FI109221B - Resin alloys for paper coating, blends for paper coatings and coated paper - Google Patents

Description

109221

Paper coating resin alloy, paper coating composition and coated paper. - Hartsblandning for pappersbeläggning, beläggninsbland-Ning for papper and belagt papper.

The present invention relates to a resin blend for paper coating and a paper coating composition consisting of a resin blend, a pigment and an aqueous binder. More particularly, there is provided a resin blend for paper coating and a paper coating blend that does not cause formaldehyde formation and can give the paper excellent printability and printability. The present invention also relates to a coated paper having a coating mainly consisting of pigment and an aqueous binder, which does not cause the formation of formaldehyde, which has excellent printability and printing result and good printing gloss. As used in this publication, the term "paper" has a broad meaning including "paperboard" in addition to paper used in the narrow sense.

Commercial papers, magazines, books and the like, because of their advantageous properties, such as excellent printing results, use coated paper obtained by using a coating composition consisting mainly of pigment 20 and an aqueous binder and performs; racket necessary treatments such as drying, calendering and the like. However; ··; other steps are also taken to improve the coated paper; quality in relation to the need to improve quality, speed up printing and the like * · · '; /, * ·. Especially in offset printing, which forms a significant part of »»; '.' 25 printing, requires the ink's absorption capacity under the influence of wetting water, waterproofing and the like, wet gloss, improved gloss and blister resistance in the web press.

In order to accomplish these objectives, conventional known '' · * methods for adding water resistance to a paper coating composition are available: 'as melamine-formaldehyde resins, urea-formaldehyde resins, as adjuvant or binder additive, in JP-P 44-11667 and JP-A-55- Polyamide-polyurea-formaldehyde resins described in? 1837 (= 2,109,221 USP 4,246,153), block glyoxal resins described in JP-A-63-120197, or the like. However, none of these conventional waterproofing agents and binder additives may work well in practice, because some properties have been found to have significant deficiencies or undue effects, although they have some functional advantages.

For example, so-called aminoplast resins such as melamine-formaldehyde resins, urea-formaldehyde resins and the like cause some problems. In addition to the remarkable formation of formaldehyde during processing or from coated paper, their low ink absorption and blister resistance properties are not easily affected by the effect of water resistance as the pH of the coating composition increases, etc.

Polyamide polyurea-formaldehyde resins provide somewhat better effects, such as Parmepi ink absorption and water resistance. However, the use of polyamide-polyurea-formaldehyde resins cannot prevent the formation of formaldehyde since formaldehyde is used in the preparation of resins.

20

Block glycoloxal resins, known as formaldehyde-free binder additive, on the other hand, have only a very slight effect on the quality of the coated paper, such as ink absorbency, blistering resistance and the like, although they may provide some water resistance against wetting water.

Another problem is that coated papers made using a coating composition blended with a waterproofing agent such as the above-mentioned aminoplast resins and polyamide-polyurea-formaldehyde resins on paper substrates often have a diminished printing finish, and a coating composition of aqueous binders. The reduction in the print gloss makes the paper feel less high quality because the sense of high quality is the result of the contrast between the non-printed parts and the printed parts and the higher the print gloss of the non-printed parts produces a higher contrast.

In this context, the present inventors have previously proposed in JP-A-10-77599 to use a crosslinked amine compound selected from the aliphatic amine and the aldehyde, glycidyl compound as a resin component in the paper coating composition to improve the quality of the coated paper. In JP-A-11-140792, the present inventors have further proposed that a crosslinked amine compound, which is a reaction product of a heterocyclic amine and a glycidyl compound, is used as a resin component in a paper coating composition.

15 Problems Solved by the Invention

When the crosslinked amine compound, which is the reaction product of the amine and glycidyl compound described in JP-A-10-77599 and JP-A-11-140792, is used as a resin component, it has been found that the coating composition may thicken, depending on the combination with other components, the use of this crosslinked amine compound; and the like. The inventors of the present invention are; further explored how such problems can be resolved and how the gloss of the printing mixture caused by the coating composition can be resolved. The present invention is the result of these studies. It is an object of the present invention to provide a resin blend for paper coating that can provide coated paper with high quality properties such as: *. *. high ink absorption, excellent water resistance and similar '·' properties; the mixture does not cause formaldehyde formation and well meets the I: 30 quality requirements for coated paper.

It is another object of the present invention to provide a resin blend for paper coating which causes hardly any such disadvantages. \ n 4 109221 thickening, dripping, and the like, and can thus be easily treated when mixed with a pigment and an aqueous binder to form a paper coating composition.

It is a further object of the present invention to provide a paper-coating composition using the above-mentioned resin mixture.

It is a further object of the present invention to provide a coated paper made using the above paper coating composition which does not cause the formation of formaldehyde which has good properties such as high ink-absorbing ability and excellent water resistance and good print gloss.

Solving Problems 15

The present invention relates to a resin blend for paper coating comprising (A) a crosslinked amine compound which is a reaction product of (a) an aliphatic amine and (b) a glycidyl compound having at least two glycidyl groups in the molecule, *; or ; * '; (a) an aliphatic amine, (b) a glycidyl compound having at least two glycols; and (c) the reaction product of a compound selected from α, β-unsaturated carbonyl compounds, α, β-unsaturated nitrile compounds, and α-halogenocarboxylic acid compounds; and (B) at least one compound selected from the group consisting of (B1) non-poly. · · *, Meric non-volatile substances and (B2) polyhydric alcohols.

The present invention also relates to a paper coating composition comprising: (A) the cross-linked amine compound described above,: (B) at least one compound selected from the group consisting of non-polymeric non-volatile substances and polyhydric alcohols, and (C) a pigment and (d) an aqueous binder.

The present invention further provides a coated paper consisting of (1) a paper substrate and (2) a coating on a paper substrate comprising (A) a crosslinked amine compound as described above, (B) at least one compound selected from the group consisting of non-polymeric non-volatile substances and polyhydric alcohols, (C) a pigment, and (D) an aqueous binder.

Useful Embodiments of the Invention 15

The paper coating resin composition of the present invention contains (A) a crosslinked amine compound obtained by reacting certain components with one another, and (B) (B1) a non-polymeric non-volatile material and / or (B2) a polyhydric alcohol.

20 • ·; The crosslinked amine compound (A) is obtained by reacting (a) an aliphatic; ·; an amine; and (b) a glycidyl compound having at least two glycidyl moieties; 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- halogeenikarboksyylihappoyhdisteistä.

. ···. The aliphatic amine (a) used herein has a compound attached to the aliphatic carbon atom. The primary or secondary amino group. The aliphatic carbon atom to which the; 30 amino group is attached may form a non-aromatic ring. The molecule may also have a group other than an aliphatic hydrocarbon group, for example an aromatic ring if the amino group is linked to an aliphatic carbon atom.

„: * In addition, several amino groups may be present in a molecule. Specific examples of aliphatic amine (a) include monoalkylamines, dialkylamines, polyamines having two or more amino groups in a molecule, aliphatic heterocyclic amines containing at least one ring member of a nitrogen atom, and the like. The amine used may be of the same quality, or these aliphatic amines may be used in combination of two or more compounds.

The monoalkylamine may be a compound wherein the primary amino group is linked to an alkyl group of 1 to 10 carbon atoms. Individual examples include methylamine, ethylamine, propylamine and the like. The dialkylamine may be a compound wherein two alkyl groups are linked to a secondary amino group, wherein the alkyl groups are the same or different and have about 1 to about 10 carbon atoms, respectively. Specific examples thereof are dimethylamine, diethylamine, dipropylamine, dibutylamine, methylethylamine and the like. Poly-15 amine has multiple amino groups in the molecule, and as used herein refers to a compound other than the heterocyclic amines described below. Specific examples thereof are ethylenediamine, diethylenetriamine, triethylenetetramine, isophorone diamine, bis (aminomethyl) cyclohexane, xylylenediamine and the like.

20 • ·; A heterocyclic amine is a cyclic compound containing as ring member: ·; in addition to the carbon atoms of at least one nitrogen atom. Heterocycle-forming; ·; atoms are not limited to carbon and nitrogen, but other heteroatoms such as oxygen and sulfur can form a ring. As long as this compound contains a heterocycle containing nitrogen as a ring atom, it may contain, in addition to this heterocycle, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, ···. aromatic hydrocarbon group, acyl group and the like. In addition, such a hydrocarbon group may be joined in addition to the cyclic amino group by another amino group and another substituent such as halogen and the like. Specific examples of the heterocyclic amine include heterocyclic monoamines such as pyrrolidine, piperidine, 2-, 3- or 4-pipecoline and 2,4-, 2,6- or 3,5-rupetidine and the like, heterocyclic diamines such as piperadine, homopiperadine, N-alkyl ''. (e.g., methyl, ethyl or propyl) piperadine, N-methyl homopiperadine N-acyl 7 109221 (e.g. acetyl) piperadine, N-acyl (e.g. acetyl) homopiperadine and 1- (chlorophenyl) piperadine and the like, heterocyclic amines coupled with aminoalkyl, such as N-aminoalkyl (e.g., ethyl or propyl) piperidine, N-aminoalkyl (e.g., ethyl or propyl) piperazine, N-aminoalkyl (e.g., ethyl or propyl) morpholine, N-aminopropyl-2-or-4 -pipecoline, 1,4-bis (aminoethyl) piperazine and 1,4-bis (aminopropyl) piperazine, and the like.

Of these aliphatic amines (a), industrially preferred are monoalkylamines, dialkylamines, ethylenediamine, diethylenetriamine, heterocyclic amines and the like, and heterocyclic amines are particularly preferred. Particularly preferred heterocyclic amines are pyrrolidine, piperidine, piperazine, N-aminoethylpiperazine, N-aminopropylpiperazine, 1,4-bis (aminoethyl) piperazine, 1,4-bis (aminopropyl) piperazine and the like.

The aliphatic amine (a) used in the present invention contains at least one primary or secondary amino group as described above. In the case where a heterocyclic amine is used, it preferably contains a at least one primary amino group in addition to the secondary or tertiary amino group forming the heterocycle, given its reactivity with the glycidyl compound. Excellent effect is achieved in particular ···; when a compound wherein the aminoalkyl group is linked to a heterocycle which; ··; contains nitrogen as a ring member such as N-aminoethylpiperazine, N-aminopropyl; pyrylpiperazine, 1,4-bis (aminoethyl) piperazine, 1,4-bis (aminopropyl) piperazine and the like are used alone or in combination with one or more other amines.

The glycidyl compound (b) which is to be reacted with (a) an aliphatic amine or (a) an aliphatic amine and (c) an α, β-unsaturated carbonyl compound, an α, β-unsaturated nitrile compound, and a- with a compound selected from halogen carboxylic acid compounds, is a compound having at least two glycidyl groups in the molecule. The group through which multiple glycidyl groups are attached is not limited, and any aliphatic groups, aromatic groups, alicyclic groups and the like can be used. Specific examples of glycidyl 8 109221 dyyliyhdisteestä (b) are alkyleeniglykolidiglysidyylieetterit, such as ethylene glycol, propylene glycol diglycidyl ether and fidiglysidyylieetteri, polyoksialkyleenigly-kolidiglysidyylieetterit as polyetyleeniglykolidiglysidyylieetteri and polypropy-leeniglykolidiglysidyylieetteri, aromatic diglycidyl ethers, such as resor-5 siinidiglysidyylieetteri and bisphenol-A diglycidyl ether, trimethylol propane or triglyseridyylieetteri , sorbitol di-, tri-, tetra-, penta- or hexaglycidyl ether, pentaerythritol di-, tri- or tetraglycidyl ether and the like. These glycidyl compounds can be used as a single compound or in combination with two or more. Of these, aromatic glycidyl ether is preferably used.

10

Compound (c) which is to be reacted with a reaction product of (a) an aliphatic amine or (a) an aliphatic amine and (b) a glycidyl compound having at least two glycidyl groups in the molecule, is selected from the group consisting of α, β-unsaturated carbonyl , α, β-unsaturated nitrile compounds and α-halogenocarboxylic acid compounds. α, β-unsaturated carbonyl compounds and α, β-unsaturated nitrile compounds which act as compound (c) have a carbon-carbon double bond (ethylene bond) or a carbon-carbon triple bond (acetylene bond) and at least one double bond or triple bond the carbon atom is attached to a carbonyl group or a syna group. When one carbon atom forming a double bond or a triple bond is •; attached to a carbonyl group or a cyano group, this carbon atom is α-carbon and; ; the other carbon atom is β-carbon. When two double bond or triple bond ;;:; the forming carbon atom is attached to the carbonyl group and / or the cyano group, one of these carbon atoms is α-carbon and the other carbon atom is β-carbon. The carbon-carbon double bond or the carbon-carbon triple bond in α, β-unsaturated carbonyl compounds and α, β-unsaturated nitrile compounds are referred to as α, β-saturated! additionally, the α-carbon and / or β-carbon may be attached to the aliphatic! ···, a hydrocarbon group, an aromatic hydrocarbon group or the like, α, β-unsaturated carbonyl compounds, and α, β-unsaturated nitrile compounds may have multiple carbonyl groups or cyano groups.

: · * 1: Examples of the α, β-unsaturated carbonyl compound are carboxylic acids such as acrylic acid, crotonic acid, isocrotonic acid, methacrylic acid, sorbic acid and cinnamic acid, carboxylic acid acrylate, butyl acrylic acid, -methacrylate, ethyl methacrylate, methyl cinnamate and ethyl cinnamate, aldehydes such as acrolein, crotonaldehyde and cinnamic aldehyde, ketones such as methyl-5-vinyl ketone, mesityl oxide, benzalacetone, dibenzalacetone, benza acid anhydrides such as maleic anhydride. Examples of the α, β-unsaturated nitrile compound are nitriles, such as acrylonitrile.

As compound (c), the α-halogenocarboxylic acid compounds are carboxylic acids, carboxylic acid salts or carboxylic acid esters wherein the halogen atoms are attached to some or all of the α-carbons which are carbon atoms attached to the carbonyl group. When the halogen atoms are attached to a portion of the α-carbon, the remaining α-carbons may be attached to an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an alicyclic hydrocarbon group or the like, examples of α-halocarboxylic , trichloroacetic acid, α-chloropropionic acid, α-chlorobutyric acid and α-bromoisobutyric acid, α-halogenocarboxylic acid esters such as methyl chloroacetate, ethyl chloroacetate, butyl chloroacetate, methyl bromoacetate; ethyl bromoacetate and propyl bromoacetate, and α-halo-carboxylic acid; *; salts such as sodium chloroacetate and sodium bromoacetate.

* *

One kind of compound (c) can be used alone or two or more compounds (c) can be used in combination. Of the above (c), industrially preferred are α, β-unsaturated carboxylic acids, and α, β → t-unsaturated carboxylic acid esters and α-chlorocarboxylic acids. Particularly * »| acrylic acid and chloroacetic acid are preferred.

; The following processes (1) to (5) may be exemplified by methods 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 compounds and α-halogenocarboxylic acid compounds.

(1) The aliphatic amine (a) and the glycidyl compound (b) are reacted and then the compound (c) is reacted with the reaction product of (a) and (b).

(2) The aliphatic amine (a) and the compound (c) are reacted and then the glycidyl compound (b) is reacted with the reaction product of (a) and (c).

(3) The aliphatic amine (a) and the compound (c) are reacted and then the glycidyl compound (b) is reacted with the reaction product of (a) and (c). Compound (c) is then further reacted with the reaction product of (a), (b) and (c). In this case, the compound (c) first reacted and compound (c) subsequently reacted may be the same or different.

(4) The aliphatic amine (a) and the glycidyl compound (b) are reacted and then the compound (c) is reacted with the reaction product of (a) and (b).

The glycidyl compound (b) is then further reacted with (a), (b) and • *; (c). In this case, the first reaction is; 1; the glycidyl compound (b) and the subsequently reacted glycidyl compound (b); can be the same or different.

(5) The aliphatic amine (a), the glycidyl compound (b) and the compound (c) are reacted at the same time.

»I

Of the above methods, method (1) is conventional, but goes; Is not limited thereto.

The 30 'v * glycidyl compound (b) is usually used in an amount of 0.1-1.5 moles, preferably 0.3 -:,': 1.2 moles, more preferably 0.5-1 moles, based on one aliphatic amine (a). * 'Per mole. When the amount of glycidyl compound (b) is increased, the reaction product also has a tendency to gel when the aliphatic amine has several reactive primary or secondary amino groups. Therefore, it is appropriate that the molar ratio of the glycidyl compound to the aliphatic amine is 1.5 or less, regardless of the number of amino groups.

5

Compound (c) is usually used in an amount of 0 to 1.5 moles, preferably 0.05 to 1 mole, more preferably 0.1 to 0.5 moles, based on one mole of the aliphatic amine (a). When the reaction of the aliphatic amine (a) with the compound (c) is carried out before the reaction of the aliphatic amine (a) with the glycidyl compound (b), there remains a portion of the 10 aliphatic amine (a) which has not reacted with the compound (c) the reaction of the amino group and the glycidyl compound (b) produces a crosslinked amine compound.

The reaction of the aliphatic amine (a) and the glycidyl compound (b) and the reaction of the aliphatic amine 15 (a), the glycidyl compound (b) and the compound (c) can be carried out in or without the use of a solvent. This reaction is usually carried out at a temperature of 30 to 100 ° C. The preferred reaction temperature is about 40-90 ° C when using a mixed water-organic solvent system and about 40 -70 ° C when using a non-aqueous organic solvent as solvent although the reaction temperature will vary depending on the presence of the solvent or its solvent. ; absence, the nature of any solvent used and the like; *; *; borrowings. The reaction time is usually about 1 to 20 hours. This reaction also proceeds t '♦ ·'; ·; without the use of a catalyst, and can also be carried out on a basic catalyst,

I I I

l,, '' such as ammonia and sodium hydroxide, or a Lewis acid catalyst such as

»T I

In the presence of aluminum chloride and the like.

Examples of the solvent used in this reaction are alcohols such as me; t, tanol, ethanol, 1- or 2-propanol, 1- or 2-butanol, 1-pentanol, 3-methyl-1-t-butanol, 1-hexanol, 4-methyl-2-pentanol, 2,4-dimethyl -3-pentanol, 2,6-; ! Dimethyl 4-heptanol, 2-ethyl-1-hexanol, 1- or 2-octanol, lauryl alcohol, • cyclohexanol and benzyl alcohol; ethers such as diethyl ether, dipropylether, di-isopropyl ether, dibutyl ether, β, β'-dichloroethyl ether, 1,4-dioxane, furfuryl alcohol. tetrahydrofurfuryl, etyleeniglykclimonometyy- 12 109221 ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and the ether-dietyleeniglykolimonobu dietyleeniglykolidibutyylieetteri; aldehydes such as butyl aldehyde, hydrocarbons such as cyclohexane, hexane, heptane, toluene and o-, m- or p-xylene; organohalogen compounds such as 1,1,1-trichloroethane, trichlorethylene, 1- or 2-bromopropane, 1-bromobutane, lauryl bromide, 1-bromo-3-chloropropane, 1,3-dibromopropane, 1,4-dibromobutane, 1,5-dibromopentane and 2,3-dibromo-1-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, mesityloxide, isophorone and 4-hydroxy-4-methyl-2-pentanone; esters such as methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, sec-butyl acetate, isobutyl acetate, amyl acetate, benzyl acetate, ethyl propionate, butyl propionate, amyl propionate, methyl propionate, methyl propionate, methyl propionate, methyl propionate, methyl propionate, and the like. They can be used alone or in combination with two or more.

A mixture of one or more of these organic solvents with water may also be used as the reaction solvent.

When the aliphatic amine (a) and the glycidyl compound (b) are reacted or the reaction product of the - - ·: aliphatic amine (a) and the compound (c) with the glycidyl compound (b), the amount of water in the reaction system is preferred-J; 20% by weight or less, more preferably 10% by weight or less, as if; If the amount of water in the reaction system is too high, an epoxy resin is formed which, due to the mutual polymerization of diglycidyl compounds, is insoluble in water and in an organic solvent.

30

• I

When the aliphatic amine (a) and compound (c) are reacted or the reaction product of the aliphatic 'I' amine (a) and the glycidyl compound (b) is reacted with

,,, I

13 109221 tea (c), the ratio of water to organic solvent is not limited. In this case, only water may be used as the solvent.

The structures of the reaction products have a high degree of structural dispersion and sometimes smaller 5 polymers may be formed which may have a certain molecular distribution depending on the nature of the aliphatic amine (a), the nature of the glycidyl compound (b), the nature of the compound (c), the aliphatic amine (a), glycidyl and the relationship between the compound (c), the order of the reaction, and the like.

The following are examples of major embodiments for the reaction of an aliphatic amine (a) with a glycidyl compound (b), provided that the glycidyl compound (b) has the structure represented by the formula Gly-R-Gly having two glycidyl groups wherein Gly R is a bivalent group. (Hereinafter in this document, Gly means a glycidyl group).

When the aliphatic amine (a) has a primary amino group represented by formula R1-NH2 wherein R1 is a monovalent aliphatic group, the following reaction occurs essentially and in some cases a glycidyl compound can be added to the secondary amino group in this product to form '··· j another structure linked to an amine molecule.

25 Y: R 1 -NH 2 + Gly-R-Gly R 1 -NH-CH 2 CH (OH) CH 2 -R-Gly 1 Y Y R 1 -NH-CH 2 CH (OH) CH 2 -R-Gly + R 1 -NH 2 -> R 1 -NH- CH2CH (OH) CH2-R-CH2CH (OH) CH2-NH-R1 ···. YY When the aliphatic amine (a) has a secondary amino group represented by the formula R1-NH-R2 (in the case of a heterocyclic monoamine, R114109221 and R2 can be thought of to form a ring), the following reaction occurs essentially.

R 1 -NH-R 2 + Gly-R-Gly -► (R 1) (R 2) N-CH 2 CH (OH) CH 2 -R-Gly 5 (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 -R-CH 2 CH (OH) CH 2 N (R 1) (R 2)

When the aliphatic amine (a), the glycidyl compound (b) and the compound (c), wherein the structure of the compound (c) 10 is represented by the formula R 1 -CH = CH-COR 2 or R 3 -C (X) H-COOR 4, are reacted respectively, exemplary embodiments of the main reaction are given below provided that the glycidyl compound (b) has the structure of formula Gly-R-Gly having two glycidyl groups.

When the aliphatic amine (a) has a primary amino group of the formula R3-NH2 wherein R3 is a monovalent aliphatic group, the reaction essentially follows, and in some cases the glycidyl compound in this product may be attached to a secondary amino group to form another structure attached to the amine molecule. . When compound (c) has the structure of formula R1-CH = CH-COR2, it is attached to the amino group remaining in the reaction product of the aliphatic amine (a) and the glycidyl compound (b). When compound (c) has the structure of formula R3-C (X) H-COOR4, the addition reaction occurs at the amino group and dehalogenates.

" ';. R 5 -NH 2 + Gly-R-Gly -►-NH-CH 2 CH (OH) CH 2 -R-Gly: f; 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 O · '^ R 2OC-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 -NR5-CHR3-COOR4 + HX

15 109221

When the apical amine (a) has multiple amino groups, when two or more kinds of aliphatic amines (a) are used, when the glycidyl compound (b) has three or more glycidyl groups, when (c) has multiple α, β-unsaturated bonds or multiple α-halogens, the reaction becomes increasingly complex, and in each case a substantially crosslinked amine compound (a) is formed in which several amine molecules are crosslinked.

As already described above, the crosslinked amine compound (a) resulting from the reaction of the aliphatic amine (a), the glycidyl compound (b) and the compound (c) may form a small polymer which, depending on the structure of the aliphatic amine used as the raw material, may have a certain molecular distribution. The viscosity of a 50% by weight aqueous solution at 25 ° C, an indicator of molecular weight, can usually be between 10 and 100,000 mPas. More preferably, this viscosity is 100 mPas or more, even more preferably 1,000 mPas or more, and 50,000,000 mPas or less.

The second component (B) of the resin composition for paper coating is non-volatile material (B1) and / or polyhydric alcohol (B2). The resin composition for paper coating can contain both non-volatile material 20 (B1) and a polyhydric alcohol (B2) in addition to the above-mentioned crosslinked amine compound. Alternatively, the resin composition for paper coating may contain either a non-volatile substance (B1) or a polyhydric alcohol (B2), although it preferably contains a non-volatile substance (B1).

The non-volatile material (B1) is an organic or inorganic non-polymeric compound which is non-volatile at normal temperature and which can be dissolved or dispersed in this mixture with an evenly crosslinked amine compound (A).

The non-polymeric compound referred to herein has a specific molecular weight. The non-volatile agent (B1) is used to reduce adverse effects such as thickening and dripping that can sometimes occur when a crosslinked amine compound is used as a component of a coating composition without losing the initial weight and ability of the crosslinked amine compound.

Individual examples of non-volatile material (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. Ureaeas referred to herein include ureas having an atomic group of formula> NC (Q =) N <where Q is oxygen or sulfur, and derivatives thereof. More specifically, they have the formula, for example, X 1 NHC (= Q) NX 2 X 3 wherein Q is oxygen or sulfur, X 1, X 2 and X 3 are each independently hydrogen, alkyl or substituted alkyl, or X 1 and X 2 are attached to form an ethylene chain which may be substituted hydroxyl group. From the ureas, 1- (2-aminoethyl) -2-imidazolidinone can be obtained through the ammonia removal reaction of diethylene triamine using urea. In addition to 1- (2-aminoethyl) -2-imidazolidinone, this reaction product also contains by-products, and the mixture containing the by-products can usually be used as such.

Of these non-volatile substances, organic compounds, especially urea, are preferred because they are compatible with the crosslinked amine compound (A), are soluble in various solvents and for similar reasons. Of the ureas, urea and imidazolidinones are preferred, and urea is particularly preferred from an industrial point of view.

When the paper coating resin composition of the present invention comprises a crosslinked amine compound (A) and a non-volatile agent (B1); and the crosslinked amine compound (A) and the non-volatile substance (B1) are dissolved or dispersed in a liquid medium, their mixing order is not particularly limited. Examples of the mixing method can be given by the following '· *' methods (1) to (3).

(1) The crosslinked amine compound is dispersed or pre-dissolved in a liquid medium, followed by addition of a non-volatile material and mixing.

»I · 17 109221 (2) The non-volatile material is dispersed or dissolved in a liquid medium beforehand and the resulting mixture is then added to the crosslinked amine compound.

(3) The crosslinked amine compound and the non-volatile compound are dispersed or dissolved in the respective liquid media, which are the same or different, and then mixed to form a uniform mixture, and so on.

For simplicity of operation, it is preferable to use process (1) wherein the crosslinked amine compound (A) is dispersed or pre-dissolved in a liquid medium and the non-volatile substance (B1) is mixed.

The temperature at which the crosslinked amine compound (A) and non-volatile material (B1) are mixed is not particularly limited, and when their solubility or miscibility with the liquid medium used is not sufficient, the mixture may be heated to such an extent that the liquid medium does not evaporate. . Conversely, when the crosslinked amine compound (A) or the non-volatile compound (B1), or both, forms a solvate with the liquid medium and significantly generates heat, the mixture can, conversely, be cooled to such an extent that no freezing occurs.

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 an aliphatic:; the reaction product of amine (a), glycidyl compound (b), and compound (c), prepared · · ·; 25 as a solution or dispersion in a liquid medium, followed by this; add the non-volatile material (B1) and mix.

! A solution or dispersion of the crosslinked amine compound (A) can be obtained by reacting the aliphatic amine (a) with the glycidyl compound (b) in a liquid medium or by reacting the aliphatic amine (a) with the glycidyl compound (b) and thereafter adding to it a liquid medium for dissolution or dispersion.

18 109221

Any liquid medium may be used to dissolve or uniformly disperse the crosslinked amine compound (A) and the non-volatile material (B1). The liquid medium may be water and / or an organic solvent. Various solvents, examples of which are given above as a solvent for the reaction of the cross-linked amine compound (A) to Preparation 5, can also be used in this case as a liquid medium. In particular, any alcohol may advantageously be used alone or in combination or in combination with two or more other organic solvents since the alcohols have excellent solubility and dispersibility of the crosslinked amine compound (A).

10

When the glycidyl compound (b), which is one of the raw materials of the crosslinked amine compound (A) in the present invention, is sparingly soluble in water only, water and an inorganic solvent can be mixed and used in the reaction between apathic amine (a) and glycidyl compound (b) medium 15 can be used without any changes as a liquid medium for the crosslinked amine compound (A). Depending on the case, it is also possible that after the reaction is completed, water is added to reduce the proportion of organic solvent in solubilizing or dispersing the crosslinked amine compound (A). in a liquid medium for germination. The ratio of the organic solvent to water in the liquid medium for dissolving or dispersing the crosslinked amine compound is not limited, and the ratio of water commonly used to the organic solvent is 1 to 100% by weight and the proportion of organic solvent is 99 to 0%. It is particularly preferred that the ratio of the water used to the organic solvent is 3 to 50% by weight and the proportion of the organic solvent used. : 25% is 97 to 50% by weight when the crosslinked amine compound (A) is mixed with : with polymeric non-volatile material (B1); and the ratio of the water used to the organic solvent is 5 to 50% by weight, and the proportion of the organic solvent used is 95 to 50% by weight when the crosslinked amine compound (A) is mixed with a polyhydric alcohol (B2).

... 30 ;;; Further, it is also possible that the liquid medium used for the crosslinked amine compound (A) consists essentially of water by applying the process wherein the reaction of the lower amine (a) with the glycidyl compound (b) is carried out in an organic solvent and upon completion of the reaction the solvent is distilled off and water is added. In this case, it is preferred that the glycidyl compound (b) is dissolved in the ketones, while the aliphatic amine (a) is dissolved in a hydrophilic organic solvent other than the ketones, and both solutions are mixed for the reaction. The ketones for solubilizing the glycidyl compounds (b) may be various compounds, examples of which are given above as solvents for the reaction of preparing the crosslinked amine compound (A), and preferably acetone is used. On the other hand, the hydrophilic organic solvent other than the ketone used to dissolve the aliphatic amine (a) may also be selected from hydrophilic organic solvents other than ketones, examples of which are given above as solvents for the reaction of the crosslinked amine compound (A). From an industrial point of view, alcohols, especially methanol, are preferably used.

Solvent distillation after the completion of the reaction is usually carried out by distillation under normal pressure, although it can also be effected by vacuum distillation and steam distillation. Two or more methods may be used in combination, such as steam distillation after distillation under normal pressure, and so on. When distillation is carried out at normal pressure, heating is preferably carried out from the boiling point of the solvent to 100 ° C, more preferably to 60 ° C, since the crosslinked amine compound (A) becomes colored if the temperature is raised too much. The addition of water after removal of the solvent is preferably carried out at a temperature between 50 and 120 ° C. Solubility may be poor when the organic solvent is distilled off if the temperature at which water is added is too low because the crosslinked compound is present alone and the viscosity is too high. Also, when water is added, too high a '' '* · temperature is not desirable for the prevention of crisis situations such as severe boiling or the like.

A paper coating resin composition according to the present invention containing a crosslinked amine compound (A) and a non-volatile material (B1) as described above is obtained by mixing them. The weight ratio (former / latter) of these 10,910,221 is usually between 1/99 and 90/10, preferably between 5/95 and 70/30, when the resin mixture does not contain polyhydric alcohol (B2).

The polyhydric alcohol (B2), which may be another component of the paper coating resin composition of the present invention, is used to reduce adverse effects such as thickening and dripping that may sometimes occur when the crosslinked amine compound (A) is used as a coating composition component. original properties of the crosslinked amine compound, such as the ability to give the paper excellent printability and print result. The polyhydric alcohol (B2) together with the crosslinked amine compound (A) is intended to remain in the coating composition as an active ingredient in a coating of a coated paper prepared by coating a paper coating composition on paper and evaporating the liquid medium, . Therefore, polyhydric alcohol with a higher boiling point than the boiling point of water is usually used. A polyhydric alcohol (B2) has at least two alcohol hydroxyl groups in the molecule.

Examples of these are diols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, polypropylene glycol, 1,3-20 propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentiol, , cyclohexanedimethanol and xylylene diol, triols such as glycerin and trimethylolpropane, tetraols such as pentaerythritol, and saccharides such as glucose, mannose, sorbitol, xylitol, sucrose and fructose. It is preferably a polyhydric alcohol having a molecular weight of 500 or less.

When the polyhydric alcohol (B2) is a saccharide, it is preferably sorbitol, xylitol i or the like which does not have a reducing group. From an industrial point of view, diethylene glycol, triethylene glycol, glycerin and saccharides which do not have the ability to reduce such as sorbitol and xylitol are preferred.

When the paper coating resin composition of the present invention contains a crosslinked amine compound (A) and a polyhydric alcohol (B2), the order of mixing is not particularly limited. It is preferred that the resinous paper resin mixture of the crosslinked amine compound (A) and the polyhydric alcohol (B2) according to the present invention be dissolved or dispersed in a liquid medium.

For the sake of simplicity of operation, it is preferable that the resin mixture is prepared by a process in which the crosslinked amine compound (A) is dispersed or dissolved beforehand in a liquid medium, to which polyvalent alcohol (B2) or a solution thereof is added and mixed. However, the preparation of the paper coating resin composition of the crosslinked amine (A) and the polyhydric alcohol (B2) according to the present invention can also be accomplished by a process of dispersing or dissolving the polyhydric alcohol (B2) in a liquid medium and then adding the crosslinked an amine compound (A), a process wherein both the crosslinked amine compound (A) and the polyhydric alcohol (B2) are dispersed or dissolved in the same liquid media, the same or different, and then mixed to give a uniform quality, and the like. 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). The temperature at which the crosslinked amine compound (A) and polyhydric alcohol (B2) are mixed is not particularly limited, and when their solubility or miscibility with the liquid medium employed is not sufficient, the mixture may be heated to such an extent that the liquid medium does not evaporate. When the crosslinked amine compound (A) or the polyhydric alcohol (B2), or both, forms a solvate with the liquid medium and the heat develops significantly, the mixture can be cooled to such an extent that freezing does not occur.

···; When used for coating paper in accordance with the present invention

* * I

; the resin mixture contains a crosslinked amine compound (A) and a polyhydric alcohol (B2) but does not contain a non-volatile substance (B1), their weight ratio (former V / n / latter) is usually in the range 1/99 to 90/10, preferably 5 / 95 - '70 / 30.

30

When the paper coating resin composition of the present invention contains a crosslinked amine compound (A), a polyhydric alcohol (B2) i- and a non-volatile substance (B1), the weight ratio of the crosslinked amine compound (A) to molar alcohol (B2) and the total amount of non-volatile matter (B1) is usually in the range 1/99 to 90/10, preferably 5/95 to 70/30. The amount of non-volatile material (B1) is preferably 5 times the weight of polyhydric alcohol (B2) or less.

The resin mixture thus prepared, comprising the crosslinked amine compound (A) and the non-volatile substance (B1) and / or the polyhydric alcohol (B2), is obtained by mixing it with a pigment (C) and an aqueous binder (D). This paper coating composition consists of pigment 10 (C), an aqueous binder (D), the cross-linked amine compound (A) described above and the non-volatile compound (B1) described above and / or the polyhydric alcohol (B2). Although it is not essential that the crosslinked amine compound (A) and the non-volatile compound (B1) and / or the polyhydric alcohol (B2) are premixed, it is usually preferred to prepare the crosslinked amine compound 15 (A) and the non-volatile compound (B1) and / or an alcohol (B2) -containing resin mixture, which is then blended with the pigment (C) and the aqueous binder (D).

In the preparation of the paper coating composition of the present invention, the use and function of the composition is related to the pigment (C) and the aqueous binder (D) in the composition; this ratio is not particularly different from the one generally used in the art. Regarding their preferred ratio in the mixture, the amount of aqueous binder (D) is about 1 to 200 parts by weight, more preferably 5 to 50 parts by weight, per 100 parts by weight of pigment (C). As far as the crosslinked amine compound (A) and the non-volatile substance (B1) and / or polyhydric alcohol (B2) are concerned, their total dry weight is preferably? 0.05 to 5 wt.%, More preferably 0, 1 to 2 parts by weight per 100 'parts by weight of pigment (C).

The pigment (C) used as a component of the paper coating composition may be the pigment conventionally commonly used for paper coating; and •; · The pigments used may be white inorganic pigments and white: · organic pigments. Examples of the white inorganic pigment I-23109221 are kaolin, talc, calcium carbonate (heavy or light), aluminum hydroxide, satin white, titanium oxide and the like. Examples of white organic pigment are polystyrene, melamine-formaldehyde resins, urea-formaldehyde resins and the like. These resins can be used alone or in combination of two or more.

Also, the aqueous binder (D) may be a substance conventionally used to coat paper; and the binders used may be water soluble binders and water emulsifiable binders. Examples of the aqueous binder (D) include unmodified or modified starches, including oxidized starch and phosphated starch, polyvinyl alcohol, water soluble protein including casein and gelatin, modified celluloses including carboxymethylcellulose. Examples of binder emulsified in water are styrene-butadiene resins which may optionally have a carboxyl group or a nitrile group (SBR latex), acrylonitrile-butadiene resins (NBR latex), chloroprene resin (CR latex), methyl methacrylate (Buta-diene), copolymer resins of two or more kinds of acrylic monomers; copolymer resins of acrylic monomer and vinyl acetate;

The acrylic monomer referred to herein refers to a compound selected from acrylic acid, methacrylic acid and their methyl, ethyl or butyl ester.

These aqueous binders may be used alone or in combination of two or more.

25

In the manufacture of a paper coating composition, the order of addition and mixing of the pigment (C), the aqueous binder (D) and the resin mixture is optional and not particularly limited. However, it is generally preferred that after the preparation of the resin mixture comprising the crosslinked amine compound (A) and the non-polymeric non-volatile substance (B1) and / or polyhydric alcohol (B2), the pigment (C) and the aqueous binder (D) are blended. For example, a method of adding and mixing a resin mixture dissolved or dispersed in a liquid medium into a mixture of pigment (C) and an aqueous binder (D), wherein the resin mixture dissolved or dispersed in the liquid medium is first added to the pigment (C) and and mixing with the aqueous binder (D) and blending the resulting mixture with the remaining component, and the like.

5

The paper coating composition of the present invention may optionally contain other resin blends, such as a waterproofing agent, a printability enhancing agent and the like, in addition to the cross-linked amine compound (A) and non-volatile agent (B1) and / or polyhydric alcohol (B2) described above. . In addition, the dispersant, the viscosity and flow modifier, the antifoam, the preservative, the lubricant and the water retaining agent, and the coloring agents, such as color or colored pigment, and the like, may also be included as another component, if necessary.

The paper coating composition of the present invention is coated onto a paper substrate by a conventional known method, for example, using a variety of known coating devices, such as a blade coating, an air sweep coating, a bar coating, a surface coating coating, a coating coating, a casting coating. The coated paper according to the present invention can be made by subsequently carrying out the necessary drying and, if necessary, further sliding treatment with a supercalender, etc.

In the coated paper of the present invention, a coating is formed on top of the paper substrate 25, which consists of the aforementioned particulars:. ·: Ingredients. The coating is formed on at least one surface of the paper substrate, i. The coating may be formed on each surface of the paper substrate. Coat * · *: 'You contain (C) pigment; (D) an aqueous binder; (A) a crosslinked amine compound which is a reaction product of (A) an aliphatic amine and (B) a glycidyl compound having at least two glycidyl groups in the molecule, or (A) an aliphatic amine, (B) a glycidyl compound having at least two the glycidyl group ·; · 'in the molecule, and (C) II · 1 »* i * · selected from α, β-unsaturated carbonyl compounds, α, β-unsaturated nitrile compounds and α-halogenocarboxylic acid compounds.

I I

»» * »K ► 1 · t ♦> 25 109221 reaction product of compound; and (B) at least one substance selected from the group consisting of non-polymeric non-volatile substances and polyhydric alcohols.

The coating of the coated paper of the present invention may further comprise, if necessary, another resin blend, such as a waterproofing agent, a printability enhancing agent and the like. In addition, other substances, for example, a dispersant, a viscosity and flow control agent, an antifoam agent, a preservative, a lubricant and a water retaining agent, and coloring agents such as color and colored pigment, and the like, may be incorporated therein.

EXAMPLE

The following examples illustrate the present invention in more detail without limiting its scope. Unless stated otherwise, the percentages and parts indicating the concentration or amount are by weight in the examples. Viscosity and pH were measured at 25 ° C.

Synthesis Example 1:

516.8 g (4.00 moles) of N- (2-aminoethyl) piperazine and 396.1 g methanol were placed in a four-necked flask equipped with a thermometer, a reflux condenser and a stir bar. The internal temperature was maintained at 45-55 ° C and a solution of 802.7 g (2.36 mol) of bisphenol-A-diglycidyl ether and 416.4 g of acetone was added slowly dropwise thereto. After that

•. '': After the dropwise addition was complete, the reaction was continued for another 4 hours at 45-55 ° C

i · 1 · v 1 at indoor temperature. The reflux condenser was replaced by a Liebig condenser, after which the internal temperature was raised to 120 ° C while 30 acetone and methanol were removed from the system. Subsequently, the mixture was cooled while slowly adding 597.6 g of water to give an aqueous solution of the crosslinked amine compound having a non-volatile component content of 63.8%, a pH of 12.5, and a viscosity of 1: 89.500 mPa · s (about 10,000). mPa.s at 50% concentration).

• 1 · · 1

Synthetic Example 2: 26 109221

In a reaction vessel similar to that in Synthetic Example 1, 92.9 g (0.72 mole) of N- (2-aminoethyl) piperazine and 99.0 g of methanol were added. The internal temperature was maintained at 45-55 ° C and a solution of 105 g (0.31 mol) of bisphenol-A-diglycidyl ether and 99.0 g of acetone was added slowly dropwise thereto. After the dropwise addition was complete, stirring was continued for 4 hours at an internal temperature of 45-55 ° C. Subsequently, the reflux condenser was replaced with a Liebig condenser and then the internal temperature was raised to 120 ° C while removing acetone and methanol from the system. The mixture was then cooled while slowly adding 243.4 g of water to give a solution of the crosslinked amine compound having a non-volatile component content of 39.9%, a pH of 12.1 and a viscosity of 1.898 mPa.s (about 9000 mPa.s at 50% concentration).

15

Synthesis Example 3:

To a reaction vessel similar to that in Synthesis Example 1 was added 64.6 g (0.50 mole) of N- (2-aminoethyl) piperazine and 78.0 g of methanol. The internal temperature was maintained at 45-55 ° C and a solution of 91.3 g (0.27 mole) of bisphenol-A-diglycidyl ether and 77.9 g of acetone was added slowly dropwise thereto. After the dropwise addition was complete, the reaction was continued for an additional 4 hours at 45-55 ° C. After this, return- '·; The reflux condenser was replaced by a Liebig condenser, after which the internal temperature was raised to 120 ° C while removing acetone and methanol from the system.

The mixture was then cooled while slowly adding 188.6 g of water to give an aqueous solution of the crosslinked amine compound having a non-volatile component content of 41.8%, a pH of 12.4 and a viscosity of 1.839 mPa.s (about *). 6.500 mPa.s at 50% concentration).

30, · ·. Synthesis Example 4: »

In a reaction vessel similar to that in Synthesis Example 1, 75.6 g of → 27992221 (0.59 mol) of N- (2-aminoethyl) piperazine and 96.6 g of methanol were added. The internal temperature was maintained at 45-55 ° C and a solution of 116.6 g (0.35 mol) of bisphenol-A-diglycidyl ether and 96.6 g of acetone was slowly added dropwise thereto. After the dropwise addition was complete, the reaction was continued for an additional 4 hours at 45-55 ° C. Subsequently, the reflux condenser was replaced by a Liebig condenser, after which the internal temperature was raised to 120 ° C while removing acetone and methanol from the system.

The mixture was then cooled while slowly adding 236.4 g of water to give an aqueous solution of the crosslinked amine compound having 42.7% non-volatile component, pH 12.4 and viscosity 3.980 mPa.s. % concentration).

Synthesis Example 5: 15 To a reaction vessel similar to Synthesis Example 1 was added 90.6 g (0.70 mole) of N- (2-aminoethyl) piperazine and 78.0 g of methanol. The internal temperature was maintained at 45-55 ° C and a solution of 102.5 g (0.31 mol) of bisphenol-A-diglycidyl ether and 96.6 g of acetone was slowly added dropwise thereto. After the dropwise addition was complete, the reaction was continued for an additional 4 hours at 45-55 ° C. Subsequently, the reflux condenser was replaced by a Liebig condenser, after which the internal temperature was raised to 120 ° C while removing acetone and methanol from the system.

The mixture was then cooled while slowly adding 233.7 g of water:; to give an aqueous solution of the crosslinked amine compound having a non-volatile component content of 38.7%, a pH of 12.4 and a viscosity of 560 mPa.s (about 3000 mPa.s at 50% concentration).

I,, »i«. Synthesis Example 6: In a four neck flask equipped with a thermometer, a reflux condenser and a stir bar, 90.4 g (0.7 mole) of N- (2-aminoethyl) piperazine and 109.1 g of methanol were added. The internal temperature was maintained at 45-55 ° C, to which was added slowly a solution of 140.6 g (0.77 mole) of bisphenol-A-diglycidyl ether with 182.6 g of epoxy equivalents slowly added dropwise. eq. and 120.0 g of acetone. After the dropwise addition was complete, the reaction was continued for an additional 4 hours at 45-55 ° C. Subsequently, the reflux condenser was replaced with a Liebig condenser, and then the internal temperature was raised to 120 ° C while acetone and methanol were removed from the system. The mixture was then cooled while slowly adding 295.2 g of water to give 531.8 g of an aqueous solution of the crosslinked amine intermediate.

To a reaction vessel similar to the above was added 141.2 g of an aqueous solution of the crosslinked amine intermediate. While maintaining the internal temperature at 65-75 ° C, 8.37 g (0.093 mol) of 80% aqueous acrylic acid solution was slowly added dropwise over an hour. After completion of the dropwise addition, the reaction was continued for an additional 4 hours at 65-75 ° C to give an aqueous solution of the crosslinked amine compound with 45.3% non-volatile component, pH 9.1 and 1735 mPa.s.

Synthesis Example 7: 20 By stirring 637.6 g (3.47 moles) of bisphenol-A-diglycidyl ether with an epoxy equivalent of 184.0 g / eq. and 542.6 g of acetone, a solution was prepared. The total amount of solution obtained was 1180.2 g.

To a reaction vessel similar to Synthesis Example 6 was added 423.4 g (3.3; 25 moles) of N- (2-aminoethyl) piperazine and 516.8 g of methanol. While maintaining an internal temperature of 48-54 ° C. 1124.0 g of the above solution was slowly added dropwise over 5 hours, and after completion of the dropwise addition, the reaction was continued for an additional 4 hours at 48-54 ° C. was replaced by a Liebig condenser, after which the internal temperature, · · · 30 was raised to 120 ° C while extracting acetone and methanol from the system.

, · · ·. The mixture was then cooled while gradually adding 1285.7 g of water to give 2384.0 g of an aqueous solution of the crosslinked amine intermediate.

»I» i »· I * 29 109221

To a reaction vessel similar to Synthesis Example 6 was added 180.6 g of an aqueous solution of the crosslinked amine intermediate and 0.77 g of water. While maintaining the internal temperature at 65-75 ° C, 6.76 g (0.075 mol) of 80% w / w aqueous acrylic acid was added dropwise over 5 minutes.

After completion of the dropwise addition, the reaction was continued for an additional 4 hours at an internal temperature of 65-75 ° C to give an aqueous solution of the crosslinked amine compound with 45.1% non-volatile component, pH 9.7 and viscosity 3660 mPa.s.

Synthesis Example 8:

By stirring, 191.7 g (1.042 mol) of bisphenol A diglycidyl ether having an epoxy equivalent of 184.0 g / eq. and 180 g of acetone, a solution was prepared. The total amount of solution obtained was 371.7 g. 129.2 g (1.0 mole) of N- (2-aminoethyl) piperazine and 138.2 g of methanol were added to a reaction vessel similar to Synthesis Example 6. While maintaining the internal temperature at 48-54 ° C, 285.4 g of the above solution was added dropwise over 5 hours. After the dropwise addition was complete, the reaction was continued for an additional 4 hours at 48-54 ° C. Subsequently, the reflux condenser was replaced by a 20 Liebig condenser, after which the internal temperature was raised to 120 ° C while extracting acetone and methanol from the system. Subsequently, the mixture was cooled while 339.9 g of water was gradually added to give 637.8 g of an aqueous solution of the crosslinked amine intermediate. In a reaction vessel similar to that in Synthesis Example 6, 127.6 g of the cross-linked amine intermediate was added; ··; 25 aqueous solutions. While maintaining the internal temperature at 65-75 ° C, 3.6 g (0.04 mol) of 80% w / w aqueous acrylic acid was slowly added over 5 minutes. After completion of the dropwise addition, the reaction was continued for an additional 4 hours at 65-75 ° C to give an aqueous solution of the crosslinked amine compound with 44.4% non-volatile component, pH 9.7, and viscosity 1049 mPa.s. p.

(I I I I *

Synthesis Example 9: 30-109221

To a reaction vessel similar to Synthesis Example 6 was added 180.6 g of the aqueous solution of the crosslinked amine compound obtained in Synthesis Example 7 and 13.8 g of water. While maintaining the internal temperature at 65-75 ° C, 7.2 g (0.075 mol) of chloroacetic acid was added dropwise over 5 minutes.

After completion of the dropwise addition, the reaction was continued for an additional 4 hours at 65-75 ° C to give an aqueous solution of the crosslinked amine compound with 45.3% non-volatile component, pH 8.2 and a viscosity of 3740 mPa.s.

Comparative Example 1:

In a reaction vessel similar to that in Synthesis Example 1, 1237.9 g (12-15 moles) of diethylenetriamine and 720.8 g (12 moles) of urea were added at 80 ° C and, after heating to 145-155 ° C, was heated at the same temperature. 2 hours. The mixture was then cooled to give 1536.0 g of the reaction product consisting mainly of 1- (2-aminoethyl) -2-imidazolidinone. This reaction product is virtually non-volatile at normal temperature.

Example 1: ··· 51.3 g of 63.8% solution of the crosslinked amine compound obtained in Synthesis Example 1, 49.1 g of the reaction product obtained in Comparative Example 1 consisting of; mainly from 1- (2-aminoethyl) -2-imidazolidinone, and 33.8 g of water

t I I

and then stirred well to give a crosslinked amine-containing aqueous dispersion containing 61% active ingredient, pH 13.0 and 505 mPa.s. This is referred to as Resin Mixture A.

! .... 30 »·

Example 2: 31,109,221 79.2 g of a 63.8% solution of the crosslinked amine compound obtained in Synthesis Example 1, 50.5 g of the reaction product obtained in Comparative Example 1 consisting essentially of 1- (2-aminoethyl) -2-imidazolidinone; 0 g of water was combined and then stirred well to give an aqueous solution of the crosslinked amine with an active component content of 61%, a pH of 13.0 and a viscosity of 1.250 mPa.s.

Example 3: 80.0 g of a 63.8% solution of the crosslinked amine compound obtained in Synthesis Example 1, 34.9 g of the reaction product obtained in Comparative Example 1 consisting essentially of 1- (2-aminoethyl) -2-imidazolidinone, and 33.8 g of water was combined and then stirred well to give an aqueous dispersion of the crosslinked amine having an active component content of 61%, a pH of 12.8 and a viscosity of 2.768 mPa.s. This is referred to as resin mixture C.

Example 4: 101.3 g of a 39.9% aqueous solution of the crosslinked amine compound obtained in Synthesis Example 2 and 68.6 g of water were combined and then stirred well to give an aqueous solution of the crosslinked amine containing an effective com- the component content was 51%, the pH was 12.3 and the viscosity 17 mPa.s. 25 are referred to as resin alloy D.

Example 5: 80.9 g of a 39.9% aqueous solution of the crosslinked amine compound obtained in Synthesis Example 2, 129.1 g of urea and 106.4 g of water were combined and then mixed well to give the crosslinked amine containing aqueous solution having an active component concentration of 51%, a pH of 12.3 and a viscosity of 10 mPa.s.

This is referred to as resin alloy F

Example 6: 32,109,221 100.4 g of the 41.8% aqueous solution of the crosslinked amine compound obtained in Synthesis Example 3 and 76.0 g of water were combined and then well mixed to give an aqueous solution of the crosslinked amine containing 51% active ingredient. had a pH of 12.1 and a viscosity of 18 mPa.s.

Example 7: 85.8 g of a 41.8% aqueous solution of the crosslinked amine compound obtained in Synthesis Example 3, 143.4 g of urea and 122.3 g of water were combined and then mixed well to give an aqueous crosslinked amine containing the active component. concentration was 51%, pH 12.1 and viscosity 10 mPa.s.

15 This is referred to as G Resin Mixture.

Example 8: 97.5 g of 42.7% aqueous solution of the crosslinked amine compound obtained in Synthesis Example 4, 97.1 g of urea and 77.4 g of water were combined and then mixed well to give an aqueous crosslinked amine containing the active component. content was 51%, pH 12.1 and viscosity 23 mPa.s. This is referred to as resin blend H.

I M · ···; Example 9: 71.3 g of 42.7% aqueous solution of the crosslinked amine compound obtained in Synthesis Example 4, 121.7 g of urea and 105.4 g of water were combined and then mixed well to give an aqueous crosslinked amine containing solution. with an active component concentration of 51%, pH 12.0 and a viscosity of 10 mPa.s. referred to as resin mixture I.

Example 10: 33,109,221 129.3 g of the aqueous solution of the crosslinked amine compound obtained in Synthesis Example 5, 116.8 g of urea and 81.0 g of water were combined and then well mixed to give an aqueous solution of the crosslinked amine compound containing 51% active ingredient. The pH was 12.0 and the viscosity was 17.5 mPa.s. This is referred to as resin blend J.

Example 11: 10.0.0 g of a 45.3% aqueous solution of the crosslinked amine compound obtained in Synthesis Example 6, 181.2 g of the reaction product obtained in Comparative Example 1 consisting mainly of 1- (2-aminoethyl) -2-imidazolidinone, and 271.2 g of water. was then combined and mixed well to give an aqueous solution of the crosslinked amine 15 with an active component content of 41%, pH 10.5 and viscosity 62.5 mPa.s.

Example 12: 100.0 g of a 45.3% aqueous solution of the crosslinked amine compound obtained in Synthesis Example 6, 105.7 g of the reaction product obtained in Comparative Example 1 consisting essentially of 1- (2-aminoethyl) -2-imidazolidinone, and 162.6 g. g of water was combined and then stirred well to give the crosslinked amine '··; aqueous solution containing 41% active ingredient, pH; ··; 10.7 and a viscosity of 78.3 mPa.s.

Example 13: 100.0 g of a 45.3% aqueous solution of the crosslinked amine compound obtained in Synthesis Example 6, 68.0 g of the reaction product obtained in Comparative Example 1, formed mainly from 1- (2-aminoethyl) -2-imidazolidinone, and 108.3 g of water were combined and then stirred well to give an aqueous solution of the crosslinked amine 34109221 with an active component content of 41%, a pH of 11.0 and a viscosity of 98.8 mPa.s.

Example 14: 97.2 g of a 45.1% aqueous solution of the crosslinked amine compound in Synthesis Example 7, 167.8 g of urea and 246.6 g of water were combined and then mixed well to give an aqueous crosslinked amine containing 41% active ingredient. , pH was 10.0 and viscosity 10.0 mPa.s.

Example 15: 100.0 g of a 45.1% aqueous solution of the crosslinked amine compound obtained in Synthesis Example 7, 100.8 g of urea and 150.4 g of water were combined and then mixed well to give an aqueous crosslinked amine containing 51%, pH 10.3 and viscosity 11.0 mPa.s. This is referred to as resin blend O.

Example 16.

53.3 g of 44.4% aqueous solution of the crosslinked amine compound in Synthesis Example 8, 85.7 g of urea and 122.2 g of water were combined and then well mixed to give an aqueous crosslinked amine containing • · ·; The concentration of the consumable components was 41%, the pH was 10.0 and the viscosity 9 mPa.s.

; This is referred to as resin blend B.

I »»

Example 17: 62.0 g of 44.4% aqueous solution of the crosslinked amine compound obtained in Synthesis Example 8, 58.14 g of urea and 82.4 g of water were combined and then mixed well to give an aqueous crosslinked amine containing The content of II * 35 109221 component was 41%, pH 10.2 and viscosity 10.0 mPa.s.

This is referred to as the resin mixture Q.

Example 18: 100.0 g of 45.3% aqueous solution of the crosslinked amine compound obtained in Synthesis Example 9, 181.2 g of urea and 271.2 g of water were combined and then well mixed to give an aqueous solution of the crosslinked amine containing the active ingredient. concentration was 41%, pH 8.6 and viscosity 10.0 mPa.s.

10 Hereinafter referred to as the resin alloy R.

Example 19: 81.6 g of 45.3% aqueous solution of the crosslinked amine compound in Synthesis Example 9, 86.3 g of urea and 132.7 g of water were combined and then mixed well to give an aqueous crosslinked amine containing the active component. content was 41%, pH 8.8 and viscosity 12.0 mPa.s.

This is referred to as resin alloy S.

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

: ·: Examples 20 to 37 and controls 1 to 2 25; An aqueous stock dye having the composition shown in Table 1 and having a solids content of 64.5% was prepared.

... 30 I · 36 109221

table 1

Composition of base color

Component Name Solids Ratio 5 Pigment * 1,100 parts

Dispersant * 2 0.2 parts

Aqueous binder * 3 15 parts 10 * 1: Pigment: Mixture containing 60 parts Ultra white 90 (clay grade, manufactured by

Engel Hard Minerals, US) and 40 parts Karbital 90 (calcium carbonate, manufactured by Fuji Kaolin Co. Ltd.) * 2: Dispersant: Commercially available polyacrylic acid based 15 pigment dispersant * 3: Aqueous binder: 11 parts commercially available styrene-butadiene latex and 4 parts of commercially available oxidized starch.

20

Each of the resin blends obtained in Examples 1-9 and Examples 11-19 was added to the base dye as shown in Table 1 with a solids content of 0.6 parts per 100 parts of the base dye pigment. In Control 1, the same amount as in Examples 11-19 of the hot cure polyamide polyureaformaldehyde-25 resin (in the table, the abbreviation "PAPU" in aqueous solution containing 50% of I> · *. * JP-A-55-31837 (= USP 4.246.153)) was added. in place of the above-described resin mixture.

. ·, ·, In control 2, the parent dye was used without adding the resin component.

The concentration and pH of the mixtures were adjusted by addition of water and 10% *. 30 sodium hydroxide solutions to give coating compositions having,. the total solids content was 64%.

• i ·> · 37 109221

Examples 38 and 39:

Each of resin blend A obtained in Example 1 and resin blend D obtained in Example 4 is mixed with the same commercially available styrene-Buta-5 dienyl latex used to prepare the base color of Table 1 with a 5/100 dry weight ratio of resin to latex. The resulting blend latex is further blended in the proportions shown in Table 2 with the pigment and dispersant used in the preparation of the base dye in Table 1 and with oxidized starch. The concentration and pH of the mixtures were adjusted by addition of 10 water and 10% sodium hydroxide solution to give coatings mixtures having a total solids content of 64%.

Table 2 15 Base Color Composition

Component name Dry matter ratio

Pigment 100 parts

The dispersant is 0.2 parts

Oxidized starch 4 parts 20 Aqueous binder 11 parts

The coating compositions and controls 1 and 2 obtained in Examples 20-39; cabbage properties were measured by the following methods. The results of these are! ' 1 25 shown in Tables 3 and 4.

> * * (1) PH: The hydrogen ion meter used was of the glass electrode type (manufactured by Toa Denpa Kogyo. ·, 30 K.K.). The pH of the coating composition was measured immediately after preparation. 25 ° C.

38 109221 (2) Viscosity: The apparatus used was a Type B viscosity meter (Type BL, manufactured by Tokyo Keiki K.K). Immediately after preparation, the viscosity of the coating composition was measured at 25 ° C at 60 rpm.

Each coating composition obtained was applied to one surface of a high quality paper having a basis weight of 80 g / m 2 to a roll of 14 g / m 2. Immediately after coating, it was dried for 30 seconds to 10 hours in hot air at 120 ° C and then humidity adjusted for 16 hours at 20 ° C and 65% relative humidity. Subsequently, it was supercalendered twice at 60 ° C and a load of 60 kg / cm to give a coated paper. The coated paper thus obtained was tested for water resistance and ink absorption. The results of the tests are shown in Tables 2, 3-1 and 3-2. The test methods are given below.

(3) Water Resistance: Wet Loss Method (WP Method) The apparatus used was an RI tester (manufactured by Akari Seissakusho K.K.). The surface of the coatings was wetted with a water roller and then pressed. The visual detachment of the paper was evaluated. The criteria are given below.

Water resistance (poor) 1-5 (excellent) .. T 25 (4) Ink absorption capacity

; .i: (4-1) Method A

| f I I · * '' The device used was an Rl tester. The coated surface was moistened with a water roller and then pressed. The visually observed ink absorption capacity was evaluated.

30 The criteria are set out below.

I t

Ink Absorbance (Poor) 1-5 (Excellent) I 1 »

i | I

, »*» L ♦

I i I

i I »» I »39 109221

(4-2) Method B

The device used was an Rl tester. A small clearance was left between the metal roller and the rubber roller. Water was poured into this gap and then pressed rapidly.

The visually observed ink absorption capacity was evaluated. The criteria are given below.

Ink absorption capacity (poor) 1 - 5 (excellent) 10 15 20 25 t t «t * i i * | »» '* 1 · · »I * t» »

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42 109221

Table 4

Experimental Results of Examples 38 and 39 and Controls 1-2 Numbers Example Control 38 39 1 2

Resin quality A D PAPU

Physical property of the blowing agent mixture 10 pH 9.9 9.6 9.2 9.2

Viscosity (mPa.s) 2760 2380 2080 2060 Physical Properties of Coated Paper 15

Water resistance: 4.5 4.5 2.4 1.3 WP method

Ink 4.6 4.6 3.0 1.5

Absorption capacity: Method A

Printing ink 4.2 4.6 3.0 1.5, Absorption capacity:

Method B

,:. Examples 40 and 41 and controls 3 - 4: 30. An aqueous base dye having the composition shown in Table 1 and having a solids content of 64.5% was prepared.

»·

Each of the resin blends obtained in Examples 5 and 10 was added to the base stock of Table 1 so that it had a solids content of 0.2 parts per 100 parts of the base pigment. In control 3, instead of the above-described resin blend *, an aqueous solution of a heat-curing polyamide-polyurea-formaldehyde resin (abbreviated as "PAPU" in the table) containing 50% of the method described in Example 3 of JP-A-55-31837 (= USP 4,246,153) was prepared. The active ingredient sT ^ i had a solids content of 0.6 43 109221 parts per 100 parts of the base pigment pigment.In control 4, the base color was used without adding the resin component, and the concentrations and pH were adjusted by adding water and 10- percent sodium hydroxide solution to give coating compositions having a total solids content of 64%.

5

Each coating composition obtained was applied to one surface of a high quality paper having a basis weight of 80 g / m <2> with a rolled wire | the amount was 14 g / m2. Immediately after coating, it was dried for 30 seconds in hot air at 120 ° C and then the humidity was adjusted for 16 hours! 10 na at 20 ° C and 65% relative humidity. Subsequently, it was supercalendered twice at 60 ° C and a load of 60 kg / cm to give a coated paper. The coated paper thus obtained was tested for water resistance and ink absorption. The results of the tests are shown in Table 5. The water-resistance and ink-absorbing test-15 methods are the same as above. Test methods for white paper gloss and printed paper gloss are given below.

(5) White Paper Gloss Gw 20 The "GM-26D" digital photometer (manufactured by Murakami color technology laboratory) was measured for the positive light intensity (%) of coated paper at an angle of reflection of 75 ° to 75 °.

(6) Gloss of Printed Paper With a Gp I · 25 · _ '' · RI tester, double 'duplicate printing' was performed on the coated paper. The "GM-26D" digital photometer (same photometer '·' as used in (3)) measured the positive light intensity (%) of the coated portion of the coated paper at a reflection angle of 30 ° to 30 °. the better the gloss of the printed paper.

44 109221 (7) Kiiltoero ΔΘ

The difference in gloss ΔΘ is the difference between the gloss of white paper and the gloss of printed paper, i.

Gp - Gw. The higher the AG, the greater the difference between the gloss of the printed part and the gloss of the non-printed part. The large difference allows high contrast printing.

Table 5 Experimental results of Examples 40 and 41 and controls 3-4

No. Example Control I 40 41 3 4

! Resin grade E J Bean

Physical property of the coating composition 15

Water Resistance: 2.7 3.3 2.8 1.4 WP Method 20 Ink Absorption Capacity 3.3 4.3 3.0 1.5

ky: Method A

Ink absorption capacity 3.8 4.3 3.0 1.5

ky: Method B

25_____

Gw 75.3 75.6 75.8 75.5

Gp 78.4 79.4 77.5 78.0 V · ': 30 _AG_ 3.1 3.8 1.7 2.5

The white paper glosses 35 of Example 40, Example 41, Control 3 and Control 4 differ very little. The ΔΘ of the control 3 AG using the known polyamide-polyurea-formaldehyde resin is smaller than that of the control 4,. ·. where the resin component was not doped at all. On the other hand, Examples 40 and 41, which are examples according to the present invention, have a much higher AG value of 45109221 than control 4. In addition, Example 40 and Example 41, especially Example 41, produced much better ink absorption capabilities.

The coated paper according to the present invention does not contain a component derived from formaldehyde 5. The coated paper according to the present invention does not develop formaldehyde.

The coated paper of the present invention has excellent ink absorption and water resistance, and the coated paper has only slightly reduced or even improved gloss compared to coated paper made using a coating composition which does not contain a resin component.

Synthesis Example 10: 15

To a four-necked flask equipped with a thermometer, reflux condenser and stirring bar were added 646 g (5.0 moles) of N- (2-aminoethyl) piperazine and 690 g of methanol. The internal temperature was maintained at 45-55 ° C and a solution of 807 g (2.4 moles) of bisphenol-A-diglycidyl ether and 759 g of acetone was slowly added dropwise thereto. After dropwise addition, the reaction was continued for an additional 4 hours at 45-55 ° C.

Subsequently, the reflux condenser was replaced with a Liebig condenser and the internal temperature was raised to 80 ° C and the internal pressure was lowered to 21 kPa while acetone and methanol were removed from the system. Subsequently, the internal pressure was increased to 25 atmospheres and the mixture cooled while gradually adding 1692 g of water to give an aqueous solution of the crosslinked amine having a non-volatile component content of 39.6%, a pH of 11.9 and a viscosity of 839 mPa.s. mPas at 50% concentration). This is referred to as the aqueous solution X of the cross-linked amine.

»· 30 46 109221

Synthesis Example 11:

In the same reaction vessel as used in Synthesis Example 6, 426 g (3.3 moles) of N- (2-aminoethyl) piperazine and 517 g of methanol were added. The internal temperature 5 was maintained at 45-55 ° C and a solution of 638 g (1.9 moles) of bisphenol-A-diglycidyl ether and 543 g of acetone was added slowly dropwise thereto. After dropwise addition, the reaction was continued for an additional 4 hours at 45-55 ° C. Subsequently, the reflux condenser was replaced by a Liebig condenser, and the internal temperature was raised to 120 ° C while acetone and methanol were removed from the system. The mixture was then cooled while gradually adding 1286 g of water to give an aqueous solution of the crosslinked amine compound having a non-volatile component content of 41.8%, a pH of 11.8 and a viscosity of 2420 mPa.s (about 9,000 mPa.s at 50% concentration).

This is referred to as the aqueous solution Y of the crosslinked amine.

15

Examples 42-48 and controls 5-6:

In Example 42, 25.3 parts X of the crosslinked amine prepared in Synthesis Example 10, 40 parts triethylene glycol and 32.8 parts water were mixed thoroughly to give an aqueous solution of the resin mixture containing 51% active ingredient. Similarly, in Examples 43-48, the amounts given in Table 6 were mixed with aqueous crosslinked amine, polyhydric alcohol, and in some examples, urea. The concentration was adjusted by the addition of water to give an aqueous solution of the resin mixture with an active component content of 51%.

An aqueous base dye having the composition given in Table 1 v 'and having a solids content of 64.5% and a pH of 9.2 was prepared.

Each of the resin blends obtained in Examples 42-48 was added to the base stock given in Table 1 with a solids content of 0.6 parts per 100 parts of the base color: pigment. In control 5, the same amount as in the Examples »1010221 was added

OH

42-48 aqueous solution of a thermosetting polyamide-polyurea-formaldehyde resin ("PAPU" in the table) containing 50% of the active component prepared by the method described in Example 2 of JP-A-55-31837 (= USP 4,246,153) instead of the above resin mixture. In Kontroll 5 6, the base paint was used as such without the addition of a resin component. The concentration of the mixtures was adjusted by the addition of water to give coating compositions having a total solids content of 64%. The pH and viscosity of each coating composition were measured by the above methods and the results are shown in Table 6.

10

Each coating composition obtained was applied to one surface of a high quality paper having a basis weight of 80 g / m 2 to a roll of 14 g / m 2. Immediately after coating, it was dried for 30 seconds in hot air at 120 ° C and then humidity adjusted for 16 hours at 15 ° C and 65% relative humidity. Subsequently, it was supercalendered twice at 60 ° C and a load of 60 kg / cm to give a coated paper. The coated paper thus obtained was tested for water resistance and ink absorption. The results of the tests are shown in Table 6. The water-resistance and ink-absorbency test-20 methods are the same as above.

48 109221

Table 6

Experimental Results of Evaluation Examples 42-48 and Controls 5-6 5 Example No. 42 43 44 45 46

Used for the crosslinked amine X X X Y Y

aqueous solution Quantity (parts) 25.3 25.3 25.3 23.9 23.9

10 Polyhydric alcohol * 1 TEG DEG SOL DEG DEG

Amount (pieces) 40 10 20 40 10

Urea - 30 20 - 30

Control Resin 15 Physical Properties of Coating Mixture pH 9.4 9.4 9.4 9.4 9.4 20 Viscosity (mPa s) 2700 2560 2620 2580 2440 Physical Properties of Coated Paper

Water resistance: 4.5 4.6 4.5 4.4 4.4. 25 WP Method ... ”Ink Absorption- 4.6 4.7 4.6 4.2 4.2

ability: Method A

, i; · '30 Ink absorption 4.6 4.6 4.6 4.4 4.5

ability: Method B

49 109221

No. Example Control 47 48 5 6

Used for bridged Y Y

aqueous amine solution Quantity (parts) 23.9 23.9 5

Polyhydric alcohol * 1 TMP SOL

Amount (pieces) 20 10 10 Urea 20 30

Control resin PAPU

Physical property of the coating composition 15 pH 9.4 9.4 9.1 9.2

Viscosity (mPa.s) 2480 2400 2080 2100 Physical Properties of Coated Paper 20

Water resistance: 4.4 4.6 2.6 1.7 WP method

Ink absorption capacity: 4.2 4.3 3.0 1.5

; · 25 Method A

•; Ink absorption capacity: 4.4 4.4 3.0 1.5

-: Method B

30 * 1: Polyhydric alcohol; TEG: Triethylene glycol DEG: Diethylene glycol SOL: Sorbitol TMP: Trimethylolpropane • 35 50 109221

The paper coating resin composition of the present invention does not contain a formaldehyde-derived component. The resin blend paper coating composition therefore does not formaldehyde.

The paper coating resin composition of the present invention may be prepared as a solution or dispersion in a liquid medium such as a mixture of water and an organic solvent, and substantially exclusively in water, which may be mixed with a pigment and an aqueous binder to form a paper coating composition. The paper coating composition 10 generally does not cause such disadvantages as thickening, dripping, and the like.

The paper coating composition of this resin blend yields coated paper with various improved properties such as 15 excellent ink absorption and water resistance, etc.

* · * L · t * * i · * t> t »· I» I I »

Claims (20)

51 109221 A paper coating resin composition, characterized in that it comprises a reaction product of 5 (A) crosslinked amine compounds which are (a) an aliphatic amine and (b) a glycidyl compound having at least two glycidyl groups in the molecule, or (a) an aliphatic amine, (b) a glycidyl compound having at least two glycyl-10 dyl groups in the molecule, and (c) an α, β-unsaturated carbonyl compound, an α, β-unsaturated nitrile compound, and an α-halo carboxylic acid compound; and (B) at least one compound selected from the group consisting of (B1) non-polymeric non-volatile substances and (B2) polyhydric alcohols. ! 15 2. A resin mixture for paper coating comprising (A) a cross-linked amine compound which is a reaction product of (a) an aliphatic amine and (b) a glycidyl compound having at least two glycidyl groups in the molecule: (B) at least one substance selected from the group consisting of (B1) non-polymeric non-volatile substances and (B2) polyhydric alcohols. • · · • · 3. A resin composition for coating paper, characterized in that it contains: (a) a crosslinked amine compound which is a reaction of (a) an aliphatic amine and (b) a glycidyl compound having at least two glycidyl groups in the molecule. -, '. : product; and • »». · * ·. (B1) a non-polymeric non-volatile material. 30 A paper coating resin mixture, characterized in that it contains 52,109,221 (A) crosslinked amine compounds which are a reaction product of (a) an aliphatic amine and (b) a glycidyl compound having at least two glycidyl groups in the molecule; and (B2) polyhydric alcohol. 5 A paper coating resin composition, characterized in that it comprises (A) a crosslinked amine compound which is (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, unsaturated nitrile compounds, and α-halocarboxylic acid compounds, the reaction product; and (B1) a non-polymeric non-volatile material. The resin mixture according to claim 1, 2 or 5, characterized in that the aliphatic amine (a) is a heterocyclic amine. A resin mixture according to claim 6, characterized in that the heterocyclic amine has at least one primary amino group in addition to the secondary or tertiary amine which forms the heterocycle. . ·. Resin composition according to claim 1, 2 or 5, characterized in that the glycidyl compound (b) is an aromatic glycidyl ether. s · * • · · A resin composition according to claim 5, characterized in that compound (c), ·: ·: selected from α, β-unsaturated carbonyl compounds, α, β-unsaturated nitrile compounds, and (c) is acrylic acid. • I The resin composition according to claim 5, characterized in that compound (c),; '' is selected from α, β-unsaturated carbonyl compounds, α, β-unsaturated. ···, which nitrile compounds and α- of the halocarboxylic acid compounds (c), is chloro * 4 'acetic acid. 53 109221 11. A resin composition according to claim 1, 2 or 5, characterized in that the non-volatile material is selected from ureas. The resin composition according to claim 1, characterized in that it is dispersed or dissolved in a liquid medium. The resin mixture according to claim 12, characterized in that the liquid medium is a mixture of water and an organic solvent. A resin composition according to claim 13, characterized in that the liquid medium consists essentially of water. A paper coating composition comprising a (C) pigment; (D) an aqueous binder; (A) a crosslinked amine compound which is a reaction product of (a) an aliphatic amine and (b) a glycidyl compound having at least two glycidyl groups in the molecule, or (a) an aliphatic amine, (b) a glycidyl compound having at least:. and (c) a compound selected from α, β-unsaturated:. 20 of which are carbonyl compounds, α, β-unsaturated nitrile compounds, and α-halo: carboxylic acid compounds, reaction product; and; · · R: (B) non-polymeric non-volatile compound and / or polyhydric alcohol. • · at · • · · »· ·: * · *; 16. Coated paper, characterized in that it consists of (1) a paper substrate and (2) a coating on the surface of the paper substrate containing (C) a pigment; * "*: (D) an aqueous binder; *.: (A) a crosslinked amine compound which is a reaction of (a) an aliphatic amine and (b) a glycidyl compound having at least two glycidyl groups in the molecule. or (a) an aliphatic amine, (b) a glycidyl compound having at least two glycidyl groups in molecule I, and (c) a compound selected from α, β-unsaturated carbonyl compounds, α, β-unsaturated nitrile compounds and α- halogen carboxylic acid compounds, reaction product, and 54,109,221 (B) non-polymeric non-volatile compounds and / or polyhydric alcohol. Coated paper according to claim 16, characterized in that the aliphatic amine is a heterocyclic amine. 5 Coated paper according to claim 17, characterized in that it has at least one primary amino group in the heterocyclic amine in addition to the secondary or tertiary amine forming the heterocycle. Coated paper according to one of Claims 16 to 18, characterized in that the glycidyl compound (b) is an aromatic glycidyl ether. Coated paper according to one of Claims 16 to 19, characterized in that the non-volatile compound is selected from the grooves. 15 * * * ♦ «* · * · *» · * · · I tt · • · t «1 * f · * * * *» »« »i« i »• * III> I »» I · I 55 109221 Patenkrav