JP3309543B2 - Paper coating composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

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

[0003]

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

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

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

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

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

[0008]

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

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

[0010]

That is, the present invention provides the following four components: (I) a pigment, (II) an aqueous binder, (III) at least the following three components: (a) an alkylenediamine or a polyalkylenepolyamine; b) a urea, (c) a water-soluble resin obtained by reacting a compound selected from aldehydes, epihalohydrins and α, γ-dihalo-β-hydrins, and (IV) an organic quaternary ammonium salt. An object of the present invention is to provide a paper coating composition containing as a component.

The water-soluble resin (III) comprises the above-mentioned component (a),
(b) and (c) may be reacted, and in addition to components (a), (b) and (c), further components,
For example, a compound obtained by reacting a dibasic carboxylic acid compound, an alicyclic amine having at least one active hydrogen and / or an alicyclic epoxy compound may be used.

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

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

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

In the present invention, in addition to the pigment (I) and the aqueous binder (II), a specific water-soluble resin (III)
And an organic quaternary ammonium salt (IV).

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

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

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

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

Epihalohydrins are represented by the following general formula.

[0021]

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

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

[0024]

In the formula, X and Z represent a halogen atom,
Specific examples of the compound include 1,3-dichloro-2-propanol.

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

The above three components of alkylenediamine or polyalkylenepolyamine (a), ureas (b), and compound (c) selected from aldehydes, epihalohydrins and α, γ-dihalo-β-hydrins By reacting, the water-soluble resin (III) used in the present invention
Is obtained. Further, the water-soluble resin (III) in the present invention,
In addition to these three components, other components may be further reacted. Additional reaction components preferably used include 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. Can be

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

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

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

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

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

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

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

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

For example, water-soluble resins (III) suitable for use in the present invention include (a) alkylenediamines or polyalkylenepolyamines, (b) ureas, (c) aldehydes, epihalohydrins and α, γ- It can be obtained by reacting a compound selected from dihalo-β-hydrins and, if desired, (e) an alicyclic compound selected from an alicyclic amine having at least one active hydrogen and an alicyclic epoxy compound. it can.

In this case, the order of the reaction of each component is arbitrary and is not particularly limited. For example, an alkylenediamine or polyalkylene polyamine (a) and a urea (b) are subjected to a deammonification reaction, and then An embodiment may be adopted in which a compound (c) selected from aldehydes, epihalohydrins and α, γ-dihalo-β-hydrins is reacted. When an alicyclic amine and / or an alicyclic epoxy compound (e) is used, if desired, one or more of these compounds may be added during the reaction and / or the reaction. Just do it.

In the above reaction, urea (b) may be charged at once and reacted with alkylenediamine or polyalkylene polyamine (a), or a part of urea (b) may be charged first and reacted. After the reaction, the remaining urea (b) is added and the reaction is further carried out in two steps. When an aldehyde is used as the component (c) in the above reaction, it is preferable to carry out the reaction under acidic conditions, or to carry out the reaction once under alkaline conditions, and then to carry out the reaction under further acidic conditions. On the other hand, when epihalohydrins and / or α, γ-dihalo-β-hydrins are used as component (c), they are weakly acidic or alkaline, for example, pH 5
As described above, the reaction is preferably performed in the pH range of 6 to 9.

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

Other water-soluble resins (III) suitable for use in the present invention include (a) alkylenediamine or polyalkylenepolyamine, (b) ureas, (c) aldehydes,
Compounds selected from epihalohydrins and α, γ-dihalo-β-hydrins, (d) dibasic carboxylic acid compounds, and if desired, (e) alicyclic amines and alicycles having at least one active hydrogen It can be obtained by reacting an alicyclic compound selected from formula epoxy compounds.

Here, the order of the reaction of each component is arbitrary and is not particularly limited. For example, alkylene diamine or polyalkylene polyamine (a), urea (b) and dibasic carboxylic acid compound (d) is subjected to a deammonification reaction and dehydration condensation in an arbitrary order to produce a polyamide polyurea, and then an aldehyde,
An embodiment may be employed in which a compound (c) selected from epihalohydrins and α, γ-dihalo-β-hydrins is reacted. When an alicyclic amine and / or an alicyclic epoxy compound (e) is used if desired, one or more of these compounds may be reacted during the reaction and / or the reaction. Good.

In the reaction in this case, urea
(b) can be charged at once and reacted, or a part of urea (b) can be charged first and then reacted, and the remaining urea (b) can be added at a later stage. It is also possible to take a method of performing the reaction again. For example, a method in which an alkylenediamine or a polyalkylene polyamine (a) and a dibasic carboxylic acid compound (d) are dehydrated and condensed, and then a urea (b) is subjected to a deammonification reaction. After a deammonification reaction with an alkylenediamine or a polyalkylenepolyamine (a), a method of dehydrating and condensing a dibasic carboxylic acid compound (d) and further deammonating with the remaining urea (b), an alkylenediamine or A part of urea (b) is added to polyalkylene polyamine (a) and dibasic carboxylic acid compound (d) to perform dehydration and deammonification, and the remaining urea (b) is added to remove A method of performing an ammonia reaction or the like can be employed. In other reactions, the components
When an aldehyde is used as (c), it is preferable to carry out the reaction under an acidic condition, or to carry out the reaction once under an alkaline condition and then to carry out the reaction under a further acidic condition. On the other hand, as component (c), epihalohydrins and / or α, γ
When a dihalo-β-hydrin is used, it is weakly acidic to alkaline, for example, pH 5 or more, and furthermore pH 6 to 9
It is preferable to carry out the reaction in the range of.

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

In the present invention, an organic quaternary ammonium salt (IV) is further used in addition to the water-soluble resin (III) described above. Organic quaternary ammonium salt used here
(IV) may be any compound having at least one quaternary nitrogen in one molecule, for example, a compound in which four hydrocarbon groups are bonded to a quaternary nitrogen or a compound having a quaternary nitrogen in a ring And the like. The number of quaternary nitrogens present in the quaternary ammonium salt is arbitrary, and a mono-quaternary ammonium salt having one quaternary nitrogen in one molecule and a di-quaternary ammonium salt having two quaternary nitrogens in one molecule. Quaternary ammonium salts, and 3
Although those having more than one quaternary nitrogen can be used, mono- or di-quaternary ammonium salts, especially mono-quaternary ammonium salts, are industrially suitable in view of economy and availability. Is advantageous.

Of these quaternary ammonium salts, 4
Mono or diquaternary ammonium salts in which four hydrocarbon groups are bonded to the quaternary nitrogen, at least two of which are each independently an alkyl or alkylene having 1 to 3 carbon atoms. In the case of a monoquaternary ammonium salt, all of the four hydrocarbon groups bonded to the quaternary nitrogen may be each independently an alkyl having 1 to 3 carbon atoms, and among the four hydrocarbon groups, Two or three may be each independently an alkyl having 1 to 3 carbon atoms, and the remaining one or two may be a hydrocarbon group having a relatively large number of carbon atoms. on the other hand,
In the case of a diquaternary ammonium salt, the number of carbon atoms in a hydrocarbon group (hereinafter, referred to as a “linking group”) connecting two quaternary nitrogens is arbitrary, and may include an alicyclic group or an aromatic ring. .
In the hydrocarbon group other than the linking group bonded to each quaternary nitrogen in the diquaternary ammonium salt, the linking group has 1 to 1 carbon atoms.
When it is an alkylene having 3 carbon atoms, it is optional within a range that at least one alkyl having 1 to 3 carbon atoms is bonded to each quaternary nitrogen, and is a hydrocarbon other than a linking group bonded to each quaternary nitrogen. Up to two of each group may be independently a hydrocarbon group having a relatively large number of carbon atoms. Also,
When the linking group is not an alkylene having 1 to 3 carbon atoms, the alkyl having 1 to 3 carbon atoms has at least 2
Within the range of individual bonding,
Up to one of each of the hydrocarbon groups other than the linking group bonded to the secondary nitrogen may be independently a hydrocarbon group having a relatively large number of carbon atoms. In such a mono- or diquaternary ammonium salt, the hydrocarbon group having a relatively large number of carbon atoms may be an aliphatic group, an alicyclic group, a group having an aromatic ring, or the like.

The counter anion constituting the quaternary ammonium salt may be any one of an inorganic acid and an organic acid. Examples of the inorganic anion include chloride ion, bromide ion, sulfate ion, and phosphate ion, and examples of the organic anion include acetate ion, formate ion, and oxalate ion.

The monoquaternary ammonium salt used in the present invention is, for example, diallyldimethylammonium chloride,
Relatively low carbon number quaternary ammonium salts such as hexyltrimethylammonium chloride, cyclohexyltrimethylammonium chloride, cyclohexylmethyltrimethylammonium chloride;

Octyltrimethylammonium chloride, 2-ethylhexyltrimethylammonium bromide, decyltrimethylammonium chloride, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, laurylstearyldimethylammonium chloride, hexadecyltrimethylammonium chloride, diheptadecyldimethylammonium chloride, What is generally known as an aliphatic cationic surfactant, such as stearyl dimethyl ammonium chloride,

Generally known as aromatic cationic surfactants such as lauryl dimethyl benzyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, stearyl diethyl benzyl ammonium chloride, tetradecyl dimethyl benzyl ammonium chloride and palm alkyl dimethyl benzyl ammonium chloride. And the like.

Among these monoquaternary ammonium salts, two or three of the four groups bonded to the quaternary nitrogen are each independently an alkyl having 1 to 3 carbon atoms, and the remaining one or two Those in which the number is an aliphatic hydrocarbon group having 3 to 24 carbon atoms or an araliphatic hydrocarbon group are preferred. The aliphatic hydrocarbon group referred to herein includes alkyl, alkenyl,
Ring-containing alkyl and the like, and araliphatic hydrocarbon groups include benzyl, phenethyl and the like. Further, among the four groups bonded to the quaternary nitrogen, those in which three are each independently methyl or ethyl and the remaining one is an aliphatic hydrocarbon group having 3 to 24 carbon atoms are preferable,
Particularly preferred are those in which three are methyl and the remaining one is alkyl having 8 to 12 carbon atoms. Preferred monoquaternary ammonium salts include octyltrimethylammonium chloride, decyltrimethylammonium chloride, lauryltrimethylammonium chloride and the like.

The diquaternary ammonium salts include, for example, 1,3-bis (trimethylammoniomethyl) cyclohexane dichloride, N, N, N, N ', N', N'-
Hexamethylisophorone diammonium dibromide,
N-tallow alkyl-N, N, N ', N', N'-pentamethyltrimethylenediammonium dichloride and the like.

These organic quaternary ammonium salts (IV) are
Each can be used alone or as a mixture of two or more.

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

In preparing the paper coating composition, the pigment (I)
The composition ratio of each of the aqueous binder (II) and the aqueous binder (II) is determined according to the use and purpose, and there is no particular difference from the composition generally used in the art. A preferred composition ratio of both is about 5 to 200 parts by weight, more preferably 10 to 5 parts by weight of the aqueous binder (II) per 100 parts by weight of the pigment (I).
It is about 0 parts by weight. The water-soluble resin (III) is a pigment (I) 1
It is preferable to add about 0.05 to 5 parts by weight, more preferably about 0.1 to 2 parts by weight, as a solid content with respect to 00 parts by weight. The organic quaternary ammonium salt (IV) is preferably incorporated in an amount of about 1 to 90% by weight, more preferably 3 to 80% by weight based on the weight of the solid content of the water-soluble resin (III).
It is more preferable to mix them in such a range.

The water-soluble resin (III) and the organic quaternary ammonium salt (IV) are mixed in advance and then mixed with the pigment (I) and the aqueous binder (II) when preparing a paper coating composition. Alternatively, each of these may be added and mixed alone to the pigment (I) and the aqueous binder (II). Furthermore, a mixture of the water-soluble resin (III) and the organic quaternary ammonium salt (IV), or each of them alone, is previously added to and mixed with a pigment slurry or an aqueous binder, and is blended with the remaining components. , The effects of the present invention can be achieved.

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

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

Thus, according to the present invention, a pigment can be obtained by additionally using a specific organic quaternary ammonium salt (IV).
(I), an aqueous binder (II) and a specific water-soluble resin (II
A coated paper exhibiting further improved performance is obtained as compared with the case where the coating composition comprising I) is used.

[0059]

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

Synthesis Example 1

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

Synthesis Example 2

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

Synthesis Example 3

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

Examples 1 to 13

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

[0068]

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

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

Example 1 A mixture of 225 g of the resin aqueous solution obtained in Synthesis Example 1 and 5.6 g of cyclohexyltrimethylammonium chloride was previously blended to give a viscosity of 1
A 30 cps resin aqueous solution was added to the master color shown in Table 1 at a ratio of 0.5 part solids per 100 parts of pigment.

Example 2 A mixture of 225 g of the aqueous resin solution obtained in Synthesis Example 1 and 45 g of Sanisole C (a product of Kao Corporation, 50% lauryl dimethylbenzylammonium chloride) was previously blended to obtain a viscosity of 128 cp.
s), and this resin aqueous solution was added to the master color shown in Table 1 at a ratio of 0.5 part solids per 100 parts of pigment.

Example 3 A resin aqueous solution having a viscosity of 40 cps was prepared by previously mixing 12.5 g of cyclohexyltrimethylammonium chloride with 125 g of the aqueous resin solution obtained in Synthesis Example 2, and this resin aqueous solution was shown in Table 1. To the master color was added 0.5 parts solids per 100 parts pigment.

Example 4: The aqueous resin solution obtained in Synthesis Example 2 was coated with Cotamine D86P (manufactured by Kao Corporation, 75% diheptadecyldimethylammonium chloride) at a solid content weight ratio of 5: 1. , Were individually added to the master colors shown in Table 1. At this time, the total solid content of the aqueous resin solution and Cotamine D86P was adjusted to 0.5 part per 100 parts of the pigment in the master color.

Example 5: A resin aqueous solution having a viscosity of 380 cps was prepared by previously mixing 6.9 g of Cotamine D86P with 172 g of the aqueous resin solution obtained in Synthesis Example 3, and this resin aqueous solution was used as a master color as shown in Table 1. And pigment 1
It was added at a rate of 0.5 part solids per 100 parts.

Example 6 A resin aqueous solution having a viscosity of 330 cps was prepared by previously mixing 10.4 g of sanisole C with 172 g of the aqueous resin solution obtained in Synthesis Example 3, and this resin aqueous solution was used as a master color as shown in Table 1. And pigment 10
The solid content was added at a rate of 0.5 part per 0 part.

Examples 7 to 13: A resin aqueous solution having the viscosity shown in Table 2 was prepared by previously mixing 172 g of the aqueous resin solution obtained in Synthesis Example 3 with the quaternary ammonium salt of the type and amount shown in Table 2. This aqueous solution was added to the master color shown in Table 1 at a ratio of 0.5 part of solids per 100 parts of the pigment.

[0077]

[Table 2]

Each of the coating compositions prepared as described above was adjusted with water and a 10% aqueous solution of sodium hydroxide so that the total solid content was 60% and the pH was about 9.0. Table 3 shows the mixing ratio of the resin and the amine in these examples.
And Table 4.

Measurement of Physical Properties of Coating Composition The physical properties of each coating composition were measured by the following methods, and the results are shown in Tables 3 and 4.

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

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

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

Evaluation of Physical Properties of Coated Paper The coated paper thus obtained was subjected to tests for water resistance and ink acceptability. The test results are shown in Tables 3 and 4. The test method is as follows.

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

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

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

[0087]

[Table 3] ^{* 1} Kind of quaternary ammonium salt CYTA: Cyclohexyltrimethylammonium chlorite ゛ SANC: Sanisol C QTMD: Cotamine D86P ^{* 2} Addition method of quaternary ammonium salt A: Add to resin solution beforehand B: Separate from resin solution Addition

[0088]

[Table 4] ^{* 1} Kinds of quaternary ammonium salts C ₁ : tetramethylammonium bromide C ₆ : n-hexyltrimethylammonium bromide C ₈ : n-octyltrimethylammonium bromide C ₁₀ : n-decyltrimethylammonium bromide C ₁₂ : lauryltrimethylammonium chloride C ₁₆ : n-hexadecyltrimethylammonium chloride _C18 : stearyltrimethylammonium chloride

Comparative Examples 1-4

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

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

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

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

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

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

[0096]

[Table 5]

[0097]

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

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-61-152731 (JP, A) JP-A-2-216297 (JP, A) JP-A-51-123304 (JP, A) JP-A-4- 333697 (JP, A) JP-A-4-100996 (JP, A) JP-A-4-263696 (JP, A) JP-A-1-52899 (JP, A) JP-A-59-157399 (JP, A) JP-A-4-241198 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) D21H 11/00-27/42

Claims (9)

(57) [Claims] (I) a pigment, (II) an aqueous binder, (III) at least three components: (a) alkylenediamine or polyalkylenepolyamine, (b) ureas, and (c) aldehydes, epihalohydrins And α, γ-
A water-soluble resin obtained by reacting a compound selected from dihalo-β-hydrins, and (IV) an organic quaternary ammonium salt having at least one quaternary nitrogen atom in the molecule, and Organic quaternary ammonium salt in which the quaternary nitrogen contained is bonded to four hydrocarbon groups (however, the hydrocarbon group may be an alkylene group connecting the quaternary nitrogen). Paper coating composition. 2. The water-soluble resin (III) comprises (a) an alkylenediamine or a polyalkylenepolyamine, (b) ureas, (c) aldehydes, epihalohydrins and α, γ-
The composition according to claim 1, which is a resin obtained by reacting a compound selected from dihalo-β-hydrins and (d) a dibasic carboxylic acid compound. 3. The composition according to claim 2, wherein the dibasic carboxylic compound (d) is a free acid, an ester or an acid anhydride. 4. The water-soluble resin (III) comprises (a) an alkylenediamine or a polyalkylenepolyamine, (b) ureas, (c) aldehydes, epihalohydrins and α, γ-
A resin obtained by reacting a compound selected from dihalo-β-hydrins and (e) an alicyclic compound selected from an alicyclic amine having at least one active hydrogen and an alicyclic epoxy compound. The composition of claim 1. 5. The water-soluble resin (III) comprises (a) an alkylenediamine or a polyalkylenepolyamine, (b) ureas, (c) aldehydes, epihalohydrins and α, γ-
A compound selected from dihalo-β-hydrins, (d) a dibasic carboxylic acid compound, and (e) an alicyclic compound selected from an alicyclic amine and an alicyclic epoxy compound having at least one active hydrogen The composition according to claim 1, which is a resin obtained by reacting 6. The composition according to claim 5, wherein the dibasic carboxylic compound (d) is a free acid, an ester or an acid anhydride. 7. An organic quaternary ammonium salt (IV) wherein four hydrocarbon groups are bonded to a quaternary nitrogen, at least two of which are each independently an alkyl group having 1 to 3 carbon atoms. The composition according to any one of claims 1 to 6, which is a monoquaternary ammonium salt or a diquaternary ammonium salt. 8. The organic quaternary ammonium salt (IV) is a monoquaternary ammonium salt in which three methyl groups and one alkyl having 8 to 12 carbon atoms are bonded to a quaternary nitrogen. A composition according to claim 1. 9. An aqueous binder (II) in an amount of 5 to 200 parts by weight and a water-soluble resin (III) in an amount of 0.0 to 100 parts by weight of the pigment (I).
5 to 5 parts by weight, and 1 to 9 organic quaternary ammonium salts (IV) based on the weight of the solid content of the water-soluble resin (III).
The composition according to any one of claims 1 to 8, which contains 0% by weight.