetrahydrophthalic anhydride
(1.0 mol) and 60.1 g (1.0 mol) of ethylenediamine were added, and the mixture was kept at 150 to 155 ° C. to carry out a dehydration amidation reaction for 5 hours. After the reaction is completed, water is added, and the concentration is 60%.
587.5 g of an aqueous solution of a polyamide was obtained.

Synthesis Example 9

In the same container as used in Synthesis Example 4, 60.1 g (1.0 mol) of ethylenediamine and 87.1 g (0.5 mol) of dimethyl adipate were charged, and kept at an internal temperature of 110 ° C. for 6 hours. The methanol removal reaction was performed for an hour. After completion of the reaction, water was added to obtain 194.2 g of a 60% aqueous solution of polyamide.

Synthesis Example 10

In a container similar to that used in Synthesis Example 4, 103.2 g (1.0 mol) of diethylenetriamine, 60.1 g (1.0 mol) of ethylenediamine, and 202.3 g of sebacic acid
g (1.0 mol) was charged, and the dehydration amidation reaction was performed for 5 hours while maintaining the internal temperature at 150 to 155 ° C. After the completion of the reaction, water was added to obtain 549.3 g of a 60% aqueous solution of polyamide.

Embodiment 1

225 g of the aqueous resin solution obtained in Synthesis Example 1
Then, 9.3 g of the aqueous solution of polyamide obtained in Synthesis Example 4 (5% as polyamide relative to the resin solid content) was added, the pH was adjusted to 6.5 with sulfuric acid, and 1.9 g of water was further added. 5
A 0% aqueous solution of a polyamide-containing resin having a viscosity of 198 cps was obtained. The polyamide-containing resin aqueous solution thus obtained was added to the master color shown in Table 1 at a ratio of 0.5 part of solids in the polyamide-containing resin aqueous solution per 100 parts of the pigment.

[0086]

[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.

Examples 2 to 12

A polyamide-containing resin aqueous solution was prepared in the same manner as in Example 1 except that the types and amounts of the resin aqueous solution and the polyamide were changed. Table 2 summarizes the types and mixing ratios of the water-soluble resin and the polyamide, and the physical properties of the obtained polyamide-containing resin aqueous solution together with those in Example 1. Further, the polyamide-containing resin aqueous solution thus obtained was added to the master color shown in Table 1 at a ratio of 0.5 part of solids in the resin aqueous solution per 100 parts of the pigment in the same manner as in Example 1.

[0089]

[Table 2]

Embodiment 13

The resin aqueous solution obtained in Synthesis Example 1 and Synthesis Example 4
At a weight ratio of 90: 4 (a weight ratio of solids: 95: 5) to the master color shown in Table 1, and the total solid content of both was 0.5 per 100 parts of pigment.
Parts were added separately so as to give a ratio of parts.

Preparation of Coating Composition and Measurement of Physical Properties Each of the compositions prepared in Examples 1 to 13 was
Each was adjusted with water and a 10% aqueous sodium hydroxide solution so that the total solid content was 60% and the pH was about 9.0. The physical properties of the obtained coating compositions were measured by the following methods, and the results are shown in Tables 3 and 4.

(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, it 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, and further subjected to a super calender treatment twice at a temperature of 60 ° C. and a linear pressure of 60 kg / cm. 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 Tables 3 and 4. In addition,
The test method is as follows.

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

(4) Ink acceptability (4-1) Method A Using an RI tester, printing was performed after the coated surface was wet with a water supply roll, 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 water was kneaded into the ink, and the ink receptivity was visually observed and judged. The judgment criteria were as follows. Ink acceptability (poor) 1-5 (excellent)

[0100]

[Table 3]

[0101]

[Table 4] ^* Polyamide addition method A: Add after pre-mixing in resin aqueous solution B: Add independently of resin aqueous solution

Comparative Examples 1-4

Using the master color used in the previous example and the respective resin aqueous solutions obtained in Synthesis Examples 1 to 3,
In Comparative Examples 1 to 3, in each of Comparative Examples 1 to 3, the master aqueous solution shown in Table 1 was prepared by adding the aqueous resin solutions obtained in Synthesis Examples 1 to 3 to the master color shown in Table 1 at a ratio of 0.5 part by solid content. Was added. In Comparative Example 4, the master colors shown in Table 1 were used as they were.

For each of the compositions thus obtained, the solid content and the pH were adjusted in the same manner as in the above Examples, and then a coated paper was prepared using each of the coating compositions. Was tested. The test results are shown in Table 5.

[0105]

[Table 5]

[0106]

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.

────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshifumi Yoshida 3-1-198 Kasuganaka, Konohana-ku, Osaka Sumitomo Chemical Industries, Ltd. (56) References JP-A-7-34398 (JP, A) Kaihei 4-100997 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) D21H 19/00-27/42

Claims (11)

(57) [Claims] (I) a pigment, (II) an aqueous binder, (III) at least (a) an alkylenediamine or polyalkylenepolyamine, (b) a urea, and (c) an aldehyde, an epihalohydrin and α, γ- Dihalo-β-
A water-soluble resin obtained by reacting three components of a compound selected from hydrins, and (IV) a paper containing a polyamide obtained by reacting a dibasic carboxylic acid compound with a polyamine. Coating composition. 2. The water-soluble resin (III) comprises (a) an alkylenediamine or a polyalkylenepolyamine, (b) ureas, (c) aldehydes, epihalohydrins 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 composition according to claim 2, wherein the dibasic carboxylic compound of component (d) is a free acid, ester or acid anhydride. 4. The water-soluble resin (III) comprises (a) an alkylenediamine or a polyalkylenepolyamine, (b) ureas, (c) aldehydes, epihalohydrins 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 water-soluble resin (III) comprises (a) an alkylenediamine or a polyalkylenepolyamine, (b) ureas, (c) aldehydes, epihalohydrins 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 polyamide (IV) is a polyamide obtained by reacting a dibasic carboxylic acid compound with an alicyclic diamine. 7. The composition according to claim 1, wherein the polyamide (IV) is a polyamide obtained by reacting an alicyclic dibasic carboxylic acid compound with a polyamine. 8. The composition according to claim 1, wherein the polyamide (IV) is a polyamide obtained by reacting an aromatic dibasic carboxylic acid compound with a polyamine. 9. The composition according to claim 1, wherein the polyamide (IV) is a polyamide obtained by reacting an aliphatic dibasic carboxylic acid compound having 4 or more carbon atoms with a polyamine. 10. The composition according to claim 1, wherein the dibasic carboxylic acid compound used to obtain the polyamide (IV) is a free acid, ester or acid anhydride. 11. An aqueous binder (II) is added in an amount of 5 to 200 parts by weight and a water-soluble resin (III) in an amount of 0.05 to 5 parts by weight, based on 100 parts by weight of the pigment (I). 1) to 90% by weight of polyamide (IV) based on the weight of solids
The composition according to any one of claims 1 to 10, which comprises: