JP3040935B2 - Recording material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording material, and more particularly, to a recording material having excellent water resistance, running properties, chemical resistance and manufacturing suitability.

[0002]

2. Description of the Related Art Recording materials using an electron-donating colorless dye and an electron-accepting compound are already well known as pressure-sensitive paper, heat-sensitive paper, light-sensitive heat-sensitive paper, current-heat-sensitive recording paper, heat-sensitive transfer paper and the like. For example, a thermal recording system using thermal recording paper is applied to various fields such as a facsimile, a printer, a label, a terminal for meter reading, a medical image output, a prepayment card, and the needs are expanding.

As a result, thermosensitive recording paper is increasingly used in homes and outdoors, and is often handled with wet hands. Also, the coated surface of the recording paper is wet and adhered by rain or snow. In the market, there is a strong demand for water resistance of the recording paper from a practical viewpoint.

[0004]

Heretofore, from the viewpoint of water resistance and the like, protection from a viewpoint of water resistance, etc., on a thermosensitive coloring layer, which is mainly composed of an acetoacetylated polyvinyl alcohol-based resin and / or a polyvinyl alcohol-based resin having at least acrylonitrile as a copolymer component. A heat-sensitive recording material provided with a layer is disclosed in JP-A-59-106.
No. 995.

However, since the reactivity between the acetoacetylated polyvinyl alcohol and the cross-linking agent is remarkable, stable coating cannot be performed due to a sudden increase in the viscosity of the coating liquid, and the life of the coating liquid is short due to gelation. There was a problem.

A heat-sensitive recording material containing a water-resistant agent such as an aldehyde compound together with a modified polyvinyl alcohol having an amino group or an ammonium group is disclosed in Japanese Patent Laid-Open No. 4-2.
No. 57489 and Japanese Patent Publication No. 5-3392. These heat-sensitive recording materials have improved water resistance and the like, but higher water resistance is required in the market, and at the same time, recording materials such as heat-sensitive recording materials having excellent running properties and chemical resistance are required. ing.

An object of the present invention is to provide a recording material which is excellent in water resistance, running properties, chemical resistance and manufacturing suitability.

[0008]

An object of the present invention is to provide a support containing at least a substantially colorless color-forming component A and a substantially colorless color-forming component B which reacts with the color-forming component A to form a color. In a recording material provided with a color-forming layer, a water-soluble polymer (1) containing an amino group or an ammonium group in a molecule, a blocked isocyanate compound or vinyl
And a waterproofing agent (2) comprising at least one sulfone compound .

Hereinafter, the present invention will be described in more detail. In the present invention, the water-soluble polymer having an amino group or an ammonium group in the molecule includes chitosan, a modified polyvinyl alcohol having an amino group or an ammonium group, a hydrolyzate of polyvinyl formamide, a modified polyacrylamide having an amino group or an ammonium group. ,
Modified polyacrylic acid or modified polymethacrylic acid having an amino group or an ammonium group or a salt or partial ester thereof, modified starch having an amino group or an ammonium group, a cellulose derivative having an amino group or an ammonium group, or a graft thereof Examples include a polymer or a block polymer.

Among these water-soluble polymers, a modified polyvinyl alcohol having an amino group or an ammonium group, particularly a modified polyvinyl alcohol having a primary amino group or a primary ammonium group is preferable from the viewpoint of water resistance. As the modified polyvinyl alcohol having an amino group or an ammonium group, a copolymer with a monomer having a functional group or a monomer capable of forming an amino group or an ammonium group by a saponification reaction, a hydrolysis reaction, or the like after copolymerization is used. Examples thereof include polyvinyl alcohol obtained by polymerization, and graft polymers or block polymers containing these polyvinyl alcohols as one component.

The average degree of polymerization of a modified polyvinyl alcohol having an amino group or an ammonium group is 300 to 4.0.
00, preferably 500 to 2,000. If the average degree of polymerization is less than 300, the adhesive strength as a binder is reduced, and if it exceeds 4,000, the viscosity of the solution is increased and the workability is reduced. The modified polyvinyl alcohol having an amino group or an ammonium base has a saponification degree of 75 to 1
00 mol%, preferably 90 to 100 mol%. If the saponification degree is less than 75 mol%, it is difficult to dissolve in water, which is not preferable. If the modification degree of the modified polyvinyl alcohol having an amino group or an ammonium group is small, sufficient water resistance and chemical resistance cannot be obtained, and if it is too large, the stability of the coating liquid is deteriorated. Mole% is preferred,
Further, 2 to 20 mol% is desirable.

Next, as the hydrolyzate of polyvinyl formamide, a product obtained by hydrolyzing poly N-vinyl formamide in a basic solution is desirable. This hydrolyzate has an amino group as shown in Chemical formula 1, and can be a crosslinkable polymer at room temperature.

[0013]

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In the present invention, other water-soluble or water-insoluble binders may be used in combination with the water-soluble polymer (1) as required. As a water-soluble binder, methylcellulose, carboxymethylcellulose,
Hydroxyethyl cellulose, starch, gelatin,
Arabic gum, casein, styrene-maleic anhydride copolymer hydrolyzate, ethylene-maleic anhydride copolymer hydrolyzate, isobutylene-maleic anhydride copolymer hydrolyzate, polyvinyl alcohol, modified polyvinyl alcohol, polyacrylamide, etc. Is mentioned. However,
These water-soluble binders should be used in such an amount that the water resistance of the recording material is not reduced.

As the water-insoluble binder, a synthetic rubber latex or a synthetic resin emulsion is generally used, and examples thereof include styrene butadiene rubber latex, acrylonitrile-butadiene rubber latex, methyl acrylate-butadiene rubber latex, and vinyl acetate emulsion. The amount of the binder used is 10 to 500% by weight, preferably 50% by weight, based on the pigment contained in the protective layer.
４００400% by weight.

The present invention with respect to the water-soluble polymer (1), a blocked isocyanate compound or Binirusu
Waterproofing agent consisting of at least one type of rufone compound (2)
Is used.

[0017]

[0018]

The blocked isocyanate as the water-proofing agent (2) in the present invention refers to a compound obtained by masking the terminal isocyanate group of isocyanate with a blocking agent. Blocked isocyanates include, for example, (a)
A block of a hydrophilic group consisting of a carbamoyl sulfonate group (—NHCOSO ₃ ⁻ ) formed at the end of an isocyanate compound to block an active isocyanate group, and (b) blocking an active isocyanate group using isopropylidene malonate What you did. Examples of the blocked isocyanate include (c) a compound obtained by reacting HDI isocyanurate, isopropylidene malonate, and triethylamine, in which an active isocyanate group is blocked with a phenol.

Such blocked isocyanates are:
When mixed with modified polyvinyl alcohol and heated, the modified polyvinyl alcohol is cross-linked and reformed to achieve water resistance of the modified polyvinyl alcohol.

Examples of the vinyl sulfone compound as the water-proofing agent (2) in the present invention are described in JP-A-53-572.
No. 57, JP-A-53-41221, JP-B-49-13
563 and JP-B-47-24259. These vinyl sulfone compounds are the compounds shown in Chemical formula 2 (In Chemical formula 2, a and d represent 1 or 2, b and c represent 0, 1 or 2, and both of b and c are 0 simultaneously. And R represents a mere bond or a divalent group), a compound represented by the formula (3), wherein R represents a hydrogen atom or a lower alkyl group such as methyl, ethyl, propyl, These groups may further have a substituent in another group. A represents a divalent group, but may be omitted.), A compound shown in Chemical formula 4, and a compound shown in Chemical formula 5 (in Chemical formula 5, , M is 1 to 8), and the compounds shown in Chemical formula 6 and the like.

[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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In the chemical formula (6), in the compound (1), R represents a hydrogen atom or a lower alkyl group such as methyl, ethyl, isopropyl, etc., and those groups may further have a substituent. And Z is a non-metallic atomic group of Group VA or VIA or a group represented by (1A). In (1A), R 'represents an alkyl group having 1 to 4 carbon atoms, and X represents an acid anion. The above-mentioned vinyl sulfone compound specifically includes compounds 1 to 6 shown in Table 1 and compounds 7 to 10 shown in Table 2.

[0028]

[Table 1]

[0029]

[Table 2]

The water-soluble polymer (1) and the water-proofing agent (2) are used in an amount of 2 to 100 parts by weight of the water-proofing agent (2) per 100 parts by weight of the water-soluble polymer (1). Is desirable. If the compounding amount of the water-proofing agent (2) is less than 2 parts by weight, it becomes difficult to achieve water resistance, and if it exceeds 100 parts by weight, the stability of the coating solution is undesirably deteriorated.

The above-mentioned water-soluble polymer (1) and water-proofing agent (2) comprise a color-forming layer, a protective layer formed on the color-forming layer, and a bag coat formed on the surface of the support opposite to the color-forming layer. It may be contained in any one of the layers. In particular, when the protective layer is not formed, the water-soluble polymer (1) and the waterproofing agent (2) are desirably contained in the color-forming layer. When the protective layer is formed, the water-soluble polymer (1) is used. It is desirable that the waterproofing agent (2) be contained in the protective layer. When the water-soluble polymer (1) and the waterproofing agent (2) are contained in both the protective layer and the back coat layer, the effects such as water resistance are further improved.

The coating solution for the protective layer of the present invention comprises a pigment dispersion,
Indder, water-soluble polymer (1) and waterproofing agent (2)
Obtained by mixing. If necessary, release agent,
You may add an active agent, a wax, a water repellent, etc. Obtained security
Bar coater, air knife on the thermosensitive coloring layer
Equipment for coaters, blade coaters, curtain coaters, etc.
Applying and drying using a device to obtain the protective layer of the present invention
Can be. However, the protective layer may be applied simultaneously with the coloring layer.
After applying the thermosensitive coloring layer, once dry the thermosensitive coloring layer,
And apply it on it. The dry coating amount of the protective layer is
0.5-5g / m ^TwoIs more preferable, and more preferably 0.1.
8 to 2 g / m^TwoIt is. Significant heat sensitivity when coating amount is large
And water resistance when the coating amount is too low.
Cannot be maintained. After applying the protective layer, clean as necessary.
May be applied.

As the pigment that can be used for the protective layer, all general organic or inorganic pigments can be used. Specific examples include calcium carbonate, calcium hydroxide, barium sulfate, titanium oxide, talc, wax, kaolin, calcined kaolin, amorphous silica, urea formalin resin powder, polyethylene resin powder, and benzoguanamine resin powder. These are used alone or in combination of two or more.

Next, the color-forming layer in the present invention contains at least a substantially colorless color-forming component A and a substantially colorless color-forming component B that reacts with the color-forming component A to form a color. Examples of the combination with the coloring component A and the coloring component B include a combination of a photodegradable diazo compound and a coupler, a combination of an electron-donating dye precursor and an electron-accepting compound, and a combination of an organic metal salt and a reducing agent. A typical thermosensitive coloring layer containing such a coloring component A and a coloring component B will be described. As an example, an electron-donating dye precursor (hereinafter, referred to as a coloring agent) as a coloring component A, a coloring component B
A thermosensitive coloring layer using an electron-accepting compound (hereinafter, referred to as a color developer) will be described.

The color former and the developer are separately dispersed, generally together with a water-soluble polymer aqueous solution such as polyvinyl alcohol, to a size of several microns or less by a ball mill, a sand mill or the like. These dispersions are mixed after dispersing, and further, if necessary, an oil-absorbing pigment, a binder, a wax, a metal soap, an antioxidant, an ultraviolet absorber, a surfactant, an antistatic agent, an antifoaming agent, a conductive agent, a fluorescent agent A dye, a coloring dye and the like are added to form a thermosensitive coloring layer coating solution.

The obtained heat-sensitive coating liquid is applied to a support such as a high-quality paper, a high-quality paper having an undercoat layer, a synthetic paper, a plastic film, and the like, and then dried to give smoothness by a calendering treatment. It becomes a recording material. At this time, JIS
The smoothness expected at −8119 is 500 seconds or more,
It is particularly preferable to use a support for 800 seconds or more from the viewpoint of dot reproducibility. In order to obtain a support having a smoothness of 500 seconds or more, (1) a highly smooth material such as synthetic paper or a plastic film is used, and (2) an undercoat layer containing a pigment as a main component is provided on the support. (3) Means for increasing the smoothness of the support by using a super calender or the like.

Examples of the color-forming agent used in the present invention include triphenylmethanephthalide compounds, fluoran compounds, phenothiazine compounds, indolylphthalide compounds, leucouramine compounds, rhodamine lactam compounds, and triamine compounds. There are various compounds such as a phenylmethane compound, a triazene compound, a spiropyran compound, and a fluorene compound.

Specific examples of phthalides are described in US Reissue Patent No. 23,024 and US Patent No. 3,491,1.
No. 11, 3,491, 112, 3,491,
Nos. 116 and 3,509,174, and specific examples of fluorans are described in U.S. Pat. No. 3,624,107;
No. 3,627,787, No. 3,641,011
No. 3,462,828, No. 3,681,39
No. 0, No. 3,920,510, No. 3,959,5
No. 71, specific examples of spirodipyrans are described in U.S. Pat. No. 3,971,808, and pyridine and pyrazine compounds are described in U.S. Pat. Nos. 3,775,424 and 3,853,869. No. 4,246,318 and specific examples of fluorene compounds are described in JP-A-63-94878.

Among them, black-colored 2-arylamino-
3-H, halogen, alkyl or alkoxy-6-substituted aminofluorans are effective. As specific examples, for example, 2-anilino-3-methyl-6-diethylaminofluoran, 2-anilino-3-methyl-6-N-cyclohexyl-N-methylaminofluoran, 2-p-chloroanilino-3-methyl-6 -Dibutylaminofluoran,
2-anilino-3-methyl-6-dioctylaminofluorane, 2-anilino-3-chloro-6-diethylaminofluoran, 2-anilino-3-methyl-6-N-ethyl-isoamylaminofluoran, 2- Anilino-3
-Methyl-6-N-ethyl-N-dodecylaminofluoran, 2-anilino-3-methoxy-6-dibutylaminofluoran, 2-o-chloroanilino-6-dibutylaminofluoran, 2-p-chloroanilino- 3-ethyl-6-N-ethyl-N-isoamylaminofluoran, 2-o-chloroanilino-6-p-butylanilinofluoran, 2-anilino-3-pentadecyl-6-diethylaminofluoran, 2-anilino -3-ethyl-
6-dibutylaminofluoran, 2-o-toluidino-
3-methyl-6-dibutylaminofluoran, 2-o-
Toluidino-3-methyl-6-diisopropylaminofluoran, 2-anilino-3-methyl-6-N-isobutyl-N-ethylaminofluoran, 2-anilino-3
-Methyl-6-N-ethyl-N-tetrahydrofurfurylaminofluoran, 2-anilino-3-chloro-6
N-ethyl-N-isoamylaminofluoran, 2-anilino-3-methyl-6-N-methyl-N-γ-ethoxypropylaminofluoran, 2-anilino-3-methyl-6-N-γ-ethoxy Propylaminofluoran,
2-anilino-3-methyl-6-N-ethyl-N-γ-
And propoxypropylaminofluoran.

Examples of the developer used in the present invention include:
2,2-bis (4'-hydroxyphenyl) propane (generic name bisphenol A), 2,2-bis (4'-hydroxyphenyl) pentane, 2,2-bis (4'-hydroxy-3 ', 5' -Dichlorophenyl) propane,
1,1-bis (4′-hydroxyphenyl) cyclohexane, 2,2-bis (4′-hydroxyphenyl) hexane, 1,1-bis (4′-hydroxyphenyl) propane, 1,1-bis (4 ′ -Hydroxyphenyl) butane, 1,1-bis (4′-hydroxyphenyl) pentane, 1,1-bis (4′-hydroxyphenyl) hexane, 1,1-bis (4′-hydroxyphenyl) heptane, 1, 1-bis (4'-hydroxyphenyl) octane, 1,1-bis (4'-hydroxyphenyl) -2-
Methyl-pentane, 1,1-bis (4′-hydroxyphenyl) -2-ethyl-hexane, 1,1-bis (4 ′
-Hydroxyphenyl) dodecane, 1,4-bis (p-
Hydroxyphenylcumyl) benzene, 1,3-bis (p-hydroxyphenylcumyl) benzene, bis (p
Bisphenols such as -hydroxyphenyl) sulfone, bis (3-allyl-4-hydroxyphenyl) sulfone, bis (p-hydroxyphenyl) acetic acid benzyl ester, 3,5-di-α-methylbenzylsalicylic acid, 3,5- Di-tert-butylsalicylic acid, 3-
α-α-dimethylbenzylsalicylic acid, 4- (β-p-
Salicylic acid derivatives such as methoxyphenoxyethoxy) salicylic acid, or polyvalent metal salts thereof (particularly zinc and aluminum are preferable), p-hydroxybenzoic acid benzyl ester, p-hydroxybenzoic acid-2-erhexyl ester, β-resorcinic acid- 2 (-phenoxyethyl)
Oxybenzoic acid esters such as esters, p-phenylphenol, 3,5-diphenylphenol, cumylphenol, 4-hydroxy-4′-isopropoxy-diphenylsulfone, 4-hydroxy-4′-phenoxy-diphenylsulfone, etc. Phenols. Of these, bisphenols are particularly preferred for the purpose of improving dot reproducibility. The developer is 50 to 50% of the color former.
It is preferably used in an amount of 800% by weight, more preferably 100 to 500% by weight. Further, two or more of the above electron accepting compounds may be combined.

The recording material of the present invention may contain a heat-fusible substance (hereinafter, referred to as a sensitizer) in any layer constituting the recording material in order to improve the thermal response. Examples of the sensitizer include benzyl p-pendyloxybenzoate, β-naphthyl-benzyl ether, stearamide, stearyl urea, p-benzyl bephenyl, di (2-methylphenoxy) ethane, di (2-methoxy) Phenoxy) ethane, β-naphthol- (p-methylbenzyl) ether, α-naphthyl-benzylether,
1,4-butanediol-p-methylphenyl ether, 1,4-butanediol-p-isopropylphenyl ether, 1,4-butanediol-p-tert-octylphenyl ether, 1-phenoxy-2-
(4-ethylphenoxy) ethane, 1-phenoxy-2
-(4-chlorophenoxy) ethane, 1,4-butanediol phenyl ether, diethylene glycol-bis-
(4-methoxyphenyl) ether, 4-ethoxyphenyl-p-chlorobenzyl ether, 1 (4-methoxy-phenoxy) -2-phenoxy-propane, 1,3-bis- (4-methoxyphenoxy) propane, 3-methyl 4-chlorophenyl-p-methoxybenzyl ether, 3,5-dimethyl-4-chlorophenyl-p-methoxybenzyl ether, 4-chlorophenyl-p-methoxybenzyl ether, 1-phenoxy-2 (4-methoxy- Phenoxy) -propane, dibenzyl oxalate, di (p-methylbenzyl) oxalate and the like. These sensitizers are used alone or as a mixture. In order to obtain sufficient thermal responsiveness, it is preferably used in an amount of 10 to 200% by weight, more preferably 20 to 150% by weight, based on the developer. The extras are
Either or both of the color former and the developer may be added and dispersed at the same time, or a heat eutectic with the color former or the developer may be prepared in advance and then cooled and dispersed.

As the binder, a compound soluble in water at 25 ° C. in an amount of 5% by weight or more is preferable.
Polyvinyl alcohol (including modified polyvinyl alcohol such as carboxy-modified, itaconic-acid-modified, maleic-acid-modified, silica-modified and amino-modified above), methylcellulose, carboxymethylcellulose, starches (including modified starch), gelatin, gum arabic, casein And a styrene-maleic anhydride copolymer hydrolyzate, polyacrylamide, and a saponified vinyl acetate-polyacrylic acid copolymer. These binders are used not only during dispersion but also for the purpose of improving the strength of the coating film. For this purpose, styrene-butadiene copolymer, vinyl acetate copolymer, acrylonitrile-butadiene copolymer, acrylic Acid methyl-butadiene copolymer,
A latex-based binder of a synthetic polymer such as polyvinylidene chloride can also be used in combination. If necessary, a crosslinking agent for an appropriate binder may be added according to the type of the binder.

Examples of the pigment include calcium carbonate, barium sulfate, lithopone, wax, kaolin, calcined kaolin, silica and amorphous silica. As the metal soap, higher fatty acid metal salts are used, and zinc stearate, zinc myristate, calcium stearate, and aluminum stearate are used. Examples of the wax include montan wax, paraffin wax, carnauba wax, microcrystalline wax, polyethylene wax and the like.

Further, as the back coat layer provided on the surface of the support of the recording material opposite to the color-forming layer, if necessary, any back coat layer known as a back coat layer of the recording material can be used. .

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to the following Examples. The concentration used in the text is% by weight.

[0046]

[0047]

[0048]

Example 1 A copolymer of vinylamine and vinyl acetate was saponified using a hydrochloric acid catalyst, containing 1 mol% of a primary ammonium base, a degree of saponification of vinyl acetate units of 88 mol%, and a degree of polymerization. 500 denatured polyvinyl alcohol
Alcohol is called PVA), dissolved in water and dissolved in 5%
The liquid was adjusted. This is designated as solution A. Next, as a color former,
2-anilino-3-methyl-6-N-dibutyl-amino
Fluoran, bisphenol A as a color developer, and a sensitizer
Solution A with 20 g each of β-naphthyl-benzyl ether
With a ball mill for a day and night, and the average particle size is 1.5 μm
The dispersions B, C and D were obtained as follows. Ma
Also, 80 g of calcium carbonate was added to sodium hexametaphosphate 0.5
% Solution with a homogenizer and a pigment dispersion
Solution E was obtained. Liquid B prepared as above
(Coloring agent dispersion) 5 g, Liquid C (developing agent dispersion) 10 g, Liquid D
(Sensitizer dispersion) 10g, E solution (Calcium carbonate dispersion)
5g, 21% zinc stearate emulsion 3g mixture
Then , a blocked isocyanate compound (trifunctional) having 10% of a carbamoyl sulfonate group is added as a waterproofing agent to the solid content of the amino group-modified PVA.
Thus, a heat-sensitive coating solution was obtained. Apply the obtained heat-sensitive coating liquid to a basis weight of 50 g / m ^2.
Wai as dry coating weight on a high-quality paper for become 6 g / m ²
Apply with Yer bar, dry in 50 ° C oven, heat sensitive
Recording paper was obtained.

Example 2 Solution A prepared by using a modified PVA containing 8 mol% of a primary ammonium base obtained by acetalizing PVA having a saponification degree of 98.5 mol% and a polymerization degree of 1100 with aminoacetaldehyde in an aqueous hydrochloric acid solution. And a heat-sensitive recording material was obtained in the same manner as in Example 1 except that the paint was prepared using a vinyl sulfone compound represented by Chemical Formula 7 as a water-proofing agent.

[0051]

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[0052] Examples 3 5 In Example 2, the heat-sensitive recording material in the same manner other than the Example 2 using vinyl sulfone compound shown in Chemical Formula 8 of 10 instead of the vinyl sulfone compound shown in Chemical formula 7 I got

[0053]

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[0054]

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[0055]

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Comparative Example 1 A 40% glyoxal solution was used in place of the water-proofing agent of Example 1, and this glyoxal was added in accordance with the solid fraction of ethylene polyethylene glycol diglycidyl ether in Example 1 to coat the protective layer. A thermosensitive recording material was obtained in the same manner as in Example 1 except that the liquid was adjusted.

[0057]

[0058]

[0059]

[Testing method and evaluation method] After printing using a water-resistant Kyocera printing tester, water was applied and bonded, dried, peeled off, and the state of the coating was observed.
No change in paint, (B) little paint,
(C) The coating was slightly removed, but the printed portion could be read somehow. (D) The coating was severely removed and the printed characters could not be read.
(B) and above are practical.

After printing using a chemical resistance Kyocera printing tester, the hand cream is spread evenly on the finger, pressed against the printed portion and observed.
There is no change in the printed part, (B) There is a slight change in the printed part, but the printed part can be read clearly, (C) There is bleeding and decoloration, but other than the printed part can be read somehow, (D) bleeding and The determination was made in four steps such that the color was severely erased and the printed characters could not be read. (B) and above are practical.

Running performance Printing was performed using a Kyocera printing tester, and the degree of sticking was determined as follows: (A) no occurrence of sticking; (B) printing unevenness was observed but white spotting was not observed; It was determined in four steps, such as white spots and (D) white streaks were generated on the entire surface. (B) and above are also practical. In addition, the test sample was conditioned under an environment of 23 ° C./65% RH for 1 hour or more, and then performed.

Table 3 shows the test results. In each example, the water-soluble polymer (1) and the water-proofing agent (2)
The coating liquid containing and does not cause gelation after coating liquid adjustment,
The stable coating time was 5 days or more. Therefore, the recording material of the present invention was excellent in production suitability.

[0064]

[Table 3]

As is evident from Table 3, it was found that the recording material of the present invention was excellent in all of water resistance, running property and chemical resistance.

[0066]

As described above, according to the present invention, water resistance,
It is possible to provide a recording material which is excellent in running property, chemical resistance and production suitability and has high practicality.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-5-294067 (JP, A) JP-A-6-106853 (JP, A) JP-A-6-8630 (JP, A) JP-A-4- 257489 (JP, A) JP-A-8-252976 (JP, A) JP-A-2-266977 (JP, A) JP-A-5-572 (JP, A) JP-B-5-3392 (JP, B2) (58) Field surveyed (Int.Cl. ⁷ , DB name) B41M 5/28-5/34

Claims (4)

(57) [Claims] 1. A recording material comprising a support having thereon a color-forming layer containing at least a substantially colorless color-forming component A and a substantially colorless color-forming component B which reacts with the color-forming component A to form a color. Water-soluble polymer (1) containing an amino group or an ammonium base in a molecule, and a blocked isocyanate compound
Or a waterproofing agent (2) composed of at least one vinyl sulfone compound . 2. The method according to claim 1, wherein the water-soluble polymer (1) containing an amino group or an ammonium group in the molecule is a modified polyvinyl alcohol containing an amino group or an ammonium group in the molecule. The recording material described. 3. The recording material according to claim 2, wherein the amino group is a primary amino group, and the ammonium base is a primary ammonium base. 4. The color-forming layer, wherein the water-soluble polymer (1) and the water-proofing agent (2) are formed on the color-forming layer,
The recording material according to claim 1, wherein the recording material is contained in at least one of a back coat layer formed on a side of the support opposite to the color-forming layer.