DE19957348A1 - Resin composition, useful for the production of coated paper, comprises a cross-linked amine prepared from an aliphatic amine and a glycidyl compound having at least 2 glycidyl groups - Google Patents

Abstract

A resin composition comprises a cross-linked amine prepared from an aliphatic amine and a glycidyl compound having at least 2 glycidyl groups. A resin composition (I) comprises (A) a crosslinked amine compound and (B) a compound comprising (B1) an non-volatile, non-polymeric substance or (B2) a multi-valent alcohol. (A) is prepared from (A1) an aliphatic amine (A2) a glycidyl compound having at least 2 glycidyl groups per molecule and optionally (A3) an alpha , beta -unsaturated carbonyl compound, an alpha , beta -unsaturated nitrile compound or an alpha -halocarboxylic acid. Independent claims are included for (i) a coating composition (II) comprising the resin composition (I), a pigment and an aqueous binding agent and (ii) a paper substrate coated with (II).

Description

The present invention relates to a resin composition for paper coatings and a coating comprising the resin composition, a pigment and an aqueous binder composition for paper. In particular, a resin composition for Papierbe coatings and a coating composition for paper provided that no Generate formaldehyde and excellent print suitability and printing effect on paper to lend. The present invention also relates to a coated paper having a mainly composed of a pigment and an aqueous binder Coating that does not generate formaldehyde, excellent pressure suitability and pressure has effect and good print gloss shows. The one used in this description The term "paper" has a broad meaning and includes so-called cardboard in addition to Paper in the narrow sense.

By applying one mainly of a pigment and an aqueous one Binder composite coating composition and performing neces derlicher treatments, such as drying and calender treatment, received coating This paper is characterized by its excellent properties, such as excellent printing effect, widely used for commercial prints, journals and books. However, there are still remaining efforts to be made to improve the quality of the coated paper with accompanying increased need for quality and quality To improve acceleration of printing. In particular, in offset printing, the  takes a significant part of the printing, a good ink accepting property under the influence of wetting water and water resistance during wet picking (wet pick), improvement and promotion of printing gloss and blistering Resistance to web printing required.

To solve these problems, there are well-known methods in which Addition to a coating composition for paper melamine-formaldehyde Resins, urea-formaldehyde resins, polyamide-polyurea-formaldehyde resins, such as in JP-B-44-11667 and JP-A-55-31837 (= US-A-4,246,153), or block glyoxal resins as described in JP-A-63-120197, as a means for imparting what water resistance or added as an additive for a binder. However, every one is this conventional means of imparting water resistance and additives for a binder in practice not necessarily satisfactory, since some Properties identified major disadvantages or inadequate effects although they give some effective improvements.

For example, so-called aminoplastoharze, such as melamine-formaldehyde Resins and urea-formaldehyde resins, some problems with it, such as not only that the production of formaldehyde during the work-up or from the coated Paper is strong, but also that the improvement effect of the color accepting and blistering resistance is low and manifestation effect of what water resistance is not easily obtained when the pH of a coating composition is increasing.

Polyamide-polyurea-formaldehyde resins impart to some extent improved effects, such as an improvement in the ink receptivity and Water resistance. However, using polyamide polyurea form aldehyde resins, the production of formaldehyde can not be prevented because formaldehyde hyd is used in the preparation of the resins.

On the other hand, block glyoxal resins which act as an additive to a no form aldehyde-containing binder are known, only a very slight improvement of Quality of the coated paper, such as ink accepting property and blistering effect durability, although to some extent water resistance to Be can lend network water.

There is another problem that coated papers using a coating composition are prepared on paper substrates, the Contain water resistance agents, such as aminoplastoharze and Polyamidepolyurea-formaldehyde resins as mentioned above tend to have ver have poorer print gloss compared to coated papers under Use of a coating composition consisting essentially of pigments  and aqueous binders. The deterioration of the Print gloss reduces the high quality feel of paper as the high quality feel of paper from the contrast between the unprinted parts and the be printed parts occurs and a higher print gloss in the non-printed parts hö results in higher contrast.

The present inventors have previously disclosed in ^{JP-A-10-77599} the use of a crosslinked amine compound dung a reaction product of aliphatic amine with a Verbin selected from aldehydes, glycidyl compounds and isocyanate compounds, as a resin component in a coating composition for paper for increasing the quality of proposed coated paper. The inventors have further proposed in JP-A-11-140792 the use of a crosslinked amine compound which is a reaction product of a heterocyclic amine with a glycidyl compound as a resin component in a paper coating composition.

It has been found that when such a crosslinked amine compound is a Reaction product of an amine with a glycidyl compound and in JP-A-10-77599 and JP-A-11-140792 is used as a resin component, a thickening the coating composition and deterioration of the flow properties from the combination with other ingredients and the amount of these used crosslinked amine compound can occur. The inventors have comprehensive sub This problem and the problem of a coating Composition caused deterioration of the printing gloss to solve.

An object of the present invention is to provide a resin composition for Papierbe coatings, the coated paper of high quality, d. H. z. B. with high ink receptivity and excellent water resistance; and does not cause generation of formaldehyde, meeting the requirements the quality of coated paper.

Another object of the present invention is a resin composition for paper To provide coatings that hardly disadvantages such as thickening and deterioration the flow property, and is therefore handled easily, if they are with a pigment and an aqueous binder to form a coating composition for paper is mixed.

Another object of the present invention is to provide a coating composition for paper using the above resin composition.

Yet another object of the present invention is coated paper that does not produce formaldehyde, good properties such as high color property and excellent water resistance, exhibiting and good pressure  shows gloss, using the above coating composition for Paper is made.

The present invention provides a resin composition comprising

• A) a crosslinked amine compound, the
  a reaction product of (a) an aliphatic amine and (b) a glycidyl compound having at least two glycidyl groups in the molecule or
  a reaction product of (a) an aliphatic amine, (b) a glycidyl compound having at least two glycidyl groups in the molecule and (c) a compound selected from α, β-unsaturated car bonyl compounds, α, β-unsaturated nitrile compounds and α-halocarboxylic acid compounds; and
• B) at least one compound selected from (B1) a non-polymeric, not volatile substance and (B2) polyhydric alcohols.

The present invention also provides a coating composition for paper comprising

• A) the above-described crosslinked amine compound,
• B) at least one compound selected from non-polymeric, non-volatile Substances and polyhydric alcohols, in addition to
• C) a pigment and
• D) an aqueous binder.

The present invention further provides a coated paper comprising (1) a paper substrate and (2) a coating on the surface of the paper substrate

• A) the above-described crosslinked amine compound,
• B) at least one compound selected from a non-polymeric, non-volatile substance and polyhydric alcohols,
• C) a pigment and
• D) an aqueous binder.

The resin composition of the present invention comprises (A) a crosslinked amine compound, which is obtained by reacting certain components, and (B) (B1) is not polymeric non-volatile substance and / or (B2) a polyhydric alcohol.

The crosslinked amine compound (A) is prepared by reacting (a) an aliphatic compound Amines and (b) a glycidyl compound having at least two glycidyl groups in the Mo lekül or by reacting (a) an aliphatic amine, (b) a glycidyl compound having at least two glycidyl groups in the molecule and (c) a compound selected  from α, β-unsaturated carbonyl compounds, α, β-unsaturated nitrile compounds and α-halocarboxylic acid compounds.

The aliphatic amine (a) used herein has a primary or secondary Amino group which is bonded to an aliphatic carbon atom. The aliphati The carbon atom to which an amino group is bonded may be a non-aromatic forming a ring. If an amino group ge to an aliphatic carbon atom may be, for example, other than an aliphatic hydrocarbon residual substance and an aromatic ring also be contained in the molecule. Next you can several amino groups may be contained in the molecule. Specific examples of the aliphatic Amines (a) include monoalkylamines, dialkylamines, two or more amino groups in the molecule containing polyamines and aliphatic heterocyclic amines, the Nitrogen atom as at least one ring member included, a. It can be a kind of aliphatic amine or these aliphatic amines can be used in Combination of two or more are used.

Monoalkylamines may be a compound in which a primary amino group is bonded to an alkyl group of about 1 to 10 carbon atoms. Specific Examples thereof include methylamine, ethylamine and propylamine. The dialkylamine may be a compound in which two alkyl groups are attached to one secondary amino group are bonded, wherein the alkyl radicals are the same or different and each having about 1 to 10 carbon atoms. Specific examples thereof include Dimethylamine, diethylamine, dipropylamine, dibutylamine and methylethylamine. The Polyamine has several amino groups in the molecule and here means another Compound as the heterocyclic amines described later. Special examples of these include ethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, Bis (aminomethyl) cyclohexane and xylenediamine.

The heterocyclic amine is a cyclic compound containing at least one Nitrogen atom as a ring member in addition to carbon atoms. The the hetero cyclus forming atoms are not limited to carbon and nitrogen, and other heteroatoms, such as oxygen and sulfur, can also form a ring. If this compound contains a heterocycle with nitrogen as the ring atom, can they also contain an aliphatic hydrocarbon radical, alicyclic hydrocarbon radical, aromatic hydrocarbon radical and acyl radical in addition to this heterocycle contain. Further, an amino group other than the cyclic amino group and a another substituent, such as. As a halogen atom, via such a hydrocarbon be connected. Specific examples of the heterocyclic amine include hetero cyclic monoamines such as pyrrolidine, piperidine, 2-, 3- or 4-pipecoline and 2,4-, 2,6- or 3,5-lupetidine (i.e., dimethylpiperidine), heterocyclic diamines such as piperazine,  Homopiperadine, N-alkyl (eg methyl, ethyl or propyl) piperadine, N-methyl homopiperadine, N-acyl (eg acetyl) piperadine, N-acyl (eg acetyl) homopiperadine and 1- (chlorophenyl) piperadine, heterocyclic amines to which an aminoalkyl radical is attached such as N-aminoalkyl (eg ethyl or propyl) piperidine, N-aminoalkyl (eg ethyl- or propyl) piperazine, N-aminoalkyl (eg ethyl or propyl) morpholine, N- Aminopropyl 2- or 4-pipecoline, 1,4-bis (aminoethyl) piperazine and 1,4-bis (amino propyl) piperazine.

Among these aliphatic amines (a) are monoalkylamines, dialkylamines, Ethylenediamine, diethylenetriamine and heterocyclic amines industrially advantageous and heterocyclic amines in particular advantageous. Particularly preferred heterocyclic Amines include pyrrolidine, piperidine, piperazine, N-aminoethylpiperazine, N-amino propylpiperazine, 1,4-bis (aminoethyl) piperazine and 1,4-bis (aminopropyl) piperazine.

The aliphatic amine (a) used in the present invention contains min at least one primary or secondary amino group as described above. at Use of a heterocyclic amine, it is advantageous that at least one pri amino group in addition to the forming the heterocycle secondary or tertiary amino group, in view of the reactivity with a glycidyl compound is included. In particular, an excellent effect is exhibited when an Ver Bond in which an aminoalkyl group to a heterocycle with nitrogen as a ring member such as N-aminoethylpiperazine, N-aminopropylpiperazine, 1,4-bis (amino ethyl) piperazine and 1,4-bis (aminopropyl) piperazine, singly or in combination with one or more other amines is used.

The glycidyl compound (b) containing (a) an aliphatic amine or (a) a aliphatic amine and (c) a compound selected from α, β-unsaturated car bonyl compounds, α, β-unsaturated nitrile compounds and α-halocarboxylic acid is a compound with at least two glycidyl groups in the molecule. The remainder linking several glycidyl groups is not limited, and each of aliphatic radicals, aromatic radicals and Alicyclic residues can be used. Specific examples of glycidyl ver Compound (b) include alkylene glycol diglycidyl ethers such as ethylene glycol diglycidyl ether and propylene glycol diglycidyl ether, polyalkylene glycol diglycidyl ether such as polyethylene glycoldiglycidyl ether and polypropylene glycol diglycidyl ether, aromatic diglycidyl ethers such as resorcinol diglycidyl ether and bisphenol A diglycidyl ether, trimethylol propandi- or triglycidyl ethers, sorbitol di-, tri-, tetra-, penta- or hexaglycidyl ethers and pentaerythritol di-, tri- or tetraglycidyl ether. These glycidyl compounds can be as a single compound or in combination of two or more  be used. Among them, an aromatic glycidyl ether is advantageously used used.

The compound (c) which is reacted with (a) an aliphatic amine or a reaction product (a) of an aliphatic amine and (b) a glycidyl compound having at least two glycidyl groups is to be reacted in the molecule is selected from α, β-unsaturated Carbonyl compounds, α, β-unsaturated nitrile compounds and α-halogencarbon acid compounds. The α, β-unsaturated carbonyl compounds and α, β-unsaturated Nitrile compounds as compound (c) have a carbon-carbon double bond (ethylenic bond) or a carbon-carbon triple bond (acetylenic bond), and at least one of the double bond or three Compound-forming carbon atoms bind to a carbonyl group or a Cyano group. If one is the double bond or the triple bond forming Carbon atom binds to a carbonyl group or a cyano group is the carbon atom of one α-carbon atom and the other carbon atom of a β-carbon atom. When two carbons forming the double bond or the triple bond atoms connect a carbonyl group and / or a cyano group is one of Carbon atoms is an α-carbon atom and the other carbon atom is a β- Carbon atom. The carbon-carbon double bond or carbon Carbon triple bond in the α, β-unsaturated carbonyl compounds and α, β unsaturated nitrile compounds is called α, β-unsaturated bond. The α-carbon atom of nitrogen and / or β-carbon may be further attached to an aliphatic hydrocarbon or an aromatic hydrocarbon radical. The α, β-unge saturated carbonyl compounds and α, β-unsaturated nitrile compounds can meh Other carbonyl groups or cyano groups.

Examples of the α, β-unsaturated carbonyl compound include carboxylic acids, such as Acrylic acid, crotonic acid, isocrotonic acid, methacrylic acid, sorbic acid and cinnamic acid, Carboxylic esters, such as methyl acrylate, ethyl acrylate, butyl acrylate ester, crotonic acid methyl ester, crotonic acid ethyl ester, methyl methacrylate, Methacrylsäureethylester, cinnamic acid methyl ester and cinnamic acid ethyl ester, aldehydes, such as Acrolein, crotonaldehyde and cinnamaldehyde, ketones such as methyl vinyl ketone, mesityl oxide, Benzalacetone, dibenzalacetone, benzalacetophenone and dypnone, dicarboxylic acids, such as Fumaric acid and maleic acid, and acid anhydrides such as maleic anhydride. at Examples of α, β-unsaturated nitrile compounds include nitriles such as acrylonitrile.

The α-halocarboxylic acid compounds as compound (c) are carboxylic acids, Carboxylic acid salts or carboxylic acid esters in which the halogen atoms to a part or all α-carbon atoms are bonded to those bound to the carbonyl group Are carbon atoms. When the halogen atoms are attached to a part of the α-carbon atoms  are bonded, the remaining α-carbon atoms can be attached to an aliphatic Hydrocarbon radical, an aromatic hydrocarbon radical or an ali be bound cyclic hydrocarbon radical. Examples of the α-halogencarbon acid compounds include α-halocarboxylic acids such as chloroacetic acid, bromoacetic acid acid, dichloroacetic acid, dibromoacetic acid, trichloroacetic acid, α-chloropropionic acid, α-chlorobutyric acid and α-bromoisovaleric acid, α-halocarboxylic acid esters, such as Methyl chloroacetate, ethyl chloroacetate, butyl chloroacetate, Methyl bromoacetate, ethyl bromoacetate and propyl bromoacetate and α-halocarboxylic acid salts such as sodium chloroacetate and sodium bromoacetate.

One kind of the compound (c) may be singly or two or more kinds of Compounds (c) can be used in combination. Among the above he Compounds (c) mentioned are α, β-unsaturated carboxylic acids and α, β-unsaturated Carboxylic acid esters and α-chlorocarboxylic acids from the industrial point of view advantageous. In particular, acrylic acid and chloroacetic acid are preferred.

As a method of reacting (a) an aliphatic amine, (b) a glycidyl compound having at least two glycidyl groups in the molecule and (c) a compound, selected from α, β-unsaturated carbonyl compounds, α, β-unsaturated nitrile compound and α-halocarboxylic acid compounds, the following methods (1) to (5) are given as examples.

• 1. An aliphatic amine (a) and a glycidyl compound (b) are reacted and then reacting a compound (c) with the reaction product of (a) and (b).
• 2. An aliphatic amine (a) and a compound (c) are reacted and then a glycidyl compound (b) is reacted with the reaction product of (a) and (c).
• 3. An aliphatic amine (a) and a compound (c) are reacted and then a glycidyl compound (b) is reacted with the reaction product of (a) and (c). because after a compound (c) is further reacted with the reaction product of (a), (b) and (c) implemented. In this case, the first reacted compound (c) and the later Reacted compound (c) may be the same or different.
• 4. An aliphatic amine (a) and a glycidyl compound (b) are reacted and then reacting a compound (c) with the reaction product of (a) and (b). because According to a glycidyl compound (b) further with the reaction product of (a), (b) and (c) implemented. In this case, the glycidyl compound first reacted (b) and the later-reacted glycidyl compound (b) are the same or different his.
• 5. An aliphatic amine (a), a glycidyl compound (b) and a compound (c) are implemented simultaneously.

Among the above-mentioned methods, (1) is common, but the invention is not limited to this.

The glycidyl compound (b) is in the range of usually 0.1 to 1.5 mol, preferably 0.3 to 1.2 mol, more preferably 0.5 to 1 mol, based on 1 mol of a aliphatic amine (a) used. Even if several reactive primary or secondary If amino groups are present in an aliphatic amine, the reaction tends product for gelling when the amount of the glycidyl compound (b) is increased. Therefore is suitable that the molar ratio of the glycidyl compound to an aliphatic amine regardless of the number of amino groups is 1.5 or less.

The compound (c) is in the range of usually 0 to 1.5 mol, preferably from 0.05 to 1 mol, more preferably from 0.1 to 0.5 mol, based on 1 mol of an alipha used amine (a). When the reaction of the aliphatic amine (a) and the Compound (c) before the reaction of the aliphatic amine (a) and the glycidyl ver Compound (b) is carried out, a part of the aliphatic amine (a) with the Ver Bond (c) remain unreacted, so that a crosslinked amine compound by Um Substitution of the remaining amino group and the glycidyl compound (b) is formed.

The reaction of an aliphatic amine (a) and a glycidyl compound (b) and the reaction of an aliphatic amine (a), a glycidyl compound (b) and a compound (c) can be used without the use of a solvent or in a Lö be carried out. This reaction is usually at a Tem temperature of 30 to 100 ° C carried out. The preferred reaction temperature is about 40 to 90 ° C when a mixed system of water and organic solution is used without solvent as the solvent, and about 40 to 70 ° C, if a organic solvent is used as a solvent, although the z. B. dependent the presence or absence of a solvent and the nature of the Solvent, if used, varies. The reaction time is usually about 1 to 20 hours. This reaction even occurs when no catalyst ver is used, and can also in the presence of a basic catalyst, such as ammonia or sodium hydroxide, or a Lewis acid catalyst, such as. B. aluminum to be carried out.

Examples of the solvent used in this reaction include Alko such as methanol, ethanol, 1- or 2-propanol, 1- or 2-butanol, 1-pentanol, 3-Me ethyl-1-butanol, 1-hexanol, 4-methyl-2-pentanol, 2,4-dimethyl-3-pentanol, 2,6-dime thyl-4-heptanol, 2-ethyl-1-hexanol, 1- or 2-octanol, lauryl alcohol, cyclohexanol and benzyl alcohol; Ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, β, β'-dichloro diethyl ether, 1,4-dioxane, furfuryl alcohol, tetrahydrofurfuryl alcohol, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl  ether, ethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether and diethylene glycol dibutyl ether; Alde hyde, such as butyraldehyde; Hydrocarbons such as cyclohexane, hexane, heptane, toluene and o-, m- and p-xylene; Organohalogen compounds such as 1,1,1-trichloroethane, tri chloroethylene, 1- or 2-bromopropane, 1-bromobutane, lauryl bromide, 1-bromo-3-chloroprop pan, 1,3-dibromopropane, 1,4-dibromobutane, 1,5-dibromopentane and 2,3-dibromo-1-pro propanol; Ketones, such as acetone, 2,4-pentanedione, methyl ethyl ketone, 2- or 3-pentanone, 3- Methyl 2-butanone, methyl isobutyl ketone, 2-heptanone, 2,6-dimethyl-4-heptanone, 2,4- Dimethyl 3-pentanone, cyclohexanone, mesityl oxide, isophorone and 4-hydroxy-4-methyl 2-pentanone; Esters, such as methyl acetate, ethyl acetate, acetic acid propyl ester, isopropyl acetate, butyl acetate, sec-butyl acetate, vinegar isobutyl ester, acetic acid ester, benzyl acetate, ethyl propionate, Butyl propionate, ethyl propionate, methyl benzoate, benzoic acid ethyl ester, diethyl malonate, diethyl oxalate, butyl phosphate and Ethyl acetoacetate, a. You can alone or in combination of two or several are used.

Also, a mixture of one or more of these organic Lö be used with water as a solvent for the reaction.

When an aliphatic amine (a) and a glycidyl compound (b) reacted or the reaction product of an aliphatic amine (a) and a compound (c) is reacted with a glycidyl compound (b), the amount of water in the Reaction system preferably 20% by weight or less, more preferably 10% by weight or less, because if the amount of water present in the reaction system is too large, by the mutual polymerization of Diglycidylverbindungen an epoxy resin gebil det, which is insoluble in both water and an organic solvent is.

When an aliphatic amine (a) and a compound (c) are reacted or the reaction product of an aliphatic amine (a) and a glycidyl compound (b) is reacted with a compound (c), the ratio of water and the orga niche solvents are not limited. In this case, only water can be used as a solution be used medium.

The structure of the reaction product is very diverse, and a low polymer having a certain degree of molecular distribution can sometimes be formed, depending on
the nature of the aliphatic amine (a),
the nature of the glycidyl compound (b),
the type of compound (c),
the use ratio of aliphatic amine (a), glycidyl compound (b) and compound (c) and
the reaction order.

The main embodiments of a reaction of an aliphatic amine (a) and of a glycidyl compound (b) are illustrated below with the assumption the glycidyl compound (b) has a structure with two glycidyl groups of the formula R-Gly, wherein Gly represents a glycidyl group and R is a bivalent radical represents. (Hereinafter, Gly represents a glycidyl group.)

When an aliphatic amine (a) has a primary amino group of the formula R ¹ -NH ₂ in which R ^{1 is} a monovalent aliphatic radical, the following reaction mainly proceeds, and in some cases, a glycidyl compound can be added to a secondary amino group in this product be formed, wherein another structure is formed, which binds to an amine molecule.

R ¹ -NH ₂ + Gly-R-Gly → R ¹ -NH-CH ₂ CH (OH) CH ₂ -R-Gly

R ¹ -NH-CH ₂ CH (OH) CH ₂ -R-Gly + R ¹ -NH ₂ → R ¹ -NH-CH ₂ CH (OH) CH ₂ -R-CH ₂ CH (OH) CH ₂ -NH -R ¹

When an aliphatic amine (a) has a secondary amino group represented as R ¹ -NH-R ² (in the case of a heterocyclic monoamine, it can be considered that R ¹ and R ² are joined to form a ring ), the following reaction mainly occurs.

R ¹ -NH-R ² + Gly-R-Gly → (R ¹ ) (R ² ) N-CH ₂ CH (OH) CH ₂ -R-Gly

(R ¹ ) (R ² ) N-CH ₂ CH (OH) CH ₂ -R-Gly + R ¹ -NH-R ² → (R ¹ ) (R ² ) N-CH ₂ CH (OH) CH ₂ -R -CH ₂ CH (OH) CH ₂ N (R ¹ ) (R ² )

When an aliphatic amine (a), a glycidyl compound (b) and a compound (c), wherein the structure of (c) is represented by the formula R ¹ -CH = CH-COR ² or R ³ -C (X) H- COOR ⁴ are reacted in this order, illustrating the main embodiments of the reaction below based on the assumption that the glycidyl compound (b) has a structure having two glycidyl groups of the formula Gly-R-Gly.

When an aliphatic amine (a) has a primary amino group of the formula R ³ -NH ₂ wherein R ^{3 is} a monovalent aliphatic radical, the following reaction proceeds mainly and in some cases, a glycidyl compound can be added to a secondary amino group in this product. wherein a different structure is formed, which binds to an amine molecule. When the compound (c) has a structure of the formula R ¹ -CH = CH-COR ² , it is added to the amino group remaining in the reaction product of the aliphatic amine (a) and the glycidyl compound (b). When the compound (c) has a structure of the formula R ³ -C (X) H-COOR ⁴ , an addition reaction to the amino group and dehalogenation occur.

R ⁵ -NH ₂ + Gly-R-Gly → R ⁵ -NH-CH ₂ CH (OH) CH ₂ -R-Gly

R ⁵ -NH-CH ₂ CH (OH) -R-Gly + R ⁵ -NH ₂ → R ⁵ -NH-CH ₂ CH (OH) CH ₂ -R-CH ₂ CH (OH) CH ₂ -NH-R ⁵

R ⁵ -NH-CH ₂ CH (OH) CH ₂ -R-CH ₂ CH (OH) CH ₂ -NH-R ⁵ + R ¹ -CH = CH-COR ² → R ² OC-CH ₂ CHR ¹ -NR ⁵ -CH ₂ CH (OH) CH ₂ -R-CH ₂ CH (OH) CH ₂ -NR ⁵ --CHR ¹ CH ₂ -COR ²

R ⁵ -NH-CH ₂ CH (OH) CH ₂ -R-CH ₂ CH (OH) CH ₂ -NH-R ⁵ + R ³ -C (X) H -COOR ⁴ → R ⁴ OOC-CHR ³ -NR ⁵ -CH ₂ CH (OH) CH ₂ -R-CH ₂ CH (OH) CH ₂ -NR ⁵ -CHR ³ - COOR ⁴ + HX

Further, when the aliphatic amine (a) has plural amino groups, When two or more kinds of aliphatic amines (a) are used together when the glycidyl compound (b) has three or more glycidyl groups, when the compound (c) has several α, β-unsaturated bonds or more α-halogen Atoms, the reaction further complicated, and in each case becomes a networked Amine compound (A) mainly prepared in which crosslinks several amine molecules are.

As described above, a crosslinked amine compound (A) obtained by Reaction of an aliphatic amine (a), a glycidyl compound (b) and a Ver Bond (c) is obtained, a lower polymer with a certain degree of moles molecular weight distribution, depending on the structure of the aliphatic amine as Aus transition substance. The viscosity of a 50% strength by weight aqueous solution at 25 ° C., an indicator of molecular weight, usually in the range of 10 to 100,000 mPa.s are located. Preferably, the viscosity is 100 mPa.s or more, further 1000 mPa.s or more and 50,000 mPa.s or less.

A non-volatile substance (B1) and / or a polyhydric alcohol (B2) who used as the other component (B) of a resin composition for paper coatings. The resin composition for paper coatings can contain both a non-volatile substance (B1) and a polyhydric alcohol (B2) in addition to the above-mentioned ver  comprising a primary amine compound. In an alternative embodiment, the Resin composition for paper coatings either the non-volatile substance (B1) or include the polyhydric alcohol (B2), although the nonvolatile substance (B1) is preferred.

The non-volatile substance (B1) is an organic or inorganic non-po lymere compound which has no volatility at ambient temperature and in the mass dissolved together with a crosslinked amine compound (A) or evenly can be dispersed. The non-polymeric substance referred to herein has specific molecular weight. The non-volatile substance (B1) becomes Ver Reduction of adverse effects, such as thickening and deterioration of flow property, which sometimes can be effected when networked Amine compound is used as part of a coating composition, without losing the effect, paper excellent print suitability and printing lend effect originally caused by the crosslinked amine compound become.

Specific examples of the non-volatile substance (B1) include inorganic salts such as ammonium chloride, sodium chloride, calcium chloride, magnesium chloride, aluminum chloride, ammonium sulfate, sodium sulfate and ammonium phosphate; Ureas such as urea, methylurea, dimethylurea, thiourea, 4,5-dihydroxy-2-imidazolidinone and 1- (2-aminoethyl) -2-imidazolidinone; Saccharides such as glucose and fructose. The ureas referred to herein include ureas having an atomic group of the formula <NC (= Q) N <, wherein Q represents an oxygen or sulfur atom, and derivatives thereof. In particular, they can be represented, for example, by the formula X ¹ NHC (= Q) NX ² X ³ in which Q represents an oxygen or sulfur atom, the radicals X ¹ , X ² and X ³ each independently represent a hydrogen atom, a Alkyl or substituted alkyl, or X ¹ and X ² are joined to form an ethylene chain which may be substituted with a hydroxyl group. Among the ureas, 1- (2-aminoethyl) -2-imidazolidinone can be obtained by an ammonia cleavage reaction of diethylenetriamine with urea. This reaction product also contains by-products other than 1- (2-aminoethyl) -2-imidazolidinone, and usually the mixture containing the by-products can be used as is. Among these non-volatile substances are organic compounds, in particular ureas, by the compatibility with the crosslinked amine compound (A) and solubility in various solvents, preferred. Preferred among the ureas are urea and imidazolidinones, and urea is particularly preferred from the industrial point of view.

When the resin composition for paper coatings of the present invention is crosslinked Amine compound (A) and a non-volatile substance (B1) and the crosslinked Amine compound (A) and non-volatile substance (B1) in a liquid medium are dissolved or dispersed, the mixing order of them is not particularly be limits. As the method of mixing, the following methods (1) to (3) can be listed become.

• 1. A crosslinked amine compound is previously dispersed in a liquid medium g., or dissolved, and a non-volatile substance is added and mixed.
• 2. A non-volatile substance is previously dispersed in a liquid medium or dissolved and then the resulting liquid to a crosslinked amine compound ge give.
• 3. A cross-linked amine compound and a nonvolatile compound are disclosed in U.S. Pat dispersed or dissolved in respective liquid media which are the same or different from each other are different, and then they are mixed to a uniform state receive.

From the standpoint of the simple method, the method (1) in which a crosslinked amine compound (A) previously dispersed or dissolved in a liquid medium and a non-volatile substance (B1) is mixed in, is preferred.

The temperature when a crosslinked amine compound (A) and a non-volatile Substance (B1) is not particularly limited, and when the sol or miscibility of them in a liquid medium used If necessary, the mixture may be heated to an extent, if necessary, in the liquid medium does not evaporate. In contrast, if one or both of crosslinked amine compound (A) and non-volatile compound (B1) are a sol vat with the liquid medium, producing significant heat, the Ge are cooled to a degree in which freezing does not occur.

As described above, it is preferred that the crosslinked amine compound (A) which is a reaction product of an aliphatic amine (a) and a glycidyl compound (b) or a reaction product of an aliphatic amine (a), a Glycidylverbin compound (b) and a compound (c), in the form of a solution or dispersion in one prepared liquid medium and then added a non-volatile substance (B1) and is mixed.

A solution or dispersion of a crosslinked amine compound (A) can by Reaction of an aliphatic amine (a) with a glycidyl compound (b) in one liquid medium or by reacting an aliphatic amine (a) with a Glyci dyl compound (b), followed by addition of a liquid medium for dissolution or Dispersion can be obtained.  

Any liquid medium containing a cross-linked amine compound (A) and one not Volatile substance (B1) can dissolve or evenly dispersed, can be used the. The liquid medium may be water and / or an organic solvent. Various above as solvents for the reaction to obtain the crosslinked Solvents which have been illustrated in Table 1 (A) can also be used in this case as liquid medium can be used. In particular, any alcohol can be more advantageous alone or in combination of two or more or in combination with egg Another organic solvent can be used as alcohols are excellent in the dissolving property and dispersing property for the cross-linked amine compound (A) are.

When a glycidyl compound (b) which is a starting substance for the inventions The crosslinked amine compound (A) according to the present invention is poorly soluble in water mixed with a water and an organic solvent and in the implementation of a aliphatic amine (a) with a glycidyl compound (b) are used, and this Liquid medium can be used as a liquid medium for the crosslinked amine without modification compound (A) can be used. Depending on the case, it is also possible to use water after completion of the reaction, add the ratio of an organic solvent agent in a liquid medium for dissolving or dispersing a crosslinked To reduce amine compound (A). The ratio of organic solvent to Water in a liquid medium for dissolving or dispersing a crosslinked Amine compound is not limited, and usually the ratio of ver water used to organic solvent 1 to 100 wt .-% and the proportion of organic solvent 99 to 0 wt .-%. In particular, it is preferred that the Ratio of the water used to an organic solvent 3 to 50 Wt .-% and the proportion of an organic solvent used 97 to 50 wt. % is when the crosslinked amine compound (A) does not react with a non-polymeric one volatile substance (B1) is mixed; and the ratio of water used an organic solvent 5 to 50 wt .-% and the proportion of a used organic solvent 95 to 50 wt .-%, when the crosslinked amine compound (A) with a polyhydric alcohol (B2) is mixed.

Further, it is also possible that one for a crosslinked amine compound (A) ver Essentially, liquid medium consists essentially only of water by one Apply method in which a reaction of an aliphatic amine (a) with a Glycidyl compound (b) carried out in an organic solvent and after full continuous reaction distilled off the organic solvent and added water becomes. In this case, it is advantageous that a glycidyl compound (b) in ketones while an aliphatic amine (a) in a hydrophilic organic Lö  dissolved differently from ketones, and both solutions for the reaction be mixed. The ketones for dissolving a glycidyl compound (b) can various above as solvents for the reaction to obtain a crosslinked amine compound (A), and among them Acetone is preferably used. On the other hand, the hydrophilic organic Solvents other than ketones for dissolving an aliphatic amine (A) also from various hydrophilic organic solvents other than ketones which are used as the solvent for the reaction to obtain a crosslinked amine compound (A) are illustrated. Among them are alcohols, in particular methanol, advantageously used from an industrial point of view.

The completion of the reaction carried out by distillation of a Lösungsmit Tels is usually carried out under atmospheric pressure, although they are also under reduced pressure or can be carried out as a steam distillation. Two or several methods can be combined, such. B. steam distillation after normal pressure distillation. At normal pressure distillation, heating is preferred in the range from the boiling point of the solvent up to 100 ° C, further up to 60 ° C, performed, because if the temperature is increased too much, the crosslinked amine compound (A) is discolored. The addition of water after removing the solution is preferably carried out at a temperature in the range of 50 to 120 ° C. guided. When an organic solvent is distilled off, it is liable to be bad Dissolution when the temperature at which water is added is too low the crosslinked compound is present alone and the viscosity is too high. Next is one too high temperature with addition of water from the point of view of accident prevention by critical situations, such as climbing, not preferred.

The resin composition for paper coatings according to the invention, which is a crosslinked Amine compound (A) and a non-volatile substance (B1) as described above is obtained by mixing. The weight ratio thereof (former / latter) is usually in the range of 1/99 to 90/10, preferably in the range of 5/95 to 70/30 if the resin composition does not comprise a polyhydric alcohol (B2).

The polyhydric alcohol (B2), which is a further constituent of the inventive can be resin composition for paper coatings, is disadvantageous to reduce Effects such as thickening and deterioration of the flow property used, the sometimes can occur when a crosslinked amine compound (A) as an ingredient a coating composition is used without losing the effect is going to give paper excellent printability and printing effect, the ur is caused by the crosslinked amine compound. The polyhydric alcohol (B2) is said to be an effective ingredient together with the crosslinked amine compound (A)  remain in the coating on the coated paper by applying the Coating composition for paper on paper and evaporation of the liquid Medium, usually water or a mixture of water and an organi solvent is prepared in the coating composition. Therefore Usually a polyhydric alcohol with a higher boiling point than you depunkt used by water. The polyhydric alcohol (B2) has at least two alcoholic hydroxyl groups in one molecule. Examples of these include diols, such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol col, polyethylene glycol, polypropylene glycol, 1,3-propanediol, 1,4-butadiol, 1,5-pentane diol, 1,6-hexanediol, neopentyl glycol, cyclohexanediol, cyclohexanedimethanol and Xy ethylenediol, triols such as glycerol and trimethylolpropane, tetraols such as pentaerythritol, and Saccharides such as glucose, mannose, sorbitol, xylitol, sucrose and fructose. before It is preferably a polyhydric alcohol having a molecular weight of at most 500. When the polyhydric alcohol (B2) is a saccharide, z. For example, sorbitol or xylitol preferred without reducing group. From an industrial point of view, diethylene glycols are col, triethylene glycol, glycerin and saccharides without reducing property, such as Sor bit and xylitol, preferred.

When the resin composition for paper coatings of the present invention is crosslinked Amine compound (A) and a polyhydric alcohol (B2) is the mixed series do not follow them very much. Advantageously, the erfindungsge resin composition for paper coatings containing a crosslinked amine compound (A) and a polyhydric alcohol (B2), dissolved in a liquid medium or dis pergiert. From the viewpoint of the simplicity of the method, the resin composition is preferred Example, prepared by a method in which a crosslinked amine compound (A) before dissolved or dispersed in a liquid medium and a polyhydric alcohol (B2) or a solution thereof is added and mixed. However, the Her position of the invention, a crosslinked amine compound (A) and one more valent alcohol (B2) resin composition for paper coatings also with a process in which a polyhydric alcohol (B2) previously in a liquid Medium dissolved or dispersed and then added a crosslinked amine compound (A) is carried out, and a process in which both a crosslinked amine compound (A) and a polyhydric alcohol (B2) in the respective liquid Dispersing or dissolving media that are the same or different from each other, and then mixing them to obtain a uniform state. If the polyhydric alcohol (B2) is a liquid, it can also be used as a solvent for the synthesis of the crosslinked amine compound (A) can be used. The temperature, when a crosslinked amine compound (A) and a polyhydric alcohol (B2) are mixed  is not particularly limited, and if the solubility or miscibility of which is insufficient in a liquid medium used, the mixture if necessary, are heated to the extent that the liquid medium does not evaporated. In contrast, if one or both of crosslinked amine Compound (A) and polyhydric alcohol (B2) a solvate with the liquid medium form, generating significant heat, the mixture cooled to an extent in which freezing does not occur.

When the resin composition for paper coatings of the present invention is crosslinked Amine compound (A) and a polyhydric alcohol (B2) include, but none are not volatile substance (B1), the weight ratio thereof (former / latter) is usually in the range of 1/99 to 90/10, preferably in the range of 5/95 to 70/30.

When the resin composition for paper coatings of the present invention is crosslinked Amine compound (A), a polyhydric alcohol (B2) and a non-volatile sub punch (B1), the weight ratio of the crosslinked amine compound (A) to Total amount of the polyhydric alcohol (B2) and the nonvolatile substance (B1) usually in the range of 1/99 to 90/10, preferably in the range of 5/95 to 70/30. The amount of the non-volatile substance (B1) is preferably the Sg. Ge weight or less than the amount of the polyhydric alcohol (B2).

The thus-prepared resin composition containing a crosslinked amine compound (A) and a contains nonvolatile substance (B1) and / or a polyhydric alcohol (B2) with a pigment (C) and an aqueous binder (D), wherein a Be coating composition for paper is obtained. This coating together For paper comprises a pigment (C) and an aqueous binder (D), the vorste described crosslinked amine compound (A) and those not described above Volatile compound (B1) and / or a polyhydric alcohol (B2). Although not It is crucial that the crosslinked amine compound (A) and the non-volatile verbin (B1) and / or a polyhydric alcohol (B2) are mixed beforehand It is advantageous that a resin composition containing the crosslinked amine compound (A) and contains the non-volatile compound (B1) and / or a polyhydric alcohol (B2), prepared and then with a pigment (C) and an aqueous binder (D) is mixed.

When preparing the coating composition according to the invention for Pa pier the composition ratio of a pigment (C) and an aqueous Bin demittels (D) according to the use and task set and is not particularly to generally used in the art. With respect to the before the composition ratio is the proportion of the aqueous binder (D)  about 1 to 200 parts by weight, more preferably 5 to 50 parts by weight, based on 100 Parts by weight of the pigment (C). With respect to the crosslinked amine compound (A) and the non-volatile substance (B1) and / or a polyhydric alcohol (B2) is the Ge samtmenge of them with respect to the solids weight preferably 0.05 to 5 parts by weight Parts, and more preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the Pigments (C).

Used as part of a paper coating composition Pigment (C) may be one conventionally commonly used for coating paper and white inorganic pigments and white organic pigments can be used be used. Examples of the white inorganic pigment include kaolin, Talc, calcium carbonate (heavy or light), aluminum hydroxide, satin white and Ti tanoxide. Examples of the white organic pigment include polystyrene, melamine Formaldehyde resins and urea-formaldehyde resins. These resins can be alone or in combination of two or more.

The aqueous binder (D) may also be one which is conventionally general my is used for coating paper, and water soluble binders and water-emulsified binders can be used. Examples of the aqueous Bin demittels (D) include non-modified or modified starches, including oxi starch and phosphated starch, polyvinyl alcohol, water-soluble protein finally, casein and gelatin, and modified celluloses, including carboxy methylcellulose, a. Examples of the water-emulsified binder include styrene-butene adiene resins optionally having a carboxyl group or a nitrile group (SBR latex), acrylonitrile butadiene resins (NBR latex), chloroprene resin (CR latex), methyl methacrylate butadiene resins (MBR latex), copolymer resins from two or more types of acrylic monomers, copolymer resins of an acrylic mo nomer and vinyl acetate, copolymer resins of an acrylic monomer and styrene, Vinyl acetate resins, styrene-vinyl acetate resins and ethylene-vinyl acetate resins. This one designated acrylic monomer means a compound selected from acrylic acid, Methacrylic acid and a methyl, ethyl or butyl ester thereof. This aqueous bin The agents may be used alone or in combination of two or more.

In the preparation of a coating composition for paper is the Zu addition and mixing sequence of pigment (C), aqueous binder (D) and resin composition arbitrary and not particularly limited. However, it is generally advantageous that, after a crosslinked amine compound (A) and a non-polymeric nonvolatile Substance (B1) and / or a polyhydric alcohol (B2) comprising resin composition is prepared, a pigment (C) and an aqueous binder (D) in the resin composition be mixed.  

For example, a method wherein one in a liquid medium dissolved or dispersed resin composition to a mixture of a pigment (C) and a aqueous binder (D) is added and mixed with it, and a method Ver applies, in which a dissolved or dispersed in a liquid medium resin composition a pigment (C) or an aqueous binder (D) and mixed with it and the resulting mixture is mixed with the remaining ingredient.

The coating composition for paper of the present invention may include an resin composition such as a water resistance agent and a verb if appropriate in addition to the above description a crosslinked amine compound (A) and the non-volatile substance (B1) and / or a polyhydric alcohol (B2). Also, as another ingredient For example, a dispersant, a viscosity adjusting agent, and Fluidity, an antifoaming agent, preservative, lubricant and Water retention agents and colorants such as a dye and a colored pigment if required to be mixed.

The coating composition of the invention for paper is a Paper substrate with a conventionally known method, for example a Ver drive using various known coating devices, such as a doctor coater, air knife coater, coater, two-roll size coat coater "Gate Roll Coater" and coater, applied. The coated paper according to the invention can be followed by carrying out required drying and further performing a lubricant treatment with z. B. a supercalender if required.

The coated paper of the present invention becomes a special stock As mentioned above, covers extensive coating on a paper substrate educated. The coating is applied to at least one surface of the paper substrate educated. The coating can be formed on both surfaces of the paper substrate become. The coating comprises (C) a pigment; (D) an aqueous binder; (A) a crosslinked amine compound which is a reaction product (a) of an aliphatic amine and (b) a glycidyl compound having at least two glycidyl groups in the molecule or a reaction product of (a) an aliphatic amine, (b) a glycidyl compound having at least two glycidyl groups in the molecule and (c) a compound selected from α, β-unsaturated carbonyl compounds, α, β-unsaturated nitrile compounds and α-halocarboxylic acid compounds; and (B) at least one compound, out chooses non-polymeric non-volatile substances and polyhydric alcohols.

The coating of the paper coated according to the invention can, if he necessary to further contain a different resin mass, such as a means of lending  Water resistance and a means to improve the pressure suitability. Further For example, a dispersing agent, a viscosity adjusting agent, and Fluidity, an antifoaming agent, preservative, lubricant and Water retention agents and colorants such as a dye and a colored pigment if required to be mixed with.

Examples

The following examples further illustrate the present invention individual, but do not restrict the scope of it. In the examples, press% and parts that the content or the amount used based on the weight are unless otherwise stated. The viscosity and the pH were at 25 ° C measured.

Synthetic Example 1

In a equipped with a thermometer, reflux condenser and stirring bar Four-necked flasks were 516.8 g (4.00 mol) of N- (2-aminoethyl) piperazine and 396.1 g Methanol introduced. The internal temperature was maintained at 45 to 55 ° C and to slowly added dropwise a solution prepared by previously mixing 802.7 g (2.36 g) mol) of bisphenol A diglycidyl ether and 416.4 g of acetone. To Complete dropwise, the reaction was an additional 4 hours at a Innentempe temperature of 45 to 55 ° C continued. Then, after the reflux condenser was passed through egg Liebig cooler was replaced, the internal temperature increased to 120 ° C while Acetone and methanol were extracted from the system. Then the mixture became cooled with gradual addition of 597.6 g of water, with an aqueous solution a crosslinked amine compound having a nonvolatile content of 63.8%, a pH of 12.5 and a viscosity of 89500 mPa.s (about 10,000 mPa.s with respect to a 50% concentration).

Synthesis Example 2

In the same reaction vessel as in Synthesis Example 1 were used Added 92.9 g (0.72 mol) of N- (2-aminoethyl) piperazine and 99.0 g of methanol. The Internal temperature was maintained at 45 to 55 ° C and to a solution ge slowly by preliminary mixing of 105.0 g (0.31 mol) of bisphenol A diglyci dyl ether and 99.0 g of acetone were prepared. After complete dropping the reaction was another 4 hours at an internal temperature of 45 to 55 ° C. continued. Then, after replacing the reflux condenser with a Liebig condenser The internal temperature was raised to 120 ° C while acetone and methanol were out  extracted from the system. Then the mixture was added with gradual addition of 243.4 g of water cooled, wherein an aqueous solution of a crosslinked amine compound With a non-volatile content of 39.9%, a pH of 12.1 and a viscosity of 1898 mPa.s (about 9000 mPa.s with respect to a 50% Concentration).

Synthesis Example 3

In the same reaction vessel as in Synthesis Example 1 were used 64.6 g (0.50 mol) of N- (2-aminoethyl) piperazine and 78.0 g of methanol are introduced. The Internal temperature was maintained at 45 to 55 ° C and to a solution ge slowly by mixing in advance 91.3 g (0.27 mol) of bisphenol A diglyci dyl ether and 77.9 g of acetone. After complete dropping the reaction was another 4 hours at an internal temperature of 45 to 55 ° C. continued. Then, after replacing the reflux condenser with a Liebig condenser The internal temperature was raised to 120 ° C while acetone and methanol were out extracted from the system. Then the mixture was added with gradual addition of 188.6 g of water cooled, wherein an aqueous solution of a crosslinked amine compound with a non-volatile content of 41.8%, a pH of 12.4 and a viscosity of 1839 mPa.s (about 6500 mPa.s with respect to a 50% Concentration).

Synthesis Example 4

In the same reaction vessel as in Synthesis Example 1 were used 75.6 g (0.59 mol) of N- (2-aminoethyl) piperazine and 96.6 g of methanol are introduced. The Internal temperature was maintained at 45 to 55 ° C and to a solution ge slowly by mixing beforehand 117.6 g (0.35 mol) of bisphenol A diglyci dyl ether and 96.6 g of acetone. After complete dropping the reaction was another 4 hours at an internal temperature of 45 to 55 ° C. continued. Then, after replacing the reflux condenser with a Liebig condenser The internal temperature was raised to 120 ° C while acetone and methanol were out extracted from the system. Then the mixture was added with gradual addition of 236.4 g of water cooled, wherein an aqueous solution of a crosslinked amine compound with a non-volatile content of 42.7%, a pH of 12.4 and a viscosity of 3980 mPa.s (about 12000 mPa.s with respect to a 50% Concentration).  

Synthesis Example 5

In the same reaction vessel as in Synthesis Example 1 were used Added 90.6 g (0.70 mol) of N- (2-aminoethyl) piperazine and 96.5 g of methanol. The Internal temperature was maintained at 45 to 55 ° C and to a solution ge slowly by preliminary mixing of 102.5 g (0.31 mol) of bisphenol A diglyci dyl ether and 96.6 g of acetone. After complete dropwise wur wur the reaction continued for another 4 hours at an internal temperature of 45 to 55 ° C. set. Then, after replacing the reflux condenser with a Liebig condenser The internal temperature was raised to 120 ° C while acetone and methanol were out extracted from the system. Then the mixture was added with gradual addition of 233.7 g of water cooled, wherein an aqueous solution of a crosslinked amine compound with a non-volatile content of 38.7%, a pH of 12.2 and a viscosity of 560 mPa.s (about 3000 mPa.s with respect to a 50% Concentration).

Synthetic Example 6

In one equipped with a thermometer, reflux condenser and stirring bar Four-necked flasks were 90.4 g (0.7 mol) of N- (2-aminoethyl) piperazine and 109.1 g of metha nol introduced. The internal temperature was maintained at 45 to 55 ° C and slowly added dropwise a solution prepared by previously mixing 140.6 g (0.77 mol) Bis phenol A diglycidyl ether with an epoxy equivalent of 182.6 g / eq. and 120.0 g Acetone had been produced. Upon complete addition, the reaction became continued for another 4 hours at an internal temperature of 45 to 55 ° C. Then, after the reflux condenser had been replaced by a Liebig condenser, the inside temperature increased to 120 ° C while acetone and methanol extracted from the system were. The mixture was then poured off with the gradual addition of 295.2 g of water Cooling, wherein 531.8 g of an aqueous solution of an intermediate of a crosslinked Amine compound were obtained.

Into the same reaction vessel as used above were 141.2 g of the aqueous solution of the intermediate of a crosslinked amine compound. To this was added while maintaining the internal temperature at 65 to 75 ° C 8.37 g (0.093 mol) of an 80% strength by weight aqueous solution of acrylic acid within one hour drips. After complete dropwise addition, the reaction was continued for a further 4 hours Internal temperature of 65 to 75 ° C, wherein an aqueous solution of a crosslinked amine compound with a nonvolatile content of 45.3%, a pH of 9.1 and a viscosity of 1735 mPa.s was obtained.  

Synthesis Example 7

A solution was prepared by mixing 637.6 g (3.47 mol) of bisphenol A diglyci dylether having an epoxy equivalent of 184.0 g / eq. and 542.6 g of acetone. The total amount of the solution obtained was 1180.2 g.

In the same reaction vessel as in Synthesis Example 6 were used 423.4 g (3.3 mol) of N- (2-aminoethyl) piperazine and 516.8 g of methanol were introduced. To while keeping the internal temperature at 48 to 54 ° C 1124.0 g of the above he solution slowly dripped within 5 hours. After complete dropping the reaction was another 4 hours at an internal temperature of 48 to 54 ° C. continued. Then, after replacing the reflux condenser with a Liebig condenser The internal temperature was raised to 120 ° C while acetone and methanol were out extracted from the system. Then the mixture was added with gradual addition of 1285.7 g of water cooled, with 2384.0 g of an aqueous solution of an intermediate product of a crosslinked amine compound.

In the same reaction vessel as used in Synthetic Example 6 180.6 g of the aqueous solution of the intermediate of a crosslinked amine compound and 0.77 g of water introduced. This was while keeping the internal temperature at 65 to 75 ° C slowly 6.76 g (0.075 mol) of an 80 wt .-% aqueous solution of acrylic acid dripped within 5 minutes. After complete dropping the Umset continued for about 4 hours at an internal temperature of 65 to 75 ° C, wherein an aqueous solution of a crosslinked amine compound containing not Volatile component of 45.1%, a pH of 9.7 and a viscosity of 3660 mPa.s was obtained.

Synthesis Example 8

A solution was prepared by mixing 191.7 g (1.042 mol) of bisphenol A diglyme cidyl ether having an epoxy equivalent of 184.0 g / eq. and 180 g of acetone. The total amount of the obtained solution was 371.7 g.

In the same reaction vessel as in Synthesis Example 6 were used 129.2 g (1.0 mol) of N- (2-aminoethyl) piperazine and 138.2 g of methanol are introduced. To while keeping the internal temperature at 48 to 54 ° C, 285.4 g of the above solution slowly dropped within 5 hours. After complete dropwise wur wur the reaction continued for another 4 hours at an internal temperature of 48 to 54 ° C puts. Then, after the reflux condenser was replaced with a Liebig condenser was the, the internal temperature increased to 120 ° C, while acetone and methanol from the System were extracted. Intestine, the mixture was added with gradual addition of  339.9 g of water were cooled, whereby 637.8 g of an aqueous solution of a Zwischenpro of a crosslinked amine compound were obtained.

In the same reaction vessel as in Synthesis Example 6 were used 127.6 g of the aqueous solution of the intermediate of a crosslinked amine compound brought in. To this end, while maintaining the internal temperature at 65 to 75 ° C slowly 3.6 g (0.04 mol) of an 80 wt .-% aqueous solution of acrylic acid within 5 Mi dripped. After completion of the dropping, the reaction continued for about 4 hours carried out at an internal temperature of 65 to 75 ° C, wherein an aqueous Lö solution of a crosslinked amine compound containing a non-volatile constituent of 44.4%, a pH of 9.7 and a viscosity of 1049 mPa.s has been.

Synthetic Example 9

In the same reaction vessel as in Synthesis Example 6 were used 180.6 g of the obtained in Synthesis Example 7 aqueous solution of the intermediate the crosslinked amine compound and 13.8 g of water introduced. These were under Keep the internal temperature at 65 to 75 ° C slowly 7.2 g (0.075 mol) of chloroacetic acid dripped within 5 minutes. Upon complete addition, the reaction became further carried out for about 4 hours at an internal temperature of 65 to 75 ° C, wherein an aqueous solution of a crosslinked amine compound containing not Volatile component of 45.3%, a pH of 8.2 and a viscosity of 3740 mPa.s was obtained.

Reference Example 1

In the same reaction vessel as in Synthesis Example 1 were used 1237.9 g (12 mol) of diethylenetriamine and 720.8 g (12 mol) of urea at 80 ° C turned and after heating the mixture to 145-155 ° C, the mixture became 2 Hours heated to the same temperature. Then the mixture was cooled where at 1536.0 g of a mainly consisting of 1- (2-aminoethyl) -2-imidazolidinone Reaction product were obtained. This reaction product is practically not volatile at ambient temperature.

example 1

51.3 g of a 63.8% aqueous solution obtained in Synthesis Example 1 crosslinked amine compound, 49.1 g of that obtained in Reference Example 1 mainly from 1- (2-aminoethyl) -2-imidazolidinone existing reaction product and 33.8 g Water was mixed then stirred completely to give a cross-linked amine  holding water dispersion with a content of 61% (active ingredient), a pH of 13.0 and a viscosity of 505 mPa.s. This is called Resin composition A denotes.

Example 2

79.2 g of a 63.8% aqueous solution obtained in Synthesis Example 1 crosslinked amine compound, 50.5 g of that obtained in Reference Example 1 mainly from 1- (2-aminoethyl) -2-imidazolidinone existing reaction product and 36.0 g Water was mixed then stirred completely to give a cross-linked amine holding aqueous solution containing 61% (effective ingredient), a pH of 13.0 and a viscosity of 1250 mPa.s was obtained. This is called Resin composition B referred.

Example 3

80.0 g of a 63.8% aqueous solution obtained in Synthesis Example 1 crosslinked amine compound, 34.9 g of that obtained in Reference Example 1 mainly from 1- (2-aminoethyl) -2-imidazolidinone existing reaction product and 26.1 g Water was mixed then stirred completely to give a cross-linked amine holding aqueous solution containing 61% (effective ingredient), a pH of 12.8 and a viscosity of 2768 mPa.s was obtained. This is called Resin composition C designated.

Example 4

101.3 g of a 39.9% aqueous solution obtained in Synthesis Example 2 crosslinked amine compound, 94.3 g urea and 68.6 g water were mixed, then completely stirred, with a crosslinked amine-containing aqueous solution with a content of 51% (active ingredient), a pH of 12.3 and a Viscosity of 17 mPa.s was obtained. This is called resin composition D.

Example 5

80.9 g of a 39.9% aqueous solution obtained in Synthesis Example 2 crosslinked amine compound, 129.1 g urea and 106.4 g water were mixed, then completely stirred, with a crosslinked amine-containing aqueous solution with a content of 51% (active ingredient), a pH of 12.3 and a Viscosity of 10 mPa.s was obtained. This is called resin composition E.  

Example 6

100.4 g of a 41.8% aqueous solution obtained in Synthesis Example 3 crosslinked amine compound, 98.0 g of urea and 76.0 g of water were mixed, then completely stirred, with a crosslinked amine-containing aqueous solution with a content of 51% (active ingredient), a pH of 12.1 and a Viscosity of 18 mPa.s was obtained. This is referred to as resin composition F.

Example 7

85.8 g of a 41.8% aqueous solution obtained in Synthesis Example 3 crosslinked amine compound, 143.4 g of urea and 122.3 g of water were mixed, then completely stirred, with a crosslinked amine-containing aqueous solution with a content of 51% (active ingredient), a pH of 12.1 and a Viscosity of 10 mPa.s was obtained. This is called resin composition G.

Example 8

97.5 g of a 42.7% aqueous solution obtained in Synthesis Example 4 crosslinked amine compound, 97.1 g urea and 77.4 g water were mixed, then completely stirred, with a crosslinked amine-containing aqueous solution with a content of 51% (active ingredient), a pH of 12.1 and a Viscosity of 23 mPa.s was obtained. This is referred to as resin composition H.

Example 9

71.3 g of a 42.7% aqueous solution obtained in Synthesis Example 4 crosslinked amine compound, 121.7 g of urea and 105.4 g of water were mixed, then completely stirred, with a crosslinked amine-containing aqueous solution with a content of 51% (active ingredient), a pH of 12.0 and a Viscosity of 10 mPa.s was obtained. This is called resin composition I.

Example 10

129.3 g of an aqueous solution of the crosslinked product obtained in Synthesis Example 5 Amine compound, 116.8 g of urea and 81.0 g of water were mixed, then full constantly stirred, wherein a crosslinked amine-containing aqueous solution with a Content of 51% (effective ingredient), a pH of 12.0 and a viscosity of 17.5 mPa.s was obtained. This is called resin composition J.  

Example 11

100.0 g of a 45.3% aqueous solution obtained in Synthesis Example 6 crosslinked amine compound, 181.2 g of that obtained in Reference Example 1 mainly from 1- (2-aminoethyl) -2-imidazolidinone existing reaction product and 271.2 g Water was mixed then stirred completely to give a cross-linked amine holding aqueous solution containing 41% (effective ingredient), a pH of 10.5 and a viscosity of 62.5 mPa.s. This is called Resin composition K denotes.

Example 12

100.0 g of a 45.3% aqueous solution obtained in Synthesis Example 6 crosslinked amine compound, 105.7 g of that obtained in Reference Example 1 mainly from 1- (2-aminoethyl) -2-imidazolidinone existing reaction product and 162.6 g Water was mixed then stirred completely to give a cross-linked amine holding aqueous solution containing 41% (effective ingredient), a pH of 10.7 and a viscosity of 78.3 mPa.s was obtained. This is called Resin mass L called.

Example 13

100.0 g of a 45.3% aqueous solution obtained in Synthesis Example 6 crosslinked amine compound, 68.0 g of that obtained in Reference Example 1 mainly from 1- (2-aminoethyl) -2-imidazolidinone existing reaction product and 108.3 g Water was mixed then stirred completely to give a cross-linked amine holding aqueous solution containing 41% (effective ingredient), a pH of 11.0 and a viscosity of 98.8 mPa.s. This is called Resin mass M called.

Example 14

97.2 g of a 45.1% aqueous solution obtained in Synthesis Example 7 crosslinked amine compound, 167.8 g of urea and 246.6 g of water were mixed, then completely stirred, with a crosslinked amine-containing aqueous solution with a content of 41% (active ingredient), a pH of 10.0 and a Viscosity of 10.0 mPa.s was obtained. This is called resin mass N.  

Example 15

100.0 g of a 45.1% aqueous solution obtained in Synthesis Example 7 crosslinked amine compound, 100.8 g urea and 150.4 g water were mixed, then completely stirred, with a crosslinked amine-containing aqueous solution with a content of 51% (active ingredient), a pH of 10.3 and a Viscosity of 11.0 mPa.s was obtained. This is referred to as resin composition O.

Example 16

53.3 g of a 44.4% aqueous solution obtained in Synthesis Example 8 crosslinked amine compound, 85.7 g urea and 122.2 g water were mixed, then completely stirred, with a crosslinked amine-containing aqueous solution with a content of 41% (active ingredient), a pH of 10.0 and a Viscosity of 9 mPa.s was obtained. This is referred to as resin composition P.

Example 17

62.0 g of a 44.4% aqueous solution obtained in Synthesis Example 8 crosslinked amine compound, 58.14 g of urea and 82.4 g of water were mixed, then completely stirred, with a crosslinked amine-containing aqueous solution with a content of 41% (active ingredient), a pH of 10.2 and a Viscosity of 10.0 mPa.s was obtained. This is referred to as resin composition Q.

Example 18

100.0 g of a 45.3% aqueous solution obtained in Synthesis Example 9 crosslinked amine compound, 181.2 g urea and 271.2 g water were mixed, then completely stirred, with a crosslinked amine-containing aqueous solution with a content of 41% (active ingredient), a pH of 8.6 and a Viscosity of 10.0 mPa.s was obtained. This is called resin composition R.

Example 19

81.6 g of a 45.3% aqueous solution obtained in Synthesis Example 9 crosslinked amine compound, 86.3 g urea and 132.7 g water were mixed, then completely stirred, with a crosslinked amine-containing aqueous solution with a content of 41% (active ingredient), a pH of 8.8 and a Viscosity of 12.0 mPa.s was obtained. This is called resin composition S.  

In the following examples, coating compositions for paper were used using the crosslinked amine obtained in the above Examples prepared and evaluated.

Examples 20 to 37 and controls 1 to 2

An aqueous master color having a composition shown in Table 1 and a solids content of 64.5% was prepared.

Table 1 Composition of the master color

Name of the ingredient Solid ratio Pigment * 1 100 parts Dispersant * 2 0.2 parts Aqueous binder * 3 15 parts

* 1: Pigment: A mixture of 60 parts of Ultra white 90 (clay, manufactured by Engel Hard Minerals, USA) and 40 parts of Karbital 90 (calcium carbonate, manufactured by Fuji Kaolin Co., Ltd.)
* 2: Dispersant: Commercially available pigment dispersant based on polyacrylic acid
* 3: Aqueous binder: A mixture of 11 parts of a commercially available styrene-butadiene latex and 4 parts of commercially available oxidized starch

Each resin composition obtained in Examples 1 to 9 and Examples 11 to 19 was added to the master color listed in Table 1 so that the solids content was 0.6 parts per 100 parts pigment in the master color. In control 1 was an aqueous thermosetting polyamide-polyurea-formaldehyde resin (in the Table abbreviated as "PAPU") solution containing 50% (effective ingredient), those described in Example 3 of JP-A-55-31837 (= US-A-4,246,153) Method was prepared, instead of the resin composition described above in the same amount as in Examples 11 to 19 added. In Control 2, the Master color as it is used without adding a resin component. Water and one 10% sodium hydroxide solution was added to the mixtures to remove the conc and adjust the pH thereof, wherein coating compositions obtained with a total solids content of 64%.  

Examples 38 and 39

Both the resin composition A obtained in Example 1 and those in Example 4 erhal Dene resin composition D are with the same commercially available styrene-butadiene La tex as that used to make the master color in Table 1, so that the solid content of the resin and the latex is 5/100. The obtained mixed Latex is further processed with the same pigment and dispersant as that used in the product used in Table 1, and an oxidized starch according to the mixed ratio shown in Table 2. Water and a 10% sodium hydro Oxide solution was added to the mixtures for concentration and pH thereof, wherein coating compositions having an overall strength content of 64%.

Table 2 Composition of the master color

Name of the ingredient Solid ratio pigment 100 parts dispersants 0.2 parts Oxidized starch 4 parts Aqueous binder 11 parts

The physical properties of those in Examples 20-39 and Controls 1 and 2 coating compositions obtained were obtained by the following methods measured. The results thereof are shown in Tables 3 and 4.

(1) pH

A glass ion electrode type hydrogen ion densitometer [manufactured by Toa Denpa Kogyo K.K.] was used. The pH of a coating composition immediately after preparation was measured at 25 ° C.

(2) Viscosity

A B-type viscometer [BL type, manufactured by Tokyo Keiki K.K.] was used used, and the viscosity of a coating composition immediately after Preparation was measured at 25 ° C and 60 rpm.

Each of the obtained coating compositions was applied to a surface of a high quality paper having a basis weight of 80 g / m ² using a wire rod so that the applied amount was 14 g / m ² . Immediately after coating, it was dried with hot air at 120 ° C for 30 seconds, then the moisture was adjusted for 16 hours at a temperature of 20 ° C and a relative humidity of 65%. Thereafter, a satin treatment was carried out twice at a temperature of 60 ° C and a linear load of 60 kg / cm to obtain coated paper. The coated paper thus obtained was subjected to tests for the water resistance and color-accepting property, and the results of the tests are shown in Tables 2, 3-1 and 3-2. The test methods are listed below.

(3) water resistance Wet pick method (WP method)

An RI tester (manufactured by Akari Seisakusho KK) was used. The coated surface was moistened with a water supply roller and then printed and the paper release state was examined and evaluated with the naked eye. The determination criteria are as listed below.
Water resistance: (bad) 1 to 5 (excellent)

(4) ink accepting property (4-1) Method A

An RI tester was used. The coated surface was moistened with a water supply roller and then printed, and the ink accepting property was examined and evaluated by the naked eye. The determination criteria are listed as follows.
Ink acceptance property: (poor) 1 to 5 (excellent)

(4-2) Method B

An RI tester was used. A small clearance was formed between a metal roller and a rubber roller, and water was poured to this distance, and then printing was quickly performed, and the ink accepting property was examined and judged by the naked eye. The determination criteria are as listed below.
Ink acceptance property: (poor) 1 to 5 (excellent)

Table 3-1

Test results of Examples 20 to 28

Table 3-2

Test results of Examples 29 to 37

Table 4

Test results of Examples 38 and 39 and Controls 1 to 2

Examples 40 and 41 and Controls 3 to 4

An aqueous master ink having a composition listed in Table 1 and a solids content of 64.5% was prepared.

Each resin composition obtained in Examples 5 and 10 became that in Table 1 shown master color, so that the solids content therein 0.2 parts per 100 parts Pigment in the master color was. In Control 3, an aqueous thermosetting Polyamide-polyurea-formaldehyde resin (abbreviated as "PAPU" in the table) -Lo containing 50% (active ingredient) according to the procedure described in Example 3 manufactured by JP-A-55-31837 (= US-A-4,246,153), instead of the resin composition described above, so that the solids content was 0.6 parts per 100 parts pigment in the master color. In control 4 was the master color as it is used without adding the resin component. water and A 10% sodium hydroxide solution was added to the mixtures to obtain the Concentration and adjust the pH thereof, wherein coating together were obtained with a total solids content of 64%.

Each of the obtained coating compositions was applied to a surface of a high quality paper having a basis weight of 80 g / m ² using a wire rod so that the applied amount was 14 g / m ² . Immediately after the coating, it was dried with hot air at 120 ° C for 30 seconds, then the moisture was adjusted for 16 hours at a temperature of 20 ° C and a relative humidity of 65%. Thereafter, a calendering treatment was carried out twice at a temperature of 60 ° C and a linear load of 60 kg / cm to obtain coated paper. The coated paper thus obtained was subjected to tests for the water resistance and ink-receptive property, and the results of the tests are shown in Table 5. The test methods of water resistance and ink accepting property are as mentioned above, and the test methods for examining the gloss of white paper and the gloss of printed paper are as follows.

(5) gloss of white paper Gw

Using a digital photometer "GM-26D" (manufactured by Mura kami Color Technology Laboratory) became the positive reflection of light intensity (%) of the coated paper measured at a reflection angle of 75 ° -75 °.

(6) gloss of printed paper gp

Using an RI tester, overlap printing became twice performed on coated paper. Using a digital photometer "GM-26D" (the same photometer as used in (3)) became the positive reflection the light intensity (%) of the printed part of the coated paper in one Reflection angle measured from 60 ° -60 ° C. The larger Gp, the better the shine of the printed paper.

(7) Gloss difference ΔG

The gloss difference ΔG is the difference between the gloss of white Paper and the gloss of printed paper, d. H. GP Gw. The larger ΔG, the more greater is the difference in gloss on the printed part and the gloss on the non-printed part. A big difference enables high-quality printing Contrast.  

Table 5

Test results of Examples 40 and 41 and Controls 3 to 4

The white papers of Example 40, Example 41, Control 3 and Control 4 differ very little in gloss from each other. ΔG of control 3, at a known polyamide-polyurea-formaldehyde resin has been used is smaller as the ΔG of the control 4 in which no resin component was mixed. on the other hand For example, ΔG of Example 40 and Example 41, Examples of the present invention, are many in addition, Example 40 and Example 41, ins particular example 41, greatly improved ink acceptance properties.

The coated paper according to the invention contains no abge of formaldehyde derived ingredient. The coated paper according to the invention does not produce a shape aldehyde.

The coated paper of the present invention is excellent in color pickup property and water resistance, and the gloss of the coated paper little worsened or even improved compared to coated paper that is prepared using a coating composition that does not Contains resin component.  

Synthetic Example 10

In a equipped with a thermometer, reflux condenser and stirring bar Four-necked flasks were 646 g (5.0 mol) of N- (2-aminoethyl) piperazine and 690 g of methanol brought in. The internal temperature was maintained at 45 to 55 ° C and slowly a solution was added dropwise by previously mixing 807 g (2.4 mol) of bisphenol A diglycidyl ether and 759 g of acetone had been prepared. After complete closing The reaction was allowed to drip for an additional 4 hours at an internal temperature of 45 to 55 ° C continued. Then, after the reflux condenser through a Liebig condenser was replaced, the internal temperature increased to 80 ° C and the internal pressure to 21 kPa while acetone and methanol were extracted from the system. Then The internal pressure was increased to atmospheric pressure and the mixture was gradually added to 1692 g of water, with an aqueous solution of a crosslinked amine compound with a non-volatile content of 39.6 %, a pH of 11.9 and a viscosity of 839 mPa.s (about 5000 mPa.s in with respect to a 50% concentration). This is called an aqueous solution denoted by crosslinked amine X.

Synthetic Example 11

In the same reaction vessel as in Synthesis Example 6 were used 426 g (3.3 mol) of N- (2-aminoethyl) piperazine and 517 g of methanol were introduced. The interior temperature was maintained at 45 to 55 ° C and slowly added dropwise a solution that by previously mixing 638 g (1.9 mol) of bisphenol A diglycidyl ether and 543 g of acetone had been prepared. After complete dropping the Umset continued for an additional 4 hours at an internal temperature of 45 to 55 ° C. Then After the reflux condenser had been replaced by a Liebig condenser, the Internal temperature increased to 120 ° C, while acetone and methanol from the system ex were traded. Then the mixture was added with gradual addition of 1286 g Cooled water, wherein an aqueous solution of a crosslinked amine compound with a non-volatile content of 41.8%, a pH of 11.8 and a viscosity of 2420 mPa.s (about 9000 mPa.s with respect to a 50% Concentration). This is used as an aqueous solution with crosslinked amine Y. designated.

Examples 42 to 48 and Controls 5 to 6

In Example 42, 25.3 parts of the prepared in Synthesis Example 10 aq crosslinked amine solution X, 40 parts of triethylene glycol and 32.8 parts of water mixed, then completely stirred, with an aqueous solution of the resin composition with egg  a content of 51% (active ingredient) was obtained. Similar in the Examples 43 to 48, the aqueous solution of the crosslinked amine, the polyvalent Alcohol and in some examples, urea according to the Ver mixed amount and the concentration is adjusted with the addition of water, wherein an aqueous solution of the resin composition containing 51 (more effective Component)%.

An aqueous master ink having a composition shown in Table 1, a solids content of 64.5% and a pH of 9.2 was prepared.

Each resin composition obtained in Examples 42 to 48 became that in Table 1 listed master paint, so that the solids content is 0.6 parts per 100 Parts of pigment in the master color amounted to. In Control 5, an aqueous was heat-cured polyamide-polyurea-formaldehyde resin (abbreviated in the table as "PAPU") - Solution containing 50% (active ingredient), prepared according to an in Example 3 of JP-A-55-31837 (= US-A-4,246,153) instead of the resin composition described above in the same amount as in Examples 42-48. In Control 6, the master color was as it is used without addition of a resin component. Water became the mixture given to adjust the concentration thereof, taking coating compositions were obtained with a total solids content of 64%. The pH and viscosity of each coating composition was determined according to measured above and the results are in Table 6 listed.

Each of the obtained coating compositions was applied to a surface of a high quality paper having a basis weight of 80 g / m ² using a wire rod so that the applied amount was 14 g / m ² . Immediately after coating, it was dried with hot air at 120 ° C for 30 seconds, then the moisture was adjusted for 16 hours at a temperature of 20 ° C and a relative humidity of 65%. Thereafter, a satin treatment was carried out twice at a temperature of 60 ° C and a linear load of 60 kg / cm to obtain coated paper. The coated paper thus obtained was subjected to tests for the water resistance and ink-receptive property, and the results of the tests are shown in Table 6. The test methods of water resistance and ink-receiving property are as listed above.

Table 6

Test results of the evaluation of Examples 42 to 48 and Controls 5 to 6

The resin composition for paper coatings according to the invention contains none of Formaldehyde derived ingredient. Therefore, one comprising the resin composition generates Coating composition for paper no formaldehyde.

The resin composition for paper coatings according to the invention may take the form of a Solution or dispersion in a liquid medium, such as a mixture of what and an organic solvent and essentially water alone which can be mixed with a pigment and an aqueous binder,  to prepare a coating composition for paper. The coating Composition for paper does not tend to disadvantages, such as thickening and deterioration effect on the fluidity.

The coating composition comprising the resin composition is 00375 00070 552 001000280000000200012000285910026400040 0002019957348 00004 00256 For paper, a coated paper is provided which has various ver improved abilities, such as B. excellent inking property and Water resistance.

Claims (17)

1. Resin composition comprising

• (A) a crosslinked amine compound which
  a reaction product of (a) an aliphatic amine and (b) a glycidyl compound having at least two glycidyl groups in the molecule or
  a reaction product of (a) an aliphatic amine, (b) a glycidyl compound having at least two glycidyl groups in the molecule and (c) a compound selected from α, β-unsaturated carbonyl compounds, α, β-unsaturated nitrile compounds and α-halo-carboxylic acid compounds; and
• (B) at least one compound selected from (B1) non-polymeric non-volatile substances and (B2) polyhydric alcohols.

2. Resin composition according to claim 1, wherein the crosslinked amine compound (A) a reaction product (a) of an aliphatic amine and (b) a glycidyl compound tion with at least two glycidyl groups in the molecule. 3. Resin composition according to claim 2, wherein component B is a non-polymeric, not volatile substance is. 4. A resin composition according to claim 2, wherein component B is a polyhydric alcohol. 5. Resin composition according to claim 1, wherein

• (A) a crosslinked amine compound comprising a reaction product of (a) an aliphatic amine, (b) a glycidyl compound having at least two glycidyl groups in the molecule and (c) one of α, β-unsaturated carbonyl compounds, α, β-unsaturated nitrile compounds and α Halogenated carboxylic acid compounds is selected compound; and
• (B) is a non-polymeric, non-volatile substance.

6. Resin composition according to any one of claims 1-5, wherein the aliphatic amine (a) a heterocyclic amine. The resin composition of claim 6, wherein the heterocyclic amine is at least one primary amino group in addition to a heterocycle-forming secondary or tertiary amine group.   8. Resin composition according to any one of claims 1-7, wherein the glycidyl compound (b) a aromatic glycidyl ether. 9. Resin composition according to claim 1 or 5, in which the α, β-unsaturated carbonyl compounds, α, β-unsaturated nitrile compounds and α-halocarboxylic acid compounds selected acrylic acid or chloroacetic acid. 10. Resin composition according to any one of claims 1-3 and 5-9, in which the non-volatile Substance (B1) is selected from ureas. 11. Resin composition according to any one of claims 1-10, which in a liquid medium dispersed or dissolved. 12. The resin composition of claim 11, wherein the liquid medium is a mixture of what and an organic solvent. 13. Resin composition according to claim 11, in which the liquid medium consists essentially of Water exists. 14. A coating composition comprising a resin composition according to any one of claims 1-13, and

• (C) a pigment; and
• (D) an aqueous binder.

15. Coated paper comprising

• (1) a paper substrate and
• (2) A coating according to claim 14 on at least one surface of the paper substrate.

16. Use of a resin composition according to any one of claims 1-13 for the preparation a coating composition. 17. Use of a coating composition according to claim 14 or 15 for coating paper.