JP2000108500A - Water-resistant agent composition for recording paper - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-resistant agent of recroding paper for ink jet or the like excellent in light-resistance as well as water resistance. SOLUTION: This water resistant agent composition includes a cationic polymer in which one or more kinds among monomer components are polymerizable compound having polymerizable groups and cationic nitrogen atoms in a molecule, and a water-soluble ultraviolet-absorbing agent. As the preferable cationic polymer, the homopolymer or the copolymer of cationically activated compounds such as diallyl ammonium, (meth)allyl amine, (meth)acrylic amino allyl ester or (meth)acrylic amino alkyl amide ie exemplified. As the preferable water-soluble ultraviolet-absorber, a benzophenone-based compound is exemplified.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a waterproofing composition for recording paper used for ink jet recording paper and the like.

[0002]

2. Description of the Related Art In recent years, the spread of OA equipment has been remarkable, and accordingly, the performance of printers has been improved. In particular, due to improvements in printing speed, resolution, gradation, and the like, high-speed absorption of ink, high absorption capacity, high-density printing, improvement in image quality, and the like have been required for recording paper.
By the way, since many dyes contained in the ink are anionic, it is known that if the recording paper is given a cationic property, the fixing property and the water resistance of the ink are improved. Under such demands, attempts have conventionally been made to add or apply a cationic polymer, for example, a dimethyldiallylammonium chloride polymer, to recording paper to improve bleeding of dyes and pigments and water resistance of the recording paper and weather resistance. .

For example, Japanese Patent Publication No. Hei 3-2072 discloses that
It is disclosed that a dimethyldiallylammonium chloride polymer is applied to recording paper to improve the water resistance and the like of a recorded image on an ink jet recording paper. Tokuho 5-7
No. 1393 discloses that a dimethyldiallylammonium chloride polymer and a water-soluble metal salt are similarly applied to recording paper to improve the water resistance and the like of a recorded image on an ink jet recording paper. 6-92190
Japanese Patent Application Laid-Open Publication No. H11-157, discloses that a copolymer of acrylamide and dimethyldiallylammonium chloride is applied to recording paper to improve the water resistance and the like of a recorded image on an ink jet recording paper.

[0004]

However, when a cationic polymer as described above is applied to recording paper, the water resistance of the ink is improved, but the light resistance is reduced. In order to improve light resistance, it is conceivable to add an ultraviolet absorber or the like. However, ordinary ultraviolet absorbers are not soluble in water because they are used for synthetic resins, and therefore cannot be added to recording paper unless a binder is used in combination or dispersed with a dispersant or the like. Accordingly, an object of the present invention is to provide a waterproofing agent composition for recording paper which has solved the above-mentioned problems by utilizing a water-soluble ultraviolet absorber.

[0005]

That is, the present invention comprises a cationic polymer used as a water-proofing agent and a water-soluble ultraviolet absorber having a remarkable effect of improving weatherability when used in combination therewith. Specifically, as the component (A), at least one of the monomer components is a polymerizable compound having a polymerizable group and a cationic nitrogen atom in the molecule. A cationic polymer that is;
(B) A waterproofing agent composition for recording paper containing a water-soluble ultraviolet absorber as a component.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION (A) of the waterproofing agent composition of the present invention
The component is a cationic polymer in which at least one of the monomer components is a polymerizable compound having a polymerizable group and a cationic nitrogen atom in the molecule. As the polymerizable compound having a polymerizable group and a cationic nitrogen atom in the molecule, for example,
Diallylammonium, ethyleneimine, alkylene polyamine dicyandiamidammonium, vinylpyridinium, alkylammonium (meth) acrylate,
Examples thereof include (meth) acrylamide alkylammonium, vinylbenzylalkylammonium, and (meth) allylammonium. The cationic nitrogen atom of these compounds may be a quaternary nitrogen atom, or may be a secondary or tertiary nitrogen atom which is a neutralized salt of a secondary or tertiary amine. Among the above polymerizable compounds, the most preferred is diallylammonium represented by the following general formula (1).

[0007]

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In the general formula (1), R ¹ and R ² represent a hydrogen atom or a methyl group, and R ³ and R ⁴ represent a hydrogen atom or an alkyl group. As the alkyl group, a relatively short-chain alkyl group such as a methyl group and an ethyl group is preferable.
X ₁ represents an anionic atom or group. Examples of the anionic atom or group include a halogen atom such as a chlorine atom, a bromine atom and an iodine atom, a methyl sulfate group, an ethyl sulfate group, and a hydroxyl group. Specific examples of the compound of the general formula (1) include dimethyldiallylammonium chloride, diethyldiallylammonium chloride, dimethyldimethallylammonium methyl sulfate, and diethyldimethallylammonium ethyl sulfate. As the polymerizable compound used in the present invention, a compound represented by the following general formula (2) is also preferable.

[0009]

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In the general formula (2), R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents an alkylene group or a group represented by the following general formula (3).

[0011]

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(Where B represents an oxygen atom or a group represented by —NH—, and n represents a number of 1 or more.)
R ⁷ , R ⁸ and R ⁹ represent a hydrogen atom or an alkyl group, and are preferably relatively short-chain alkyl groups such as a methyl group and an ethyl group. X ₂ represents an anionic atom or group. Examples of the anionic atom or group include a halogen atom such as a chlorine atom, a bromine atom and an iodine atom, a methyl sulfate group, an ethyl sulfate group, and a hydroxyl group.

The compound represented by the general formula (2) is, for example, a compound obtained by cationizing (meth) allylamine, (meth) acrylic acid aminoalkyl ester, (meth) acrylic acid aminoalkylamide and the like. Specifically, for example, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dibutylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) ) Acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-dibutylaminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth)
Acrylamide, N, N-dibutylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, N, N-dibutylaminopropyl (meth) acrylamide, etc. Compound, hydrochloric acid,
Examples include compounds cationized with methyl chloride, dimethyl sulfate, and the like.

The cationic polymer which is the component (A) of the present invention contains one or more quaternary nitrogen atoms or a secondary or tertiary nitrogen which is a neutralized salt of a secondary or tertiary amine in the molecule. It may be a homopolymer of a polymerizable compound having an atom or a copolymer of the same with another polymerizable compound. In this case, the ratio of the polymerizable compound having one or more cationic nitrogen atoms in the molecule in the constituent monomer is 30% by weight.
It is preferable that it is above.

Other polymerizable compounds include, for example,
Nitrogen-containing compounds such as ethyleneimine, vinylpyrrolidone, N, N-dimethylaminomethylstyrene, and halogenated vinylpyridine; vinyl compounds such as vinyl acetate, vinyl propionate, vinyl caproate, alkyl vinyl ether, alkyl vinyl ketone, and vinyl pyrrolidone; (Meth) acrylic acid, crotonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, (meth) acrylic 2-hydroxyethyl acid, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylonitrile, (meth) acrylamine, (meth) acrylamide, N , N-dialkyl Min (meth) acrylate - acrylic compounds such bets, styrene, p- chlorostyrene, alpha
-Methyl styrene, isopropyl styrene, aromatic vinyl compounds such as vinyl toluene, ethylene, propylene,
Α-olefin compounds such as 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, and 1-tetradecene; Conjugated dienes such as butadiene, isoprene, and pentadiene; halogenated olefin compounds such as vinyl chloride and vinylidene chloride; unsaturated dibasic acids such as maleic acid, fumaric acid, and itaconic acid, and their (hydroxy) esters; Trialkylmethyl sulfate or chloride, 2-hydroxy-3-methacryloxypropyltrimethylammonium methyl sulfate or chloride, sodium or ammonium styrene sulfonate, sodium-2-acrylamido-2-methylpropane sulfone Doors and the like.

The molecular weight of such a cationic polymer is not particularly limited, but is preferably from 2,000 to 400,000.
00, more preferably 3,000 to 300,000. The method for producing the cationic polymer as the component (A) of the present invention is not particularly limited. Generally, a cationic monomer such as a dialkyldiallylammonium halide dissolved or dispersed in an aqueous medium such as water is used. A polymerization initiator such as 2,2′-azobis- (2-amidinopropane) hydrochloride is added in an amount of about 0.02 to 5% by weight of the monomer component,
The temperature is between room temperature and 100 ° C, preferably between 60 and 80 ° C.
It can be produced by reacting for about 0 to 24 hours.

Examples of the polymerization initiator that can be used include persulfates such as hydrogen peroxide, ammonium persulfate, sodium persulfate and potassium persulfate; azobis (2-methylpropanenitrile) and 2,2'-azobis- (2 -Amidinopropane) hydrochloride, dimethyl 2,2′-azobisisobutyrate,
Azobiscyanovaleric acid, azobiscyanovaleric acid chloride, 1,1′-azobis- (cyclohexane-1-carbonitrile), 2,2′-azobis- (2,4-dimethylvaleronitrile), azobismethylbutyronitrile,
2,2′-azobis- (4-methoxy-2,4-dimethylvaleronitrile), 4,4′-azobis- (4-cyanopentanol), 2,2′-azobis- (2-cyanopropanol), 2,2′-azobis- (2-methyl-
Azo compounds such as N-2-hydroxypropionamide); peroxides such as lauroyl peroxide, benzoyl peroxide and cumene hydroperoxide; As the polymerization initiator, an azo compound is most preferable. Also, redox initiators such as sulfites and peroxide compounds, and hydrogen peroxide and Fe ²⁺ salts can be used. Further, as the polymerization accelerator, for example, sodium hydrogen sulfite, ferrous ammonium sulfate and the like can be used. Further, as a crosslinking agent, for example, divinylbenzene, ethylene glycol di (meth) acrylate, or the like can be used. As the polymerization regulator, for example, dodecyl mercaptan and the like can be added.

The component (B) of the waterproofing agent composition of the present invention comprises:
It is a water-soluble ultraviolet absorber. As the water-soluble ultraviolet absorber, a benzophenone-based compound represented by the following general formula (4) is preferable.

[0019]

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Here, Y represents a hydrogen atom or a hydroxyl group, and R ¹⁰ and R ¹¹ represent a hydrogen atom, a halogen atom, a hydroxyl group, a hydrocarbon group, an alkoxy group or an acyl group,
Z ¹ and Z ² represent a hydrogen atom or a hydrophilic group, and p, q,
r and s represent numbers from 1 to 4. However, Z ¹ and Z ² are not simultaneously hydrogen atoms.

As R ¹⁰ and R ¹¹ , in addition to a hydrogen atom, a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom; a hydroxyl group; a hydrocarbon group such as methyl, ethyl, propyl, isopropyl, and butyl; Propoxy, butoxy, hexyloxy, heptyloxy,
Octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, isodecyloxy, dodecyloxy, stearyloxy, oleyloxy, phenoxy,
An alkoxy group such as benzyloxy; an acyl group such as acetyl, benzoyl, methylbenzoyl, and methoxybenzoyl.

Z ¹ and Z ² represent a hydrogen atom or a hydrophilic group. As the hydrophilic group, -SO ₃ M (sulfonic acid group),-
OSO ₃ M (sulfate group), - _OPO 3 _{M 2} (phosphoric acid ester group), - _PO 3 _{M 2} (phosphite group), - COOM (carboxy _group), - _(CH 2) _k
—COOM (alkyl carboxylic acid group) and the like.
Most preferred groups are sulfonic acid groups. p, q, r and s represent the number of substitution of each group, and are 1 to 4. However, Z ¹ and Z ² are not simultaneously hydrogen atoms.

In the above general formula representing a hydrophilic group,
Is a hydrogen atom, a metal atom or ammonium. Examples of the metal atom include lithium, sodium, potassium, magnesium, calcium and the like. As ammonium, ammonia, methylamine, dimethylamine, ethylamine, diethylamine, (iso) propylamine, di (iso) propylamine, monoethanolamine, N-methylmonoethanolamine, N-ethylmonoethanolamine, diethanolamine, triethanolamine Ethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, 2-amino-2-methyl-1,3-propanediol, aminoethylethanolamine, N, N, N ′, N′-tetrakis (2-hydroxy Propyl) and ammonium such as ethylenediamine. As the compound represented by the general formula (4), specifically,

[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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(Where R is H, CH ₃ , C
_{7 H 15, C 8 H 17} , i-C 8 H 17, i-C 10 H
_{21, Ph-CH} 2 _-, a _C 18 _{H 37} and the like. ) And the like.

The amount of the water-soluble ultraviolet absorber is not particularly limited. However, if the amount is too large, it will not be sufficiently soluble in water, so that it will be difficult to apply it to recording paper.
Since the ultraviolet absorbent itself is colored, the recording paper is colored when coated. If the amount is too small, the light resistance of the recording paper will be insufficient, so the appropriate amount is preferably 1 to 30% by weight, more preferably 3 to 20% by weight, based on the cationic polymer.

The waterproofing agent composition for recording paper of the present invention is usually used in the form of an aqueous solution or aqueous dispersion by dissolving it in water. The preferred concentration of the waterproofing agent composition is preferably 1 to 50% by weight, more preferably 5 to 40%, based on the total amount of the aqueous solution or aqueous dispersion. The form of use of the waterproofing agent composition for recording paper of the present invention is not particularly limited as long as it is used for recording paper. Usually, in the state of the aqueous solution or the aqueous dispersion as described above, spraying on the surface of the recording paper, size press during the paper making process, or applied or impregnated on the surface by a roll coater, or a known coat type What is necessary is just to mix in a coating material for recording paper, and apply or impregnate with a coating machine such as a blade, an air knife, a roll coater, a brush coater, a curtain coater, a bar coater, a gravure coater, and a champlex coater. In the drying and solidifying step, room temperature or hot air drying, heat rays, infrared radiation, or a drying method using a heat drum can be used. The recording paper coated with the water-proofing agent composition of the present invention by the above method or the like has excellent water resistance and light resistance, and can be suitably used particularly as a recording paper for inkjet recording.

In the use of the waterproofing agent for recording paper of the present invention, it is usually used by dissolving or dispersing it in water or another organic solvent and coating and / or impregnating the recording paper as a coating liquid. . In that case, arbitrarily as other components of the coating liquid, talc, kaolin, calcium carbonate, various fillers such as urea formalin resin fine powder, fine silica, colloidal silica, silica sol, acid clay, clay, talc, calcium carbonate, Diatomaceous earth, titanium oxide, white pigments such as barium sulfate, oxidized starch, gelatin, casein, polyvinyl alcohol (including denatured products), cellulose derivatives, water-soluble binders such as polyvinylpyrrolidone, sodium poly (meth) acrylate Dispersants, thickeners, wetting agents, thermal gelling agents, antifoaming agents, foaming agents, optical brighteners, UV inhibitors, antioxidants, preservatives, antistatic agents, crosslinking agents, lubricants, plasticizers, It may contain a pH adjuster, a waterproofing agent and the like.
Further, the recording paper may be applied and / or impregnated as a coating liquid separate from these optional components.

[0034]

The present invention will be described more specifically with reference to the following examples. In the following examples, parts and percentages are by weight unless otherwise specified. Various cationic polymers and ultraviolet absorbers shown in Table 1 below were dispersed or dissolved in water to prepare water-proofing agent compositions. In addition, the compounding amount of the cationic polymer was shown in Table 1 by solid content, and the compounding amount of the ultraviolet absorber was shown by the ratio to the cationic polymer.

[0035]

[Table 1]

As the water-soluble ultraviolet absorbers in Table 1, those having the following structures were used.

[0037]

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[0038]

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Water was added to 30 parts by weight of the above water-resistant agent composition, 70 parts by weight of fine particle silica, 19 parts by weight of polyvinyl alcohol, 0.5 parts by weight of sodium polyacrylate, and 0.5 parts by weight of an antifoaming agent. Stir and mix until solid concentration is 1
A 5% by weight paper coating liquid was obtained. 60 g of rice tsubo
/ M ² , and coated on a commercially available high-quality paper base paper having a Steckigt sizing degree of 20 seconds with a wire bar so as to have an application amount of 10 g / m ² , followed by drying and smoothing to obtain an ink jet recording paper. The color difference (△
E) was measured based on Comparative Example 1. The larger the color difference is, the more colored the paper is. If the color difference is less than 1.0, the level is practically no problem.

Next, a commercially available ink jet printer (MJ-800) was applied to the obtained ink jet recording paper.
C: Epson), characters and graphics (solid printing) were printed for each color of cyan, magenta, and yellow, and after drying, the following test was performed. <Water resistance test> The printed matter was immersed in running water at 25 ° C for 5 minutes, and bleeding of the ink was visually observed, and evaluated according to the following scale. ：: No bleeding ○: Bleeding but acceptable B: Bleeding <Lightfastness test> The printed matter was exposed to sunlight for 20 hours.
The magenta color difference (ΔE) was measured before and after exposure to sunlight. For the measurement, a spectrophotometer CM-3700D (manufactured by Minolta) was used. If the color difference is less than 1.0, it is at a level at which a color difference cannot be visually recognized. Table 2 shows these results.
Shown in

[0041]

[Table 2]

As is clear from the results, the water-proofing agent composition of the present invention using a cationic polymer and a water-soluble UV absorber has good water resistance and excellent light resistance, It can be seen that the water-resistant agent containing no agent has considerably poor light resistance.

[0043]

The effect of the present invention is to provide a waterproofing agent composition for recording paper which is excellent in water resistance and light resistance.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification FI FI Theme Court ゛ (Reference) D21H 19/24 D21H 19/24 Z (72) Inventor Kaoru Komiya 7-35 Higashiogu, Arakawa-ku, Tokyo F-term in Asahi Denka Kogyo Co., Ltd. (reference)

Claims (5)

[Claims] 1. The component (A) comprises one of the monomer components
At least one species, a cationic polymer which is a polymerizable compound having a polymerizable group and a cationic nitrogen atom in a molecule; and
(B) A waterproofing agent composition for recording paper containing a water-soluble ultraviolet absorber as a component. 2. The waterproofing agent composition for recording paper according to claim 1, wherein the cationic nitrogen atom is a secondary to quaternary nitrogen atom. 3. A polymerizable compound having a polymerizable group and a cationic nitrogen atom is represented by the following general formula (1): (Wherein, R ¹ and R ² represent a hydrogen atom or a methyl group, R ³ and R ⁴ represent a hydrogen atom or an alkyl group,
X ₁ represents an anionic atom or group. ) Or the following general formula (2): [In the formula, R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents an alkylene group or the following general formula (3). (Wherein B represents an oxygen atom or a group represented by —NH—, n represents a number of 1 or more), and R ⁷ , R ⁸ and R ⁹ represent a hydrogen atom or an alkyl group. And X ₂ represents an anionic atom or group. The water-proofing agent composition for recording paper according to claim 1 or 2, wherein 4. The water-soluble ultraviolet absorber according to the following general formula (4): (Wherein, Y represents a hydrogen atom or a hydroxyl group, R ¹⁰ and R ¹¹ represent a hydrogen atom, a halogen atom, a hydroxyl group, a hydrocarbon group, an alkoxy group or an acyl group, and Z ¹ and Z ²
Represents a hydrogen atom or a hydrophilic group, and p, q, r and s are 1
Represents the number of ４4. However, Z ¹ and Z ² are not simultaneously hydrogen atoms. The water-proofing agent composition for recording paper according to any one of claims 1 to 3, which is a compound represented by the formula: 5. An ink jet recording paper obtained by applying an aqueous solution or an aqueous dispersion containing the water repellent composition for recording paper according to any one of claims 1 to 4 to water.