JPH0987996A - Coating composition for paper - Google Patents

Abstract

(57) [Abstract] [PROBLEMS] To provide a paper coating composition capable of improving the quality of a coated paper by, for example, imparting a high degree of ink acceptability and water resistance to the paper. SOLUTION: A paper coating composition containing the following components (I) to (III). (I) pigment, (II) aqueous binder, and (III) at least, (a) an amine selected from alkylenediamine and polyalkylenepolyamine, (b) ureas,
And (c) aldehydes, epihalohydrins and α,
A water-soluble resin (A) obtained by reacting three components of a compound selected from γ-dihalo-β-hydrins, and (x) α, β
A resin component which is a mixture or a reaction product with an aminonitrile compound (B) obtained by reacting two components of an unsaturated nitrile compound and (y) a primary or secondary amino compound.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD 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 that can impart excellent printability and printing effect to paper.

The term "paper" used in this specification has a broad sense, and includes paper and paperboard in a narrow sense.

[0003]

2. Description of the Related Art A coated paper obtained by applying a coating composition mainly composed of a pigment and an aqueous binder to paper and performing necessary treatments such as drying and calendering is characterized by its excellent printing effect. Therefore, it is widely used in commercial printed matter, magazines, books, etc., but with the sophistication of quality requirements and the speeding up of printing, efforts to improve the quality of coated paper are still ongoing. Especially in offset printing, which accounts for the majority of printing, improvements and improvements in ink acceptability under the influence of dampening water, water resistance such as wet picking, and blister resistance in rotary printing are important issues in the industry. There is.

Conventionally, melamine-formaldehyde resin, urea-formaldehyde resin, or polyamide polyurea-formaldehyde resin,
For example, there is known a method of adding a water resistance agent, a printability improving agent and the like as shown in JP-B-44-11667 and JP-B-59-32597. However, while these conventional waterproofing agents, printability improvers, etc. all have effective characteristics, some of them have serious drawbacks or insufficient effects, so they are not always practically satisfactory. Not profitable.

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 acceptability and blister resistance. However, there is a problem in that the water resistance effect is difficult to be exhibited when the pH of the coating composition is high. Polyamide-polyurea formaldehyde resin is effective not only for improving water resistance but also for improving ink acceptability and blister resistance, but the degree of improvement is not sufficient for the recent demand for higher quality coated paper. I didn't want to say that. Therefore, efforts have been made to further improve the quality, and further improvements have been attempted by, for example, JP-A-62-104995, JP-A-4-100997, and JP-A-4-263696. However, with the sophistication of the demand for coated paper quality thereafter,
There is a need for higher performance.

[0006]

It is an object of the present invention to meet the demand for coated paper quality and to impart a higher degree of ink acceptability and blister resistance to paper, and to further improve coated paper quality. An object of the present invention is to provide a paper coating composition that can be improved in quality.

As a result of intensive studies for solving the above problems, the present inventors have found that a composition containing a mixture or reaction product of a specific water-soluble resin and a specific compound is superior to paper. The present invention has been completed by finding that it imparts performance.

[0008]

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

(I) pigment, (II) aqueous binder, and (III) at least (a) an amine selected from alkylenediamines and polyalkylenepolyamines, (b) ureas, and (c) aldehydes, epihalohydrins and α , A water-soluble resin (A) obtained by reacting three components of a compound selected from γ-dihalo-β-hydrins, (x) α, β-unsaturated nitrile compound, and (y) primary or 2 A resin component which is a mixture or reaction product with an aminonitrile compound (B) obtained by reacting two components of a primary amino compound.

The water-soluble resin (A) is the amine
In addition to (a), ureas (b) and compound (c), other components, for example, dibasic carboxylic acid compound (d), alicyclic amine having at least one active hydrogen and / or It may be one obtained by reacting an alicyclic epoxy compound (e) or the like.

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

[0012]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Pigments to be used as components of paper coating compositions
(I) may be those generally used in the past for paper coating, and white inorganic pigments and white organic pigments can be used.
Examples of white inorganic pigments include kaolin, talc, calcium carbonate (heavy or light), aluminum hydroxide, satin white, titanium oxide and the like. Examples of the white organic pigment include polystyrene, melamine-formaldehyde resin, urea-formaldehyde resin and the like. These pigments can be used alone or in combination of two or more. Furthermore, a colored inorganic or organic pigment can be used together.

The water-based binder (II) may also be one conventionally used for coating paper, and a water-soluble binder or a water-emulsion type binder can be used.
Examples of the water-soluble binder include, for example, unmodified or modified starches such as oxidized starch and phosphate esterified starch, water-soluble proteins such as polyvinyl alcohol, casein and gelatin, and carboxymethyl cellulose. Modified celluloses to be used. In addition, as a water-emulsified binder,
For example, styrene-butadiene resin, vinyl acetate resin,
Examples thereof include ethylene-vinyl acetate resin and methyl methacrylate resin. These aqueous binders may be used alone or in combination of two or more.

In the present invention, a specific resin component (III) is used in addition to the pigment (I) and the aqueous binder (II). The resin component (III) is a mixture or reaction product of the water-soluble resin (A) and the aminonitrile compound (B).

The water-soluble resin (A) is (a) an amine selected from alkylenediamines and polyalkylenepolyamines,
It is obtained by reacting at least three components of (b) ureas and (c) aldehydes, epihalohydrins and compounds selected from α, γ-dihalo-β-hydrins. When the water-soluble resin (A) forms a reaction product with the aminonitrile compound (B), the water-soluble resin (A) may be formed when the aminonitrile compound (B) reacts. For example, the water-soluble resin (A) may be formed in advance before being introduced into the reaction system with the aminonitrile compound (B), and, for example, the water-soluble resin (A) may be dissolved in the reaction system with the aminonitrile compound (B). The resin (A) may be formed. In the latter case, the compound (c) is not used or a part thereof is used to react with the amine (a) or urea (b), and then the compound (c) is used.
It is possible to employ a method in which the water-soluble resin (A) is formed by further reacting in the system in which the rest of (c) and the aminonitrile compound (B) are added.

Amine (a) used for producing the water-soluble resin (A)
Examples of ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, aliphatic diamines such as hexamethylenediamine, and diethylenetriamine, triethylenetetramine, tetraethylenepentamine, iminobispropylamine, 3 -Azahexane-1,6-diamine, 4,7-diazadecane-1,10
-Polyalkylene polyamines such as diamines. Among these, diethylenetriamine and triethylenetetramine are industrially advantageous. Amine
(a) can be used alone or in combination of two or more kinds.

Examples of ureas (b) include urea, thiourea, guanylurea, methylurea and dimethylurea. The ureas (b) can also be used alone or in combination of two or more. From an industrial point of view, urea is preferably used. The amount of the ureas (b) used is generally 0.3 to 1 mol, preferably 0.5 to 1 mol, per 1 mol of the amino group in the amine (a).

Examples of the aldehydes in the compound (c) include alkylaldehydes such as formaldehyde, acetaldehyde and propylaldehyde, alkylenedialdehydes such as glyoxal, propanedial and butanedial. Industrially, formaldehyde and glyoxal are preferred.
These aldehydes can be used alone or in combination of two or more.

Epihalohydrins are represented by the following general formula.

[0020]

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 in combination of two or more.

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

[0023]

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

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 kinds. For example,
Aldehydes and epihalohydrins can be used in combination, or aldehydes and α, γ-dihalo-β can be used.
-Hydrins can be used in combination, or aldehydes, epihalohydrins and α, γ-dihalo-β-hydrins can be used in combination. The amount of the compound (c) used is generally 0.1 to 2 mol, preferably 0.2 to 1 mol, per 1 mol of the amine (a).

The water-soluble resin (A) used in the present invention can be obtained by reacting at least three components of the amine (a), ureas (b), and compound (c) as described above. Further, the water-soluble resin (A) may be one obtained by reacting other components in addition to these three components. As the additional reaction component preferably used, a dibasic carboxylic acid compound (d) and an alicyclic compound (e) selected from an alicyclic amine and an alicyclic epoxy compound having at least one active hydrogen are Can be mentioned.

The dibasic carboxylic acid compound (d) is a compound having two carboxyl groups in the molecule or a compound derived therefrom, and examples thereof include free acids, esters and acid anhydrides. it can.

Dibasic carboxylic acids include aliphatic, aromatic,
It may be either alicyclic. Examples of the free acid include aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid and fumaric acid, aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid, and tetrahydro Phthalic acid, hexahydrophthalic acid, cyclohexane-1,3- or -1,4
Alicyclic dicarboxylic acids such as dicarboxylic acids, cyclopentanedicarboxylic acids, 3- or 4-methyltetrahydrophthalic acid, 3- or 4-methyltetrahydrophthalic acid, endomethylenetetrahydrophthalic acid. In addition, when the alicyclic group has an unsaturated bond and the position of the unsaturated bond is not specified, the position of the unsaturated bond should be understood to be arbitrary, and also in the following description. It is the same.

As the dibasic carboxylic acid compound (d), in addition to these free dibasic carboxylic acids, their esters, acid anhydrides and the like can also be used. Examples of the esters include mono- or di-esters of the above free acids and lower alcohols, and polyesters of the above free acids and glycols. Specific examples of the acid anhydride include succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3- or 4-methylhexahydrophthalic anhydride, 3- or 4-methyltetrahydrophthalic anhydride. , Endomethylene tetrahydrophthalic anhydride and the like.

Polyesters, which are the reaction products of dibasic carboxylic acids and glycols, are also advantageously used, but those having free carboxyl groups are preferred.
Examples of glycols used here include alkylene glycols such as ethylene glycol, propylene glycol, butanediol and neopentyl glycol, cyclopentanediol, cyclohexanediol, cycloalkylene glycols such as cyclohexanedimethanol, butenediol and octenediol. Examples include alkenylene glycols, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, polyalkylene glycols such as polytetramethylene glycol, ethylene oxide adducts of bisphenol A, ethylene oxide adducts of hydrogenated bisphenol A, and the like. can do. In the reaction between dibasic carboxylic acid and glycols,
If the reaction is carried out at a carboxylic acid excess molar ratio, 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. Dibasic carboxylic acid compound
The amount of (d) used is generally 1 mol or less, preferably 0.5 mol or less, relative to 1 mol of the amine (a).

Among the alicyclic compounds (e), the alicyclic amine having at least one active hydrogen usually has 5 ring carbon atoms.
A compound having at least about 12 alicyclic rings, preferably a cyclohexane ring, and at least one primary or secondary amino group, wherein the amino group is directly bonded to the alicyclic ring. Or 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, N-methylcyclohexylamine, 1,3- or 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-aminopropylcyclohexylamine, 1,5- or 2,6-
Bis (aminomethyl) octahydro-4,7-methanoindene, 2,2-bis (4-aminocyclohexyl) propane, bis (4-aminocyclohexyl) methane,
4,4'-oxybis (cyclohexylamine), 4,
4'-sulfone bis (cyclohexylamine), 1,
3,5-triaminocyclohexane, 2,4'- or 4,4'-diamino-3,3 ', 5,5'-tetramethyldicyclohexylmethane, menthanediamine, N-methyl-1,3-diaminocyclohexane, Examples thereof include N, N-dimethyl-1,3-diaminocyclohexane, 3-N-methylamino-3,5,5-trimethylcyclohexylamine and N, N-dimethylbis (4-aminocyclohexyl) methane. When these alicyclic amines are used, they can be used alone or in combination of two or more.

The alicyclic epoxy compound of the alicyclic compound (e) is usually an alicyclic ring having about 5 to 12 ring carbon atoms, preferably an epoxy group directly or indirectly bonded to 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, 3- (3 , 4-epoxycyclohexyl)-
8,9-Epoxy-2,4-dioxaspiro [5.5]
Undecane, diglycidyl hexahydrophthalate,
2,2-bis (4-glycidyloxycyclohexyl)
Examples include propane. Also when these alicyclic epoxy compounds are used, they can be used alone or in combination of two or more kinds.

As the alicyclic compound (e), alicyclic amine and alicyclic epoxy compound may be used in combination. The amount of the alicyclic compound (e) used is generally 1 mol or less, preferably 0.5 mol or less, relative to 1 mol of the amine (a).

The water-soluble resin (A) in the present invention is obtained by reacting the above-mentioned three components of amine (a), urea (b) and compound (c), or optionally further other components, For example, it can be obtained by reacting the dibasic carboxylic acid compound (d) and / or the alicyclic compound (e).

Water-soluble resin (A) suitable for use in the present invention
Are, for example, amine (a), ureas (b), compound (c),
And, if desired, by reacting the alicyclic compound (e). The order of reaction of each component is arbitrary and is not particularly limited.
A mode can be adopted in which (a) and ureas (b) are subjected to a deammonification reaction, and then compound (c) is reacted.
When the alicyclic compound (e) is used, if desired, one or more alicyclic compounds (e) may be reacted during the reaction and / or the reaction.

In the reaction (1), the ureas (b) may be charged all at once to react, or a part of the ureas (b) may be initially charged and reacted with the amine (a), The remaining ureas (b) are added to carry out the deammonification reaction.
It is also possible to employ a stepwise reaction. When aldehydes are used as the compound (c) in the reaction (1), it is preferable to carry out the reaction under acidic conditions, or to carry out the reaction once under alkaline conditions and then carry out the reaction under acidic conditions.
On the other hand, when epihalohydrins and / or α, γ-dihalo-β-hydrins are used as the compound (c), they are weakly acidic or alkaline, for example, pH 5 or more, further pH.
It is preferable to carry out the reaction in the range of 6 to 9. Further, when the water-soluble resin (A) forms a reaction product with the aminonitrile compound (B), the reaction of, for example, after the reaction of, first charging a part of the compound (c) and reacting, Then, the rest of the compound (c) can be added together with the aminonitrile compound (B) and further reacted in the system, or after the reaction of, all of the compound (c) is amino-containing. It is also possible to add it together with the nitrile compound (B) and carry out the reaction in the system.

These reactions can be carried out according to known methods. For example, amine (a), ureas
The reaction of (b) and compound (c) is known from JP-A No. 4-100997 and can be carried out according to the method described therein.

Another water-soluble resin (A) suitable for use in the present invention is amine (a), urea (b), compound (c),
It can be obtained by reacting the dibasic carboxylic acid compound (d) and, if desired, the alicyclic compound (e). Again, the order of reaction of each component is arbitrary and is not particularly limited, and for example, amine (a), ureas (b) and dibasic carboxylic acid compound (d) can be used in any order. It is possible to employ a mode in which the polyammonium polyurea is produced by subjecting it to a deammonification reaction and dehydration condensation, and then reacting the compound (c). When the alicyclic compound (e) is used if desired, one or more alicyclic compounds (e) may be reacted during the reaction and / or the reaction.

Also in the reaction in this case, ureas
(b) can be charged all at once to react, or a portion of ureas (b) can be charged first to carry out the deammonification reaction, and the remaining ureas (b) can be added at a later stage and re-reacted. It is also possible to adopt a two-step method of performing a deammonification reaction. For example, dehydration condensation of amine (a) and dibasic carboxylic acid compound (d), and then addition of ureas (b) for deammonia reaction, part of ureas (b) being amine
After deammonia reaction with (a), dibasic carboxylic acid compound (d) is dehydrated and condensed, and the remaining ureas
Method of adding ammonia (b) to deammonia reaction, amine (a)
And a method of performing a dehydration condensation and a deammonification reaction by adding a part of the urea (b) to the dibasic carboxylic acid compound (d) and further adding the remaining urea (b) to perform a deammonification reaction. Can be adopted. Also in the other reaction, when aldehydes are used as the compound (c), it is preferable to carry out the reaction under acidic conditions, or to carry out the reaction once under alkaline conditions and then carry out the reaction under acidic conditions. On the other hand, as the compound (c), epihalohydrins and / or α, γ-
When using dihalo-β-hydrins, it is preferable to carry out the reaction in a weakly acidic or alkaline manner, for example, at a pH of 5 or higher, more preferably in the range of 6 to 9. Also in this case, the reaction in the case where the water-soluble resin (A) forms a reaction product with the aminonitrile compound (B), for example, after the reaction of, first, a part of the compound (c) is charged and reacted. Next compound
It can be carried out by adding the rest of (c) together with the aminonitrile compound (B) and further reacting in the system, or after the reaction of, all of the compound (c) is converted to the aminonitrile compound ( It is also possible to add together with B) and carry out the reaction in the system.

These reactions can also be carried out according to known methods. For example, amine (a), ureas
(b), compound (c) and dibasic carboxylic acid compound (d)
The reaction described in JP-A-55-31837 and JP-A-57-167315
JP-A No. 62-104995, JP-A No. 62-125092, JP-A No. 62-125093, etc. are known, and the methods described therein can be used. Further, in addition to the amine (a), the urea (b), the compound (c) and the dibasic carboxylic acid compound (d), an alicyclic compound is further added.
The reaction in the case of using (e) is known from JP-A-2-216297 and JP-A-2-221498, and can be carried out according to the methods described therein.

In the present invention, the water-soluble resin (A) as described above is used as a mixture or a reaction product with the specific aminonitrile compound (B). The aminonitrile compound (B) used here is an α, β-unsaturated nitrile compound (x)
It is obtained by reacting with a primary or secondary amino compound (y).

Examples of the α, β-unsaturated nitrile compound (x) used as a raw material for the aminonitrile compound (B) include acrylonitrile and methacrylonitrile.

The primary or secondary amino compound (y), which is the other starting material for the aminonitrile compound (B), has 1
Although it is a compound having a secondary or secondary amino group, a compound having two or more amino groups is preferable, and a compound having four or more carbon atoms and two or more amino groups is particularly preferable. When there are two or more amino groups, those having a tertiary amino group in addition to the primary or secondary amino group are also preferable. Specific examples of the amino compound (y) include water-soluble resins.
The compounds exemplified as the amine (a) used for the synthesis of (A) and the compounds exemplified as the alicyclic amine in the alicyclic compound (e) are included. Furthermore, butylamine,
Pentylamine, hexylamine, heptylamine, 2
-Ethylhexylamine, octylamine, benzylamine, diisopropylamine, monoamines such as N-methylbenzylamine, N-ethylethylenediamine,
Diamines such as N, N-dimethyl-1,3-propanediamine, N-methylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine and xylylenediamine, and N-ethyliminobisethylamine, N
Also included are polyamines such as -methyliminobispropylamine, N, N-dimethylaminoethylethylenediamine.

The aminonitrile compound (B) is obtained by combining the α, β-unsaturated nitrile compound (x) with a primary or secondary amino compound.
(y) and 0 to 100 in the presence or absence of a solvent.
It can be obtained by reacting at 0 ° C, preferably 20 to 80 ° C for about 1 to 10 hours. The amount of the α, β-unsaturated nitrile compound (x) used is based on the active hydrogen constituting the primary and secondary amino groups in the primary or secondary amino compound (y).
Generally, it is preferably 0.2 to 2 times by mole, more preferably 0.4 to 1 times by mole.

Water-soluble resin (A) and aminonitrile compound
According to the invention, (B) is used as the resin component (III) in the form of a mixture or reaction product of the two. The reaction product of the water-soluble resin (A) and the aminonitrile compound (B) contains 2
It can be obtained by reacting at 0 to 100 ° C. for about 1 to 10 hours. As mentioned above, water-soluble resin
Part or all of the compound (c) of the constituent components of (A) is
When the aminonitrile compound (B) is reacted, it can be simultaneously reacted.

The paper coating composition of the present invention contains the pigment (I), the aqueous binder (II) and the resin component (III) described above. In preparing the coating composition for paper,
The composition ratio of the pigment (I) and the aqueous binder (II) is determined according to the application or purpose, and is not particularly different from the composition generally adopted in the art. The preferable composition ratio of both is based on 100 parts by weight of the pigment (I) and the aqueous binder (I
I) is about 5 to 200 parts by weight, more preferably 10 to 50
It is about parts by weight. The resin component (III) is a pigment (I) 10
The solid content is preferably about 0.05 to 5 parts by weight, and more preferably about 0.1 to 2 parts by weight, based on 0 parts by weight. Resin component (III) is water-soluble resin (A)
In the case of a mixture of the aminonitrile compound (B) with
The aminonitrile compound (B) is preferably blended in the range of 1 to 90% by weight, and more preferably in the range of 3 to 80% by weight, based on the solid content weight of the resin component (III). More preferable. Resin component (III) is a water-soluble resin
Also in the case of the reaction product of (A) and the aminonitrile compound (B),
The use ratio of both can be the same as in the case of the above mixture.

In preparing the paper coating composition, a pigment is used.
The order of addition and mixing of (I), the aqueous binder (II) and the resin component (III) is arbitrary and is not particularly limited, but for example, the following method can be adopted. That is, when a mixture of the water-soluble resin (A) and the aminonitrile compound (B) is used as the resin component (III), both components are mixed in advance, and this is mixed with the pigment slurry and the aqueous binder. Method, without mixing both components in advance, a method of mixing with a pigment slurry and an aqueous binder, at least one of the resin component (III) is previously added and mixed into the pigment slurry or the aqueous binder,
Examples thereof include a method of mixing this with the remaining components. When the reaction product of the water-soluble resin (A) and the aminonitrile compound (B) is used as the resin component (III), the reaction product is mixed with the pigment slurry and the aqueous binder, and the reaction product is previously prepared. Examples thereof include a method in which the pigment slurry or the aqueous binder is added and mixed, and this is mixed with the remaining components.

Other components of the paper coating composition of the present invention include, for example, a dispersant, a viscosity / fluidity adjusting agent, an antifoaming agent, an antiseptic, a lubricant, a water retention agent, and a dye / colored pigment. Such colorants and the like can be blended as necessary.

The paper coating composition of the present invention uses various conventionally 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. The method is applied to a paper substrate. After that, necessary drying is performed, and if necessary, smoothing treatment is performed with a super calendar or the like, whereby a coated paper can be manufactured.

Thus, according to the present invention, the pigment is obtained by additionally using the specific aminonitrile compound (B).
As compared with the case where the coating composition comprising (I), the aqueous binder (II) and the water-soluble resin (A) is used, a coated paper showing improved performance can be obtained.

[0052]

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,% and parts indicating the content or the addition amount are based on weight unless otherwise specified. Also viscosity and pH
Is a value measured at 25 ° C. First, the water-soluble resin (A) used in the examples was prepared according to the following Synthesis Examples 1 to 4. The aminonitrile compound (B) was prepared according to Synthesis Examples 5 to 11, and the reaction product of the water-soluble resin (A) and the aminonitrile compound (B) was prepared from Synthesis Examples 12 to 1.
Prepared according to 6.

Synthesis Example 1: Triethylenetetramine 1 was placed in a four-necked flask equipped with a thermometer, a reflux condenser and a stir bar.
46.2 g (1.0 mol) and urea 30.0 g (0.5 mol) were charged, and the internal temperature was kept at 150 to 160 ° C. to carry out the deammonification reaction for 5 hours. After that, 73.1 g of adipic acid (0.5
Mol) was charged and the dehydration amidation reaction was carried out for 5 hours while maintaining the internal temperature at 150 to 160 ° C. Next, the internal temperature was lowered to 130 ° C., and urea (10.1 g, 2.0 mol) was charged, and
The deammonification reaction was performed at 30 ° C. for 2 hours. Then 27
An aqueous resin solution was prepared by adding 0 g of water. In addition, 37% formalin (60.9 g, 0.75 mol) was charged, and the system was diluted with sulfuric acid to obtain p.
The H was adjusted to 4 to 5 and the reaction was carried out at an internal temperature of 70 ° C. for 4 hours.
Then adjust the pH to 6.5 and the concentration to 5 with sodium hydroxide solution.
Adjusted to 0%, water-soluble resin aqueous solution 67 with viscosity 140 cP
5 g was obtained.

Synthesis Example 2: 146.2 g (1.0 mol) of triethylenetetramine and 30.0 g (0.5 mol) of urea were charged in the same vessel as used in Synthesis Example 1, and the internal temperature was 120 to 1
A deammonification reaction was performed at 40 ° C. for 3 hours. Then, 77.1 g (0.5 mol) of hexahydrophthalic acid was charged, and a dehydration amidation reaction was carried out at an internal temperature of 150 to 160 ° C. for 5 hours.
Next, the internal temperature was lowered to 130 ° C., 120.1 g (2.0 mol) of urea was charged, and a deammonification reaction was performed at a temperature of 120 to 130 ° C. for 2 hours. After the reaction, cool to 100 ° C. and add water 27
An aqueous resin solution was prepared by adding 0 g. Then, 81.2 g (1.0 mol) of 37% formalin was added, and the pH of the system was adjusted to 5 with sulfuric acid.
Adjusted to. This is heated to 60 ° C., reacted for 5 hours, then cooled, neutralized with an aqueous sodium hydroxide solution, and adjusted to pH.
7. Water-soluble resin aqueous solution 688 with a concentration of 50% and a viscosity of 45 cP
g was obtained.

Synthesis Example 3: The same container used in Synthesis Example 1 was charged with 146.2 g (1.0 mol) of triethylenetetramine and 180.2 g (3.0 mol) of urea, and the internal temperature was 120-.
The deammonification reaction was performed at 140 ° C. for 2 hours. afterwards,
150 g of water was added to make an aqueous resin solution. Furthermore, 48.7 g (0.6 mol) of 37% formalin was added, and the internal temperature was 70 ° C for 4
After reacting for a time, adjust the pH of the system to 4.0 with sulfuric acid,
While keeping the internal temperature at 70 ° C. again, the reaction was carried out for 4 hours. After that, the pH was adjusted to 7 with an aqueous sodium hydroxide solution to obtain 506 g of a water-soluble resin aqueous solution having a concentration of 60% and a viscosity of 210 cP.

Synthetic Example 4: 146.2 g (1.0 mol) of triethylenetetramine was added to the same container used in Synthetic Example 1.
1,5- (or 2,6-) bis (aminomethyl) octahydro-4,7-methanoindene 48.6 g (0.25 mol), cyclohexene oxide 24.5 g (0.25 mol) and urea 60.1 g ( (1.0 mol), 150 ℃
Deammonia reaction is carried out for 2 hours, and then urea 120.1.
g (2.0 mol) was added, and a deammonification reaction was performed at 120 ° C. for 4 hours. Next, water was added to make an aqueous solution having a concentration of 70%. 37% formalin 60.9g (0.75mol)
Add pH, adjust the pH to 5 with sulfuric acid, and stir to 70
Hold at 2 ° C for 2 hours. Thereafter, the pH was adjusted to 7 with aqueous ammonia and water was added to obtain 553 g of a water-soluble resin aqueous solution having a concentration of 60% and a viscosity of 310 cP.

Synthesis Example 5: 154.8 g (1.5 mol) of diethylenetriamine and 203 g of water were charged in the same container used in Synthesis Example 1, and 318.4 g of acrylonitrile (318.4 g (while maintaining the system temperature at 40 to 50 ° C.). (6 mol) was added dropwise over 2 hours, and the mixture was further reacted at 70 to 80 ° C. for 4 hours to obtain 676 g of a 70% aqueous solution of an aminonitrile compound.

Synthesis Examples 6 to 11: Synthesis examples except that the primary or secondary amino compound and the α, β-unsaturated nitrile compound shown in Table 1 were used in the molar ratios shown therein and the amount of water was appropriately changed. The reaction was performed in the same manner as in 5 to obtain a 70% aqueous solution of the corresponding aminonitrile compound.

[0059]

[Table 1] ^{* 1} AN: Acrylonitrile MN: Methacrylonitrile ^{* 2} Molar ratio: Molar ratio of nitrile to active hydrogen of amine

Synthesis Example 12: 450 g of a water-soluble resin aqueous solution obtained in the same manner as in Synthesis Example 1 and 36 g of an amino nitrile compound aqueous solution obtained in the same manner as in Synthesis Example 5 were placed in the same container as used in Synthesis Example 1. After charging, the mixture was reacted at 60 to 70 ° C for 2 hours. Then adjust the pH to 7 and the concentration to 50% with sulfuric acid and water to obtain a viscosity of 200.
A resin component solution of cP was obtained.

Synthesis Examples 13 to 16: The reaction was performed in the same manner as in Synthesis Example 12 except that the water-soluble resin aqueous solution and the aminonitrile compound aqueous solution shown in Table 2 were used in the weight ratios shown therein, and the physical properties shown in Table 2 were obtained. A resin component liquid was obtained.

[0062]

[Table 2]

Example 1: To 95 g of the water-soluble resin aqueous solution obtained in Synthesis Example 1, 3.6 g of the aminonitrile compound aqueous solution obtained in Synthesis Example 5 and 1.4 g of water were added, and the pH was adjusted to 7 with sulfuric acid. A resin component liquid having a concentration of 50% and a viscosity of 150 cP was obtained.
The resin component liquid thus obtained was applied to the master colors shown in Table 3 and the solid content in the resin component liquid was 0.5 per 100 parts of the pigment.
It was added at a ratio of parts.

[0064]

[Table 3] ^{* 1} Ultra White 90: Clay manufactured by Engel Hard Minerals, Inc. in the US ^{* 2} Carbital 90: Calcium carbonate manufactured by Fuji Kaolin Co., Ltd. ^{* 3} Sumirez 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} Blending ratio: Expressed as a percentage by solid content.

Examples 2 to 14: Resin component liquids were prepared in the same manner as in Example 1 except that the kinds and amounts of the water-soluble resin and aminonitrile compound were changed. The types and blending amounts of the water-soluble resin and the aminonitrile compound, and the physical property values of the obtained resin component liquid are summarized in Table 4 together with those in Example 1. Further, the resin component liquid thus obtained was changed to the master color shown in Table 3 in the same manner as in Example 1,
The solid content in the resin component liquid was added at a ratio of 0.5 parts per 100 parts of the pigment.

[0066]

[Table 4] ^{* 1} Amount of amino nitrile compound = (weight of amino nitrile compound / weight of resin component) x 100 (same in each table below)

Examples 15 to 19: The resin component liquids obtained in Synthesis Examples 12 to 16 were mixed with the master components shown in Table 3 so that the solid content in the resin component liquid was 0.5 parts per 100 parts of the pigment. Added to the color.

Examples 20-24: Examples 1, 7, 9, 1
The water-soluble resin and the aminonitrile compound used in 1 and 14 were each alone without mixing them in advance at the ratios shown in Table 7, and the ratio of the total solid content of both resins was 0.5 parts per 100 parts of the pigment. To the master color shown in Table 3.

Preparation of coating composition and measurement of physical properties : Each of the compositions prepared in Examples 1 to 24 above contained water and 10% water so that the total solid content was 60% and the pH was about 9.
It was adjusted with an aqueous sodium hydroxide solution. For each coating composition obtained, the physical property values were measured by the following methods,
The results are shown in Tables 5-7.

(1) pH: The pH of the coating composition immediately after preparation was measured at 25 ° C. using a glass electrode type hydrogen ion concentration meter (manufactured by Toa Denpa Co., Ltd.).

(2) Viscosity: Using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd., BL type), the viscosity of the coating composition immediately after preparation was measured at 25 ° C. at 60 rpm and 25 ° C.

Preparation of coated paper : Each coating composition obtained as described above was applied to one side of a high-quality paper having a basis weight of 80 g / m ² with a wire rod to give a coated amount of 14 g. / M ²
It applied so that it might become. Immediately after application, at 120 ° C for 3
Dry with hot air for 0 seconds, then temperature 20 ℃, relative humidity 65%
Humidity control for 16 hours, temperature 60 ℃, linear pressure 60kg /
Super calendering was performed twice under the condition of cm to obtain coated paper.

Evaluation of physical properties of coated paper : The coated paper thus obtained was tested for water resistance and ink acceptability, and the test results are shown in Table 5.
7 are shown. The test method is as follows.

(3) Water resistance: Wet pick strength (WP
Method) Using a RI tester (manufactured by Akira Seisakusho Co., Ltd.), the coated surface was made to absorb water with a water-absorbing roll and then printed, and the state of paper peeling was visually observed and judged. The judgment criteria were as follows. Water resistance (poor) 1-5 (excellent)

(4) Ink acceptability (4-1) Method A Using a RI tester, the coated surface was made to absorb water with a water-absorbing 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, ink was printed while kneading water, and the ink acceptability was judged by observing with the naked eye. The judgment criteria were as follows. Ink acceptability (poor) 1-5 (excellent)

Comparative Examples 1 to 5: Using the master color used in the previous example and the respective water-soluble resin aqueous solutions obtained in Synthesis Examples 1 to 4, without adding an aminonitrile compound, In No. 4, to the master color shown in Table 3, the aqueous resin solutions obtained in Synthesis Examples 1 to 4 were added at a solid content of 0.5 parts per 100 parts of the pigment. Further, in Comparative Example 5, the master colors shown in Table 3 were used as they were.

After adjusting the solid content and pH of each composition thus obtained in the same manner as in the above-mentioned example, coated paper was prepared using each coating composition and The test was conducted. The test results are shown in Table 8.

[0079]

[Table 5] ^* Preparation method X: The water-soluble resin and the aminonitrile compound are directly mixed, but the reaction is not performed.

[0080]

[Table 6] ^* Preparation method X: The water-soluble resin and the aminonitrile compound are directly mixed, but the reaction is not performed. Y: A water-soluble resin is reacted with an aminonitrile compound.

[0081]

[Table 7] ^* Preparation method Y: A water-soluble resin is reacted with an aminonitrile compound. Z: Add the water-soluble resin and the aminonitrile compound individually to the master color without premixing.

[0082]

[Table 8]

[0083]

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

Front page continued (72) Inventor Ken Tanigawa 3-98 Kasugade, Konohana-ku, Osaka Sumitomo Chemical Co., Ltd.

Claims (8)

[Claims] 1. An (I) pigment, (II) an aqueous binder, and (III) at least (a) an amine selected from alkylenediamines and polyalkylenepolyamines, (b) ureas, and (c) aldehydes, epihalohydrins. And a water-soluble resin (A) obtained by reacting three components of a compound selected from α, γ-dihalo-β-hydrins, (x) α, β-unsaturated nitrile compound, and (y) primary Alternatively, a paper coating composition comprising a resin component which is a mixture or reaction product of an aminonitrile compound (B) obtained by reacting two components of a secondary amino compound. 2. The composition according to claim 1, wherein the resin component (III) is a mixture of the water-soluble resin (A) and the aminonitrile compound (B). 3. The composition according to claim 1, wherein the resin component (III) is a reaction product of the water-soluble resin (A) and the aminonitrile compound (B). 4. The water-soluble resin (A) is an amine selected from (a) alkylenediamine and polyalkylenepolyamine,
A compound obtained by reacting a compound selected from (b) ureas, (c) aldehydes, epihalohydrins and α, γ-dihalo-β-hydrins, and (d) a dibasic carboxylic acid compound. The composition according to any one of 1 to 3. 5. The composition according to claim 4, wherein the dibasic carboxylic acid compound (d) is a free acid, ester or acid anhydride. 6. The water-soluble resin (A) is (a) an amine selected from alkylenediamines and polyalkylenepolyamines,
(b) ureas, (c) compounds selected from aldehydes, epihalohydrins and α, γ-dihalo-β-hydrins, and (e) alicyclic amine and alicyclic epoxy having at least one active hydrogen The composition according to claim 1, which is obtained by reacting an alicyclic compound selected from the compounds. 7. The water-soluble resin (A) is an amine selected from (a) alkylenediamine and polyalkylenepolyamine,
(b) urea, (c) aldehydes, compounds selected from epihalohydrins and α, γ-dihalo-β-hydrins, (d) dibasic carboxylic acid compounds, and (e) at least one active hydrogen The composition according to any one of claims 1 to 3, which is obtained by reacting an alicyclic compound selected from an alicyclic amine and an alicyclic epoxy compound. 8. The aminonitrile compound (B) is (x) α, β
-The composition according to any one of claims 1 to 7, which is obtained by reacting an unsaturated nitrile compound and (y) a di- or poly-amino compound having two or more primary or secondary amino groups.