JPH11277868A - Ink jet recording sheet and waterproofness enhancing agent therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress blur of ink by coating a recording sheet with cationic resin having structural unit shown by a specified formula produced through reaction of class 2nd amine, an amine compound having more than one amino group, and xylene dihalide thereby waterproofness of image or character on the recording sheet. SOLUTION: A recorcling sheet is coated with cationic resin having structural unit shown by formulas I, II produced through reaction of class 2nd amine, an amine compound having more than one amino group, and xylene dihalide to produce an ink jet recording sheet. In formula I, R<1> , R<2> represents alkyl group, benzyl group of 1-4C, and X<-> represents halogen ion. In formula II, R<3> , R<4> , R<5> , R<6> represents hydrogen, alkyl group, benzyl group of 1-4C, R<7> represents alkylene group of 1-6C, or the like, and X represents halogen ion. Mixing molar ratio of resins shown by formulas I, II is preferably set in the range of 10:90-70:30.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a water resistance improver for ink jet recording paper and an ink jet recording paper. More specifically, the present invention is to mix the pulp fiber and form a slurry, or by impregnating or coating plain paper or coated paper to reduce the water resistance of images and characters recorded on recording paper. The present invention relates to a water resistance improver for ink jet recording paper capable of improving and reducing ink bleeding, and an ink jet recording paper coated with the water resistance improver.

[0002]

2. Description of the Related Art An ink jet printer is a printer that jets ink from nozzles in a jet state to print. Ink-jet recording is quiet, has no process of development and fixing, the recording device is simple, plain paper or coated paper can be used, and colorization is easy, and images and character figures can be freely used. It has the characteristic of being able to record, rapid growth is seen today, and its future potential is attracting attention. However, when plain paper is used as the ink jet recording paper, a problem such as dye bleeding due to adhesion of water after recording occurs, and therefore, a water resistance improver is generally used. As a water resistance improver, for example, cationic resins such as dicyandiamide condensate, polyamine, and polyethyleneimine have been proposed, but problems such as insufficient water resistance, discoloration of color tone, yellowing of a white paper portion, and ink bleeding have been proposed. There is a need for a water-resistance improver for ink jet recording paper and ink jet recording paper which is generated, has good water resistance, does not change color tone or yellowing of a white paper portion, and does not cause ink bleeding.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to improve the water resistance of images and characters recorded on recording paper and reduce ink bleeding by coating plain paper or coated paper. The purpose of the present invention is to provide a water resistance improver for ink jet recording paper and an ink jet recording paper which can be used.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that the reaction of a secondary amine with an amine compound having two or more amino groups and xylylene dihalide. The recording paper coated with the cationic resin obtained by the above is found that the water resistance of the print recorded by the ink jet printer is good, and that ink bleeding does not occur, and based on this finding, the present invention has been completed. . That is, the present invention provides (1) the second
Cation having a structural unit represented by general formula [1] and a structural unit represented by general formula [2] obtained by reacting a secondary amine with an amine compound having two or more amino groups and xylylene dihalide Water resistance improver for inkjet recording paper, characterized by containing a hydrophilic resin,

Embedded image (Wherein, R ¹ and R ² are an alkyl group having 1 to 4 carbon atoms or a benzyl group, R ¹ and R ² may be the same or different, and X ⁻ is a halogen ion .)

Embedded image (Wherein, R ³ , R ⁴ , R ⁵ and R ⁶ are hydrogen, an alkyl group having 1 to 4 carbon atoms or a benzyl group, and R ³ , R ⁴ ,
R ^5, R ⁶ may be different even in the same, R ⁷ is an alkylene group having 1 to 6 carbon atoms ^{- [R 8 -NR 10 -R 9} ]
a q-group, R ⁸ and R ⁹ are alkylene groups having 1 to 4 carbon atoms, R ⁸ and R ⁹ may be the same or different, and R ¹⁰ is hydrogen, and has 1 to 4 carbon atoms. X ^- is a halogen ion, and q is 1-4.
It is. (2) the water-resistant improver for inkjet recording paper according to (1), wherein the secondary amine is dimethylamine; (3) the amine compound having two or more amino groups is ethylenediamine, diethylenetriamine; (1) The inkjet according to (1), which is triethylenetetramine, tetraethylenepentamine, propylenediamine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylpropylenediamine. A water resistance improver for recording paper, and (4) the item (1), (2) or
(3) An ink jet recording paper, which is coated with the water resistance improver for ink jet recording paper described in (3). Further, as a preferred embodiment of the present invention, (5) the molar ratio of the structural unit represented by the general formula [1] to the structural unit represented by the general formula [2] is 1
0:90 to 70:30, wherein the water-resistance improver for ink-jet recording paper according to item (1) and (6) a 20% by weight aqueous solution of the cationic resin at 30 ° C.
The viscosity measured using a B-type viscometer is 20 to 400 mPa
• The water-resistance improver for inkjet recording paper according to item (1), which is s.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The water resistance improver for ink jet recording paper of the present invention has a general formula [1] obtained by reacting a secondary amine with an amine compound having two or more amino groups and xylylene dihalide. ] And a cationic resin having a structural unit represented by the general formula [2].

Embedded image In the general formula [1], R ¹ and R ² are an alkyl group or a benzyl group having 1 to 4 carbon atoms, R ¹ and R ² may be the same or different, and X ⁻ is a halogen ion. is there.

Embedded image In the general formula [2], R ³ , R ⁴ , R ⁵ and R ⁶ are hydrogen,
An alkyl group having 1 to 4 carbon atoms or a benzyl group,
R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different. R ⁷ is an alkylene group having 1 to 6 carbon atoms or-[R
⁸ is -NR ¹⁰ -R ^9] q- group, R ⁸ and R ⁹ are 1 to carbon atoms
R ⁸ and R ⁹ may be the same or different, R ¹⁰ is hydrogen, an alkyl group having 1 to 4 carbon atoms or a benzyl group, X ⁻ is a halogen ion , Q is 1 to 4. As the secondary amine used in the present invention, for example, dimethylamine, diethylamine,
Examples thereof include dipropylamine, dibutylamine, dibenzylamine, methylethylamine, methylpropylamine, methylbutylamine, and methylbenzylamine. One of these secondary amines can be used alone, or two or more can be used in combination. Among them, dimethylamine can be suitably used.

In the present invention, the amino group of the amine compound having two or more amino groups may be a monoalkylamino group or a dialkylamino group in which hydrogen is substituted by an alkyl group or an aralkyl group, in addition to the --NH ₂ group. , A monoaralkylamino group, a diaralkylamino group and the like. Examples of the amine compound having two or more amino groups used in the present invention include, for example, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, propylenediamine, dipropylenetriamine, tetramethylenediamine, hexamethylenediamine, N, N, N ', N'-tetramethylmethylenediamine, N, N, N', N'-tetraethylmethylenediamine,
N, N, N ', N'-tetrabenzylmethylenediamine, N,
N-dimethylethylenediamine, N, N'-dimethylethylenediamine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetraethylethylenediamine, N, N, N ', N'- Tetrapropylethylenediamine, N, N, N ', N'-tetrabutylethylenediamine,
N, N, N ', N'-tetrabenzylethylenediamine, N,
N, N ', N'-tetramethylpropylenediamine, N, N,
N ', N'-tetraethylpropylenediamine, N, N,
N ', N'-tetrapropylpropylenediamine, N, N,
N ', N'-tetrabutylpropylenediamine, N, N,
N ', N'-tetrabenzylpropylenediamine, N, N,
N ', N'-tetramethylbutylenediamine, N, N, N',
N'-tetraethylbutylenediamine, N, N, N ', N'-
Tetrapropyl butylene diamine, N, N, N ', N'-tetrabutyl butylene diamine, N, N, N', N'-tetrabenzyl butylene diamine, N, N, N ', N'-tetramethyl-4- Azaheptane-1,7-diamine, N, N,
N ', N'-tetramethyl-4-aza-4-methylheptane-1,7-diamine, N, N, N', N'-tetramethyl-
4-aza-4-ethylheptane-1,7-diamine, N,
N, N ', N'-tetramethyl-4-aza-4-propylheptane-1,7-diamine, N, N, N', N'-tetramethyl-4-aza-4-butylheptane-1, 7-diamine, N, N, N ', N'-tetramethyl-4-aza-4-benzylpentane-1,7-diamine, N, N, N', N'-tetramethyl-5-azanonane-1 , 9-Diamine, N,
N, N ', N'-tetramethyl-5-aza-5-methylnonane-1,9-diamine, N, N, N', N'-tetramethyl-
5-aza-5-ethylnonane-1,9-diamine, N,
N, N ', N'-tetramethyl-5-aza-5-propylnonane-1,9-diamine, N, N, N', N'-tetramethyl-5-aza-5-butylnonane-1,9 -Diamine, N,
N, N ', N'-tetramethyl-5-aza-5-benzylnonane-1,9-diamine, N, N, N', N'-tetramethyl-3,6-diazaoctane-1,8-diamine , N, N,
N ', N'-tetramethyl-3,6-diaza-3,6-dimethyloctane-1,8-diamine, N, N, N', N'-tetramethyl-3,6-diaza-3,6 -Diethyloctane-
1,8-diamine, N, N, N ′, N′-tetramethyl-3,
6-diaza-3,6-dipropyloctane-1,8-diamine, N, N, N ', N'-tetramethyl-3,6-diaza-
3,6-dibutyloctane-1,8-diamine, N, N,
N ', N'-tetramethyl-3,6-diaza-3,6-dibenzyloctane-1,8-diamine, N, N, N', N'-tetramethyl-3,6,9-triaza Undecane-1,11
-Diamine, N, N, N ', N'-tetramethyl-3,6,9
-Triaza-3,6,9-trimethylundecane-1,1
1-diamine, N, N, N ', N'-tetramethyl-3,6,
9-triaza-3,6,9-triethylundecane-1,
11-diamine, N, N, N ', N'-tetramethyl-3,
6,9-triaza-3,6,9-tripropylundecane-1,11-diamine, N, N, N ', N'-tetramethyl-
3,6,9-triaza-3,6,9-tributylundecane-1,11-diamine, N, N, N ', N'-tetramethyl-
3,6,9-Triaza-3,6,9-tribenzylundecane-1,11-diamine and the like can be mentioned. These amine compounds having two or more amino groups include 1
The species can be used alone, or two or more can be used in combination. Among these, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, propylenediamine, N, N, N ', N'-tetramethylethylenediamine,
N, N, N ', N'-tetramethylpropylenediamine can be suitably used.

The xylylene dihalide used in the present invention is not particularly limited. For example, α, α'-dichloro-o-xylene, α, α'-dichloro-m-xylene, α, α'-dichloro-p- Xylene, α, α′-dibromo-o-xylene, α, α′-dibromo-m-xylene, α, α′-dibromo-p-xylene and the like can be mentioned. One of these xylylene dihalides can be used alone, or two or more can be used in combination. Among these xylylene dihalides, α, α′-dichloro-p-xylene can be suitably used.
The cationic resin used in the present invention comprises a structural unit represented by the general formula [1] formed by a reaction between a secondary amine and xylylene dihalide, and an amine compound having two or more amino groups and a xylylene dihalide. Having a structural unit represented by the general formula [2] produced by the reaction of In the cationic resin, there is no particular limitation on the arrangement of the structural unit represented by the general formula [1] and the structural unit represented by the general formula [2]. For example, the structural unit represented by the general formula [1] And a cationic resin in which the structural units represented by the general formula [2] are arranged in a completely random manner, and represented by the structural units represented by the general formula [1] and the general formula [2] It is also possible to use a cationic resin in which the structural units are arranged in a block shape. Further, the structural unit represented by the general formula [1] or a part of the structural unit represented by the general formula [2] is formed in a block shape. It can be a cationic resin that is arranged and the remainder is arranged randomly.

[0008] In the cationic resin used in the present invention,
Although there is no particular limitation on the ratio of the structural unit represented by the general formula [1] and the structural unit represented by the general formula [2], the general formula [1]
Is preferably from 10:90 to 70:30, and more preferably from 15:85 to 60:40. When the molar ratio of the structural unit represented by the general formula [1] to the structural unit represented by the general formula [2] is less than 10:90,
Ink bleeding may occur. When the molar ratio of the structural unit represented by the general formula [1] to the structural unit represented by the general formula [2] exceeds 70:30, the effect of improving water resistance may not be sufficiently exhibited. In the cationic resin used in the present invention, the structure of the terminal group is not particularly limited. For example, a resin in which both terminal groups have an amine structure, a resin in which both terminal groups are both xylylene dihalide residues, and one terminal group Has an amine structure, and the other terminal group is a xylylene dihalide residue. When the terminal group is a xylylene dihalide residue, the halogen is further converted to a hydroxyl group, an alkyl group, an aryl ether group,
It can be substituted by an acyl group or the like. When the terminal group has an amino group, an imino group or a tertiary amine structure, a salt is formed with an inorganic acid or an organic acid, or a salt is formed with an alkyl halide, an aralkyl halide, a dialkyl sulfate, an alkylene oxide, or the like. The tertiary amine structure can be quaternized. As the inorganic acid, for example,
Examples include hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid.
Examples of the organic acid include formic acid, acetic acid, lactic acid, malic acid, citric acid and the like. Examples of the alkyl halide include, for example, methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, ethyl iodide,
Propyl chloride, propyl bromide, propyl iodide, isopropyl chloride, isopropyl bromide, isopropyl iodide,
Examples thereof include butyl chloride, butyl bromide, and butyl iodide. As the aralkyl halide, for example,
Benzyl chloride, p-chlorobenzyl chloride and the like can be mentioned. Examples of the dialkyl sulfate include dimethyl sulfate and diethyl sulfate. Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin and the like.

The method for producing the cationic resin used in the present invention is not particularly limited. For example, a secondary amine, an amine compound having two or more amino groups, and xylylene dihalide are simultaneously charged into a reactor to carry out addition polymerization. Can be
After reacting a part of the xylylene dihalide with the secondary amine, the reaction can be continued by adding the amine compound having two or more amino groups and the remaining xylylene dihalide, or After reacting a part of the xylylene dihalide with the amine compound having
The reaction can be continued by adding the tertiary amine and the remaining xylylene dihalide. Further, a mixture of an arbitrary ratio of a tertiary amine and an amine compound having two or more amino groups and a part of the xylylene dihalide can be obtained. After the reaction, the reaction can be continued by adding the remaining secondary amine, an amine compound having two or more amino groups, and xylylene dihalide. The amounts of the secondary amine or the amine compound having two or more amino groups and the xylylene dihalide to be added to the reactor are preferably approximately equivalent. The reaction between the secondary amine and the amine compound having two or more amino groups and xylylene dihalide may be performed by adding water or an organic solvent, if necessary, to control the reaction rate or the viscosity of the reaction system. Can be. Examples of the organic solvent to be added to the reaction system include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and diisobutyl ketone; alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; N, N-dimethylformamide;
Examples thereof include a nitrogen-based solvent such as methylpyrrolidone, and dimethyl sulfoxide. The organic solvent added to the reaction system can be removed by means such as distillation after the completion of the reaction. There are no particular restrictions on the conditions under which the secondary amine is reacted with the amine compound having two or more amino groups and xylylene dihalide.
Can react for ~ 8 hours.

Although the molecular weight of the cationic resin used in the present invention is not particularly limited, the viscosity of a 20% by weight aqueous solution of the cationic resin measured at 30 ° C. using a B-type viscometer is 20 to 400 mPa · s. s, more preferably 50 to 300 mPa · s, and even more preferably 100 to 200 mPa · s. If the viscosity measured at 30 ° C. of the 20% by weight aqueous solution is less than 20 mPa · s, the effect of improving water resistance may not be sufficiently exhibited. When the viscosity measured at 30 ° C. of the 20% by weight aqueous solution exceeds 400 mPa · s, the viscosity becomes too high, and the workability such as coating may be reduced. The form of the water resistance improver for inkjet recording paper of the present invention is not particularly limited. For example, the structural unit represented by the general formula [1] and the general formula [2]
The cationic resin having the structural unit represented by is dissolved in an aqueous medium. The aqueous medium to be used is not particularly limited, and may be, for example, a medium in which a polar organic solvent is added to water. As the polar solvent to be added, for example, methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, n
-Butyl alcohol, sec-butyl alcohol, t-butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, alcohols such as dodecyl alcohol, phenols, phenols such as cresol, 3-methyl-3-
Methoxybutanol, 3-methyl-3-methoxybutyl acetate, ethylene glycol monomethyl ether,
Ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol ethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether,
Glycol ethers such as diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol dibutyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, and tripropylene glycol monomethyl ether; ethylene glycol, propylene glycol; And glycols such as 3,3-butanediol, hexylene glycol, diethylene glycol and dipropylene glycol. By adding a polar organic solvent to the aqueous medium, the stability of the water resistance improver for inkjet recording paper can be improved.

The water resistance improver for ink jet recording paper of the present invention may contain a known binder, inorganic pigment, organic pigment and the like, if necessary. Examples of the binder include oxidized starch and polyvinyl alcohol. Examples of the inorganic pigment include light calcium carbonate, heavy calcium carbonate, kaolin (white clay), talc, calcium sulfate, barium sulfate,
Examples include titanium oxide, zinc oxide, zinc sulfate, zinc carbonate, satin white, aluminum silicate, diatomaceous earth, calcium silicate, synthetic silica, aluminum hydroxide, alumina, and lithopone. Examples of the organic pigment include styrene-based plastic pigment, acrylic-based plastic pigment, and urea resin pigment. The method of using the water resistance improver for inkjet recording paper of the present invention is not particularly limited. For example, pulp that has been refined in a mixing chest at the time of preparation of a stock is used together with fillers, chemicals, dyes, and the like. Papermaking can be performed by adding a water resistance improver for recording paper. The pulp fibers to be used are mainly used wood pulp, but may be used in combination with fibrous substances such as synthetic pulp, synthetic fibers and glass fibers. Further, after preparing a treatment bath containing the water resistance improver for inkjet recording paper of the present invention and impregnating plain paper or coated paper, the excess impregnating liquid on the front and back of plain paper or coated paper is sized. It can be removed by pressing and dried. Further, the water resistance improver for ink jet recording paper of the present invention can be coated on plain paper or coated paper. Among these methods, the method of coating a water resistance improver for ink jet recording paper is easy in process control, can cope with high-mix low-volume production, and applies a cationic resin only to the surface layer of paper. The present invention can be used particularly effectively because it can be used effectively. When coating the water resistance improver for inkjet recording paper of the present invention, the coating amount is preferably from 0.1 to 10.0 g / m ² as a cationic resin,
More preferably, it is 0.2 to 5.0 g / m ² . There is no particular limitation on the method of coating the water resistance improver for inkjet recording paper of the present invention, for example, air knife coater, roll coater, blade coater, bar coater, brush coater, champlex coater,
Plain paper or coated paper can be coated with a gravure coater and dried.

When using the water resistance improver for ink jet recording paper of the present invention, a dye mordant, a defoamer, a dispersant, a thickener, a colorant, an antistatic agent, a preservative, a water-soluble resin, an adhesive, etc. Can be used in combination. Examples of the dye mordant include dicyandiamide condensate, polyamine, and polyethyleneimine. Examples of the water-soluble resin and the adhesive include oxidized starch, etherified starch, carboxymethylcellulose, cellulose derivatives such as hydroxyethylcellulose, casein, gelatin, soybean protein, polyvinyl alcohol and its derivatives, maleic anhydride resin, styrene-
Butadiene copolymer, conjugated diene polymer latex such as methyl methacrylate-butadiene copolymer, acrylic polymer latex such as acrylic acid ester, methacrylic acid ester polymer or copolymer, ethylene-
Vinyl polymer latex such as vinyl acetate copolymer,
Melamine resins, aqueous adhesives of thermosetting resins such as urea resins, polymethyl methacrylate, polyurethane resins, unsaturated polyester resins, vinyl chloride-vinyl acetate copolymers, polyvinyl butyral, thermoplastic resins such as alkyd resins, etc. be able to. The plain paper is generally used acidic paper or neutral paper, and the coated paper is coated paper coated with a binder, an inorganic pigment, an organic pigment, or the like. When recording with an aqueous ink on the inkjet recording paper treated with the water resistance improver for an inkjet recording paper of the present invention, the dye in the aqueous ink and the cationic resin in the inkjet recording paper are bonded, elution of the dye is prevented, and water resistance is improved. It is thought that the property is improved.
The aqueous ink used contains an anionic direct dye or an acid dye as a dye, and in addition, a wetting agent, a dye dissolving agent,
It preferably contains a preservative or the like.

The anionic direct dye used in the aqueous ink includes, for example, CI Direct Black.
2, 4, 9, 11, 14, 17, 19, 22, 27, 3,
2, 36, 38, 41, 48, 49, 51, 56, 6
2, 71, 74, 75, 77, 78, 80, 105, 1
06, 107, 108, 112, 113, 117, 13
2, 146, 154, 194, CI Direct Y
yellow 1,2,4,8,11,12,24,2
5, 26, 27, 28, 33, 34, 39, 41, 4,
2, 44, 48, 50, 51, 58, 72, 85, 8
6, 87, 88, 98, 100, 110, CI Dir
ect Orange 3, 8, 10, 26, 29, 3
9, 41, 49, 51, 102, C.I.Direct
Red 1, 2, 4, 8, 9, 11, 13, 17, 1
8, 20, 23, 24, 28, 31, 33, 37, 3
9, 44, 46, 47, 48, 51, 59, 62, 6
3, 73, 75, 77, 80, 81, 83, 84, 8
5, 90, 94, 99, 101, 108, 110, 14
5, 189, 197, 220, 224, 225, 22
6, 227, 230, C.I. Direct Violet
t 1, 7, 9, 12, 35, 48, 51, 90, 9
4, CI Direct Blue 1, 2, 6, 8, 1
5, 22, 25, 34, 69, 70, 71, 72, 7
5, 76, 78, 80, 81, 82, 83, 86, 9
0, 98, 106, 108, 110, 120, 123,
158, 163, 165, 192, 193, 194, 1
95, 196, 199, 200, 201, 202, 20
3, 207, 218, 236, 237, 239, 24
6, 258, CI Direct Green 1, 6,
8, 28, 33, 37, 63, 64, CI Direct
t Brown 1, 2, 6, 25, 27, 44, 58,
95, 100, 101, 106, 112, 173, 19
4, 195, 209, 210, 211 and the like.

Further, examples of the acid dye include CI.
Acid Black 1, 2, 7, 15, 17, 24,
26, 28, 31, 41, 48, 52, 60, 63, 9
4, 107, 109, 112, 118, 119, 12
1, 122, 131, 155, 156, CI Acid
Yellow 1, 3, 4, 7, 11, 12, 13, 1
4, 17, 18, 19, 23, 25, 29, 34, 3
6, 38, 40, 41, 42, 44, 49, 53, 5
5, 59, 61, 71, 72, 76, 78, 99, 11
1, 114, 116, 122, 135, 161, 17
2, CI Acid Orange 7, 8, 10, 3
3, 56, 64, CI Acid Red 1, 4, 6,
8, 13, 14, 15, 18, 19, 21, 26, 2
7, 30, 32, 34, 35, 37, 40, 42, 5
1, 52, 54, 57, 80, 82, 83, 85, 8
7, 88, 89, 92, 94, 97, 106, 108,
110, 115, 119, 129, 131, 133, 1
34, 135, 154, 155, 172, 176, 18
0, 184, 186, 187, 249, 254, 25
6, 317, 318, CI Acid Violet
7, 11, 15, 34, 35, 41, 43, 49, 7
5, CI Acid Blue 1, 7, 9, 22, 2
3, 25, 27, 29, 40, 41, 43, 45, 4,
9, 51, 53, 55, 56, 59, 62, 78, 8
0, 81, 83, 90, 92, 93, 102, 104,
111, 113, 117, 120, 124, 126, 1
45, 167, 171, 175, 183, 229, 23
4, 236, CI Acid Green 3, 12, 1
9, 27, 41, CI Acid Brown 4, 14
And the like.

[0015]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. In Examples and Comparative Examples, the evaluation of the water resistance improver for inkjet recording paper was performed by the following method. (1) Measurement of viscosity The viscosity was measured at 30 ° C. using a B-type viscometer. (2) Preparation of ink jet recording paper The water resistance improver for ink jet recording paper was diluted with water to obtain an aqueous solution having a nonvolatile content of 2.6% by weight.
The basis weight of 64 g / m ² of the printing paper A as defined in 1, by 19.2 g / m ² coated with dried using a bar coater, was coated with a cationic resin 0.5 g / m ² inkjet Make recording paper. (3) Evaluation of Water Resistance Using an inkjet printer [Epson Corporation, MJ-700V2C] as an inkjet recording paper, black (Black), cyan (Cyan), and magenta (Ma) were used.
genta) and a solid color of yellow (Yellow) are solid-printed, left for 1 hour, immersed in running water for 5 minutes, and visually observed for changes in the printed portion, and evaluated according to the following criteria. ：: The printed portion is not washed away by water or does not bleed. Δ: The printed portion is slightly blurred. ×: The printed portion is clearly washed away with water and bleeds. (4) Evaluation of Ink Bleeding Prevention Using an inkjet printer [Epson Corporation, MJ-700V2C], a single black dot was printed on the inkjet recording paper, and the dot portion was observed using a loupe with a magnification of 50 times. The evaluation is made according to the following criteria. ：: no bleeding Δ: There is slight bleeding. ×: There is clearly bleeding.

EXAMPLE 1 9.0 g of a 50% by weight aqueous solution of dimethylamine and isopropyl alcohol 3 were placed in a four-necked flask having a capacity of 1 liter.
2.5 g, α, α′-dichloro-p-xylene 87.5 g,
24.0 g of ethylenediamine and 137.0 g of water were charged and reacted at 70 ° C. for 4 hours. After the completion of the reaction, 322.5 g of water was further added, isopropyl alcohol was removed by distillation under reduced pressure, the nonvolatile content was adjusted to 20% by weight with water, and a water resistance improver for inkjet recording paper having a viscosity of 144 mPa · s was obtained. Obtained. An ink jet recording paper was prepared using this water resistance improver for ink jet recording paper, and the water resistance and ink bleeding prevention were evaluated. Black,
For any single color of cyan, magenta and yellow,
The printed portion was not washed away by water or bleeding. In addition, no bleeding was observed in the dot portion where the black single color was printed. Example 2 Instead of 24.0 g of ethylenediamine, 41.2 g of diethylenetriamine was used, and the amount of water charged during the reaction was 1
63.0 g, and the amount of water added after the completion of the reaction was 365.4 g.
Except that the viscosity was 170 m
A water resistance improver for ink jet recording paper having a Pa · s was obtained. An ink jet recording paper was prepared using this water resistance improver for ink jet recording paper, and the water resistance and ink bleeding prevention were evaluated. Regarding any single color of black, cyan, magenta and yellow, the printed portion was not washed away by water or bleeding. In addition, no bleeding was observed in the dot portion where the black single color was printed. Example 3 Instead of 24.0 g of ethylenediamine, 58.4 g of triethylenetetramine was used, the amount of water charged at the time of the reaction was 189.0 g, and the amount of water added after the completion of the reaction was 408.9.
g, except that the viscosity was 180 g.
A water resistance improver for ink jet recording paper of mPa · s was obtained. An ink jet recording paper was prepared using this water resistance improver for ink jet recording paper, and the water resistance and ink bleeding prevention were evaluated. Regarding any single color of black, cyan, magenta and yellow, the printed portion was not washed away by water or bleeding. In addition, no bleeding was observed in the dot portion where the black single color was printed. Example 4 Instead of 24.0 g of ethylenediamine, 75.6 g of tetraethylenepentamine was used, the amount of water charged during the reaction was 214.0 g, and the amount of water added after the completion of the reaction was 451.
Except that the viscosity was 19 g in the same manner as in Example 1 except that the viscosity was 19 g.
A water resistance improver for inkjet recording paper of 4 mPa · s was obtained. An ink jet recording paper was prepared using this water resistance improver for ink jet recording paper, and the water resistance and ink bleeding prevention were evaluated. Regarding any single color of black, cyan, magenta and yellow, the printed portion was not washed away by water or bleeding. In addition, no bleeding was observed in the dot portion where the black single color was printed.

Example 5 Instead of 24.0 g of ethylenediamine, 29.6 g of propylenediamine was used, and the amount of water charged during the reaction was 14
The viscosity was 250 mP in the same manner as in Example 1 except that the amount of water after the completion of the reaction was 336.1 g.
As a water resistance improver for inkjet recording paper was obtained. An ink jet recording paper was prepared using this water resistance improver for ink jet recording paper, and the water resistance and ink bleeding prevention were evaluated. Regarding any single color of black, cyan, magenta and yellow, the printed portion was not washed away by water or bleeding. In addition, no bleeding was observed in the dot portion where the black single color was printed. Example 6 Instead of 24.0 g of ethylenediamine, N, N, N ', N'
-The viscosity was adjusted in the same manner as in Example 1 except that 46.4 g of tetramethylethylenediamine was used, the amount of water charged during the reaction was 171.0 g, and the amount of water added after the reaction was 378.9 g. A water resistance improver for ink jet recording paper of 176 mPa · s was obtained. An ink jet recording paper was prepared using this water resistance improver for ink jet recording paper, and the water resistance and ink bleeding prevention were evaluated. Regarding any single color of black, cyan, magenta and yellow, the printed portion was not washed away by water or bleeding. In addition, no bleeding was observed in the dot portion where the black single color was printed. Example 7 Instead of 24.0 g of ethylenediamine, N, N, N ', N'
Using 52.0 g of tetramethylpropylenediamine,
Water resistance for ink-jet recording paper having a viscosity of 330 mPa · s in the same manner as in Example 1 except that the charged amount of water at the time of the reaction was 179.0 g and the added amount of water after the reaction was 392.5 g. An improver was obtained. An ink jet recording paper was prepared using this water resistance improver for ink jet recording paper, and the water resistance and ink bleeding prevention were evaluated.
Regarding any single color of black, cyan, magenta and yellow, the printed portion was not washed away by water or bleeding. In addition, no bleeding was observed in the dot portion where the black single color was printed. Example 8 Instead of α, α′-dichloro-p-xylene, α, α′-
A water resistance improver for ink jet recording paper having a viscosity of 54 mPa · s was obtained in the same manner as in Example 1 except that dichloro-m-xylene was used. An ink jet recording paper was prepared using this water resistance improver for ink jet recording paper, and the water resistance and ink bleeding prevention were evaluated. For black, cyan and magenta single colors, the printed part was not washed away by water or bleeding,
Slight bleeding was observed in the single yellow color. In addition, no bleeding was observed in the dot portion where the black single color was printed. Example 9 Instead of α, α′-dichloro-p-xylene, α, α′-
A water resistance improver for an ink jet recording paper having a viscosity of 58 mPa · s was obtained in the same manner as in Example 6 except that dichloro-m-xylene was used. An ink jet recording paper was prepared using this water resistance improver for ink jet recording paper, and the water resistance and ink bleeding prevention were evaluated. For black, cyan and magenta single colors, the printed part was not washed away by water or bleeding,
Slight bleeding was observed in the single yellow color. In addition, no bleeding was observed in the dot portion where the black single color was printed.

Example 10 Instead of α, α′-dichloro-p-xylene, α, α′-
A water resistance improver for ink jet recording paper having a viscosity of 30 mPa · s was obtained in the same manner as in Example 1 except that dichloro-o-xylene was used. An ink jet recording paper was prepared using this water resistance improver for ink jet recording paper, and the water resistance and ink bleeding prevention were evaluated. For black, cyan and magenta single colors, the printed part was not washed away by water or bleeding,
Slight bleeding was observed in the single yellow color. In addition, no bleeding was observed in the dot portion where the black single color was printed. Example 11 Instead of α, α′-dichloro-p-xylene, α, α′-
A water resistance improver for ink jet recording paper having a viscosity of 32 mPa · s was obtained in the same manner as in Example 6 except that dichloro-o-xylene was used. An ink jet recording paper was prepared using this water resistance improver for ink jet recording paper, and the water resistance and ink bleeding prevention were evaluated. For black, cyan and magenta single colors, the printed part was not washed away by water or bleeding,
Slight bleeding was observed in the single yellow color. In addition, no bleeding was observed in the dot portion where the black single color was printed. Example 12 9.0 g of a 50% by weight aqueous solution of dimethylamine and isopropyl alcohol 3 were placed in a four-necked flask having a capacity of 1 liter.
After charging 2.5 g, 17.5 g of α, α'-dichloro-p-xylene and 137.0 g of water and reacting at 70 ° C. for 4 hours, 70.0 g of α, α'-dichloro-p-xylene and ethylenediamine 24.0 g was added, and the mixture was further reacted at 70 ° C. for 4 hours. After the reaction, 322.5 g of water was added, and isopropyl alcohol was removed by distillation under reduced pressure.
Adjusted to a nonvolatile content of 20% by weight with water, the viscosity was 146m
A water resistance improver for ink jet recording paper having a Pa · s was obtained. An ink jet recording paper was prepared using this water resistance improver for ink jet recording paper, and the water resistance and ink bleeding prevention were evaluated. Regarding any single color of black, cyan, magenta and yellow, the printed portion was not washed away by water or bleeding. In addition, no bleeding was observed in the dot portion where the black single color was printed.

Example 13 In a 1-liter four-necked flask, 9.0 g of a 50% by weight aqueous solution of dimethylamine and isopropyl alcohol 3 were added.
After charging 2.5 g, 17.5 g of α, α′-dichloro-p-xylene and 171.0 g of water and reacting at 70 ° C. for 4 hours, 70.0 g of α, α′-dichloro-p-xylene and N , N, N ', N'-tetramethylethylenediamine 46.4
g was added and the mixture was further reacted at 70 ° C. for 4 hours. After completion of the reaction, 378.9 g of water was added, and isopropyl alcohol was removed by distillation under reduced pressure.
To obtain a water resistance improver for ink jet recording paper having a viscosity of 178 mPa · s. An ink jet recording paper was prepared using this water resistance improver for ink jet recording paper, and the water resistance and ink bleeding prevention were evaluated.
Regarding any single color of black, cyan, magenta and yellow, the printed portion was not washed away by water or bleeding. In addition, no bleeding was observed in the dot portion where the black single color was printed. Example 14 A 1-liter four-necked flask was charged with 9.0 g of a 50% by weight aqueous solution of dimethylamine and isopropyl alcohol 3
2.5 g, α, α′-dichloro-p-xylene 87.5 g,
12.0 g of ethylenediamine, 2 of diethylenetriamine
0.6 g and 150.0 g of water were charged and reacted at 70 ° C. for 4 hours. After the completion of the reaction, 344.1 g of water was added, isopropyl alcohol was removed by distillation under reduced pressure, the nonvolatile content was adjusted to 20% by weight with water, and the viscosity was 160 mPa · s.
Was obtained. An ink jet recording paper was prepared using this water resistance improver for ink jet recording paper, and the water resistance and ink bleeding prevention were evaluated. Black, cyan, magenta and yellow, for any single color, the printed part is flushed with water,
There was no bleeding. In addition, no bleeding was observed in the dot portion where the black single color was printed. Example 15 Instead of 20.6 g of diethylenetriamine, N, N,
Same as Example 14 except that 23.2 g of N ′, N′-tetramethylethylenediamine was used, the amount of water charged during the reaction was 154.0 g, and the amount of water added after the reaction was 355.7 g. Thus, a water resistance improver for ink jet recording paper having a viscosity of 164 mPa · s was obtained. An ink jet recording paper was prepared using this water resistance improver for ink jet recording paper, and the water resistance and ink bleeding prevention were evaluated. Regarding any single color of black, cyan, magenta and yellow, the printed portion was not washed away by water or bleeding. In addition, no bleeding was observed in the dot portion where the black single color was printed. Example 16 12.0 g of ethylenediamine and diethylenetriamine 2
Instead of 0.6 g, 23.2 g of N, N, N ', N'-tetramethylethylenediamine and 26.0 g of N, N, N', N'-tetramethylpropylenediamine were used, and water was charged during the reaction. In the same manner as in Example 14, except that the amount was 175.0 g, and the amount of water added after the completion of the reaction was 383.9 g,
A water resistance improver for ink jet recording paper having a viscosity of 196 mPa · s was obtained. An ink jet recording paper was prepared using this water resistance improver for ink jet recording paper, and the water resistance and ink bleeding prevention were evaluated. Regarding any single color of black, cyan, magenta and yellow, the printed portion was not washed away by water or bleeding. Also, in the dot part where the black single color is printed,
No bleeding was observed.

Example 17 A 1-liter four-neck flask was charged with 18.0 g of a 50% by weight aqueous solution of dimethylamine, 32.5 g of isopropyl alcohol, and 87.5 g of α, α'-dichloro-p-xylene.
g, 18.0 g of ethylenediamine and 130.0 g of water were charged and reacted at 70 ° C. for 4 hours. After completion of the reaction, water 31
8.5 g was added, isopropyl alcohol was removed by distillation under reduced pressure, and the nonvolatile content was adjusted to 20% by weight with water to obtain a water resistance improver for inkjet recording paper having a viscosity of 88 mPa · s. An ink jet recording paper is prepared using the water resistance improver for the ink jet recording paper,
The water resistance and the ink bleeding prevention were evaluated. Regarding any single color of black, cyan, magenta and yellow, the printed portion was not washed away by water or bleeding. Also, in the dot part where the black single color is printed,
No bleeding was observed. Example 18 Instead of 18.0 g of ethylenediamine, N, N, N ', N'
-The viscosity was adjusted in the same manner as in Example 17 except that 34.8 g of tetramethylethylenediamine was used, the amount of water charged during the reaction was 155.0 g, and the amount of water added after the reaction was 360.3 g. A water resistance improver for ink jet recording paper having a pressure of 108 mPa · s was obtained. An ink jet recording paper was prepared using this water resistance improver for ink jet recording paper, and the water resistance and ink bleeding prevention were evaluated.
Regarding any single color of black, cyan, magenta and yellow, the printed portion was not washed away by water or bleeding. In addition, no bleeding was observed in the dot portion where the black single color was printed. Example 19 In a 1-liter four-necked flask, 27.0 g of a 50% by weight aqueous solution of dimethylamine, 32.5 g of isopropyl alcohol, and 87.5 of α, α'-dichloro-p-xylene were added.
g, N, N, N ', N'-tetramethylethylenediamine 2
3.2 g and 140.0 g of water were charged and reacted at 70 ° C. for 4 hours. After the completion of the reaction, 342.7 g of water was added, isopropyl alcohol was removed by distillation under reduced pressure, the nonvolatile content was adjusted to 20% by weight with water, and the viscosity was 80 mPa · s.
Was obtained. An ink jet recording paper was prepared using this water resistance improver for ink jet recording paper, and the water resistance and ink bleeding prevention were evaluated. Black, cyan, magenta and yellow, for any single color, the printed part is flushed with water,
There was no bleeding. In addition, no bleeding was observed in the dot portion where the black single color was printed.

Example 20 In a four-necked flask having a capacity of 1 liter, 9.0 g of a 50% by weight aqueous solution of dimethylamine and isopropyl alcohol 3 were added.
2.5 g, α, α′-dichloro-p-xylene 87.5 g,
N, N, N ', N'-tetramethylethylenediamine 46.4
g and 171.0 g of water were charged and reacted at 70 ° C. for 4 hours. After the completion of the reaction, 388.0 g of water and 2.5 g of sulfuric acid were added, isopropyl alcohol was removed by distillation under reduced pressure, and the nonvolatile content was adjusted to 20% by weight with water.
A water resistance improver for inkjet recording paper of 0 mPa · s was obtained. An ink jet recording paper was prepared using this water resistance improver for ink jet recording paper, and the water resistance and ink bleeding prevention were evaluated. Regarding any single color of black, cyan, magenta and yellow, the printed portion was not washed away by water or bleeding. In addition, no bleeding was observed in the dot portion where the black single color was printed. Example 21 In a 1-liter four-necked flask, 9.0 g of a 50% by weight aqueous solution of dimethylamine and isopropyl alcohol 3 were added.
2.5 g, α, α′-dichloro-p-xylene 87.5 g,
N, N, N ', N'-tetramethylethylenediamine 46.4
g and 171.0 g of water were charged and reacted at 70 ° C. for 4 hours. After completion of the reaction, 389.5 g of water and 3.2 ml of dimethyl sulfate were added.
g, and after further reacting at 70 ° C. for 2 hours,
The isopropyl alcohol was removed by distillation under reduced pressure, the nonvolatile content was adjusted to 20% by weight with water, and the viscosity was 174 mPa.
S water-proofing improver for inkjet recording paper was obtained. An ink jet recording paper was prepared using this water resistance improver for ink jet recording paper, and the water resistance and ink bleeding prevention were evaluated. Regarding any single color of black, cyan, magenta and yellow, the printed portion was not washed away by water or bleeding. In addition, no bleeding was observed in the dot portion where the black single color was printed. Comparative Example 1 Ink jet recording using polyethyleneimine (molecular weight 1,200) instead of the cationic resin having the structural unit represented by the general formula [1] and the structural unit represented by the general formula [2] Paper was prepared and evaluated for water resistance and ink bleeding prevention. For black and magenta single colors, the printed portion was slightly blurred, and for cyan and yellow single colors, the printed portion was clearly washed away with water and blurred. In addition, bleeding was clearly observed in a dot portion where a single black color was printed. Table 1 shows the raw material compositions of Examples 1 to 21 and the evaluation results of the water resistance and the ink bleeding prevention properties of Examples 1 to 21 and Comparative Example 1.

[0022]

[Table 1]

[0023]

[Table 2]

[0024]

[Table 3]

[0025]

[Table 4]

As is evident from the results in Table 1, the ink jet recording papers of Examples 1 to 21 prepared by coating the water resistance improvers for ink jet recording papers of the present invention are excellent in all inks. Water resistant,
In addition, the ink has excellent ink bleeding prevention properties. On the other hand, the ink jet recording paper of Comparative Example 1 produced using polyethyleneimine, which has been conventionally used as a water resistance improver for ink jet recording paper, is inferior in water resistance and ink blur prevention.

[0027]

By coating the water resistance improver for ink jet recording paper of the present invention, the water resistance of images and characters recorded using an ink jet printer can be improved, and an image with excellent image quality without ink bleeding can be obtained. It is possible to obtain an ink jet recording paper capable of recording.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Toshio Genmasa 4-23-1, Bunkyo, Fukui City, Fukui Prefecture Inside Nikka Kagaku Co., Ltd.

Claims (4)

[Claims] 1. A structural unit represented by the general formula [1] and a structural unit represented by the general formula [2] obtained by reacting a secondary amine, an amine compound having two or more amino groups, and xylylene dihalide. A water resistance improver for inkjet recording paper, comprising a cationic resin having a structural unit represented by the formula: Embedded image (Wherein, R ¹ and R ² are an alkyl group having 1 to 4 carbon atoms or a benzyl group, R ¹ and R ² may be the same or different, and X ⁻ is a halogen ion .) (Wherein, R ³ , R ⁴ , R ⁵ and R ⁶ are hydrogen, an alkyl group having 1 to 4 carbon atoms or a benzyl group, and R ³ , R ⁴ ,
R ^5, R ⁶ may be different even in the same, R ⁷ is an alkylene group having 1 to 6 carbon atoms ^{- [R 8 -NR 10 -R 9} ]
a q-group, R ⁸ and R ⁹ are alkylene groups having 1 to 4 carbon atoms, R ⁸ and R ⁹ may be the same or different, and R ¹⁰ is hydrogen, and has 1 to 4 carbon atoms. X ^- is a halogen ion, and q is 1-4.
It is. ) 2. The water-resistant improver for ink jet recording paper according to claim 1, wherein the secondary amine is dimethylamine. 3. An amine compound having two or more amino groups is ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, propylenediamine, N, N, N ', N'-tetramethylethylenediamine, N, N The water resistance improver for ink jet recording paper according to claim 1, which is N, N ', N'-tetramethylpropylenediamine. 4. An ink jet recording paper coated with the water resistance improver for ink jet recording paper according to claim 1, 2 or 3.