JPH09286856A - Water-soluble polyamide/polyurea resin and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating composition which scarcely emits formaldehyde and can give high-quality coated paper, for example, coated paper having high ink receptivity and high water resistance and to provide a water-soluble resin useful therefor. SOLUTION: This resin is obtained by reacting at least a polyamine selected among alkylenediamines and polyalkylenepolyamines, a urea, a dibasic carboxylic compound, a lactam, and a crosslinking compound selected among epihalohydrins, α,γ-dihalo-β-hydrins, glycidyl compounds and isocyanates. The resin may be reacted with an alicyclic compound. It is useful for coating paper and mixed with a pigment and a water-based binder to form a paper coating composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-soluble resin useful for coating paper, particularly for coating paper by mixing it with a pigment and an aqueous binder, and its application to paper coating. is there. More specifically, the present invention aims to provide a paper coating composition which does not generate formaldehyde and can impart excellent printability and printing effect to paper, and a water-soluble resin useful for the same. The term "paper" used in the present specification has a broad sense, and includes paper and paperboard in a narrow sense.

[0002]

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 topics, and blister resistance in rotary printing are important issues for the industry. Has become.

To solve these problems, melamine-formaldehyde resin, urea-formaldehyde resin, polyamide polyurea-formaldehyde resin as disclosed in JP-B-44-11667, JP-A-63-120197.
There is known a method of adding a block glyoxal resin or the like as disclosed in Japanese Patent Laid-Open Publication No. 2003-242242 as a waterproofing agent or an additive for a binder. However, these conventional waterproofing agents and additives for binders all have effective merits, but on the other hand, serious defects or insufficient effects are observed in some properties, and therefore, they are not always satisfactory in practice. Not a thing.

[0004] For example, so-called 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 improve ink acceptability and blister resistance. That they have little effect,
When the pH of the coating composition is increased, there is a problem that the water resistance effect is hardly exhibited. On the other hand, block glyoxal resin, which is known as an additive for formaldehyde-free binders, can impart water resistance to dampening water to some extent, but it is almost impossible to improve the quality of coated paper such as ink acceptability and blister resistance. has no effect.

[0005]

SUMMARY OF THE INVENTION The object of the present invention is to improve the quality of coated paper by satisfying the requirements for the quality of coated paper and imparting high ink acceptability and water resistance to the paper. The present invention is to provide a coating composition for paper which is capable of producing no particular formaldehyde.

Another object of the present invention is to provide a formaldehyde-free water-soluble resin or paper coating resin useful for such a paper coating composition.

The inventors of the present invention have conducted extensive studies to solve such problems, and as a result, have found that a water-soluble resin obtained by reacting a specific component is useful for coating paper, and containing this resin. It was found that the paper coating composition to give excellent performance to paper, and furthermore, if this water-soluble resin is used in combination with a specific amide compound, even better performance is given to paper. The present invention has been completed and the present invention has been completed.

[0008]

That is, the present invention is to provide at least a polyamine (a) selected from alkylenediamines and polyalkylenepolyamines, ureas (b), dibasic carboxylic acid compound (c), lactam. (D) and epihalohydrins, α, γ-dihalo-β-hydrins, water-soluble resin (A) obtained by reacting five components of a crosslinkable compound (e) selected from glycidyl compounds and isocyanates It is provided.

The water-soluble resin (A) is the above polyamine (a),
In addition to the ureas (b), the dibasic carboxylic acid compound (c), the lactams (d) and the crosslinkable compound (e), other components may be reacted. For example, an alicyclic compound (f) selected from an alicyclic amine having at least one active hydrogen and an alicyclic epoxy compound can be reacted.

The water-soluble resin (A) is useful for coating paper, and therefore the present invention also provides a paper coating resin containing the water-soluble resin (A) as an active ingredient. Water-soluble resin (A)
When used for paper coating, it can be used alone or in addition to other resin components such as α, β-unsaturated carboxylic acid compound (x) and amine having a primary or secondary amino group. It can also be used as a mixture or a reaction product of the two in combination with the amide compound (B) obtained by reacting (y).

The paper coating resin containing the water-soluble resin (A) as an active ingredient is particularly effective when applied to a paper coating composition containing a pigment and an aqueous binder. Therefore, the present invention further comprises (I) a pigment, (II) an aqueous binder, and (II)
I) A coating composition for paper containing the water-soluble resin (A) is also provided.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The water-soluble resin (A) is a polyamine (a) selected from alkylenediamines and polyalkylenepolyamines, ureas (b), dibasic carboxylic acid compounds.
(c), lactams (d) and epihalohydrins,
It is obtained by reacting at least five components of the crosslinkable compound (e) selected from α, γ-dihalo-β-hydrins, glycidyl compounds and isocyanates.

Polyamine used for producing water-soluble resin (A)
(a) is a compound that has two secondary amino groups and is bonded to each other by an alkylene in which a secondary amino group may be present. Specific examples thereof include ethylenediamine,
Alkylenediamines such as 1,2-propanediamine, 1,3-propanediamine, hexamethylenediamine, and diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, iminobispropylamine, and 3-azahexane-1 , 6-Diamine, 4,7-diazadecane-1,10
-Polyalkylene polyamines such as diamines. Among these, diethylenetriamine and triethylenetetramine are industrially advantageous. These polyamines (a) can be used alone or in combination of two or more.

The ureas (b) are usually urea having an atomic group represented by the formula --NHC (= Q) NHR and its derivatives, wherein Q represents oxygen or sulfur, and R represents hydrogen or a carbon number of 1. ~ 4
Represents a degree of alkyl. Specific examples of ureas (b) include:
For example, urea, thiourea, guanylurea, methylurea,
Dimethylurea and the like can be mentioned. Urea (b)
Can be used alone or in combination of two or more. From an industrial point of view, urea is preferably used. The ureas (b) are the primary and secondary compounds in the polyamine (a).
It is used in an amount of generally from 0.3 to 1 mole, preferably from 0.5 to 1 mole, based on the total amount of primary amino groups.

The dibasic carboxylic acid compound (c) is a compound having two carboxyl groups in the molecule or a compound derived therefrom, and examples thereof include free acids, esters,
It can be an acid anhydride or the like. The dibasic carboxylic acid compound (c) may be aliphatic, aromatic or alicyclic.

Examples of the free dibasic carboxylic 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, terephthalic acid, and 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 mentioned. Incidentally, when the alicyclic group has an unsaturated bond, and the position of the unsaturated bond is not clearly indicated,
It should be understood that the position of the unsaturated bond is arbitrary, and the same applies to the following description.

The dibasic carboxylic acid compound (c) may be, in addition to these free acids, esters thereof, acid anhydrides and the like. 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-methyltetrahydrophthalic anhydride, and 3- or 4-methylhexahydrohydrogen. And phthalic anhydride.

Polyesters, which are reaction products of dibasic carboxylic acids and glycols, are also advantageously used, but those having free carboxyl groups 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, and ethylene oxide adducts of bisphenol A. 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.

These dibasic carboxylic acid compounds (c)
May be used alone or in combination of two or more. The dibasic carboxylic acid compound (c) is
The polyamine (a) is used in an amount of generally 0.1 to 1 mol, preferably 0.2 to 0.8 mol, per 1 mol.

The lactams (d) are cyclic compounds having an atomic group of -CONH- in the ring, and for example, those generally used in industry such as ε-caprolactam and lauryllactam are preferably used. . Lactams (d)
Is generally 0.01 with respect to 1 mol of the polyamine (a).
It is used in the range of up to 0.3 mol, preferably in the range of 0.03 to 0.2 mol.

The crosslinkable compound (e) is an epihalohydrin, α, γ-dihalo-β-hydrin, glycidyl compound or isocyanate. Epihalohydrins of the crosslinkable compound (e) 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 in combination of two or more.

The α, γ-dihalo-β-hydrins of the crosslinkable compound (e) 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 and the like.

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

The isocyanates in the crosslinkable compound (e) also usually have at least two isocyanato groups in the molecule. Specific examples thereof include isophorone diisocyanate, 3- (2-isocyanatocyclohexyl) propyl isocyanate, bis (isocyanatomethyl) cyclohexane, isopropylidenebis (cyclohexyl isocyanate), transcyclohexane-
Alicyclic isocyanates such as 1,4-diisocyanate and bicycloheptane triisocyanate, hexamethylene diisocyanate, trimethylhexane-1,6
Aliphatic isocyanates such as diisocyanate, methyl 2,6-diisocyanatohexanoate (also called lysine diisocyanate), and tolylene diisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, phenylene diisocyanate; Aromatic isocyanates such as dianisidine diisocyanate and diphenyl ether diisocyanate are exemplified.

These crosslinkable compounds (e) can be used alone or in combination of two or more kinds.
Of course, epihalohydrins, α, γ-dihalo-β-
Among hydrins, glycidyl compounds and isocyanates, two or more of them belonging to different types can be used in combination. The crosslinking compound (e) is generally used in the range of 0.1 to 2 mol, preferably 0.2 to 1 mol, based on 1 mol of the polyamine (a).

In the present invention, polyamine (a), ureas (b), dibasic carboxylic acid compound (c), lactams
The water-soluble resin (A) is obtained by reacting at least five components of (d) and the crosslinkable compound (e). The water-soluble resin (A) is, in addition to the above polyamine (a), ureas (b), dibasic carboxylic acid compound (c), lactams (d) and crosslinkable compound (e), It may be one obtained by reacting the components of. For example, an alicyclic compound (f) selected from an alicyclic amine having at least one active hydrogen and an alicyclic epoxy compound can be reacted.

Among the alicyclic compounds (f), 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. Or an indirect bond with an 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'-dimethylbicyclohexyl, 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'-Sulfonebis (cyclohexylamine), 1,3,5-triaminocyclohexane, 2,
4'- or 4,4'-diamino-3,3 ', 5,5'-
Tetramethyldicyclohexylmethane, menthanediamine, N-methyl-1,3-diaminocyclohexane,
N, N-dimethyl-1,3-diaminocyclohexane,
3-N-methylamino-3,5,5-trimethylcyclohexylamine, N, N-dimethylbis (4-aminocyclohexyl) methane and the like.

The alicyclic epoxy compound of the alicyclic compounds (f) is usually a compound having an alicyclic ring having about 5 to 12 ring carbon atoms, preferably a cyclohexane ring, and further having an epoxy group. Yes, where the epoxy group is
Even if formed between adjacent carbon atoms in the alicyclic ring,
Further, it may be formed outside the alicyclic ring. An epoxy group outside the alicyclic ring may be directly bonded to the alicyclic ring, for example, a glycidyl group or a glycidyloxy group,
It can also be indirectly attached to the alicyclic ring, such as in the form of a glycidyloxycarbonyl group. 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) propane and the like.

When these alicyclic compounds (f) are used, they can be used alone or in combination of two or more kinds. As the alicyclic compound (f), it is possible to use alicyclic amine and alicyclic epoxy compound together. The alicyclic compound (f) is generally used in a proportion of 1 mol or less, preferably 0.5 mol or less, relative to 1 mol of the polyamine (a).

The order of the reaction for producing the water-soluble resin (A) is not particularly limited, but in general, polyamine (a), ureas (b), dibasic carboxylic acid compound (c) and lactams are generally used. After reacting (d) in any order, the crosslinkable compound
The method of reacting (e) is adopted. Alicyclic compound (f)
Can be used at any stage of these reactions.

The reaction order of the polyamine (a), the ureas (b), the dibasic carboxylic acid compound (c) and the lactams (d) is arbitrary, but among them, the ureas (b) are Alternatively, it is possible to charge them all at once to react them, or to charge a portion of the ureas (b) first to carry out the deammonification reaction, and then add the remaining ureas (b) at a later stage to carry out the deammonification reaction again. It is also possible to carry out the reaction in two steps. For example,
Polyamine (a) and dibasic carboxylic acid compound (c) are dehydrated or dealcoholized and reacted with lactams (d), or polyamine (a), dibasic carboxylic acid compound (c) And lactams (d) are simultaneously reacted,
A method of producing polyamide and then charging ureas (b) for deammonification condensation, a part of ureas (b) is subjected to deammonification condensation with polyamine (a), and then a dibasic carboxylic acid compound ( c) and lactams (d) in any order,
Or at the same time, dehydration or dealcohol condensation and ring-opening addition, and further deammonia condensation of the remaining ureas (b), polyamine (a) and dibasic carboxylic acid compound (c), urea (b) ) Is added to carry out dehydration or dealcoholization condensation and deammonification condensation, and at the same time, the lactams (d) are reacted, or the polyamine (a),
After the reaction of the urea (b) and the dibasic carboxylic acid compound (c) is completed, the lactam (d) is reacted, and then the remaining urea (b) is added to carry out deammonification condensation. Can be adopted.

The dehydration or dealcoholization condensation reaction is usually about 120 to 200 ° C., preferably 130 to 1
This is performed at a temperature of 80 ° C. for about 2 to 10 hours while removing generated water or alcohol from the system. The deammonification condensation reaction is usually carried out at a temperature of about 80 to 180 ° C., preferably 90 to 160 ° C. for about 1 to 18 hours while removing generated ammonia out of the system. Polyamine (a), ureas (b) and dibasic carboxylic acid compounds
When (c) is reacted at the same time, it is usually at a temperature of about 80 to 200 ° C., preferably 90 to 160 ° C., while removing generated ammonia and water or alcohol out of the system,
~ 18 hours. When the reaction of the lactam (d) is carried out separately, it is usually about 120 to 200 ° C, preferably 1
It is carried out at a temperature of 30 to 180 ° C. for about 1 to 15 hours, preferably about 5 to 10 hours.

The reaction of the polyamine (a), the ureas (b), the dibasic carboxylic acid compound (c) and the lactams (d) gives a polyamide polyurea, which is then crosslinked. It is subjected to reaction with the compound (e).

When epihalohydrins or α, γ-dihalo-β-hydrins are used as the crosslinkable compound (e), this reaction is usually carried out in an aqueous solution having a solid content concentration of about 10 to 80% by weight. Alkaline, for example, pH 7 or more, preferably pH 8 to 12, at a temperature of about 30 to 90 ° C. for about 1 to 10 hours. When a glycidyl compound or isocyanates is used as the crosslinkable compound (e), this reaction usually has a solid content concentration of 10 to 8
It is carried out in a 0% by weight aqueous solution at a temperature of about 30 to 100 ° C, preferably 40 to 90 ° C for about 1 to 10 hours, preferably about 3 to 8 hours. When two or more crosslinkable compounds (e) are used, these two or more crosslinkable compounds (e)
May be reacted together or may be reacted individually for each compound. When the reaction is performed for each compound, it is preferable to employ the above conditions for each reaction.

When the alicyclic compound (f) is reacted, if desired, this reaction can be carried out at any stage. For example, the alicyclic compound (f) is present at any stage of reacting the four components of the polyamine (a), the ureas (b), the dibasic carboxylic acid compound (c) and the lactams (d). By reacting these, polyamines can be reacted.
(a), urea (b), dibasic carboxylic acid compound (c) and lactam (d) after the reaction to produce polyamide polyurea, before the reaction with the crosslinkable compound (e) It is possible to react the alicyclic compound (f), or in the step of reacting the polyamide polyurea with the crosslinkable compound (e),
These can also be reacted by allowing the alicyclic compound (f) to be present. When the alicyclic compound (f) is an alicyclic amine, this alicyclic amine is deammonia-condensed with a partial amount of the ureas (b) in advance, and then the polyamine (a) and the ureas are further condensed. It is also possible to react with the residual amount of (b) and the lactam (d). The deammonification condensation reaction between the ureas (b) and the alicyclic amine is usually performed at a temperature of about 80 to 180 ° C., preferably 90 to 160 ° C. for 2 to 18 hours while removing the generated ammonia out of the system. Degree is done. When the alicyclic compound (f) is an alicyclic epoxy compound, the alicyclic epoxy compound is previously subjected to an addition reaction with the polyamine (a), and the alicyclic epoxy compound is added to the dibasic carboxylic acid compound (c) and It can also be used for the reaction of lactams (e) and further ureas (b). The addition reaction between the polyamine (a) and the alicyclic epoxy compound is usually carried out at a temperature of about 30 to 100 ° C, preferably 40 to 90 ° C for about 1 to 10 hours.

The water-soluble resin (A) thus obtained is useful for paper coating. The water-soluble resin (A) can be used alone for paper coating, and can also be used as a mixture or reaction product with the specific amide compound (B). The amide compound (B) used here is obtained by reacting an α, β-unsaturated carboxylic acid compound (x) with an amine (y).

The α, β-unsaturated carboxylic acid compound (x), which is the starting material for the amide compound (B), can be used in the form of esters, acid anhydrides, etc. in addition to the free acid. Specifically, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, itaconic acid, itaconic anhydride, crotonic acid, methyl crotonic acid, etc. may be mentioned.

The amine (y), which is the other raw material of the amide compound (B), is a compound having a primary or secondary amino group in the molecule, but one having 4 or more carbon atoms is preferable, and among them, Particularly preferred are those having 4 or more carbon atoms and having at least 2 amino groups in the molecule. 2 amino groups
When there are two or more, at least one may be a primary or secondary amino group, and may have a tertiary amino group in addition. Specific examples of the amine (y) include those exemplified as the polyamine (a) and those exemplified as the alicyclic amine among the alicyclic compounds (f), butylamine, pentylamine, hexylamine, heptylamine, 2-ethylhexylamine, octylamine, benzylamine, diisopropylamine, monoamines such as N-methylbenzylamine, N-ethylethylenediamine, N, N
-Dimethyl-1,3-propanediamine, N-methylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, diamines such as xylylenediamine, and N-ethyliminobisethylamine, N-methyliminobis Included are polyamines such as propylamine, N, N-dimethylaminoethylethylenediamine.

The amide compound (B) is a mixture of an α, β-unsaturated carboxylic acid compound (x) and an amine (y), usually 100 to 2
At a temperature of about 50 ° C., preferably 130 to 200 ° C., while removing generated water or alcohol out of the system, 2 to 2
It can be obtained by reacting for about 0 hours.
In addition, a method in which both raw material compounds are reacted at 10 to 80 ° C. for about 1 to 5 hours and then the temperature is raised to 100 to 250 ° C. and the distillate is removed, and the reaction is further performed for about 2 to 15 hours. preferable. An acid catalyst such as sulfuric acid or phosphoric acid may be used in this reaction. α, β-Unsaturated carboxylic acid compounds
It is preferable to use (x) in an amount of about 0.2 to 0.5 mole times the total amount of primary and secondary amino groups of the amine (y). The amide compound (B) is such that its 70% by weight aqueous solution has a viscosity at 25 ° C. of 1 to 100 P, especially 5 to 500.
The one having P is preferable.

When the amide compound (B) thus obtained is used as a reaction product with the water-soluble resin (A), this reaction is usually
It is carried out at a temperature of about 0 to 100 ° C. for about 1 to 10 hours. The crosslinkable compound (e) constituting the water-soluble resin (A) is an epihalohydrin or α, γ-dihalo-β-hydrin, and the water-soluble resin (A) is reacted with an amide compound (B) to produce paper. When used as a coating resin, this water-soluble resin (A) is
It may be formed when the amide compound (B) reacts. For example, before introduction into the reaction system with the amide compound (B), epihalohydrins or α, γ-dihalo-β-
A water-soluble resin (A) containing a hydrin as a constituent may be formed in advance, and for example, in a reaction system with an amide compound (B), an epihalohydrin or α, γ-dihalo-
A water-soluble resin (A) containing β-hydrin as a constituent may be formed. In the latter case, without using epihalohydrins or α, γ-dihalo-β-hydrins,
Or using a part of the final required amount thereof, at least polyamine (a), urea (b), dibasic carboxylic acid compound
(c) and the lactams (d) are reacted, and then the amide compound (B) and the remaining amount of epihalohydrins or α, γ-
The water-soluble resin (A) can be formed by further proceeding the reaction in the reaction system containing the dihalo-β-hydrins.

The paper coating resin containing the water-soluble resin (A) as an active ingredient is usually mixed with a pigment and an aqueous binder to give a paper coating composition. The pigment that is a component of this paper coating composition may be one that has been generally used for paper coating, and a white inorganic pigment and a white organic pigment 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, and urea-formaldehyde resin. These pigments may be used alone or in combination of two or more. Furthermore, a colored inorganic or organic pigment can be used in combination.

The water-based binder may also be one conventionally used for coating paper, and a water-soluble binder or a water-emulsified binder can be used. Examples of the water-soluble binder include, for example, unmodified or modified starches including oxidized starch and phosphate esterified starch, polyvinyl alcohol, water-soluble proteins including casein and gelatin, and carboxymethyl cellulose. And modified celluloses. Examples of the water-emulsifying binder include styrene-butadiene resin, vinyl acetate resin, ethylene-vinyl acetate resin, methyl methacrylate resin and the like. These aqueous binders can be used alone or in combination of two or more.

In preparing the coating composition for paper, the composition ratio of the pigment and the aqueous binder is determined according to the application and purpose, but is not particularly different from the composition generally adopted in the art. The preferable composition ratio of both is Pigment 1
The amount of the aqueous binder is about 5 to 200 parts by weight, more preferably about 10 to 50 parts by weight, based on 00 parts by weight. The resin component consisting of the water-soluble resin (A) alone or a mixture or reaction product of the water-soluble resin (A) and another compound, for example, an amide compound (B), is a solid content based on 100 parts by weight of the pigment. The amount is preferably about 0.05 to 5 parts by weight, more preferably about 0.1 to 2 parts by weight. Water-soluble resin
When the mixture or reaction product of (A) and the amide compound (B) is used as the resin component, the amide compound (B) is contained in the range of about 1 to 90% by weight, and further 3% by weight based on the solid content weight of the resin component. It is preferably in the range of about 80% by weight.

In preparing the coating composition for paper, the order of addition and mixing of the pigment, the aqueous binder and the resin component is arbitrary and is not particularly limited. For example, the following method can be adopted. When the water-soluble resin (A) is used alone as a resin component, the water-soluble resin is added to and mixed with the pigment and the aqueous binder, and the water-soluble resin is previously added and mixed with the pigment slurry or the aqueous binder. It is possible to employ a method of blending with the remaining ingredients. Water-soluble resin
When (A) is mixed with the amide compound (B) to form a resin component, a method of previously mixing the water-soluble resin (A) and the amide compound (B), and then adding and mixing this to the pigment and the aqueous binder, Method of adding and mixing the water-soluble resin (A) and the amide compound (B) individually to the pigment and the aqueous binder, water-soluble resin
One or both of (A) and the amide compound (B) may be added to and mixed with the pigment slurry or the aqueous binder, and all the components may be mixed in the stage of preparing the coating composition. Further, when the water-soluble resin (A) is reacted with the amide compound (B) to form a resin component, a method of adding and mixing the reaction product to a pigment and an aqueous binder, the reaction product in advance into a pigment slurry or an aqueous binder. A method of adding and mixing and then blending this with the rest of the components can be adopted.

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. A colorant such as the above can be blended as necessary.

The coating composition for paper of the present invention is 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. Is applied to the 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.

[0051]

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 representing the content or the amount used are based on weight unless otherwise specified. Also, viscosity and p
H is a value measured at 25 ° C. First, an example of synthesizing the water-soluble resin (A) according to the present invention will be shown.

Synthesis Example 1: A four-necked flask equipped with a thermometer, a reflux condenser and a stir bar was charged with 232.4 g (1 mol) of pentaethylenehexamine and 73.1 g (0.5 mol) of adipic acid, A dehydration amidation reaction was performed by heating at an internal temperature of 140 to 160 ° C. for 5 hours while removing generated water out of the system. Next, the internal temperature is lowered to 120 ° C., 6.8 g (0.06 mol) of ε-caprolactam is charged, and the internal temperature is 140 to 16
The ring-opening addition reaction was performed by heating at 0 ° C. for 5 hours. There,
264.3 g (4.4 mol) of urea and 139.6 g of water were charged, and the deammonification reaction was carried out for 12 hours while keeping the internal temperature at 90 to 110 ° C. Thereafter, the internal temperature was lowered to 40 ° C., 27.8 g (0.3 mol) of epichlorohydrin and 201.4 g of water were charged, and the reaction was carried out at an internal temperature of 70 ° C. for 4 hours. Further adjust the pH and concentration with sulfuric acid and water, 60% concentration, pH 7.
861.9 g of a water-soluble resin aqueous solution having a viscosity of 250 cP was obtained.

Synthetic Example 2: 92.9 g (0.4 mol) of pentaethylenehexamine and 43.8 g (0.3 mol) of adipic acid were charged into the same reaction vessel as used in Synthetic Example 1, and the internal temperature was adjusted. A dehydration amidation reaction was carried out by heating at 140 to 160 ° C. for 5 hours while removing generated water out of the system. Next, the internal temperature was lowered to 120 ° C., and ε-caprolactam 5.7 g (0.0
(5 mol) was charged and heated at an internal temperature of 140 to 160 ° C. for 5 hours to carry out a ring-opening addition reaction. 78.1g of urea there
(1.3 mol) and 52.4 g of water were charged, and the internal temperature was 90 to 1.
Deammonification reaction was carried out for 12 hours while keeping at 10 ° C. After that, the internal temperature was lowered to 40 ° C, and epichlorohydrin was 27.8 g.
(0.3 mol), resorcin diglycidyl ether 44.4
g (0.2 mol) and water 120.8 g are charged, and the internal temperature is 70
The reaction was performed at 4 ° C. for 4 hours. Further, the pH and the concentration were adjusted with sulfuric acid and water to obtain 452.4 g of a water-soluble resin aqueous solution having a concentration of 60%, a pH of 7.0 and a viscosity of 760 cP.

Synthesis Example 3: 139.4 g (0.6%) of pentaethylenehexamine was placed in a reaction vessel similar to that used in Synthesis Example 1.
Mol) and 43.8 g (0.3 mol) of adipic acid,
A dehydration amidation reaction was performed by heating at an internal temperature of 140 to 160 ° C. for 5 hours while removing generated water out of the system. Next, lower the internal temperature to 120 ℃, 4.1 g of ε-caprolactam
(0.036 mol) was charged, and the internal temperature was 140-160 ° C for 5
After heating for a period of time, ring-opening addition reaction was performed. There, urea 1
44.2 g (2.4 mol) and 80.2 g of water were charged, and the deammonification reaction was carried out for 12 hours while keeping the internal temperature at 90 to 110 ° C. Then, the internal temperature was lowered to 40 ° C., 66.7 g (0.3 mol) of resorcin diglycidyl ether and 150.8 g of water were charged, and the reaction was carried out at an internal temperature of 70 ° C. for 4 hours. Further, adjust the pH and concentration with sulfuric acid and water to obtain a concentration of 60%, pH
599.1 g of a water-soluble resin aqueous solution having a viscosity of 340 cP and 7.0 was obtained.

Synthesis Example 4: In a reaction vessel similar to that used in Synthesis Example 1, 75.7 g (0.4 mol) of tetraethylenepentamine, 9.9 g (0.1 mol) of cyclohexylamine, and isophthalic acid were used. 41.5 g (0.25 mol) was charged, and a dehydration amidation reaction was performed by heating at an internal temperature of 140 to 160 ° C. for 5 hours while removing generated water outside the system. Next, the internal temperature was lowered to 80 ° C., 5.7 g (0.05 mol) of ε-caprolactam and 6 g (0.1 mol) of urea were simultaneously charged, and the mixture was further heated at an internal temperature of 140 to 160 ° C. for 5 hours, The ring-opening addition reaction and the deammonification reaction were performed simultaneously. There urea 6
Charge 6.1 g (1.1 mol) and 49.0 g of water, and set the internal temperature to 9
Deammonification reaction was carried out for 12 hours while maintaining at 0 to 110 ° C. Then, the internal temperature was lowered to 40 ° C., and 26.1 g (0.15 mol) of ethylene glycol diglycidyl ether and 8 parts of water were added.
4.3 g was charged and the reaction was carried out at an internal temperature of 70 ° C. for 4 hours. Further, adjust the pH and concentration with sulfuric acid and water to obtain a concentration of 60
%, PH 7.0, viscosity 580 cP water-soluble resin aqueous solution 35
5.3 g were obtained.

Synthesis Example 5: A reaction vessel similar to that used in Synthesis Example 1 was charged with 117 g (0.8 mol) of triethylenetetramine and 44.4 g (0.3 mol) of phthalic anhydride.
At the internal temperature of 140 to 160 ° C., the produced water was removed from the system and heated for 5 hours to carry out a dehydration amidation reaction. Next, the internal temperature was lowered to 120 ° C, and lauryl lactam was 7.9 g.
(0.04 mol) was charged and the ring-opening addition reaction was carried out by heating at an internal temperature of 140 to 160 ° C. for 5 hours. There, urea 12
0.1 g (2 mol) and 71 g of water were charged, and the internal temperature was 90-
Deammonification reaction was carried out for 12 hours while maintaining at 110 ° C.
Thereafter, the internal temperature was lowered to 40 ° C., 50.5 g (0.3 mol) of hexamethylene diisocyanate and 129.3 g of water were charged, and the reaction was carried out at an internal temperature of 70 ° C. for 4 hours. Further adjust the pH and concentration with sulfuric acid and water, concentration 60%, pH 7.0,
355.3 g of a water-soluble resin aqueous solution having a viscosity of 490 cP was obtained.

Next, an example of synthesizing the amide compound (B) is shown.

Synthesis Example 6: A four-necked flask equipped with a thermometer, a Liebig condenser, a dropping funnel, and a stirring rod was charged with 232 g (2 mol) of hexamethylenediamine, while maintaining the system temperature at 40 to 50 ° C. , Methyl methacrylate 150
g (1.5 mol) was added dropwise over 1 hour, and further 60 to 7
After reacting at 0 ℃ for 1 hour, the internal temperature is 120 ~ 150 ℃
As the above, the reaction was carried out for 5 hours while distilling methanol. After completion of the reaction, add water to give a concentration of 70% and a viscosity of 74P.
477.1 g of an aqueous solution of the amide compound was obtained.

Synthesis Example 7: A reaction vessel similar to that used in Synthesis Example 6 was charged with 204 g (2 mol) of N, N-dimethyl-1,3-propanediamine, and further 86 g (1 mol) of methyl acrylate. To prepare 100-130 in the system.
While maintaining the temperature at 0 ° C, the reaction was carried out for 5 hours while distilling methanol. After completion of the reaction, water was added to obtain 368.5 g of an aqueous solution of an amide compound having a concentration of 70% and a viscosity of 7.3P.

Synthetic Example 8: Into the same reaction vessel as used in Synthetic Example 6 was charged 170.3 g (1 mol) of isophoronediamine, and while maintaining the temperature in the system at 60 to 80 ° C., 80% thereto. 45.0 g (0.5 mol) of an aqueous acrylic acid solution was added dropwise, and after completion of the addition, the mixture was kept at 60 to 80 ° C. for 1 hour for reaction. Next, a dehydration amidation reaction was performed by heating at an internal temperature of 140 to 160 ° C. for 5 hours. After the reaction, add water,
Aqueous solution of amide compound with concentration 70% and viscosity 54.3P 28
1.9 g was obtained.

Synthesis Example 9: 198.4 g (2 mol) of cyclohexylamine was charged in the same reaction vessel as used in Synthesis Example 6, and the temperature in the system was kept at 60 to 80 ° C.
86.1 g (1 mol) of methyl acrylate was added dropwise, and after completion of the addition, the mixture was kept at 60 to 80 ° C. for 1 hour for reaction.
Next, the internal temperature was kept at 140 to 160 ° C., and the reaction was carried out for 5 hours while distilling methanol. After completion of the reaction, water was added to obtain 360.6 g of a 70% concentration suspension of the amide compound.

Synthetic Example 10: 60.1 g (1 mol) of ethylenediamine was charged in the same reaction vessel as used in Synthetic Example 6, and the temperature in the system was kept at 60 to 80 ° C. to 80%.
45.0 g (0.5 mol) of an aqueous acrylic acid solution was added dropwise, and after completion of the addition, the mixture was kept at 60 to 80 ° C. for 1 hour for reaction. Next, the internal temperature was maintained at 140 to 160 ° C., and the reaction was carried out for 5 hours while distilling water. After the reaction was completed, water was added to the mixture to prepare an amide compound aqueous solution having a concentration of 70% and a viscosity of 5.1 P.
24.4 g was obtained.

Synthesis Example 11: In a reaction vessel similar to that used in Synthesis Example 6, 172.3 g (1
Mol) and keeping the temperature in the system at 60 to 80 ° C.,
45.0 g (0.5 mol) of 80% acrylic acid aqueous solution was added dropwise, and after completion of the addition, the mixture was kept at 60 to 80 ° C. for 1 hour for reaction. Next, the internal temperature was maintained at 140 to 160 ° C., and the reaction was carried out for 5 hours while distilling water. After completion of the reaction, water was added to obtain 284.7 g of an aqueous solution of an amide compound having a concentration of 70% and a viscosity of 50.5P.

Next, the water-soluble resin (A) and the amide compound (B)
An example of synthesizing the reaction product of

Synthesis Example 12: An approximately 60% aqueous solution of resin having a concentration of about 60% before pH adjustment was synthesized in the same manner as in Synthesis Example 1 in a four-necked flask equipped with a thermometer, a reflux condenser and a stirring rod.
g, 70% aqueous solution of the amide compound obtained in Synthesis Example 8 16.2
g and 2.8 g of water were charged and reacted at 60 to 70 ° C. for 2 hours. Finally, the pH and concentration were adjusted with sulfuric acid and water to obtain a resin component aqueous solution having a concentration of 60%, pH 7.0 and a viscosity of 300 cP.

Synthetic Example 13: In a reaction vessel similar to that used in Synthetic Example 12, 170.5 g of a resin aqueous solution having a concentration of about 60% before pH adjustment, which was synthesized in the same manner as in Synthetic Example 1, was synthesized.
36.5 g of a 70% aqueous solution of the amide compound obtained in 1. and 6.2 g of water were charged and reacted at 60 to 70 ° C for 2 hours. Finally, adjust the pH and concentration with sulfuric acid and water to a concentration of 60%,
An aqueous resin component solution having a pH of 6.9 and a viscosity of 340 cP was obtained.

Synthetic Example 14: In a reaction vessel similar to that used in Synthetic Example 12, 170.5 g of a resin aqueous solution having a concentration of about 60% before pH adjustment, which was synthesized in the same manner as in Synthetic Example 1, was synthesized.
Charged 16.2 g of a 70% aqueous solution of the amide compound obtained in 1., 1.9 g of epichlorohydrin and 4.1 g of water at 60 to 80 ° C.
For 4 hours. Finally, the pH and concentration were adjusted with sulfuric acid and water to obtain a resin component aqueous solution having a concentration of 60%, pH 7.0 and a viscosity of 380 cP.

Synthesis Example 15: 192.5 g of a resin aqueous solution having a concentration of about 60% before pH adjustment, which was synthesized in the same manner as in Synthesis Example 3, was placed in the same reaction vessel used in Synthesis Example 12.
A 70% aqueous solution of the amide compound obtained in 1 above (18.3 g) and water (3.0 g) were charged, and the mixture was reacted at 60 to 70 ° C. for 2 hours. Finally, adjust the pH and concentration with sulfuric acid and water to a concentration of 60%,
An aqueous resin component solution having a pH of 7.0 and a viscosity of 400 cP was obtained.

Synthetic Example 16: 144.4 g of a resin aqueous solution having a concentration of about 60% before pH adjustment, which was synthesized in the same manner as in Synthetic Example 3, was placed in the same reaction vessel as that used in Synthetic Example 12.
13.8 g of a 70% aqueous solution of the amide compound obtained in 1 and 2.1 g of water were charged and reacted at 60 to 70 ° C for 2 hours. Finally, adjust the pH and concentration with sulfuric acid and water to a concentration of 60%,
An aqueous resin component solution having a pH of 7.0 and a viscosity of 410 cP was obtained.

Synthesis Example 17: 125.2 g of a resin aqueous solution having a concentration of about 60% before pH adjustment, which was synthesized in the same manner as in Synthesis Example 5, was placed in the same reaction vessel used in Synthesis Example 12.
11.9 g of a 70% aqueous solution of the amide compound obtained in 1. and 1.9 g of water were charged and reacted at 60 to 70 ° C for 2 hours. Finally, adjust the pH and concentration with sulfuric acid and water to a concentration of 60%,
An aqueous resin component solution having a pH of 7.0 and a viscosity of 540 cP was obtained.

Next, an example is shown in which a coating composition for paper is prepared and evaluated using each compound or resin obtained in the above synthesis example. In the following examples, master colors having the compositions shown in Table 1 were used.

[0072]

[Table 1]

(Footnote in Table 1) ^{* 1} Ultra White 90: Clay made by Engelhard Minerals, Inc. ^{* 2} Carbital 90: Calcium carbonate made by Fuji Kaolin Co., Ltd. ^{* 3} Sumirez Resin DS-10: Sumitomo Chemical Co., Ltd. ) Polyacrylic acid pigment dispersant ^{* 4} SN-307: Sumika ABS Latex Co., Ltd. styrene-butadiene latex ^{* 5} Oji Ace A: Oji National Co., Ltd. oxidized starch ^{* 6} Mixing ratio: solid content Percentage by weight

Application Examples 1 to 5: To the master color shown in Table 1, the water-soluble resin aqueous solution obtained in each of Synthesis Examples 1 to 5 was added to 100 parts of the pigment, and the solid content of the aqueous solution was 0.5. It was added in a ratio of 5 parts. Each composition was adjusted with water and a 10% aqueous solution of caustic soda to give a total solid content of 60% and a pH of about 9, thereby obtaining a coating composition. The physical properties of the obtained coating compositions were measured by the following methods, and the results are shown in Table 2.

(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 Kogyo KK].

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

Each of the coating compositions obtained above was applied to one side of a high-quality paper having a basis weight of 80 g / m ² using a wire rod so that the coating amount was 14 g / 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. 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 pick method (WP method) Using an RI tester (manufactured by Akira Seisakusho Co., Ltd.), the coated surface was wetted with a water supply roll and then printed, and the peeled state was visually observed. It was 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 acceptability of the ink 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)

[0081]

[Table 2]

Application Example 6: The 60% water-soluble resin aqueous solution obtained in Synthesis Example 1 and the 70% aqueous solution of the amide compound obtained in Synthesis Example 6 were adjusted so that the amide compound content was 10% in terms of solid content. After mixing, the pH and concentration were adjusted with water and sulfuric acid to obtain a resin component aqueous solution having a concentration of 60%, pH 7.0 and a viscosity of 280 cP. This aqueous resin component solution was added to a master color having the composition shown in Table 1 so that the solid content in the aqueous resin component solution was 0.5 part per 100 parts of the pigment therein.

Application Examples 7 to 22: Physical properties shown in these tables were the same as in Application Example 6 except that the kinds and amounts of the water-soluble resin and the amide compound were changed as shown in Tables 3 and 4, respectively. An aqueous solution of a resin component having the above was prepared and further added to the master color at the same ratio as in Application Example 6.

For each of the compositions obtained in Application Examples 6 to 22 described above, the total solid content concentration and pH were adjusted in the same manner as in Application Examples 1 to 5, and then the respective coating compositions were applied. A coated paper was prepared by using the same, and the same test was conducted. The results are shown in Tables 3 and 4. The amount of the amide compound in Tables 3 and 4 represents the weight ratio of the amide compound to the total solid content in the resin component aqueous solution which is a mixture of the water-soluble resin and the amide compound, and is a value calculated by the following formula. Is.

[0085]

[0086]

[Table 3]

[0087]

[Table 4]

Application Examples 23 to 28: To the master color shown in Table 1, per 100 parts of the pigment therein, Synthesis Example 12 to.
Each of the aqueous resin component solutions obtained in Step 17 was added so that the solid content therein was 0.5 parts. For each of the obtained compositions, the solid content concentration and pH were adjusted in the same manner as in Application Examples 1 to 5, and then coated paper was prepared using each coating composition, and the same test was conducted. I went. Table 5 shows the results.

[0089]

[Table 5]

Comparative Synthesis Example 1: A four-necked flask equipped with a thermometer, a reflux condenser and a stirring bar was charged with 435 g of a 40% aqueous glyoxal solution (3 mol as glyoxal), which was kept at 16 ° C. with stirring. Heurea 60g
(1 mol) was added, and then the temperature was raised to 45 ° C. over 1 hour. After further maintaining the temperature at 45 ° C for 4.5 hours and confirming that the pH did not change, cool to 20 ° C, then add 0.85 g of 50% caustic soda aqueous solution and 3.5 g of water to obtain a solid content. An aqueous solution of block glyoxal resin having a pH of 46.9 and a pH of 6.9 was obtained.

Comparative Synthesis Example 2: 406 g of a 40% aqueous glyoxal solution was placed in the same container as used in Comparative Synthesis Example 1.
(Glyoxal as 2.8 mol) was charged, 60 g (1 mol) of urea was added thereto with stirring at 15 ° C., and the temperature was raised to 46 ° C. over 1 hour. After further keeping the temperature at 46 ° C for 4 hours, it was cooled to 20 ° C, and then 4 g of 10% caustic soda aqueous solution was added to obtain a solid content of 47.3.
%, PH 6.0, an aqueous solution of block glyoxal resin was obtained.

Comparative Synthesis Example 3: In a container similar to that used in Comparative Synthesis Example 1, 464 g of 40% aqueous glyoxal solution was added.
(3.2 mol as glyoxal) was charged, 60 g (1 mol) of urea was added thereto while stirring at 12 ° C., and then the temperature was raised to 44 ° C. over 1 hour. After further maintaining the temperature at 44 ° C for 4 hours, it was cooled to 20 ° C, and then 4 g of 10% caustic soda solution was added to give a solid content of 46.5.
%, PH 6.0, an aqueous solution of block glyoxal resin was obtained.

Comparative Application Examples 1-4: Comparative Synthesis Example 1 to 100 parts of pigment in the master color shown in Table 1.
Compositions of Comparative Application Examples 1 to 3 were prepared by adding the resin aqueous solutions obtained in Examples 1 to 3 so that the solid content was 0.5 parts. In Comparative Application Example 4, the master colors shown in Table 1 were used as they were. After adjusting the solid content concentration and pH of each composition in the same manner as in the above-mentioned application example, coated paper was prepared using each coating composition, and the same test was conducted. The results are shown in Table 6.

[0094]

[Table 6]

[0095]

INDUSTRIAL APPLICABILITY The water-soluble resin of the present invention is useful for coating paper and does not contain formaldehyde. Therefore, there is no fear of formaldehyde generation during paper coating work or from coated paper. The paper coating composition prepared by blending this water-soluble resin gives a coated paper showing various improved performances such as excellent ink acceptability and water resistance. Further, by using this water-soluble resin in combination with a specific amide compound, a coated paper showing further improved performance can be obtained.

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[Procedure amendment]

[Submission date] September 3, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0013

[Correction method] Change

[Correction contents]

Polyamine used for producing water-soluble resin (A)
(a) is a compound that has two primary amino groups and is bonded to each other by an alkylene in which a secondary amino group may be present. Specific examples thereof include ethylenediamine,
Alkylenediamines such as 1,2-propanediamine, 1,3-propanediamine, hexamethylenediamine, and diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, iminobispropylamine, and 3-azahexane-1 , 6-Diamine, 4,7-diazadecane-1,10
-Polyalkylene polyamines such as diamines. Among these, diethylenetriamine and triethylenetetramine are industrially advantageous. These polyamines (a) can be used alone or in combination of two or more.

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Sonoe Sato 3-1-198 Kasuganaka, Konohana-ku, Osaka Sumitomo Chemical Co., Ltd.

Claims (6)

[Claims] 1. A polyamine (a) selected from at least alkylenediamines and polyalkylenepolyamines.
, Ureas (b), dibasic carboxylic acid compounds (c), lactams (d), and crosslinkable compounds selected from epihalohydrins, α, γ-dihalo-β-hydrins, glycidyl compounds and isocyanates A water-soluble resin obtained by reacting the five components of (e). 2. The water-soluble resin according to claim 1, wherein the dibasic carboxylic acid compound (c) is a free acid, ester or acid anhydride. 3. The water-soluble resin according to claim 1, which is further reacted with an alicyclic compound (f) selected from an alicyclic amine having at least one active hydrogen and an alicyclic epoxy compound. . 4. A paper coating resin containing the water-soluble resin (A) according to any one of claims 1 to 3 as an active ingredient. 5. An amide compound (B) obtained by reacting an α, β-unsaturated carboxylic acid compound (x) with an amine (y) having a primary or secondary amino group. The resin for paper coating according to claim 4, which is a mixture or reaction product of the water-soluble resin (A) and the amide compound (B). 6. An (I) pigment, (II) an aqueous binder, and
(III) A paper coating composition comprising the paper coating resin according to claim 4 or 5.