JP2003301084A - Resin composition and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To be excellent as a heat-sensitive coloring layer and a protective layer of a thermal recording medium, an ink receiving layer and a protective layer of an inkjet recording medium, etc., having excellent water resistance and excellent viscosity stability of an aqueous solution. To provide a suitable resin composition. SOLUTION: An R-[(CH) containing an acetoacetic ester group-containing polyvinyl alcohol (A), an amino group-containing compound (B) represented by the following general formula (1), and a β-diketone compound (C): ₂ ) _n- NHR ₁ ] _m (1) (where R is a residue of a cyclic compound selected from an aromatic ring, an aliphatic ring, and a heterocyclic ring, excluding hydrogen, R ₁ is hydrogen, an alkyl group) Wherein n represents 0 or a positive integer, and m represents a positive integer, respectively.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition containing acetoacetic acid ester group-containing polyvinyl alcohol (hereinafter abbreviated as AA-PVA), and more specifically, it is excellent in water resistance and viscosity stability of an aqueous solution and is heat-sensitive. The present invention relates to a resin composition useful as a recording medium or an inkjet recording medium.

[0002]

2. Description of the Related Art Conventionally, polyvinyl alcohol resins have been used as dispersants, adhesives, sizing agents, films, paper processing agents, etc. PVA is also widely used in applications such as adhesives and paper processing agents. The present situation is that such AA-PVA is usually used in combination with a cross-linking agent and exhibits properties such as water resistance due to the cross-linking reaction. As such a cross-linking agent, various ones have been proposed, and among them, an amine-based cross-linking agent is relatively easily available,
The present applicant also proposed an amino group-containing compound represented by the following general formula (1) as a cross-linking agent capable of obtaining excellent water resistance by heat treatment at low temperature for a short time (Japanese Patent Application No. 2002-016306).
issue). R - _{[(CH 2)} n -NHR _{1] m} ··· (1) (wherein, R represents residues except for hydrogen of an aromatic ring, aliphatic ring, cyclic compound selected from heterocyclic, _{R 1} Is hydrogen or an alkyl group, n is 0 or a positive integer, and m is a positive integer.)

[0003]

Then, the present inventor conducted further detailed study on the above-mentioned cross-linking agent. As a result, when the cross-linking agent was added to or mixed with the AA-PVA aqueous solution immediately before use, or when AA There is no problem when it is used as a so-called two-pack type, such as when an aqueous solution of PEGylated PVA and a cross-linking agent are separately applied to a substrate, but one-pack type, that is, AA-PV
When A and the cross-linking agent are mixed in advance and the obtained aqueous solution is used, the viscosity of the aqueous solution may be rapidly increased depending on use conditions, storage conditions, etc., and finally gelation may occur. It has been found. That is, when a cross-linking agent is added to an aqueous solution of AA-PVA and coated on various substrates for practical use, the cross-linking reaction of the AA-PVA does not proceed during solution preparation and storage near room temperature, It is desired that the crosslinking reaction proceeds during the drying and heat treatment of the coating liquid to obtain sufficient water resistance.

[0004]

The present inventor has made diligent studies in view of such circumstances, and as a result, AA-PVA
The present invention was found to find that a resin composition containing (A), an amino group-containing compound (B) represented by the following general formula (1) and a β-diketone compound (C) meets the above-mentioned object. Has been completed. R - _{[(CH 2)} n -NHR _{1] m} ··· (1) (wherein, R represents residues except for hydrogen of an aromatic ring, aliphatic ring, cyclic compound selected from heterocyclic, _{R 1} Is hydrogen or an alkyl group, n is 0 or a positive integer, and m is a positive integer. Further, in the present invention, the alkylamino group-containing compound represented by the above general formula (1) (B)
Is particularly preferably meta-xylenediamine, 1,3-bisaminomethylcyclohexane or norbornanediamine, and further preferably the β-diketone compound (C) is acetylacetone.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The AA-modified PVA (A) used in the present invention is obtained by reacting polyvinyl alcohol with diketene, or by reacting polyvinyl alcohol with acetoacetic ester to transesterify the polyvinyl alcohol to form an acetoacetic acid ester group. Introduced, as such polyvinyl alcohol, generally, a saponified product or a derivative thereof obtained by saponifying a lower alcohol solution of polyvinyl acetate with a saponification catalyst such as an alkali or an acid is used. It is also possible to use a saponified product of a copolymer of a copolymerizable monomer and vinyl acetate.

Examples of such a monomer include ethylene,
Olefin such as propylene, isobutylene, α-octene, α-dodecene, α-octadecene, vinylene carbonates, acrylic acid, methacrylic acid, crotonic acid,
Maleic acid, maleic anhydride, unsaturated acids such as itaconic acid or salts or mono- or dialkyl esters thereof, acrylonitrile, nitriles such as methacrylonitrile, amides such as acrylamide and methacrylamide, ethylene sulfonic acid, allyl sulfonic acid, Olefin sulfonic acids such as methallyl sulfonic acid or salts thereof, alkyl vinyl ethers, N-acrylamidomethyl trimethyl ammonium chloride, allyl trimethyl ammonium chloride, dimethyl diallyl ammonium chloride, dimethyl allyl vinyl ketone, N-vinyl pyrrolidone, vinyl chloride, vinylidene chloride , Polyoxyethylene (meth) allyl ether, polyoxypropylene (meth) allyl ether, etc. Ether, polyoxyethylene (meth) acrylate, polyoxypropylene (meth) acrylate and other polyoxyalkylene (meth) acrylates, polyoxyethylene (meth) acrylamide, polyoxypropylene (meth) acrylamide and other polyoxyalkylene (meth) Acrylamide, polyoxyethylene (1- (meth) acrylamide-1,1-dimethylpropyl) ester, polyoxyethylene vinyl ether, polyoxypropylene vinyl ether, polyoxyethylene allylamine, polyoxypropylene allylamine, polyoxyethylene vinylamine, polyoxy Examples include propylene vinylamine.

The polyvinyl alcohol used as a raw material for the AA-PVA (A) is not particularly limited, but the saponification degree is 70 mol% or more (further 75 mol% or more, particularly 8 mol%).
0 mol% or more) is preferable, and if the saponification degree is less than 70 mol%, the water solubility becomes poor, which is not preferable. The average degree of polymerization of the polyvinyl alcohol (JIS K
6726) is also not particularly limited, but 100 to 50
00 (further 200 to 4500, especially 300 to 40)
00) is preferable, and when the average degree of polymerization is less than 100, sufficient water resistance may not be obtained, and conversely 500.
If it exceeds 0, the viscosity of the aqueous solution becomes too high, and the workability and the penetrability into a paper base material when used as a paper processing agent are deteriorated, which is not preferable.

To obtain AA-PVA (A), a method of reacting polyvinyl alcohol with diketene as described above,
Examples include a method of transesterifying polyvinyl alcohol and acetoacetate ester, a method of copolymerizing vinyl acetate and vinyl acetoacetate, and the like. However, since the production process is simple and high-quality AA-PVA can be obtained. Preferably, it is produced by a method of reacting polyvinyl alcohol (powder) with diketene. As a method of reacting polyvinyl alcohol and diketene, polyvinyl alcohol and gaseous or liquid diketene may be directly reacted, or after organic acid is adsorbed and absorbed in polyvinyl alcohol in advance, it is liquid or under an inert gas atmosphere. A method of spraying and reacting gaseous diketene, or spraying and reacting polyvinyl alcohol with a mixture of an organic acid and liquid diketene is used.

As a reaction apparatus for carrying out the above reaction, an apparatus capable of heating and equipped with a stirrer is sufficient. For example, a kneader, a Henschel mixer, a ribbon blender, other various blenders, and a stirring / drying device can be used.

The content of acetoacetic acid ester group in the AA-modified PVA (A) thus obtained is 0.1 to 40 mol%.
(Further, 0.3 to 30 mol%, particularly 0.5 to 20 mol%) is preferable, and if the content is less than 0.1 mol%, sufficient water resistance may not be obtained. If it exceeds 40 mol%, the water solubility tends to decrease, and the storage stability of the aqueous solution tends to decrease, such being undesirable.

The amino group-containing compound (B) used in the present invention is represented by the following general formula (1), wherein R is selected from an aromatic ring, an aliphatic ring and a heterocycle. R ₁ is a hydrogen atom or an alkyl group, n is 0 or a positive integer, and m is a positive integer. R - _{[(CH 2)} n -NHR _{1] m} ··· (1) according alkylamino group-containing compound as (B) is specifically meta-xylene diamine, norbornane diamine,
1,3-bisaminomethylcyclohexane, bisaminopropylpiperazine, 3,3'-dimethyl-4,4'-
Diaminodicyclohexylmethane, 4,4'-diaminodicyclohexylmethane, 4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetramethyl-4,
4'-diaminodiphenylmethane, 3,3 ', 5,5'
-Tetraethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diamino-5,
5'-diethyldiphenylmethane, 4,4'-diaminodiphenyl ether, diaminodiphenyl sulfone,
1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, 3-methyl-1,
2-phenylenediamine, 4-methyl-1,2-phenylenediamine, 2-methyl-1,3-phenylenediamine, 4-methyl-1,3-phenylenediamine, 2-methyl-4,6-diethyl-1, Examples include 3-phenylenediamine, 2,4-diethyl-6-methyl-1,3-phenylenediamine, 2,4,6-trimethyl-1,3-phenylenediamine, 2-chloro-1,4-phenylenediamine. In view of water solubility or water dispersibility, it is particularly preferable to use any of metaxylenediamine, 1,3-bisaminomethylcyclohexane, and norbornanediamine.

The β-diketone compound (C) used in the present invention is represented by the following general formula (2), in which R ₂ and R ₃ may be the same or different from each other in carbon number. 1 to 6 alkyl groups. Such R ₂ , R
Examples of ₃ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a t-butyl group and a hexyl group. R ₂ COCH ₂ COR ₃ (2) Specific examples of the β-diketone compound include acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, and 2,4-. Octanedione, 2,4-nonanedione, 5-methylhexanedione, 2,2,6,6-tetramethyl-3,5-heptanedione and the like can be mentioned. Considering water solubility or water dispersibility, Above all, it is particularly preferable to use acetylacetone.

The resin composition of the present invention comprises the above-mentioned AA-PVA (A), the amino group-containing compound (B) and the β-diketone compound (C), and the content ratio thereof is particularly limited. However, the content ratio (A / B) of the AA-modified PVA (A) and the amino group-containing compound (B) is 100 /
0.1-100 / 30 (further 100 / 0.3-10
0/25, particularly 100 / 0.5 to 100/20) (weight ratio), and the content ratio is 100.
If it exceeds /0.1, sufficient water resistance may not be obtained, and if it is less than 100/30, the stability after mixing with the crosslinking agent tends to decrease, which is not preferable.

The content ratio (B / C) of the amino group-containing compound (B) and the β-diketone compound (C) is 100 /
0.1-100 / 1000 (further 100 / 1-10
0/800, particularly 100/10 to 100/500), and the content ratio is 100 / 0.1.
When it exceeds, the viscosity stabilization of the aqueous solution tends to decrease, and when it is less than 100/1000, the water resistance tends to decrease, which is not preferable.

Thus, the resin composition of the present invention containing the AA-modified PVA (A), the amino group-containing compound (B) and the β-diketone compound is obtained. The resin composition is water resistant and aqueous solution. It has excellent viscosity stability and is useful for a dispersant, an adhesive, a sizing agent, an emulsifier, a film, a fiber, a paper coating, various coating applications, and the like, and particularly, a thermosensitive coloring layer or a protective layer of a thermosensitive recording medium, or It is preferably contained in the ink-receiving layer or the protective layer of the inkjet recording medium, and such use will be further described.

In such a thermosensitive recording medium, a thermosensitive coloring layer and a protective layer are provided on a substrate. In the present invention, the above resin composition may be applied to either or both of these layers. it can. That is, the composition layer containing the above resin composition is laminated on the substrate directly and / or via another layer to form a thermosensitive recording medium.

Each of these layers will be described in detail below. In the case of a thermosensitive coloring layer, an aqueous solution or an aqueous dispersion is prepared by further mixing the above-mentioned AA-PVA (A), amino group-containing compound (B) and β-diketone compound (C) with a coloring substance and a developer. Then, the aqueous solution or the aqueous dispersion may be applied to the substrate. AA PVA (A) at this time
The compounding amount is 1 with respect to the total amount of the color-developing substance and the developer.
0 to 200% by weight is suitable. The solid content concentration of the aqueous solution is selected from the range of 10 to 40% by weight in consideration of workability.

Examples of the above-mentioned color forming substance include 3,3-
Bis (p-dimethylaminophenyl) -phthalide, 3,
3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide [crystal violet lactone],
3,3-bis (p-dimethylaminophenyl) -6-diethylaminophthalide, 3,3-bis (p-dimethylaminophenyl) -6-chlorophthalide, 3-dimethylamino-6-methoxyfluorane, 7-acetamino -3
-Diethylaminofluorane, 3-diethylamino-
5,7-Dimethylfluorane, 3-diethylamino 5,
Examples thereof include leuco forms of triphenylmethane dyes such as 7-dimethylfluorane, 3,6-bis-β-methoxyethoxyfluorane and 3,6-bis-β-cyanoethoxyfluorane.

Further, the color developer is one which reacts with the above-mentioned color-forming substance to give a color when heated, and which liquefies or vaporizes at room temperature or higher, preferably at 70 ° C. or higher, such as phenol, p-methylphenol, p. -Tert-butylphenol, p-phenylphenol, α-naphthol, β-naphthol, 4,4'-isopropylidenediphenol [bisphenol A], 4,4'-secondary butylidene diphenol, 4,4'-cyclohexylidenediene Phenol, 4,4'-isopropylidene bis (2-tert-butylphenol), 4,4'-
(1-methyl-n-hexylidene) diphenol, 4,
4'-isopropylidene dicatechol, 4,4'-benzylidene diphenol, 4,4'-isopropylidene bis (2-chlorophenol), phenyl-4-hydroxybenzoate, salicylic acid, 3-phenylsalicylic acid, 5-methylsalicylic acid, 3,5-di-tert-butylsalicylic acid, 1-oxy-2-naphthoic acid, m-
Examples thereof include oxybenzoic acid, 4-oxyphthalic acid, and gallic acid, but the color-forming substance and the color developer are not limited to these.

In coating the substrate with the aqueous solution or the aqueous dispersion, any known method such as a roll coater method, an ear doctor method, a blade coater method, a bar coater method, a two roll size press method, a gate roll method, etc. can be used. The method is adopted. The coating amount of the aqueous solution or aqueous dispersion is
0.1 to 20 g / m ² (more preferably 0.5 to 1) by dry weight
The amount is preferably about 5 g / m ² , particularly about 1 to 10 g / m ² ).

Next, the protective layer will be described. The protective layer is a layer formed (coated) on the thermosensitive coloring layer composed of the above-mentioned color-developing substance, developer, binder (for example, polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose, starches, latexes, etc.). Therefore, a thin film layer made of the above resin composition may be formed.

At the time of the coating, an aqueous solution or an aqueous dispersion containing the AA-modified PVA (A), the amino group-containing compound (B) and the β-diketone compound (C) described above and, if necessary, the following A coating liquid obtained by mixing and stirring pigments and various auxiliaries may be used, and the coating amount at this time is 0.5 to 5 g as a dry weight of AA-PVA (A).
/ M ² is preferable. After coating, the target coating layer is formed by performing air-drying or mild heat treatment. Examples of such pigments include inorganic pigments such as calcium carbonate, zinc oxide, aluminum oxide, talc, kaolin, and clay, nylon resin fillers, urea / formalin resin fillers, and organic pigments such as starch particles. Examples thereof include lubricants such as zinc stearate, calcium stearate, and paraffin wax, surfactants, ultraviolet absorbers, fluorescent dyes, release agents, and antioxidants.

For the coating, a roll coater method,
It can be carried out by any known means such as an air-coater method, a blade coater method, a bar coater method, a two-roll size press method, and a gate roll method.

There are no particular restrictions on the base material used in the above-mentioned thermal recording medium, and paper (manila balls, white balls, paperboard such as liners, printing paper such as general high-quality paper, medium-quality paper, gravure paper, etc.). , Upper / middle / lower grade paper, newsprint, release paper, carbon paper, non-carbon paper, glassine paper, synthetic paper, etc., and plastic films (polyester film, nylon film, polyolefin film, polyvinyl chloride film and laminated layers of these. Body etc.) can be used.

The heat-sensitive recording medium obtained is as follows.
Substrate / Undercoat layer / Thermal coloring layer / Protective layer, Substrate /
It is possible to have a layer structure such as undercoat layer / thermosensitive coloring layer, substrate / thermosensitive coloring layer / protective layer or substrate / thermosensitive coloring layer. The undercoat layer is provided for the purpose of improving recording sensitivity and recording image quality, and is a layer containing an oil absorbing pigment such as baked clay and a binder resin such as polyvinyl alcohol as main components.

Next, the ink jet recording medium will be described. The ink jet recording medium has an ink receiving (physical) layer and a protective layer provided on a substrate. In the present invention, the above resin composition may be applied to one or both of these layers. it can. That is, the composition layer containing the above resin composition is laminated on the substrate directly and / or via another layer to form an inkjet recording medium.

Each of these layers will be described in detail below. In the case of the ink receiving layer, the above-mentioned AA-modified PVA (A),
After obtaining an aqueous dispersion in which the amino group-containing compound (B) and the β-diketone compound (C) are further mixed with a pigment and an ink fixing agent, if necessary, the aqueous dispersion may be applied to a substrate. . At this time, the blending amount of the AA-PVA (A) is appropriately 10 to 200% by weight based on the pigment. Further, the solid content concentration of the aqueous dispersion is 5 to 20% by weight in consideration of workability.
Is appropriate.

Examples of the above pigments include dry process silica,
Examples thereof include wet method silica, sol-gel method silica, synthetic amorphous silica such as colloidal silica, and alumina fine particles.

The ink fixing agent is a compound which can form a water-insoluble compound by ionic bonding with anionic functional groups such as sulfonic acid groups and carboxylic acid groups of dye molecules in the inkjet ink. Polyvalent metal ions such as Mg, cationic surfactants such as benzalkonium chloride, or polyethyleneimine salts which are cationic polymers, dimethylamine epihalohydrin condensates,
Examples thereof include polyvinylamine salts, polyallylamine salts, polydimethylaminoethyl methacrylate quaternary salts, polydiallyldimethylammonium salts, diallylamine acrylamide copolymer salts, and cationic compounds such as cation-modified PVA.

When the aqueous dispersion is applied to a substrate, known methods such as roll coater method, eardactor method, blade coater method, bar coater method, two-roll size press method, gate roll method, curtain coater method and the like are known. Any method is adopted. The coating amount of the aqueous dispersion on the substrate is 0.1 to 40 g / m ² in terms of dry weight, and particularly preferably 0.1.
It is suitable to set it to about 5 to ²⁰ g / m ² . After coating, the volatile components are removed by heating and drying to form the target coating layer.

Next, the protective layer will be described. The protective layer is a layer formed (coated) on an ink receiving layer composed of a pigment, a binder (for example, polyvinyl alcohol, starches, gelatins, polyvinylpyrrolidone, etc.) and an ink fixing agent, A thin film layer may be formed from the above resin composition.

In the coating, the above-mentioned AA-PVA (A), amino group-containing compound (B) and β-diketone compound (C), and if necessary, the following pigments and various auxiliaries are mixed. The coating liquid obtained by stirring may be used, and the coating amount at this time is preferably about 0.5 to 5 g / m ² in terms of dry weight of AA-PVA (A). After coating, the volatile components are removed by heating and drying to form the desired coating layer. Examples of the pigment include fine particle silica such as colloidal silica and vapor phase method silica, or fine particle alumina, and examples of the auxiliary agent include surfactant, ultraviolet absorber, and fluorescent dye.

In the coating, a roll coater method,
It can be carried out by any known means such as an air-coater method, a blade coater method, a bar coater method, a two-roll size press method, and a gate roll method.

The substrate used in the above ink jet recording medium is, for example, a resin film such as polyester, polyamide, polystyrene, polyvinyl chloride, polymethylmethacrylate, cellulose acetate, polycarbonate, polyimide, cellophane or celluloid,
Examples include papers such as sheets, high-quality papers, medium-quality papers, (semi) glassine papers, glossy papers, (resin) coated papers, synthetic papers, and films, sheets of cloth, wood, metal, etc. However, the present invention is not limited to these.

[0035]

EXAMPLES The present invention will be described in more detail with reference to examples. In the examples, “%” and “part” are based on weight unless otherwise specified.

Example 1 AA-PVA (A) 2 having a saponification degree of 99.1 mol%, an average degree of polymerization of 1200 and an acetoacetic acid ester group of 4.8 mol%
0 parts and meta-xylene diamine [Mitsubishi Gas Chemical Co., Ltd. "MX
DA ″] (B) 1 part and acetylacetone (C) 3 parts were obtained to obtain the resin composition of the present invention. In order to investigate the water resistance of the obtained resin composition, 180 parts of water was added to the resin composition to prepare an aqueous solution, which was then poured onto a PET film, and the mixture was placed at 23 ° C. and 50% RH for 48 hours. After leaving, 7
Heat treatment is performed at 0 ° C. for 5 minutes to prepare a resin composition film (thickness: about 100 μm).
The dissolution rate (%) of the film was measured by immersing the film in hot water at ℃ for 1 hour. In calculating the elution rate (%), the weight of the film before and after immersion in hot water (g) was calculated,
{(Film weight before immersion-film weight after immersion) /
The film weight before immersion} × 100.

In order to examine the stability of the resin composition aqueous solution, 380 parts of water was added to the resin composition obtained above to prepare an aqueous solution, and the change in the aqueous solution viscosity at 40 ° C. was changed every 1 minute. It was measured with a Brookfield viscometer, and the time at which the viscosity exceeded 1000 mPa · s was taken as the gelation time. Further, with respect to the sample that did not gel within 1 hour, the sample was allowed to stand in a thermostat at 40 ° C. as it was, and the time until the fluidity disappeared was examined by visual observation.

Further, a thermosensitive recording medium was prepared in the following manner and its evaluation was also carried out. First, the following aqueous solution (AC
Liquid) was prepared. [Liquid A] Crystal violet lactone 10 parts 5% aqueous solution of polyvinyl alcohol (saponification degree 98 mol%, average degree of polymerization 1100) 10 parts water 15 parts

[0039] [B liquid]   Bisphenol A 50 parts   5% water of polyvinyl alcohol (saponification degree 98 mol%, average degree of polymerization 1100) 50 parts of solution   75 parts of water

[0040] [C liquid]   AA-PVA (saponification degree 99.1 mol%, average degree of polymerization 1200, acetoacetic acid 100 parts of 10% aqueous solution containing 4.8 mol% of stell group   Metaxylylenediamine [Mitsubishi Gas Chemical Co., Ltd. "MXDA"] 0.5 part   Acetylacetone 1.5 parts   Kaolin clay part 5

The above liquids A and B were separately pulverized with a sand grinder until the average particle size became about 2μ, and then A
Solution, B solution, 50 parts of calcium carbonate and 15% aqueous solution of polyvinyl alcohol resin same as that used in A solution 2
50 parts were mixed to obtain a color developing solution. Next, the color-developing liquid was applied on a high-quality paper (base material) having a basis weight of 50 g / m ² so that the coating amount after drying was 8 g / m ² , and dried to form a color-developing layer. After that, the liquid C was applied onto the layer using a bar coater so that the coating amount after drying was 5 g / m ² , and the temperature was 60 ° C.
And dried to obtain a thermosensitive recording paper.

The water resistance of the resulting thermal recording paper was evaluated in the following manner. 1 using a thermal tilt tester (manufactured by Toyo Seiki Co., Ltd.)
The color is printed under the conditions of 20 ° C., 2 kg / cm ² , and 5 seconds, and the printed color density is measured by a Macbeth densitometer (“R
D-100R type ", using an amber filter), and the color-developed heat-sensitive recording paper was immersed in water at 20 ° C for 2 days.
After soaking for 4 hours, it was naturally dried and the color density of the printed part was measured in the same manner, and the ratio of the print density after immersion to the print density before immersion was calculated to be used as an index of water resistance.

Further, an ink jet recording medium was prepared and evaluated in the following manner. First, the following aqueous solution (solution D) was prepared. [Liquid D] 10% aqueous solution of AA-PVA (saponification degree 99.1 mol%, average degree of polymerization 1200, acetoacetate ester group 4.8 mol%) 400 parts meta-xylene diamine [Mitsubishi Gas Chemical Co., Ltd. "MXDA ] 2 parts Acetylacetone 6 parts Amorphous silica [Tokuyama "Fineseal"] 40 parts Polyamine dye fixing agent [Sumitomo Chemical's "Smiraze Resin 1001"] 40 parts

The above-mentioned liquid D was 5,000 with a homogenizer.
The coating liquid was prepared by stirring at rpm for 5 minutes. Next, the coating liquid is applied onto a woodfree paper (base material) having a basis weight of 75 g / m ² so that the coating amount after drying becomes 10 g / m ² , and 10
An inkjet recording paper was obtained by drying at 5 ° C.

The water resistance of the obtained ink jet recording paper was evaluated in the following manner. After printing with an inkjet printer (“PM-770C” manufactured by Seiko Epson Corporation) on the inkjet recording paper, the recording paper is printed with 20
After standing for 5 minutes in an atmosphere of 65% RH at 65 ° C., water droplets were dripped on the printed surface, and the state of the printed portion when the surface was rubbed with a finger was visually observed and evaluated as follows. ○: No breakage or peeling of the printed surface was observed. △: Some peeling was observed, but the image was retained. ×: The printed surface was broken and peeled from the substrate.

Example 2 Example 1 was repeated except that as the AA-modified PVA (A), an AA-modified PVA having a saponification degree of 95 mol%, an average degree of polymerization of 1700 and an acetoacetic ester group of 3 mol% was used.
A resin composition was obtained in the same manner as above and evaluated in the same manner.

Example 3 A resin composition was obtained in the same manner as in Example 1 except that the compounding amount of metaxylenediamine (B) was changed to 2 parts, and the same evaluation was performed.

Example 4 A resin composition was obtained in the same manner as in Example 1 except that 1.5 parts of norbornanediamine (B) was used instead of metaxylenediamine (B). An evaluation was made.

Example 5 A resin composition was obtained in the same manner as in Example 1 except that 1,3-bisaminomethylcyclohexane (B) was used in place of metaxylenediamine (B) in Example 1. It evaluated similarly.

Example 6 A resin composition was obtained in the same manner as in Example 1 except that the compounding amount of acetylacetone (C) was changed to 2 parts, and the same evaluation was performed.

Comparative Example 1 A resin composition was obtained in the same manner as in Example 1 except that acetylacetone (C) was not used, and the same evaluation was performed.

Comparative Example 2 A resin composition was obtained and evaluated in the same manner as in Example 1 except that methyl acetoacetate was used instead of acetylacetone (C).

Table 1 shows the evaluation results of Examples and Comparative Examples.

[Table 1] Resin composition Thermal recording medium Ink jet recording medium Water resistance Stability Water resistance Water resistance Example 1 16% 1 day <0.93 ○ 〃 2 13% 1 day <0.95 ○ 〃 3 11% 1 day <0.96 ○ 〃 4 19% 1 day <0.91 ○ 〃 5 17% 1 day <0.92 ○ 〃 6 14% 1 day <0.95 ○ Comparative example 1 12% 12 minutes 0.97 ○ 〃 2 15% 16 minutes 0.94 ○

[0055]

The resin composition of the present invention has excellent water resistance,
In addition, since the viscosity stability of the aqueous solution is also excellent, it can be used for paper processing,
It can be used for coating various substrates, adhesives, etc., and is particularly useful as a thermosensitive coloring layer or protective layer of a thermosensitive recording medium, or an ink receiving layer or protective layer of an inkjet recording medium.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] January 29, 2003 (2003.1.2
9)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Claims

[Correction method] Change

[Correction content]

[Claims]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0004

[Correction method] Change

[Correction content]

[0004]

The present inventor has made diligent studies in view of such circumstances, and as a result, AA-PVA
The present invention was found to find that a resin composition containing (A), an amino group-containing compound (B) represented by the following general formula (1) and a β-diketone compound (C) meets the above-mentioned object. Has been completed. R - _{[(CH 2)} n -NHR _{1] m} ··· (1) (where residues R are other than hydrogen of an aromatic ring, aliphatic ring, cyclic compound selected from heterocyclic, R1 is In any one of hydrogen and an alkyl group, n represents 0 or a positive integer, and m represents a positive integer. Further, in the present invention, an alkylamino group-containing compound represented by the above general formula (1) ( B) is Metakishi Li Ren <br/> diamines, particularly preferably at one of 1,3-bis-aminomethyl cyclohexane or norbornane diamine, be more above β- diketone compound (C) is acetylacetone Particularly preferred.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0036

[Correction method] Change

[Correction content]

Example 1 AA-PVA (A) 2 having a saponification degree of 99.1 mol%, an average degree of polymerization of 1200 and an acetoacetic acid ester group of 4.8 mol%
0 parts of Metakishi re-diamine [manufactured by Mitsubishi Gas Chemical Co., Ltd. "M
XDA ″] (B) 1 part and acetylacetone (C) 3 parts were obtained to obtain the resin composition of the present invention. In order to investigate the water resistance of the obtained resin composition, 180 parts of water was added to the resin composition to prepare an aqueous solution, which was then poured onto a PET film, and the mixture was placed at 23 ° C. and 50% RH for 48 hours. After leaving
A resin composition film (thickness: about 100 μm) is produced by performing a heat treatment at 70 ° C. for 5 minutes.
The dissolution rate (%) of the film was measured by immersing the film in hot water at ℃ for 1 hour. In calculating the elution rate (%), the weight of the film before and after immersion in hot water (g) was calculated,
{(Film weight before immersion-film weight after immersion) /
The film weight before immersion} × 100.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0040

[Correction method] Change

[Correction content]

[0040] [C liquid] AA reduction PVA (saponification degree 99.1 mol%, average polymerization degree of 1200, acetoacetic ester group 4.8 mole% content) of 10% aqueous solution of 100 parts of Metakishi Li diamine [Mitsubishi Gas Chemical Company Made by "MXDA"] 0.5 parts Acetylacetone 1.5 parts Kaolin clay 5 parts

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0043

[Correction method] Change

[Correction content]

Further, an ink jet recording medium was prepared and evaluated in the following manner. First, the following aqueous solution (solution D) was prepared. [D solution] AA reduction PVA (saponification degree 99.1 mol%, average polymerization degree of 1200, acetoacetic ester group 4.8 mole% content) of 10% aqueous solution of 400 parts of Metakishi Li diamine [Mitsubishi Gas Chemical Co. " MXDA ”] 2 parts Acetylacetone 6 parts Amorphous silica [“ Fineseal ”manufactured by Tokuyama Corporation] 40 parts Polyamine dye fixing agent [“ Sumiraz resin 1001 ”manufactured by Sumitomo Chemical Co., Ltd.] 40 parts

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0047

[Correction method] Change

[Correction content]

[0047] In Example 3 Example 1, except for changing the amount of Metakishi Li diamine (B) to 2 parts Interested in resin composition as in Example 1 and evaluated in the same manner.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0048

[Correction method] Change

[Correction content]

[0048] In Example 4 Example 1, except for using 1.5 parts of norbornane diamine (B) instead of Metakishi Li diamine (B) is obtained in the same manner as in the resin composition as in Example 1, the same Was evaluated.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0049

[Correction method] Change

[Correction content]

[0049] In Example 5 Example 1, instead of the Metakishi Li diamine (B), 1,3-bis-aminomethyl cyclohexane (B)
A resin composition was obtained in the same manner as in Example 1 except that was used and evaluated in the same manner.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08K 5/07 C08K 5/17 5/17 C09D 129/04 C09D 129/04 B41M 5/18 111 101E 101C F Terms (reference) 2H026 AA07 CC05 DD43 DD45 DD53 DD55 FF01 FF11 2H086 BA05 BA15 BA31 BA35 4J002 BE011 EE047 EN016 EN036 EN076 EN096 EU136 HA04 HA07 4J038 CE021 GA02 JA34 JA13 HA13 HA13 HA13 HA13 HA13 DA31 NA13 P3111

Claims (7)

[Claims] 1. An acetoacetic acid ester group-containing polyvinyl alcohol (A), an amino group-containing compound (B) represented by the following general formula (1), and a β-diketone compound (C). Resin composition. R - _{[(CH 2)} n -NHR _{1] m} ··· (1) (wherein, R represents residues except for hydrogen of an aromatic ring, aliphatic ring, cyclic compound selected from heterocyclic, _{R 1} Is hydrogen or an alkyl group, n is 0 or a positive integer, and m is a positive integer.) 2. The amino group-containing compound (B) represented by the general formula (1) is any one of metaxylene diamine, 1,3-bisaminomethylcyclohexane and norbornanediamine. The resin composition according to 1. 3. The resin composition according to claim 1 or 2, wherein the β-diketone compound (C) is acetylacetone. 4. The content ratio (A / B) of the acetoacetic acid ester group-containing polyvinyl alcohol (A) and the amino group-containing compound (B) represented by the general formula (1) is 100/0.
It is 1-100 / 30 (weight ratio), The resin composition in any one of the Claims 1-3 characterized by the above-mentioned. 5. The content ratio (B / C) of the amino group-containing compound (B) represented by the general formula (1) and the β-diketone compound (C) is 100 / 0.1 to 100/1000 (weight. Ratio). The resin composition according to claim 1. 6. A thermosensitive recording medium comprising a thermosensitive coloring layer and / or a protective layer coated with the resin composition according to claim 1. 7. An ink jet recording medium comprising an ink receiving layer and / or a protective layer coated with the resin composition according to claim 1.