JP2001199154A - Latex for inkjet recording, and binder composition - Google Patents

Abstract

(57) [Summary] [PROBLEMS] In ink jet printing in a high image quality mode in which the amount of ink is increased compared to conventional inks, ink absorption is good, water resistance and light resistance of printed matter are improved, and print density is further improved. To provide a cationic latex for ink jet recording and a binder composition thereof, which can highly improve the ink jet recording quality and does not lower the surface strength of the ink receiving layer. (1) (A) a radical polymerizable monomer having a tertiary amino group and / or a quaternary ammonium group in a molecule in the presence of 0.5 to 5 parts by weight of a water-soluble resin,
And (B) a cationic latex for inkjet recording used in an ink receiving layer, obtained by polymerizing 100 parts by weight of a radical polymerizable monomer composed of a radical polymerizable monomer copolymerizable therewith, or an inorganic filler and the latex A binder composition for inkjet recording used in an ink receiving layer, comprising:

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a binder composition for ink-jet recording, and more particularly, to a high-strength ink-receiving layer, a high ink-absorbing ink absorbency, a high print density, a high water resistance and a high light fastness to a printed material. And a binder composition excellent in the

[0002]

2. Description of the Related Art Ink-jet recording systems have been rapidly spreading in recent years because they can be easily made full-color, have low noise, and have excellent print quality. Water-based inks are mainly used for inkjet recording from the viewpoint of safety and recording suitability. This water-based ink is turned into fine droplets from the nozzle,
Printing is performed by flying toward the recording sheet. Therefore, the recording sheet is required to absorb the ink promptly. That is, in a recording sheet having a low ink absorbency, the ink remains on the surface of the recording sheet even after the recording is completed, leading to contamination of the apparatus and the next printed matter.

On the other hand, in order to improve the ink absorbency, the problem has been solved by combining an ink receiving layer with a filler such as silica and a hydrophilic resin. However, in recent years, in order to make the image quality in ink jet printing more similar to photographic image quality, for example, a large amount of low-density ink is made to fly on a recording sheet finely compared to the related art. On the other hand, in addition to the conventional technology described above, although the ink absorbency is improved by further increasing the inorganic filler, increasing the inorganic filler leads to a decrease in the strength of the ink receiving layer itself, In addition, the water resistance of the printed matter is reduced.

[0004] Further, along with the improvement of the surface strength of the ink jet recording paper and the water resistance of the printed matter, the improvement of the durability of the printed matter has been required at the same time. This is required to prevent the print density from fading when exposed to sunlight through a window glass, although the image quality of the printed matter approaches the photographic image quality. Therefore, an ink-receiving layer that absorbs ink more, maintains the water resistance of the printed matter, has color development close to photographic quality, and improves the durability, particularly the light resistance of the printed matter, has been desired. To solve these problems, JP-A-62-83178 describes
JP-A-8-216504, JP-A-10-2645
No. 11 discloses a technique in which the water resistance and printability of an ink jet recording sheet are improved based on a cationic latex. However, although the water resistance of the printed matter is greatly improved, the ink absorption and surface strength required at present are not sufficient.

Further, Japanese Patent Application Laid-Open No. 9-505005, Japanese Patent Application Laid-Open No. H10-195276, and Japanese Patent Application Laid-Open No. H11-2466.
No. 40 discloses that a cationic latex obtained by using a water-soluble polymer as a protective colloid is used as a coating agent for inkjet recording. The combination of the cationic latex obtained by these disclosed technologies and an inorganic filler does not sufficiently improve the currently required high water resistance, ink absorption balance, and surface strength. Furthermore, the amount of the protective colloid used in the disclosed technology increases the viscosity of the compound with the inorganic filler, making it difficult to handle. Therefore, the concentration of the compound must be reduced. As a result, in order to obtain a constant application amount, for example, an operation such as performing coating twice is necessary, and thus, a problem of a decrease in productivity becomes a problem. In addition, in recent years, improvements in the surface strength of the ink jet recording paper and the water resistance of the printed matter, as well as the durability of the printed matter, have been required at the same time. Therefore,
There is a demand for an ink-receiving layer that absorbs ink more, maintains the water resistance of the printed matter, has color development close to photographic quality, and improves the durability, especially the light resistance of the printed matter.

[0006]

SUMMARY OF THE INVENTION According to the present invention, ink absorption is good in ink jet printing in a high image quality mode in which the amount of ink is increased as compared with the prior art, and the water resistance and light resistance of the printed matter are improved. It is another object of the present invention to provide a cationic latex for ink jet recording, which can improve the print density to a high degree and does not lower the surface strength of the ink receiving layer, and a binder composition thereof.

[0007]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventor uses a cationic latex obtained by polymerizing a cationic monomer in the presence of a water-soluble resin for an ink receiving layer for inkjet. As a result, the inventors have found that the above-mentioned problems have been solved, and have accomplished the present invention.

That is, the present invention provides: (1) In the presence of 0.5 to 5 parts by weight of a water-soluble resin, (2)
(A) a radical polymerizable monomer having a tertiary amino group and / or a quaternary ammonium group in a molecule, and (B)
A cationic latex obtained by polymerizing 100 parts by weight of a radical polymerizable monomer comprising a radical polymerizable monomer copolymerizable therewith, wherein the cationic latex for inkjet recording is used for an ink receiving layer. 1. (1) In the presence of 0.5 to 5 parts by weight of a water-soluble resin, (2)
(A) a radical polymerizable monomer having a tertiary amino group and / or a quaternary ammonium group in a molecule, and (B)
A composition comprising a cationic latex obtained by polymerizing 100 parts by weight of a radical polymerizable monomer comprising a radical polymerizable monomer copolymerizable therewith, and an inorganic filler, wherein the composition is used in an ink receiving layer. A binder composition for ink-jet recording characterized by:

3. A cationic latex having a multilayer structure having a core portion and a shell portion, wherein the shell portion is a radical polymerizable monomer having a tertiary amino group and / or a quaternary ammonium group in a molecule, and is copolymerizable therewith; A nonionic radical polymerizable monomer comprising a copolymer (a) with a radical polymerizable monomer,
(B) with a crosslinking and radically polymerizable monomer
It is a cationic latex for inkjet recording, characterized by comprising

[0010] 4. A cationic latex having a multilayer structure having a core portion and a shell portion, wherein the shell portion is a radical polymerizable monomer having a tertiary amino group and / or a quaternary ammonium group in a molecule, and is copolymerizable therewith; A nonionic radical polymerizable monomer comprising a copolymer (a) with a radical polymerizable monomer,
(B) with a crosslinking and radically polymerizable monomer
4. A binder composition for ink-jet recording, characterized by using a composition comprising a cationic latex consisting of: and an inorganic filler in an ink receiving layer; This is a binder composition for inkjet recording in which the inorganic filler is amorphous synthetic silica.

[0011] The present invention relates to a tertiary amino group and / or a quaternary amino group.
When polymerizing a radical polymerizable monomer having a quaternary ammonium group, and a copolymer with a radical polymerizable monomer copolymerizable therewith, by using a specific amount of a water-soluble resin, surface strength, ink absorbability, inkjet The coloring property in printing, the water resistance of the printed matter, and the light resistance are improved. Hereinafter, the present invention will be described in detail. Examples of the water-soluble resin used in the present invention include polyvinyl alcohols such as polyvinyl alcohol, cationized polyvinyl alcohol, ethylene-modified polyvinyl alcohol, and silanol-modified polyvinyl alcohol, and cellulose resins (methyl cellulose, ethyl cellulose, hydroxy cellulose, carboxy cellulose, and the like). , Chitin, chitosan, starch, cationic starch, polyethylene glycol, polypropylene glycol, polyvinyl ether, gelatin, caseins, cyclodextrins, and aqueous nitrified cotton. The polyvinyl alcohol may be completely saponified or partially saponified.

Preferred are nonionic and cationic water-soluble resins, and particularly preferred are polyvinyl alcohol, cationized polyvinyl alcohol, silanol-modified polyvinyl alcohol, cyclodextrin, and celluloses. More preferably polyvinyl alcohol,
One or more water-soluble resins selected from cationized polyvinyl alcohol and silanol-modified polyvinyl alcohol. Polyvinyl alcohols preferably have a degree of polymerization of 30.
0 to 2000, which is a completely saponified product.

The amount of the water-soluble resin is 0.5 to 5 parts by weight.
When it is 0.5 parts by weight or more, there is no problem in light resistance, and when it is 5 parts by weight or less, there is no problem in water resistance. Preferably it is 1 to 5 parts by weight. Examples of the radically polymerizable monomer having a tertiary amino group and / or a quaternary ammonium group used in the present invention include various radically polymerizable monomers having a tertiary amino group or a base thereof, and quaternary ammonium. Various radically polymerizable monomers having a base or capable of forming a quaternary ammonium base can be used.

For example, di C _1-4 alkylamino-C _2-3
Alkyl (meth) acrylamide or a salt thereof [dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide or a salt thereof], di C _1-
4 alkylamino-C _2-3 alkyl (meth) acrylate or a salt thereof [dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate or a salt thereof Etc.], di C _1-4 alkylamino-C _2-3 alkyl group-substituted aromatic vinyl or a salt thereof [4- (2-dimethylaminoethyl) styrene, 4- (2-dimethylaminopropyl)
Styrene and the like and salts thereof], a nitrogen-containing heterocyclic monomer or a salt thereof [vinylpyridine, vinylimidazole, vinylpyrrolidone or a salt thereof] and the like. Salts include hydrohalides (hydrochlorides, hydrobromides, etc.), alkyl halides (methyl chloride, ethyl chloride, propyl chloride, butyl chloride, benzyl chloride,
Epichlorohydrin, methyl bromide, ethyl bromide, propyl bromide, butyl bromide, etc.), sulfate, alkyl sulfate (methyl sulfate, ethyl sulfate, etc.), alkyl sulfonate, aryl sulfonate, carboxylate (Formate, acetate, etc.).

Preferably, di C _1-4 alkylamino-C
_2-3 alkyl (meth) acrylamide or a salt thereof, di C
_1-4 alkylamino-C _2-3 alkyl (meth) acrylate or a salt thereof. The radical polymerizable monomer copolymerizable with the radical polymerizable monomer having a tertiary amino group and / or a quaternary ammonium group used in the present invention includes, for example, an aromatic unsaturated compound, α, β-unsaturated Examples thereof include monocarboxylic acid alkyl esters and unsaturated carboxylic acids.

Examples of the aromatic unsaturated compound include styrene, α-methylstyrene and vinyltoluene. Examples of the alkyl ester of α, β-unsaturated monocarboxylic acid include, for example, alkyl acid of acrylic acid or methacrylic acid. Esters are mentioned. Examples of the alkyl ester of acrylic acid or methacrylic acid include, for example, methyl acrylate, ethyl acrylate, propyl acrylate,
Isopropyl acrylate, butyl acrylate, isobutyl acrylate, hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl acrylate, butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl Examples include methacrylate and lauryl methacrylate.

Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid and monoalkyl itaconate. Radical polymerizable monomers other than those described above may be combined as necessary. For example, a hydroxyl-containing monomer such as 2
-Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate,
Hydroxypropyl methacrylate, polyethylene glycol acrylate; amide group-containing monomer, for example,
Acrylamide, methacrylamide, N, N-methylenebisacrylamide, diacetone acrylamide, maleic amide, maleimide; and the like.

Preferred copolymerizable monomers include:
Aromatic unsaturated compounds, α, β-unsaturated monocarboxylic acid alkyl esters, amide group-containing monomers, and hydroxyl group-containing monomers. The ratio of the monomer copolymerizable with the radical polymerizable monomer having a tertiary amino group and / or a quaternary ammonium group may be a tertiary amino group and / or a quaternary ammonium group.
Radical polymerizable monomer having a quaternary ammonium group is 5
６０60% by weight, and monomers copolymerizable therewith are 40〜
95% by weight. When the content of the radical polymerizable monomer having a tertiary amino group and / or a quaternary ammonium group is 5% by weight or more, there is no problem in color development, and when it is 60% by weight or less, there is no problem in water resistance of a printed matter. Preferably, the radical polymerizable monomer having a tertiary amino group and / or a quaternary ammonium group is 10 to 50% by weight, and the monomer copolymerizable therewith is 50 to 90% by weight.

For the polymerization of the present invention, for example, emulsion polymerization can be used. There is no particular limitation on the method of emulsion polymerization,
A conventionally known method can be applied. For example, the radical polymerizable monomer is polymerized in an aqueous medium in the presence of a radical polymerizable monomer, a radical polymerization initiator, a surfactant, a chain transfer agent as needed, and other additives. As the radical polymerization initiator used in the polymerization, known persulfates, peroxides, water-soluble azobis compounds, and redox systems of peroxide-reducing agents can be used. Preferred are initiators that provide a cationic end.

The following can be used as the cationic polymerization initiator. For example, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis (N, N '
-Dimethyleneisobutylamidine) dihydrochloride, 2,2 '
-Azobis (2-methylbutanamide oxime) dihydrochloride tetrahydrate and the like. In addition to these, the following initiators are used as needed. Examples of the persulfate include ammonium persulfate, potassium persulfate, and sodium persulfate, and examples of the peroxide include hydrogen peroxide, t-butyl hydroperoxide, t-butylperoxymaleic acid, and succinic peroxide. Water-soluble azobis compounds include, for example, 2,2′-azobis (N-hydroxyethylisobutylamide),
4,4′-azobis (4-cyanopentanoic acid) and the like.

The redox system of the peroxide-reducing agent includes, for example, sodium sulfoxylate formaldehyde, sodium bisulfite, sodium thiosulfate, sodium hydroxymethanesulfinate, L-ascorbic acid, and salts thereof in the above peroxide. , Cuprous salts, ferrous salts and the like. Examples of the oil-soluble polymerization initiator include peroxides, oil-soluble azobis compounds and the like, and examples of the peroxide include dibutyl peroxide, benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide and the like. Examples of the oil-soluble azobis compound include, for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis-2-methylbutyronitrile,
2,2′-azobis-2,4-dimethylvaleronitrile and the like.

The following are examples of the cationic surfactant. For example, a quaternary ammonium type, an aliphatic amine type, and a heterocyclic amine type are exemplified. Examples of the quaternary ammonium type include a long-chain primary amine salt, a dialkyldimethylammonium salt, a long-chain tertiary amine salt, Examples thereof include alkyltrimethylammonium salts and alkylpyridinium salts, examples of the aliphatic amine type include polyoxyethylene alkylamines, and examples of the heterocyclic amine type include alkylimidazoline.

Examples of the nonionic surfactant include ether type, ester type, alkanolamide type and the like. Examples of the ether type include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl thioether and the like. Examples of the ester type include polyoxyethylene monofatty acid ester, polyoxyethylene difatty acid ester, polyoxyethylene propylene glycol fatty acid ester, polyoxyethylene sorbitan monofatty acid ester, glycerin monofatty acid ester, and sucrose fatty acid ester. Examples of the alkanolamide type include fatty acid diethanolamide, polyoxyethylene alkylamide and the like.

In addition to these, if necessary, anionic and amphoteric surfactants may be used. Examples of the anionic surfactant include a carboxylic acid type, a sulfate type, a sulfonic acid type, and a phosphate type.
Examples of the amphoteric surfactant include an N-alkyl amino acid type and an imidazoline type.

A reactive surfactant may be used together with the non-reactive surfactant described above. The reactive surfactant has a functional group of a radical polymerizable double bond in one molecule and has a polyoxyethylene, polyoxypropylene, polyoxyethylene polyoxypropylene composite type alkyl ether or alcohol. Further, those having a radically polymerizable double bond in one molecule and having at least one functional group selected from sulfonic acid groups, sulfonic acid ester groups, sulfonic acid groups, and sulfonic acid ester bases (the salt and Represents a sodium salt, a potassium salt, or an ammonium salt).

The glass transition temperature of the cationic latex of the present invention is preferably from -40 to 60 ° C. There is no problem in water resistance at -40 ° C or higher, and no problem in surface strength at 60 ° C or lower.
More preferably, it is -30 to 40C. The particle size of the cationic latex is from 10 nm to 500 nm. 10
No problem in latex production at 500 nm or more, 500 nm
There is no problem in the stability of the compound below. Preferably 50n
m to 300 nm.

In the present invention, the cationic latex is
A multi-layered cationic latex having a core and a shell may be used. For example, the shell part comprises a radical polymerizable monomer having a tertiary amino group and / or a quaternary ammonium group in the molecule, and a copolymer (a) with a radical polymerizable monomer copolymerizable therewith, The core may be a cationic latex composed of a copolymer (b) with a nonionic radically polymerizable monomer and a crosslinkable radically polymerizable monomer.

The nonionic radically polymerizable monomer referred to herein is, for example, the above-mentioned aromatic unsaturated compound, α,
Examples thereof include β-unsaturated monocarboxylic acid alkyl esters, hydroxyl group-containing monomers, and amide group-containing monomers. Preferred nonionic radically polymerizable monomers are α, β-unsaturated monocarboxylic acid alkyl esters,
It is a hydroxyl group-containing monomer. The crosslinkable radically polymerizable monomer used in the present invention has two or more radically polymerizable double bonds or has a functional group that gives a self-crosslinking structure after polymerization during polymerization. It is a radical polymerizable monomer.

The radical polymerizable monomer having two or more radical polymerizable double bonds is, for example, divinylbenzene, polyoxyethylene diacrylate, polyoxyethylene dimethacrylate, polyoxypropylene diacrylate, polyoxypropylene diacrylate. Methacrylate,
Neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, butanediol diacrylate, butanediol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, and the like.

During the polymerization, examples of the radical polymerizable monomer having a functional group that gives a crosslinked structure after the polymerization include, for example,
Epoxy group-containing monomers such as glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, methyl glycidyl acrylate, methyl glycidyl methacrylate, and methylol group-containing monomers such as N-methylol acrylamide, N-methylol methacrylamide, dimethylol acrylamide, dimethylol methacrylamide, etc. , Alkoxymethyl group-containing monomers such as N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-butoxymethylacrylamide, N-butoxymethylmethacrylamide, etc., hydroxyl group-containing monomers, silyl group-containing monomers such as vinyltrichlorosilane, vinyl Trimethoxysilane, vinyltriethoxysilane, tris-2-methoxyethoxyvinyl Orchids, .gamma.-methacryloxypropyl trimethoxysilane, .gamma.-methacryloxypropyl methyl dimethoxy silane, and the like.

Preferred crosslinkable radically polymerizable monomers are trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, and silyl group-containing radically polymerizable monomers. Particularly preferred is a silyl group-containing radical polymerizable monomer. The ratio of the nonionic radical polymerizable monomer to the crosslinkable radical polymerizable monomer is such that the ratio of the nonionic radical polymerizable monomer is 90 to 9
9.95% by weight, and the crosslinkable radical polymerizable monomer is 0.05 to 10% by weight. When the crosslinkable radical polymerizable monomer is 0.05% by weight or more, there is no problem in color development,
There is no problem in polymerizability at 10% by weight or less. Preferably, the nonionic radical polymerizable monomer is 95 to 99.9% by weight, and the crosslinkable radical polymerizable monomer is 0.1 to 5% by weight.

As the polymerization method, for example, the copolymer (a)
Is polymerized, and then the copolymer (b) is added in the presence of the copolymer (a).
Alternatively, the copolymer (a) may be polymerized after the copolymer (b) is polymerized. Preferably, after the copolymer (a) is polymerized, the copolymer (b) is polymerized in the presence of the copolymer (a). In the present invention, since the copolymer (a) is composed of a radical polymerizable monomer having a tertiary amino group and / or a quaternary ammonium group and a monomer copolymerizable therewith, the copolymer (b) )
It seems to be more hydrophilic than. Therefore, the copolymer (a) is more present on the shell side.

The ratio of copolymer (a) to copolymer (b) is
For example, 10 to 90% by weight of the copolymer (a) and 90 to 10% by weight of the copolymer (b) are preferable. Copolymer (a)
Is 10% by weight or more, there is no problem in color development, and 90% by weight or less, there is no problem in water resistance of printed matter. In the case of the cationic latex having a core-shell structure of the present invention, the core Tg1
The relationship between the shell and the shell Tg2 may be Tg1 <Tg2 or Tg1> Tg2. Preferably Tg1
> Tg2. The core side Tg1 is preferably 10 to 60.
° C, and the shell side Tg2 is preferably −30 to 20 ° C.
It is.

The difference between Tg1 and Tg2 is preferably 10 to 6
0 ° C., no difference in water resistance with a difference of 10 ° C. or more,
With a difference of 0 ° C. or less, there is no problem in the strength of the ink receiving layer. The inorganic filler used in the present invention is synthetic silica, alumina, calcium carbonate, magnesium carbonate, zinc carbonate, magnesium oxide, titanium oxide, zinc oxide, aluminum oxide,
Barium sulfate, satin white, lithopone, kaolin,
Examples include aluminum silicate, magnesium silicate, aluminum hydroxide, clay, calcined clay, diatomaceous earth, synthetic zeolite, smectite, and layered inorganic polymer. Ink absorption, preferably calcium carbonate from the color development, etc.,
Synthetic silica, more preferably amorphous synthetic silica.

The inorganic filler is cationic latex 100
It is 10 to 500 parts by weight with respect to parts by weight (solid content). When the amount of the inorganic filler is 10 parts by weight or more, there is no problem in color development, and when the amount is 500 parts by weight or less, there is no problem in water resistance. It is preferably 50 to 400 parts by weight based on 100 parts by weight (solid content) of the cationic latex. The cationic latex of the present invention, and the composition thereof, if necessary, a surfactant, a silane coupling agent, a dispersant, a preservative, an antifoaming agent,
You may add a thickener, a solvent, a crosslinking agent, a water-soluble metal compound, etc. Examples of the surfactant include, in addition to the above-mentioned surfactants, for example, sulfosuccinic acid-based surfactants, silicone-based surfactants, and the like.

The silicone-based surfactant referred to herein is:
It is a water-soluble compound in which a hydrophobic portion is made of a silicone resin, and a hydrophilic group is introduced into a terminal and / or a side chain of the silicone resin. The silane coupling agent referred to here is, for example, a compound having two or more different functional groups in one molecule, one is an alkoxysilyl group, and the other is, for example, an amino group, an epoxy group, a vinyl group. And so on.

Further, water-soluble metal compounds include, for example, chlorides, sulfates, formates, acetates such as calcium ions, magnesium ions, aluminum ions, zinc ions, iron ions, titanium ions, zirconium ions and barium ions. And the like, and one or more selected from these are used. The amount of the water-soluble metal compound to be added is 0.1 mmol to 100 mmol per 100 g of the inorganic filler. 0.1m
If it is at least 100 mol, the light resistance will be good, and if it is at most 100 mmol, there will be no problem in absorbency and bleeding. Preferably 0.5m
mol to 50 mmol.

The following materials may be blended in the binder composition of the present invention, if necessary. For example, a water-soluble quaternary ammonium salt oligomer can be used. Examples of the water-soluble quaternary ammonium salt oligomer include polyethyleneimine salts, dimethylamine epihalohydrin condensates, polyvinylamine salts, polyallylamine salts, polydimethylaminoethyl methacrylate quaternary salts, polydiallyldimethylammonium salts, diallylamine acrylamide copolymers And quaternary ammonium salts of polystyrene.

The cationic latex and the binder composition of the present invention are used, for example, in the following support. Examples of the support include paper, synthetic paper, plastic paper, film, metal plate, metal foil, and plastic film on which aluminum or the like is deposited. The ink receiving layer comprising the cationic latex and the binder composition of the present invention may be applied directly on a support, or may have a multilayer structure as required. For example, an anchor layer may be provided below the ink receiving layer, and a gloss layer may be provided above the ink receiving layer.

The method of applying the ink receiving layer comprising the cationic latex and the binder composition of the present invention is not limited. For example, roll coater, air knife coater,
General coaters such as a blade coater, a rod blade coater, a curtain coater, a bar coater, a die coater, and a gravure coater are exemplified. The ink receiving layer comprising the cationic latex and the binder composition of the present invention may be applied to a support at 1 to 50 g / m ² . 1g /
m there is no problem in coloration in a ² or more, there is no problem in water resistance in a 50g / m ² or less. Preferably it is 3 to 30 g / m ² . The ink receiving layer comprising the cationic latex of the present invention and the binder composition is coated on a support, and then coated with an 80 to 160
It can be obtained by drying at a temperature of 5 to 300 seconds.

[0041]

EXAMPLES Examples of the present invention will be described below, but they do not limit the scope of the present invention. Unless otherwise specified, it is based on weight. The evaluation of various physical properties in the present invention is as follows. (1) Ink Chromogenicity Solid printing of black, cyan, magenta, and yellow was performed on an inkjet recording sheet by an inkjet color printer (PM-750C; manufactured by Epson Corporation). When printing, set the paper, paper: photo print paper,
Ink: color, mode: recommended setting of "clean". The density of solid printing is measured by Macbeth densitometer (RD-91
8; manufactured by Sakata Inx Co., Ltd.).

(2) Ink Absorption Immediately after the solid printing of (1), the printed surface was rubbed with a finger and the state was observed. The evaluation criteria are as follows. ：: no ink adhered to finger △: slight ink adhered to finger ×: Adhesion of ink to fingers was observed. △ or more was considered as a pass.

(3) Bleeding property Bleeding between boundaries of solid printing of cyan, magenta and yellow was visually observed. The evaluation criteria are as follows. ：: no bleeding Δ: no bleeding of 0.5 mm or more at the boundary portion ×: bleeding of 0.5 mm or more at the boundary portion △ or more was considered as a pass.

(4) Water Resistance The solid printed matter was immersed in running water for 5 minutes, and the printed state was visually observed. The evaluation criteria are as follows. ：: No ink leakage. Δ: Slight outflow of ink ×: Outflow of ink is observed in all colors. △ or more was considered as a pass.

(5) Surface Strength The surface of the ink jet recording sheet was rubbed with a finger, and the state was observed. The evaluation criteria are as follows. ：: No pigment transfer to finger. Δ: Pigment slightly transferred to finger ×: Pigment transferred to finger △ or more was considered as a pass.

(6) Light Resistance Test A solid printed matter left at room temperature for 1 hour after printing was used. The test temperature was set to 62 ° C using an ultraviolet long life fade meter FAL-3 manufactured by Suga Test Instruments as a test device.
Irradiation was performed for 0 hours. The black ink density before and after the irradiation of the solid printing portion was compared, and the value obtained by dividing the ink density after the irradiation by the ink density before the irradiation was evaluated as a residual ratio. (7) Particle size: measured by a light scattering method. The number average particle size was adopted. (8) Glass transition temperature (Tg): Measured by DSC. The heating rate was 10 ° C./min, and the inflection point was Tg. Next, a production example of the cationic latex is shown below.

[0047]

[Production Example 1] 750 parts of distilled water and 25% aqueous solution of dodecyltrimethylammonium chloride in a flask equipped with a stirrer 80
Parts, 80 parts of a 10% aqueous solution of PVA117 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.) and heated to 80 ° C.
40 parts of a 5% aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride are added. Leave for 5 minutes after addition. 5
Minutes later, 25% of dodecyltrimethylammonium chloride
16 parts of an aqueous solution, 48 parts of a 5% aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride, 186 parts of distilled water, 120 parts of dimethylaminopropylacrylamide methyl chloride chloride, 200 parts of methyl methacrylate
Parts, 320 parts of butyl acrylate and 160 parts of styrene are separately charged over 90 minutes. After the introduction, stirring was continued for 60 minutes. Thereafter, the temperature was cooled to 30 ° C. or lower, and then filtration was performed using an 80-mesh wire net. After filtration, water was added to adjust the solid content to 40%. The particle size of the obtained latex was 135 nm. Tg was 15 ° C.

[0048]

Production Example 2 590 parts of distilled water and 25% aqueous solution of dodecyltrimethylammonium chloride in a flask equipped with a stirrer 80
Parts, PVA117 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.) and 240 parts of a 10% aqueous solution were charged, and the temperature was raised to 80 ° C.
40 parts of a 5% aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride are added. Leave for 5 minutes after addition. 5
Minutes later, 25% of dodecyltrimethylammonium chloride
16 parts of an aqueous solution, 48 parts of a 5% aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride, 186 parts of distilled water, 120 parts of dimethylaminopropylacrylamide methyl chloride chloride, 200 parts of methyl methacrylate
Parts, 320 parts of butyl acrylate and 160 parts of styrene are separately charged over 90 minutes. After the introduction, stirring was continued for 60 minutes. Thereafter, the temperature was cooled to 30 ° C. or lower, and then filtration was performed using an 80-mesh wire net. After filtration, water was added to adjust the solid content to 40%. The particle size of the obtained latex was 121 nm.

[0049]

[Production Example 3] In a flask equipped with a stirrer, 470 parts of distilled water, 25% aqueous solution of dodecyltrimethylammonium chloride 80%
Parts, 360 parts of a 10% aqueous solution of PVA117 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.) and heated to 80 ° C.
40 parts of a 5% aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride are added. Leave for 5 minutes after addition. 5
Minutes later, 25% of dodecyltrimethylammonium chloride
16 parts of an aqueous solution, 48 parts of a 5% aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride, 186 parts of distilled water, 120 parts of dimethylaminopropylacrylamide methyl chloride chloride, 200 parts of methyl methacrylate
Parts, 320 parts of butyl acrylate and 160 parts of styrene are separately charged over 90 minutes. After the introduction, stirring was continued for 60 minutes. Thereafter, the temperature was cooled to 30 ° C. or lower, and then filtration was performed using an 80-mesh wire net. After filtration, water was added to adjust the solid content to 40%. The particle size of the obtained latex was 116 nm.

[0050]

Production Example 4 510 parts of distilled water and 25% aqueous solution of dodecyltrimethylammonium chloride in a flask equipped with a stirrer
Parts, 320 parts of a 10% aqueous solution of R-1130 (silanol-modified polyvinyl alcohol, manufactured by Kuraray Co., Ltd.)
C., and 40 parts of a 5% aqueous solution of 2,2'-azobis (2-amidinopropane) dihydrochloride are added. Leave for 5 minutes after addition.

After 5 minutes, 16 parts of a 25% aqueous solution of dodecyltrimethylammonium chloride, 2,2'-azobis (2
-Amidinopropane) 48 parts of a 5% aqueous solution of dihydrochloride and 186 parts of distilled water, and 120 parts of dimethylaminopropylacrylamide methyl chloride, 200 parts of methyl methacrylate, 320 parts of butyl acrylate and 160 parts of styrene Are separately charged over 90 minutes. After the introduction, stirring was continued for 60 minutes. Thereafter, the temperature was cooled to 30 ° C. or lower, and then filtration was performed using an 80-mesh wire net. After filtration, water was added to adjust the solid content to 40%. The particle size of the obtained latex is 1
43 nm.

[0052]

Production Example 5 510 parts of distilled water and 25% aqueous solution of dodecyltrimethylammonium chloride in a flask equipped with a stirrer 80
Parts, 320 parts of a 10% aqueous solution of PVA117 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.) and heated to 80 ° C.
40 parts of a 5% aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride are added. Leave for 5 minutes after addition. 5
Minutes later, 25% of dodecyltrimethylammonium chloride
16 parts of an aqueous solution, 48 parts of a 5% aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride, 186 parts of distilled water, 200 parts of dimethylaminopropylacrylamide methyl chloride chloride, 200 parts of methyl methacrylate
Parts, 320 parts of butyl acrylate and 80 parts of styrene are separately charged over 90 minutes. After the introduction, stirring was continued for 60 minutes. Thereafter, the temperature was cooled to 30 ° C. or lower, and then filtration was performed using an 80-mesh wire net. After filtration, water was added to adjust the solid content to 40%. The particle size of the obtained latex was 127 nm. Tg was 14 ° C.

[0053]

Production Example 6 830 parts of distilled water and 25% aqueous solution of dodecyltrimethylammonium chloride 80 in a flask equipped with a stirrer
, And the temperature is raised to 80 ° C., and 40 parts of a 5% aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride is added. Leave for 5 minutes after addition. After 5 minutes, 16 parts of a 25% aqueous solution of dodecyltrimethylammonium chloride, 5% aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride 48
, 186 parts of distilled water, 120 parts of dimethylaminopropylacrylamide methyl chloride chloride, 200 parts of methyl methacrylate, 320 parts of butyl acrylate
Parts and 160 parts of styrene, 90 parts separately.
Charge over a minute. After the introduction, stirring was continued for 60 minutes. Thereafter, the temperature was cooled to 30 ° C. or lower, and then filtration was performed using an 80-mesh wire net. After filtration, the solid content is 40%
Water was added and adjusted to be. The particle size of the obtained latex was 257 nm.

[0054]

Production Example 7 30 parts of distilled water and 25% aqueous solution of dodecyltrimethylammonium chloride in a flask equipped with a stirrer 80
Parts, 800 parts of a 10% aqueous solution of PVA117 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.) and heated to 80 ° C.
40 parts of a 5% aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride are added. Leave for 5 minutes after addition. 5
Minutes later, 25% of dodecyltrimethylammonium chloride
16 parts of an aqueous solution, 48 parts of a 5% aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride, 186 parts of distilled water, 120 parts of dimethylaminopropylacrylamide methyl chloride chloride, 200 parts of methyl methacrylate
Parts, 320 parts of butyl acrylate and 160 parts of styrene are separately charged over 90 minutes. After the introduction, stirring was continued for 60 minutes. Thereafter, the temperature was cooled to 30 ° C. or lower, and then filtration was performed using an 80-mesh wire net. After filtration, water was added to adjust the solid content to 40%. The particle size of the obtained latex was 364 nm.

[0055]

Production Example 8 750 parts of distilled water and 25% aqueous solution of dodecyltrimethylammonium chloride in a flask equipped with a stirrer
Parts, 80 parts of a 10% aqueous solution of PVA117 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.) and heated to 80 ° C.
40 parts of a 5% aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride are added. Leave for 5 minutes after addition. 5
After minutes, 8 parts of a 25% aqueous solution of dodecyltrimethylammonium chloride, 24 parts of a 5% aqueous solution of 2,2'-azobis (2-amidinopropane) dihydrochloride, 83 parts of distilled water, and dimethylaminopropylacrylamide chloride 100 parts of methyl salt, 100 parts of methyl methacrylate,
A monomer part composed of 120 parts of butyl acrylate and 80 parts of styrene is separately charged over 50 minutes. After input, 3
Stirring was continued for 0 minutes.

Next, 8 parts of a 25% aqueous solution of dodecyltrimethylammonium chloride, 24 parts of a 5% aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride, 83 parts of distilled water,
Aqueous solution part consisting of
A monomer portion consisting of 240 parts of butyl acrylate, 72 parts of styrene and 8 parts of γ-methacryloxypropyltrimethoxysilane is separately charged over 50 minutes. After input, 6
Stirring was continued for 0 minutes. Thereafter, the temperature was cooled to 30 ° C. or lower, and then filtration was performed using an 80-mesh wire net.
After filtration, water was added to adjust the solid content to 40%. The particle size of the obtained latex was 128 nm.
The core portion had a Tg of 26 ° C and the shell portion had a Tg of 4 ° C.

[0057]

[Production Example 9] A flask equipped with a stirrer was charged with 590 parts of distilled water and a 25% aqueous solution of dodecyltrimethylammonium chloride 80%.
Parts, PVA117 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.) and 240 parts of a 10% aqueous solution were charged, and the temperature was raised to 80 ° C.
40 parts of a 5% aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride are added. Leave for 5 minutes after addition. 5
After minutes, 8 parts of a 25% aqueous solution of dodecyltrimethylammonium chloride, 24 parts of a 5% aqueous solution of 2,2'-azobis (2-amidinopropane) dihydrochloride, 83 parts of distilled water, and dimethylaminopropylacrylamide chloride 100 parts of methyl salt, 100 parts of methyl methacrylate,
A monomer part composed of 120 parts of butyl acrylate and 80 parts of styrene is separately charged over 50 minutes. After input, 3
Stirring was continued for 0 minutes.

Next, 8 parts of a 25% aqueous solution of dodecyltrimethylammonium chloride, 24 parts of a 5% aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride, and 83 parts of distilled water
Aqueous solution consisting of 1 part by weight and 80 parts of methyl methacrylate,
A monomer portion consisting of 240 parts of butyl acrylate, 72 parts of styrene and 8 parts of γ-methacryloxypropyltrimethoxysilane is separately charged over 50 minutes. After input, 6
Stirring was continued for 0 minutes. Thereafter, the temperature was cooled to 30 ° C. or lower, and then filtration was performed using an 80-mesh wire net.
After filtration, water was added to adjust the solid content to 40%. The particle size of the obtained latex was 124 nm.

[0059]

[Production Example 10] 470 parts of distilled water was placed in a flask equipped with a stirrer.
Dodecyltrimethylammonium chloride 25% aqueous solution 8
0 parts, 360 parts of a 10% aqueous solution of PVA117 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.), and the temperature was raised to 80 ° C.
40 parts of a 5% aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride are added. Leave for 5 minutes after addition. 5
After minutes, 8 parts of a 25% aqueous solution of dodecyltrimethylammonium chloride, 24 parts of a 5% aqueous solution of 2,2'-azobis (2-amidinopropane) dihydrochloride, 83 parts of distilled water, and dimethylaminopropylacrylamide chloride 100 parts of methyl salt, 100 parts of methyl methacrylate,
A monomer part composed of 120 parts of butyl acrylate and 80 parts of styrene is separately charged over 50 minutes. After input, 3
Stirring was continued for 0 minutes.

Next, 8 parts of a 25% aqueous solution of dodecyltrimethylammonium chloride, 24 parts of a 5% aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride, 83 parts of distilled water
Aqueous solution consisting of 1 part by weight and 80 parts of methyl methacrylate,
A monomer portion consisting of 240 parts of butyl acrylate, 72 parts of styrene and 8 parts of γ-methacryloxypropyltrimethoxysilane is separately charged over 50 minutes. After input, 6
Stirring was continued for 0 minutes. Thereafter, the temperature was cooled to 30 ° C. or lower, and then filtration was performed using an 80-mesh wire net.
After filtration, water was added to adjust the solid content to 40%. The particle size of the obtained latex was 119 nm.

[0061]

[Production Example 11] 470 parts of distilled water was placed in a flask equipped with a stirrer.
Dodecyltrimethylammonium chloride 25% aqueous solution 8
0 parts, 360 parts of a 10% aqueous solution of PVA117 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.), and the temperature was raised to 80 ° C.
40 parts of a 5% aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride are added. Leave for 5 minutes after addition. 5
Minutes later, 5 parts of a 25% aqueous solution of dodecyltrimethylammonium chloride, 15 parts of a 5% aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride, 50 parts of distilled water, and dimethylaminopropylacrylamide chloride. A monomer part consisting of 100 parts of a methyl salt, 35 parts of methyl methacrylate, 70 parts of butyl acrylate, and 35 parts of styrene is separately charged over 30 minutes. After the introduction, stirring was continued for 30 minutes.

Next, 11 parts of a 25% aqueous solution of dodecyltrimethylammonium chloride, 33 parts of a 5% aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride, 1 part of an aqueous solution of distilled water,
Aqueous solution consisting of 16 parts and methyl methacrylate 10
0 parts, butyl acrylate 360 parts, styrene 92 parts,
A monomer portion composed of 8 parts of γ-methacryloxypropyltrimethoxysilane is separately charged over 70 minutes. After the introduction, stirring was continued for 60 minutes. Thereafter, the temperature was cooled to 30 ° C. or lower, and then filtration was performed using an 80-mesh wire net. After filtration, water was added to adjust the solid content to 40%. The particle size of the obtained latex was 115 nm. The core portion had a Tg of 20 ° C and the shell portion had a Tg of -10 ° C.

[0063]

Production Example 12 470 parts of distilled water was placed in a flask equipped with a stirrer.
Dodecyltrimethylammonium chloride 25% aqueous solution 8
0 parts, 360 parts of a 10% aqueous solution of PVA117 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.), and the temperature was raised to 80 ° C.
40 parts of a 5% aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride are added. Leave for 5 minutes after addition. 5
After a minute, 11 parts of a 25% aqueous solution of dodecyltrimethylammonium chloride, 33 parts of a 5% aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride, 116 parts of distilled water, and dimethylaminopropylacrylamide chloride 100 parts of methyl salt, 140 of methyl methacrylate
, 200 parts of butyl acrylate and 120 parts of styrene are separately charged over 70 minutes. After the introduction, stirring was continued for 30 minutes.

Next, 5 parts of a 25% aqueous solution of dodecyltrimethylammonium chloride salt, 15 parts of a 5% aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride, 50 parts of distilled water,
Aqueous solution consisting of 50 parts of methyl methacrylate,
A monomer part consisting of 150 parts of butyl acrylate, 32 parts of styrene and 8 parts of γ-methacryloxypropyltrimethoxysilane is separately charged over 30 minutes. After input, 6
Stirring was continued for 0 minutes. Thereafter, the temperature was cooled to 30 ° C. or lower, and then filtration was performed using an 80-mesh wire net.
After filtration, water was added to adjust the solid content to 40%. The particle size of the obtained latex was 137 nm.

[0065]

Production Example 13 470 parts of distilled water was placed in a flask equipped with a stirrer.
Dodecyltrimethylammonium chloride 25% aqueous solution 8
0 parts, 360 parts of a 10% aqueous solution of PVA117 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.), and the temperature was raised to 80 ° C.
40 parts of a 5% aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride are added. Leave for 5 minutes after addition. 5
After minutes, 8 parts of a 25% aqueous solution of dodecyltrimethylammonium chloride, 24 parts of a 5% aqueous solution of 2,2'-azobis (2-amidinopropane) dihydrochloride, 83 parts of distilled water, and dimethylaminopropylacrylamide chloride A monomer part consisting of 150 parts of a methyl salt, 90 parts of methyl methacrylate, 130 parts of butyl acrylate, and 30 parts of styrene is separately charged over 50 minutes. After input, 30
Stirring was continued for minutes.

Next, 8 parts of a 25% aqueous solution of dodecyltrimethylammonium chloride, 24 parts of a 5% aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride, 83 parts of distilled water,
Aqueous solution consisting of 1 part by weight and 80 parts of methyl methacrylate,
A monomer portion consisting of 240 parts of butyl acrylate, 72 parts of styrene and 8 parts of γ-methacryloxypropyltrimethoxysilane is separately charged over 50 minutes. After input, 6
Stirring was continued for 0 minutes. Thereafter, the temperature was cooled to 30 ° C. or lower, and then filtration was performed using an 80-mesh wire net.
After filtration, water was added to adjust the solid content to 40%. The particle size of the obtained latex was 139 nm.

[0067]

[Production Example 14] A flask equipped with a stirrer was charged with 470 parts of distilled water.
Dodecyltrimethylammonium chloride 25% aqueous solution 8
0 parts, 360 parts of a 10% aqueous solution of PVA117 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.), and the temperature was raised to 80 ° C.
40 parts of a 5% aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride are added. Leave for 5 minutes after addition. 5
After minutes, 8 parts of a 25% aqueous solution of dodecyltrimethylammonium chloride, 24 parts of a 5% aqueous solution of 2,2'-azobis (2-amidinopropane) dihydrochloride, 83 parts of distilled water, and dimethylaminopropylacrylamide chloride 100 parts of methyl salt, 120 parts of methyl methacrylate,
A monomer part consisting of 80 parts of butyl acrylate and 100 parts of styrene is separately charged over 50 minutes. After input, 3
Stirring was continued for 0 minutes.

Next, 8 parts of a 25% aqueous solution of dodecyltrimethylammonium chloride, 24 parts of a 5% aqueous solution of 2,2'-azobis (2-amidinopropane) dihydrochloride, 83 parts of distilled water,
Aqueous solution consisting of 1 part by weight and 80 parts of methyl methacrylate,
A monomer portion consisting of 240 parts of butyl acrylate, 72 parts of styrene and 8 parts of γ-methacryloxypropyltrimethoxysilane is separately charged over 50 minutes. After input, 6
Stirring was continued for 0 minutes. Thereafter, the temperature was cooled to 30 ° C. or lower, and then filtration was performed using an 80-mesh wire net.
After filtration, water was added to adjust the solid content to 40%. The particle size of the obtained latex was 120 nm.
The core portion had a Tg of 45 ° C. and the shell portion had a Tg of −4 ° C.

[0069]

[Production Example 15] 470 parts of distilled water was placed in a flask with a stirrer.
Dodecyltrimethylammonium chloride 25% aqueous solution 8
0 parts, 360 parts of a 10% aqueous solution of PVA117 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.), and the temperature was raised to 80 ° C.
40 parts of a 5% aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride are added. Leave for 5 minutes after addition. 5
After minutes, 8 parts of a 25% aqueous solution of dodecyltrimethylammonium chloride, 24 parts of a 5% aqueous solution of 2,2'-azobis (2-amidinopropane) dihydrochloride, 83 parts of distilled water, and dimethylaminopropylacrylamide chloride 100 parts of methyl salt, 100 parts of methyl methacrylate,
A monomer part consisting of 120 parts of butyl acrylate and 80 parts of styrene is separately charged over 50 minutes. After input, 3
Stirring was continued for 0 minutes.

Next, 8 parts of a 25% aqueous solution of dodecyltrimethylammonium chloride salt, 24 parts of a 5% aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride, 83 parts of distilled water
Aqueous solution consisting of 1 part by weight and 80 parts of methyl methacrylate,
A monomer part consisting of 280 parts of butyl acrylate, 32 parts of styrene and 8 parts of γ-methacryloxypropyltrimethoxysilane is separately charged over 50 minutes. After input, 6
Stirring was continued for 0 minutes. Thereafter, the temperature was cooled to 30 ° C. or lower, and then filtration was performed using an 80-mesh wire net.
After filtration, water was added to adjust the solid content to 40%. The particle size of the obtained latex was 121 nm.
The core portion had a Tg of 26 ° C and the shell portion had a Tg of -18 ° C.

[0071]

Production Example 16 470 parts of distilled water was placed in a flask equipped with a stirrer.
Dodecyltrimethylammonium chloride 25% aqueous solution 8
0 parts and 360 parts of a 10% aqueous solution of R-1130 (silanol-modified polyvinyl alcohol, manufactured by Kuraray Co., Ltd.)
The temperature is raised to 0 ° C., and 40 parts of a 5% aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride is added. 5 after addition
Leave for a minute. After 5 minutes, 8 parts of a 25% aqueous solution of dodecyltrimethylammonium chloride, 24 parts of a 5% aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride, 8 parts of distilled water
Aqueous solution consisting of 3 parts, 100 parts of dimethylaminopropylacrylamide methyl chloride, 100 parts of methyl methacrylate, 120 parts of butyl acrylate, styrene 8
The monomer parts consisting of 0 parts are charged separately over 50 minutes. After the introduction, stirring was continued for 30 minutes.

Next, 8 parts of a 25% aqueous solution of dodecyltrimethylammonium chloride, 24 parts of a 5% aqueous solution of 2,2'-azobis (2-amidinopropane) dihydrochloride, 83 parts of distilled water
Aqueous solution consisting of 1 part by weight and 80 parts of methyl methacrylate,
A monomer portion consisting of 240 parts of butyl acrylate, 72 parts of styrene and 8 parts of γ-methacryloxypropyltrimethoxysilane is separately charged over 50 minutes. After input, 6
Stirring was continued for 0 minutes. Thereafter, the temperature was cooled to 30 ° C. or lower, and then filtration was performed using an 80-mesh wire net.
After filtration, water was added to adjust the solid content to 40%. The particle size of the obtained latex was 138 nm.

[0073]

[Production Example 17] A flask equipped with a stirrer was charged with 830 parts of distilled water.
Dodecyltrimethylammonium chloride 25% aqueous solution 8
0 parts, the temperature is raised to 80 ° C., and 40 parts of a 5% aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride is added.
Leave for 5 minutes after addition. After 5 minutes, 8 parts of a 25% aqueous solution of dodecyltrimethylammonium chloride, 24 parts of a 5% aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride,
An aqueous solution part composed of 83 parts of distilled water and a monomer part composed of 100 parts of dimethylaminopropylacrylamide chloride methyl salt, 100 parts of methyl methacrylate, 120 parts of butyl acrylate and 80 parts of styrene are separately charged over 50 minutes. After the introduction, stirring was continued for 30 minutes.

Next, 8 parts of a 25% aqueous solution of dodecyltrimethylammonium chloride, 24 parts of a 5% aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride, 83 parts of distilled water,
Aqueous solution consisting of 1 part by weight and 80 parts of methyl methacrylate,
A monomer portion consisting of 240 parts of butyl acrylate, 72 parts of styrene and 8 parts of γ-methacryloxypropyltrimethoxysilane is separately charged over 50 minutes. After input, 6
Stirring was continued for 0 minutes. Thereafter, the temperature was cooled to 30 ° C. or lower, and then filtration was performed using an 80-mesh wire net.
After filtration, water was added to adjust the solid content to 40%. The particle size of the obtained latex was 239 nm.

[0075]

[Production Example 18] 470 parts of distilled water was placed in a flask equipped with a stirrer.
Dodecyltrimethylammonium chloride 25% aqueous solution 8
0 parts, 360 parts of a 10% aqueous solution of PVA117 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.), and the temperature was raised to 80 ° C.
40 parts of a 5% aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride are added. Leave for 5 minutes after addition. 5
After minutes, 8 parts of a 25% aqueous solution of dodecyltrimethylammonium chloride, 24 parts of a 5% aqueous solution of 2,2'-azobis (2-amidinopropane) dihydrochloride, 83 parts of distilled water, and dimethylaminopropylacrylamide chloride 100 parts of methyl salt, 100 parts of methyl methacrylate,
A monomer part consisting of 120 parts of butyl acrylate, 72 parts of styrene and 8 parts of γ-methacryloxypropyltrimethoxysilane is separately charged over 50 minutes. After input, 3
Stirring was continued for 0 minutes.

Then, 8 parts of a 25% aqueous solution of dodecyltrimethylammonium chloride, 24 parts of a 5% aqueous solution of 2,2'-azobis (2-amidinopropane) dihydrochloride, 83 parts of distilled water
Aqueous solution part consisting of
A monomer part consisting of 240 parts of butyl acrylate and 80 parts of styrene is separately charged over 50 minutes. After input, 6
Stirring was continued for 0 minutes. Thereafter, the temperature was cooled to 30 ° C. or lower, and then filtration was performed using an 80-mesh wire net.
After filtration, water was added to adjust the solid content to 40%. The particle size of the obtained latex was 136 nm.

[0077]

Examples 1 to 20 The materials shown in Tables 1 and 2 were blended as follows. (Note that the numerical values in Tables 1 and 2 represent solid contents. All amounts are parts by weight.) 800 parts of water with stirring, followed by amorphous synthetic silica (Fine Seal X37: Co., Ltd.) A predetermined amount of
Stirring was continued for 15 minutes. Next, a predetermined amount of latex was charged, and stirring was continued for another 15 minutes. Additives were added as needed after the latex was charged. Thereafter, water was added under stirring so that the solid content of the blended product became 18 to 20%, to obtain a blended product.

Next, the blended product was applied to a high-quality paper having a basis weight of 70 g with a bar coater. After the application, the coated paper was immediately left for 90 seconds in a hot air dryer controlled at 130 ° C., and dried to obtain a coated paper. The number of the bar coater was adjusted so that the coating amount was 10 g / m ² . Dry coated paper with a linear pressure of 50
An ink jet recording sheet was obtained by passing through a calendar of 0 N / cm. Tables 1 and 2 show the evaluation results of the obtained ink jet recording sheet of the present invention.

Comparative Examples 1 to 6 Compounds shown in Table 3 were prepared in the same manner as in the examples. (The numerical values in Table 3 represent solid contents.) Further, a recording sheet was prepared in the same manner as in the examples, and the ink jet recording sheet was evaluated in the same manner as in the examples. Table 3 shows the evaluation results.

[0079]

[Table 1]

[0080]

[Table 2]

[0081]

[Table 3]

[0082]

According to the present invention, in ink jet printing in a high image quality mode in which the amount of ink is increased as compared with the prior art, the ink absorption is good, and the water resistance, light resistance, and coloring of printed matter are high. It is possible to provide a cationic latex for inkjet recording which can be improved and the strength of the ink receiving layer does not decrease, and a binder composition thereof.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 5/02 C09D 7/12 Z 7/12 151/00 151/00 157/12 157/12 201/00 201/00 B41J 3/04 101Y F-term (reference) 2C056 EA13 FC06 2H086 BA01 BA15 BA32 BA36 BA45 4J002 BN231 DE076 DE106 DE136 DE146 DE236 DE246 DG026 DG046 DJ006 DJ016 DJ036 FD016 GH00 HA07 4J026 AA02 AA03 AA21A BA07 BA08 BA25 BA27 BA28 BA29 BA30 BA32 BA34 BA38 BA40 BA43 BA50 DB04 DB08 DB12 DB13 DB14 DB15 DB16 DB28 DB30 FA04 FA07 GA01 GA06 GA09 4J038 BA012 BA022 BA082 BA112 BA162 BA192 CC091 CE022 CE052 CG141 CG171 CH201 CH220 KA0220 KA041 MA03 MA08 MA10 NA01 NA02 NA04 NA17 PB11 PC10

Claims (5)

[Claims] (1) (A) a radically polymerizable monomer having a tertiary amino group and / or a quaternary ammonium group in a molecule in the presence of 0.5 to 5 parts by weight of a water-soluble resin,
And (B) a cationic latex obtained by polymerizing 100 parts by weight of a radical polymerizable monomer composed of a radical polymerizable monomer copolymerizable therewith, which is used for an ink receiving layer, for inkjet recording. Cationic latex. (2) (A) a radical polymerizable monomer having a tertiary amino group and / or a quaternary ammonium group in a molecule in the presence of 0.5 to 5 parts by weight of a water-soluble resin,
And (B) a composition comprising a cationic latex obtained by polymerizing 100 parts by weight of a radical polymerizable monomer comprising a radical polymerizable monomer copolymerizable therewith, and an inorganic filler. A binder composition for inkjet recording, which is used. 3. The cationic latex is a multilayered latex having a core portion and a shell portion, wherein the shell portion is a radical polymerizable monomer having a tertiary amino group and / or a quaternary ammonium group in a molecule, and It is assumed that the core portion is composed of a copolymer (a) with a radical polymerizable monomer copolymerizable therewith, and the core portion is composed of a copolymer (b) with a nonionic radical polymerizable monomer and a crosslinkable radical polymerizable monomer. The cationic latex for inkjet recording according to claim 1, wherein 4. The cationic latex is a multilayered latex having a core portion and a shell portion, wherein the shell portion is a radical polymerizable monomer having a tertiary amino group and / or a quaternary ammonium group in a molecule, and It is assumed that the core is composed of a copolymer (a) with a radical polymerizable monomer copolymerizable therewith, and the core is composed of a copolymer (b) with a nonionic radical polymerizable monomer and a crosslinkable radical polymerizable monomer. The binder composition for ink-jet recording according to claim 2, characterized in that: 5. The ink-jet recording binder composition according to claim 2, wherein the inorganic filler is amorphous synthetic silica.