JPH10291377A - Information recording material with protective coating layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To simply obtain an information recording material having excellent flaw resistance, water resistance, stickiness resistance, writability, and image preservability with high added value, at a low cost. SOLUTION: This recording material comprises at least one image carrier layer made mainly of hydrophilic polymer on a support. In this case, a protective coating layer containing a heat reaction water polyurethane resin or thermoplastic water polyurethane resin at outer side from the carrier layer and silicone release agent is provided on the support.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an information recording material having a protective coating layer, and more particularly, to an information recording material having a protective coating layer and having at least one image-bearing layer made of a hydrophilic polymer on a support. Related to recording materials. More specifically, the present invention relates to a printed matter of an ink jet printer excellent in scratch resistance, water resistance, adhesive resistance, writing properties and image storability, a printed photograph, and a postcard with a photograph.

[0002]

2. Description of the Related Art In general, printed matter of an ink jet printer,
Thermal transfer recording materials, or information recording materials having an image bearing layer made of a hydrophilic polymer such as a silver halide photosensitive material,
Deterioration occurs even with the attachment of a small amount of water droplets weakly to water, fingerprints easily adhere, and sticking occurs.

For this reason, a protective layer is conventionally provided on the image recording surface. As a protective layer, it is possible to apply a radiation-curable resin and to cure it with radiation.
No. 7023, No. 61-201248, No. 62-211
No. 50. However, these layers have insufficient adhesion to the image bearing layer, have a problem with safety to living organisms, or have difficulty in controlling the reaction,
It requires a device for irradiating radiation, and has many disadvantages in terms of cost, safety, and simplicity.

Further, laminating an information recording material having an image bearing layer is disclosed in JP-A-62-62360 and JP-A-62-62360.
No. 259570. However, these methods are expensive, and are not widely used in general inexpensive printed matter or printed photographs except for special uses.

A method for obtaining a protective coating layer of an information recording material with a resin latex is described in JP-A-62-247370 and JP-A-6-110169, and a method for obtaining a protective coating layer with an ionic polyester is described in JP-A-3-212640. But
In these methods, the water resistance was slightly improved, the scratch resistance was deteriorated, and the adhesion resistance was poor, so that these methods were hardly at a level that could be used in the market.

It is well known that a polyurethane resin is used for a photographic recording material and that it is used together with gelatin, which is a hydrophilic colloid. For example,
-36365, JP-A-56-67841, JP-A-61-67841.
145556, 62-56651, British Patent 1,
Nos. 345,741, 2,063,500, European Patent 185,248, German Patent 1,472,746, and US Pat. No. 3,607,289 disclose the use of an ionic polyurethane resin to improve the brittleness and sensitivity of gelatin films. For example, an attempt to use the method is disclosed. However, these forms of use of an anionic polyurethane resin are those in which a binder is formed by being mixed with gelatin, which is a hydrophilic colloid, and the polyurethane resin is not used for a protective coating layer as in the present invention. In addition, we conducted a study to provide a protective coating layer using these ionic polyurethane resins,
Evaluation of scratch resistance, water resistance, adhesive resistance, writing properties, and the like was carried out, and it was found that the target performance of the present invention was never reached.

Although it is known to use a water-based polyurethane resin for the protective coating layer, these methods have a large effect of improving water resistance and scratch resistance, but greatly degrade the adhesive resistance. Are almost the same, and do not reach the target performance of satisfying all of the scratch resistance, water resistance, adhesive resistance, writing properties, and image storability according to the present invention.

Further, the use of polysiloxane compounds in photographic light-sensitive materials is widely known. For example, JP-A-7-128790 describes the use of a polysiloxane compound in a silver halide color photographic light-sensitive material. The purpose of adding these silicone release agents is to impart slipperiness to the surface of the recording material, and nothing is described about the effects of the present invention, namely, the improvement in water resistance, scratch resistance, and writing property.

[0009]

DISCLOSURE OF THE INVENTION The object of the present invention is to achieve scratch resistance, water resistance, adhesive resistance, writability, and the like, which cannot be achieved by using an aqueous polyurethane resin for a conventional protective coating layer.
An object of the present invention is to provide a high value-added information recording material having excellent image storability in a simple and inexpensive manner.

[0010]

Means for Solving the Problems The present inventor has conducted intensive studies to achieve the above object, and as a result, has found that the object of the present invention can be achieved by adopting the following constitution.

(1) In an information recording material having at least one layer of an image bearing layer mainly composed of a hydrophilic polymer on a support, a heat-reactive aqueous polyurethane resin or An information recording material comprising a thermoplastic water-based polyurethane resin and a protective coating layer containing a silicone release agent.

(2) The information recording material as described in (1) above, wherein the silicone release agent is an aqueous emulsion.

(3) The information recording material as described in (1) or (2) above, wherein the protective coating layer has a thickness of 1 μm or more and 10 μm or less.

Hereinafter, the present invention will be described. The information recording material according to the present invention is a material in which a hydrophilic binder layer is coated on a support and image information is carried. Such information recording materials are preferably color photographic prints, black and white photographic prints, postcards with photographs, reverse photographic prints, index prints, autopositive photographic prints, color photographic negative films, black and white photographic negative films, medical X photographic films, B. micro photographic film, instant photographic print, heat development photographic print, silver dye bleach print, dye transfer photographic print, E. FIG. Me
es, T .; H. James: The Theory o
f Photographic Process (3
rd ed. ), The Macmillan C
o. (1966), W.C. Thomas Jr. : SP
SE Handbook of Photograph
ic Science and Engineerine
g, Jhon Wiley and Sons (197
3). Sturge, V .; Walworth,
A. Sheep: Imaging Process
s Materials (NEBLETS 8th
ed), VanNorstrand Reinhol
d (1989) and other well-known photographic recording materials to those skilled in the art, and ink-jet printed materials using water-soluble inks.

In the present invention, more preferred information recording materials are silver halide photographic prints using gelatin as a hydrophilic binder, and particularly preferred are color photographic prints and postcards with photographs.

The hydrophilic binder used in the information recording material according to the present invention is, for example, a natural polymer such as gelatin, cellulose fiber or polysaccharide, or a water-absorbing material such as polyvinyl alcohol or polyethylene glycol. High polymers. When the information recording material is a silver halide photographic light-sensitive material, gelatin is preferable (some types contain polysaccharides such as dextran), and when it is an ink jet print, polyvinyl alcohol or gelatin is preferable.

Next, the water-based polyurethane resin according to the present invention will be described. 2. Description of the Related Art Conventionally, polyurethane resins have been widely used as useful materials for adhesives, paints, resin modifiers, and the like, and are broadly classified into solvent-based and water-based resins depending on the form of the resin. When a solvent-based polyurethane resin is used for the protective coating layer of an information recording material having an image bearing layer made of a hydrophilic polymer, despite its excellent water resistance, the image information falls off and the image storability is remarkable. There have been situations in which unacceptable defects, such as degradation, occur. In addition, during drying, there is also a problem that the solvent contained in the polyurethane resin is scattered into the air and pollutes the environment and the human body. So instead of solvent-based polyurethane resins using conventional organic solvents, water-soluble or aqueous emulsion type adhesives,
They are being used in the field of paints and the like, and their use is being studied.

The water-based polyurethane resin in the present invention refers to both types of polyurethane resins, that is, a water-soluble polyurethane resin and an aqueous emulsion polyurethane resin. The water-based polyurethane resin is a macroscopic solution such as an aqueous solution, an emulsion or a solubilized material. Look and say a uniform system.

The term "thermal reaction type" as used in the present invention refers to a type in which a formed film is formed into a network structure by a thermal reaction and the water resistance of the formed film and the adhesiveness to an adherend are obtained. It is a type in which a film layer is formed without drying out. In the present invention, the equipment surface, heat resistance of the adherend,
From the viewpoint of energy saving and environmental suitability, it is preferable to use a thermoplastic water-based polyurethane resin. More preferably, it is a thermoplastic aqueous emulsion type polyurethane resin.

The polyurethane resin referred to in the present invention is a general term for a polymer compound having a large number of urethane bonds in a molecule.
More specifically, in the resin structure, a urethane bond, a urea (urea) bond, a burette / urea bond obtained by a polyaddition reaction between a polyisocyanate and an active compound such as a polyol utilizing the reactivity of an isocyanate group with an active hydrogen compound. A bond resulting from the reaction between an isocyanate group such as an allophanate bond and active hydrogen, an ester bond, an ether bond, an amide bond contained in the active hydrogen compound molecule,
Also, it is a polymer compound containing uretdione, isocyanurate, carbodiimide and the like generated by the reaction between isocyanate groups. In general, polyurethane resin has excellent mechanical properties, abrasion resistance, durability, and chemical resistance due to intermolecular secondary bonds such as urethane bonds and urea bonds that have large cohesive energy in the molecule. have. In addition, the performance can be greatly changed by controlling the type of raw materials used such as polyisocyanate and active hydrogen compound, the composition ratio reaction conditions, and the like.

Examples of the polyisocyanate used for synthesizing the polyurethane resin of the present invention include the following, but are not limited thereto. Toluene diisocyanate, diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, 2,
2,4 (2,4,4) -trimethylhexamethylene diisocyanate, p-phenylene diisocyanate,
4'-dicyclohexylmethane diisocyanate, 3,
3'-dimethyldiphenyl-4,4'-diisocyanate, dianisidine diisocyanate, m-xylene diisocyanate, 1,3-bis (isocyanatomethyl)
Cyclohexane, tetramethylxylene diisocyanate, isophorone diisocyanate, 1,5-naphthalenediisocyanate, 1,4-cyclohexyl diisocyanate, lysine diisocyanate, dimethyltriphenylmethanetetraisocyanate, triphenylmethanetriisocyanate, tris (isocyanatophenyl) thiophosphate, urethane Modified toluene diisocyanate, allophanate modified toluene diisocyanate,
Biuret-modified toluene diisocyanate, isocyanurate-modified toluene diisocyanate, urethane-modified diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, uretonimine-modified diphenylmethane diisocyanate, acylurea-modified diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, and the like.

These isocyanate compounds may be used alone, and may be used in advance as a reaction product of a plurality of types of polyisocyanates, a reaction product of an ethylene oxide adduct of methanol or ethanol with a polyisocyanate,
Further, it may be used as a compound having a free isocyanate group obtained by reacting a compound having two or more active hydrogens in one molecule with a polyisocyanate.

The polyol having an active hydrogen used in the synthesis of the polyurethane resin of the present invention is mainly a low molecular weight polyol, a polyether polyol, a polyester polyol, a polyether ester polyol, a polycarbonate polyol, a graft modified or dispersed product of a polyether polyol. , A high molecular weight polyol such as a hydrocarbon skeleton polyol, or a polyadduct thereof.

Aqueous emulsion type polyurethane resins include anionic self-emulsifying type, nonionic self-emulsifying type,
Three types of forced emulsification type are known. To obtain an anionic self-emulsifying aqueous emulsion polyurethane resin,
Sulfonic acid, phosphoric acid, a method of introducing a polar group such as a carboxylic acid into the polyol portion to be reacted with the polyisocyanate, and when performing a chain extension reaction after reacting the polyol with the polyisocyanate, sulfonic acid, phosphoric acid, There is a method of introducing a polar group using a compound having a polar group such as a carboxylic acid and an amino alcohol such as a diol, a diamine, or 2- (2-aminoethylamino) ethanol. At this time, if a counter ion such as triethylamine or diethylamine is appropriately introduced into the system, an aqueous emulsion having a desired particle size can be obtained. Among these, the use of an anionic self-emulsifying type is preferred in the present invention, and more preferred is an anionic self-emulsifying type polyurethane resin containing a carboxyl group in a constitutional unit.

Examples of the polyol starting materials having a carboxyl group include 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxymethyl) butanoic acid,
Examples thereof include, but are not limited to, 2,5,6-trimethoxy-3,4-dihydroxyhexanoic acid and 2,3-dihydroxy-4,5-dimethoxypentanoic acid. As a polyol starting material having no carboxyl group, ethylene glycol, 1,2-propanediol,
1,3-propanediol, 1,2-butanediol,
1,3-butanediol, 1,4-butanediol,
2,3-butanediol, 2,2-dimethyl-1,3-
Propanediol, 1,2-pentanediol, 1,4
-Pentanediol, 1,5-pentanediol, 2,
4-pentanediol, 3,3-dimethyl-1,2-butanediol, 2-ethyl-2-methyl-1,3-propanediol, 1,2-hexanediol, 1,5-hexanediol, 1,6- Hexanediol, 2,5-hexanediol, 2-methyl-2,4-pentanediol, 2,2-diethyl-1,3-propanediol,
2,4-dimethyl-2,4-pentanediol, 1,7
-Heptanediol, 2-methyl-2-propyl-1,
3-propanediol, 2,5-dimethyl-2,5-hexanediol, 2-ethyl-1,3-hexanediol, 1,2-octanediol, 1,8-octanediol, 2,2,4-trimethyl -1,3-pentanediol, propylene glycol, diethylene glycol,
Dipropylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, pentaethylene glycol, hexaethylene glycol,
Heptaethylene glycol, dipropylene glycol,
Glycerin, trimethylolpropane, 1,2,6-hexanetriol, triethanolamine, pentaerythritol, ethylenediamine, tolylenediamine, diphenylmethanediamine, tetranotyrolcyclohexane, methylglucoside, 2,2,6,6-tetrakis (hydroxy Methyl) cyclohexanol, diethylenetriamine, sorbitol, mannitol, dulcitol, sucrose, and the like, but are not limited thereto.

Various combinations of the above polyisocyanates and polyols can be selected from the viewpoints of solubility of the polyadduct, hydrophilicity / hydrophobicity, and ease of production of the polyadduct.

Many water-based polyurethane emulsions that can be used in the present invention are known. One of them is a heat-reactive polyurethane emulsion having a relatively low to medium molecular weight region utilizing a blocked isocyanate group. Another example is a thermoplastic polyurethane emulsion having a relatively high molecular weight region mainly composed of a linear structure. These are self-emulsifying or dispersing by introducing hydrophilic groups such as anions, cations and non-ions into the urethane resin skeleton, or dispersing in water by adding an emulsifier to a hydrophobic resin.

Specific methods for synthesizing these aqueous polyurethane resins are described in JP-A-5-127306 and JP-A-6-6732.
No. 8, 6-293821, JP-A-4-96919.
And JP-A-58-63716 and 58-80320.
No. 63-301251, No. 56-151753
And JP-A Nos. 2-269723 and 7-10950. In addition, there are detailed descriptions of polyurethane synthesis methods in "Polyurethane Handbook" (1985) by Gunter Otel, "Polyurethane Foam" (1987) by Yoshio Imai, "Water-based Paint and Coating Technology" (1992) published by Technical Information Association.

Examples of commercially available thermoplastic water-soluble polyurethane resins or aqueous emulsion type polyurethane resins include, but are not limited to, the following. Super Flex Series 107, 110, 126, 150, 16 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
0, 190, 300, 361, 410, 460, 75
0, 820, Superflex E Series E-20
00, E-2500, E-4500. Takeda Pharmaceutical Co., Ltd. Bamboo Rack W Series W-6015, W-6
21, W-511, XW-75-P15, W-512
A, W-635, W-7004, XW-97-W6, A
W-605, ACW-54HD, Takelac XW series containing a silanol group, HYDRAN series manufactured by Dainippon Ink and Chemicals, Inc. Examples of the heat-reactive aqueous polyurethane resin include Elastron series manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., Takenate WB series manufactured by Takeda Pharmaceutical Co., Ltd. WB-700, WB-710, WB-720,
WB-730, WB-920 and the like.

Next, the silicone release agent according to the present invention will be described. Silicone in the present invention is a general term for compounds having a siloxane bond in the structure.
An organic silicon polymer compound in which a siloxane bond is used as a skeleton and an organic group or the like is directly bonded to the silicon atom. Therefore, it is different from silicon which is inorganic metallic silicon. Known as release agents include mica,
Although there are talc, metal salts, waxes, animal and vegetable fats and oils, higher fatty acid soaps, etc., they have various disadvantages such as low releasability, generation of thermal decomposition products, and reduction in surface gloss. On the other hand, the silicone release agent according to the present invention has the advantages of being colorless and odorless, having excellent heat resistance and mold release properties, having less thermal decomposition products, and having a high boiling point and a high flash point and being safe.

Examples of the type of the silicone release agent include, but are not limited to, the following. Oil types include dimethyl oil, methyl phenyl oil, alkyl / aralkyl modified oil, polyether modified oil, fluoroalkyl modified oil, amino modified oil, epoxy modified oil and the like. Dispersion type, such as dimethyl oil and resin. Emulsion types include dimethyl oil, alkyl / aralkyl modified oil, carboxyl modified oil, methylphenyl oil, resin, dimethyl oil, polyether modified oil, and elastomer. Compound type, such as silicon dioxide + silicone oil. As a spray type,
Examples include dimethyl oil, alkyl-aralkyl modified oils, and compounds. In the present invention, among these, use of a water-soluble or aqueous emulsion type is preferable, and an aqueous emulsion type is more preferable. Commercially available silicone release agents include, but are not limited to, the following. Shin-Etsu Silicone KF96L, KF96, KF-9
6H, TSF451 manufactured by Toshiba Silicone Co., Ltd.
SH200 manufactured by Dow Coating Silicone Co., Ltd.
SH7071, SH7072, SH510, SH55
0, SH710 and the like. Further, as an aqueous emulsion type silicone release agent, SH7025, SH4 manufactured by Dow Coating Silicone Toray Co., Ltd.
90, SM8706, SM8715, SH3746, S
H7036, SM7060, SM8708, SH871
0, SM8701, SM8705, SM7027, and the like, but are not limited thereto.

Next, a method for forming a protective coating layer on the information recording material according to the present invention will be described. Although the protective coating layer can be formed on the information recording material by any known coating method, it is desirable to select an optimal means depending on the type of the information recording material. For example, in the case of an ink-jet print, spray coating, ink-jet coating using an ink-jet head, and the like are desirable. The coating solution for the protective coating layer used for coating here is a composition containing the aqueous polyurethane resin and the silicone release agent according to the present invention. The silicone release agent may be mixed with the water-based polyurethane resin at an arbitrary ratio.
Desirably, it is 10%. More preferably, it is 0.
1 to 5%. That is, the solid content concentration is 0.0001.
%, The effect of the present invention is not exhibited, and if it is more than 10%, the film-forming properties, water resistance, and writing properties are deteriorated. As the type of the silicone release agent, any type such as an oil type, a dispersion type, a compound type, and an emulsion type may be added, but from the viewpoint of dispersion stability and workability in mixing with an aqueous polyurethane resin,
It is preferred to use water-soluble or aqueous emulsion types. More preferably, it is an aqueous emulsion type. The solid content concentration of the water-based polyurethane is arbitrarily set depending on the coating method and the required amount of resin attached, but is generally about 1 to 40%. Known coating methods include, for example, in addition to the methods described above, a method in which an information recording material is immersed in a coating solution and then dried, roll coating, gravure coating, air knife coating, extrusion coating, curtain coating, wire bar coating, cloth or sponge-like material. There is a method of drying after applying with a oozing liquid. In particular, when the information recording material is a silver halide photographic light-sensitive material, it may be passed through a coating solution for the protective coating before the drying step in the developing process, or may be added to the coating solution for the protective coating in a washing bath.

The protective coating layer resin used in the present invention may be used in combination of two or more water-soluble polyurethane resins or water-based emulsion polyurethane resins having different compositions. Further, the protective coating layer resin used in the present invention,
If necessary, film forming aids, leveling agents, high boiling solvents,
Higher fatty acids, higher fatty acid esters, higher alcohols, tackifiers, silane coupling agents such as aminosilane, epoxysilane and acrylic silane, crosslinkers such as carbodiimide and epoxy resin, liquid paraffin, surfactants,
Thickener, ultraviolet absorber, deodorant, fungicide, fluorescent brightener,
Antistatic agent, water-soluble dye, pigment, water-soluble polymer or, for example, acrylic, ethylene vinyl acetate, natural rubber, S
It can be used in combination with or blended with a general synthetic resin emulsion such as a synthetic rubber latex such as BR and NBR. However, in order to obtain the effects of the present invention, the protective coating layer desirably contains at least 60% (by weight) or more of the water-based polyurethane resin according to the present invention.

The amount of the protective coating layer of the information recording material of the present invention is determined in order to obtain the effects of the present invention.
From the viewpoint of drying properties and film physical properties, it is necessary that the thickness be 1 μm or more and 10 μm or less, and preferably 1 μm or more and 5 μm or less.
It is as follows. When the protective coating layer of the present invention is composed of two or more layers, the sum of the thicknesses of all the protective coating layers is defined as the thickness of the protective coating layer of the present invention.

The drying temperature after application of the composition containing the aqueous polyurethane resin used in the present invention is not particularly limited, but when the information recording material is a printed photograph, the drying temperature is preferably 110 ° C. or less from the viewpoint of the heat resistance of the support. Desirably, particularly preferably 45 ° C to 90 ° C.

When the protective coating layer of the information recording material having the protective coating layer of the present invention is the outermost layer, printing suitability for inks other than water-based ink is also improved. And character information can be added, and it becomes a high value-added information recording material.

By providing the protective coating layer on the uppermost layer on the image bearing side of the support at the same time as providing it on the uppermost layer (back layer) on the opposite side of the support, the water resistance and the writeability of the back surface are improved. An information recording material such as a photographic post card is obtained.

[0038]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples.

Example 1 An ink jet printer (Epson: Esper Machjet Color) was used and an ink jet printer paper (Epson: High Quality Gl) was used.
The sample image was printed on a glossy film dedicated to ossyPaper). This ink is Epson MJIC.
2C was used.

To the above-mentioned printed matter, a silicone release agent shown in Table 1 was added in an amount shown in Table 1 to a coating solution in which the thermoplastic resin shown in Table 1 was adjusted to a solid concentration of 20% to obtain a coating solution for a protective coating layer. . This protective coating layer coating solution was spray-coated so that the film thickness of the protective coating layer became the value shown in Table 1, dried in a drying box set at 80 ° C. for 15 minutes, and dried.
19 samples were obtained.

These samples were evaluated as described below, and the results are shown in Table 1.

<Scratch resistance (scratch strength)> radius 0.3
mm with a sapphire needle
The minimum load (scratch strength) at which scratches occur on the film surface of the sample was determined by continuously changing the pressure applied to the fire needle in the range of 200 g. The larger the value in the table, the better the scratch resistance.

<Water Resistance> A sample cut to a size of 15 × 15 cm was immersed in pure water at 20 ° C. for 3 minutes, and then the surface moisture was wiped off to calculate the rate of weight increase. The smaller the value is, the higher the waterproof property of the protective coating layer is.

<Adhesiveness (album sticking)> 3.5 ×
The sample cut to 10 cm was put into a pocket album (A-M323) manufactured by KOKUYO Co., Ltd. so that the image surface provided with the protective coating layer and the transparent resin surface of the pocket album were adhered to each other, and this was sandwiched between metal plates and 1 kg. Was left in an environment of 40 ° C. and 80% for 14 days under a load, and then taken out, and the adhesiveness was evaluated as follows.

(Evaluation criteria for album sticking property) ○ No sticking occurs at all △ Can be peeled off without being damaged despite sticking × When peeled, an image or a protective coating layer is damaged.

<Adhesiveness (sticking property to surface)> 3.5 × 1
The image surfaces of the sample cut to 0 cm were attached to each other, and this was sandwiched between metal plates.
The sample was allowed to stand for 3 days in an environment of 0 ° C. and 80%, then taken out, and the adhesion between samples was evaluated as follows.

(Criteria for Evaluation of Surface Sticking Property) ○ No sticking occurs at all △ Can be peeled off without damage, but sticking × When peeled, an image or a protective coating layer is damaged.

<Evaluation of Writability> A ballpoint pen (RB-100, manufactured by Zebra Co., Ltd.) is provided on the image recording surface provided with the protective coating layer.
Of the sample on which the characters were written, the surfaces were rubbed for about 10 seconds immediately after writing between the writing surfaces. Thereafter, the degree of bleeding of the written characters was observed and evaluated as follows.

(Writability Evaluation Criteria) ○ No bleeding Δ Bleed on part of characters × Bleed on entire character.

[0050]

[Table 1]

As is clear from Table 1, the water-based polyurethane was used as the resin, and the sample of the present invention containing a silicone release agent was superior to the comparative example in all of the scratch resistance, water resistance, adhesiveness, and writing property. You can see that there is. It can be seen that these effects are remarkable when the thickness of the protective coating layer is 1 to 10 μm, and that the maximum effect is obtained when the thickness is 1 to 5 μm. When an oil-type silicone release agent is added, the same effect as in the case of the aqueous emulsion-type silicone release agent can be obtained. There are drawbacks such as aggregation of the type polyurethane resin. From the viewpoints of workability and dispersion stability, use of an aqueous emulsion type silicone release agent is more preferable.

The compounds described in the examples were used as heat-reactive water-based polyurethane resins, Elastron series manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and Takenate W manufactured by Takeda Pharmaceutical Co., Ltd.
B series WB-700, WB-710, WB-72
0, WB-730, WB-920
Even at 00 ° C., the effect of the present invention was recognized.

Example 2 A photographic paper (Konica Color Type QA: manufactured by Konica) was exposed to a sample image, and then subjected to normal development processing to produce a color print photograph. On the other hand, a silicone mold release agent shown in Table 2 was added in an amount shown in Table 2 to a coating solution in which the thermoplastic resin shown in Table 2 was adjusted to a solid content concentration of 20% to prepare a coating solution for protective coating layer. This protective coating layer coating solution is applied to the obtained color print photograph with a wire bar so that the film thickness of the protective coating layer becomes the value shown in Table 2, and then applied in a drying box set at 80 ° C. Dried for 201 minutes and shown in Table 2
Was prepared. The obtained samples were evaluated for the five types of evaluations performed in Example 1 and the following image storability. The results are shown in Table 2.

<Preservation of Image> After the sample was left in a thermostat at 85 ° C. and 60% for 3 weeks, the degree of image deterioration of the sample image was visually observed. The degree of fading, color bleeding and perspiration was evaluated on the following three scales.

(Evaluation Criteria for Image Preservability) ○ Less fading, sweating, and color bleeding Δ Fairly fading, sweating, and color bleeding × Notable fading, sweating, and color bleeding.

[0056]

[Table 2]

As is apparent from Table 2, the samples of the present invention containing polyurethane as the resin and containing a silicone release agent were all comparative examples in terms of scratch resistance, water resistance, adhesiveness, writing properties and image storability. You can see that it is superior to It can be seen that these effects are remarkable when the thickness of the protective coating layer is 1 to 10 μm, and that the maximum effect is obtained when the thickness is 1 to 5 μm. For the same reason as in Example 1, it is preferable to use an aqueous emulsion type silicone release agent.

The compounds described in the examples were obtained by using a heat-reactive aqueous polyurethane resin, Elastron series manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Takenate W manufactured by Takeda Pharmaceutical Co., Ltd.
B series WB-700, WB-710, WB-72
0, WB-730, WB-920
Even at 00 ° C., the effect of the present invention was recognized.

[0059]

As can be seen from the above examples, the information recording material of the present invention is excellent in scratch resistance, water resistance, adhesive resistance, writing properties and image storability, is inexpensive and has high added value. Become.

Continued on the front page (51) Int.Cl. ⁶ identification code FI G03C 1/76 501 B41M 5/26 H

Claims (3)

[Claims] 1. An information recording material having at least one image carrying layer mainly composed of a hydrophilic polymer on a support, wherein a heat-reactive water-based polyurethane resin or a heat An information recording material comprising a plastic water-based polyurethane resin and a protective coating layer containing a silicone release agent. 2. The information recording material according to claim 1, wherein said silicone release agent is an aqueous emulsion. 3. The protective coating layer has a thickness of 1 μm or more and 10 μm or more.
The information recording material according to claim 1, wherein the thickness is not more than μm.