JPH06340185A - Heat-sensitive recording type transparent recorded body and its manufacture - Google Patents

Abstract

PURPOSE:To be superior in sheet feeding properties and running properties of a recorded body at the time of recording by making use of a heat-sensitive recording device without using a protective sheet and obtain a clear projected image which is free from dirt by adhesion of trash or dust in the case where information such as the image recorded to the recorded body is projected. CONSTITUTION:In a heat-sensitive transfer recording type transparent recorded body, wither an easily slippable coating layer after performance of antistatic treatment or the easily slippable coating layer to which an antistatic agent is added or applied is formed on one surface of a transparent base and a transparent accepting layer accepting dyes transferring away from a thermal transfer sheet by heating is formed on the other surface, wherein a haze value, the coefficient of friction between the transparent accepting surface and rear face and surface resistance of the easily slippable coating surface are taken respectively as at most 7%, 1 or lower, and 1X10<15>OMEGA or lower.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transmissive recording material used in a thermal transfer recording system. More specifically, it does not have a protective sheet and has excellent running properties and high transparency. The present invention relates to a transmissive recording medium of a thermal transfer recording system.

[0002]

2. Description of the Related Art A thermal transfer recording method in which information such as an image is recorded by heating a thermal transfer sheet with a thermal head and transferring a dye or the like carried on the thermal transfer sheet onto a recording medium is quiet in recording. Therefore, the device is small and inexpensive, easy to maintain, and has a short output time. Therefore, it is used as an information recording means in various fields.
In recent years, it is also used as a recording medium used in a projection device such as an overhead projector (OHP).
As a transmissive recording medium used when a transmissive original of this kind is subjected to a thermal transfer recording system, there is disclosed in Japanese Patent Laid-Open No. 29198/1989.
As described in Japanese Patent Laid-Open No. 5-264893 and Japanese Patent Laid-Open No. 1-264893, a transparent receptor for receiving a dye or the like transferred from a thermal transfer sheet on the surface of a sheet-shaped substrate made of polyethylene terephthalate having a thickness of about 100 μm A protective sheet such as synthetic paper, cellulose fiber paper or synthetic resin sheet is provided on the surface opposite to the surface on which the layer is formed and the receiving layer is formed through an adhesive layer so that it can be peeled off. There is.

With respect to the recording medium of the thermal transfer system provided with such a protective sheet, it takes time and effort to peel off the protective sheet when projecting a document, and it has been desired to develop a recording medium without the protective sheet. . However, in a recording medium that does not use a protective sheet, when recording information such as an image using a thermal recording device or the like, the recording medium set in superposition may not be fed or a plurality of recording mediums may not be fed. Were fed at the same time and jammed in the device, and the running property was poor.

Therefore, a recording medium without a protective sheet has been used in which the surface of the recording medium has been sandblasted or matted to improve the paper feeding and running properties of the recording medium.

[0005]

However, in the conventional recording medium, the transparency of the recording medium itself is remarkably lowered due to sandblasting, matting, etc., and the information such as an image recorded on the recording medium by the projection device is recorded. There is a problem that a clear projected image cannot be obtained when projected.

The present invention solves the above-mentioned drawbacks of the prior art, and relates to a transmissive recording material which does not use a protective sheet, the paper feeding property of the recording material when recording using a thermal recording device and the like. An object of the present invention is to provide a transmissive recording material of a thermal transfer recording system which is excellent in running property and which can clearly project information such as an image recorded on the recording material.

[0007]

The inventors of the present invention have arrived at the present invention as a result of extensive studies in view of such a situation. That is, the transmissive recording material of the thermal transfer recording system of the present invention comprises a transparent base material, a transparent receiving layer provided on one surface of the base material, and a transparent receiving layer for receiving a dye transferred from a thermal transfer sheet by heating, A transparent slippery coating layer provided on the other surface of the substrate, having a haze value of 7% or less, a friction coefficient between the transparent receiving surface and the back surface of 1 or less, and a surface resistance of the slippery coating surface of 1 It is characterized in that it is × 10 ¹⁵ Ω or less. Further, in the method for producing a transmissive recording medium of the thermal transfer recording system which is the second invention, at least one surface of the transparent substrate is subjected to an antistatic treatment, and one surface subjected to the antistatic treatment is transparent and easy to slide. A transparent coating layer is formed on the other surface to receive the dye transferred from the thermal transfer sheet by heating. The haze value is 7% or less, and the friction coefficient between the transparent receiving surface and the back surface is 1 or less. The feature of the present invention is to produce a transmissive recording material of a thermal transfer recording system in which the surface resistance of the slippery coating surface is 1 × 10 ¹⁵ Ω or less.

The recording medium of the present invention comprises a transparent base material and a transparent receiving layer provided on one surface of the base material, and as a sheet or film material constituting the transparent base material, polyethylene, polypropylene, Polyvinyl chloride, polyvinyl alcohol, polyethylene terephthalate, polyethylene naphthalate, polycyclohexane terephthalate, polycarbonate, nylon, polystyrene, ethylene vinyl acetate copolymer and the like can be mentioned. Among them, polyethylene terephthalate is a sheet or film in terms of strength and heat resistance. preferable. As these sheets or films, those having high transparency are used, and those having a haze value of preferably 5% or less, more preferably 3% or less.

The thickness of the transparent substrate is 25 to 200 μm, preferably about 75 to 150 μm. Further, the transparent substrate, the purpose of the present invention, in particular, within the range not impairing the transparency of the substrate, if necessary, cleaning, etching, corona discharge,
Treatments such as active energy ray irradiation, dyeing, printing, easy adhesion treatment, antistatic treatment and the like may be performed.

The resin constituting the transparent, slippery coating layer formed on the back surface of the transmissive recording medium of the present invention is a fluorine-based resin such as vinylidene fluoride-tetrafluoroethylene copolymer, ethyl cellulose, ethyl hydroxyethyl cellulose. Cellulosic resins such as hydroxypropylmethylcellulose, polymethylmethacrylate-dimethylsiloxane copolymer, and the like. The transparent, slippery coating layer is formed by dissolving these resins in water, trichloroethylene, a mixed solution of toluene / ethanol, a solvent such as methyl ethyl ketone, and coating the transparent substrate so that the film thickness becomes 1 to 100 μm. Can be formed.

Further, in the present invention, by adding or applying an antistatic agent or the like to the transparent slippery coating layer, the friction coefficient of the recording medium is further lowered and the surface resistance of the slippery coating surface is reduced. Can be lowered.

Antistatic agents that can be added or applied to the transparent, slippery coating layer of the present invention include polyoxyethylene alkylamines, polyoxyethylene alkylamides, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, Nonionic surfactants such as glycerin fatty acid ester and sorbitan fatty acid ester, anionic surfactants such as alkyl sulfonate, alkylbenzene sulfonate, alkyl sulfate, and alkyl phosphate, quaternary ammonium chloride, quaternary ammonium sulfate, quaternary Cationic surfactants such as primary ammonium nitrate, amphoteric surfactants such as alkyl betaine type, alkyl imidazoline type, alkyl alanine type, fluorine type surfactants, or Polyvinyl benzyl type cation, a conductive resin such as polyacrylic acid type cation, and the like, may be used in combination of two or more of these antistatic agents.

On the other hand, when the slippery coating layer is formed after the surface of the transparent substrate is subjected to the antistatic treatment, the slippery coating layer is not added or coated with an antistatic agent or the like, It is possible to obtain a recording medium having a low surface resistance on the slippery coating surface. In the present invention,
As the antistatic treatment, for example, a method of kneading an antistatic agent or the like into a transparent base material, coating the surface of the transparent base material with an antistatic agent or the like, or performing a treatment such as corona treatment on the transparent base material surface, etc. Is mentioned. Among these, a material in which an antistatic agent or the like is coated on the surface of a transparent substrate has the most antistatic effect and is preferable. In the present invention, the surface of the transparent base material may be subjected to an antistatic treatment and an easily coating layer containing an antistatic agent may be formed. Further, a releasing agent, a lubricant, a filler and the like may be added to the transparent, slippery coating layer together with the resin for the purpose of further reducing the friction coefficient of the recording medium. further,
The slippery coating layer can also be formed by adding a cross-linking agent described below and curing it with heat or active energy rays.

In the heat-sensitive transfer recording type transmissive recording material of the present invention, the coefficient of friction between the transparent receiving surface and the back surface must be 1 or less, preferably 0.5 or less. . This is because when the coefficient of friction exceeds 1, when recording information such as an image using a thermal recording device or the like, the recording mediums set in superposition are not fed or a plurality of recording mediums are not fed. This is because the sheets are fed at the same time and jammed in the apparatus, and the running property of the recording medium in the apparatus is reduced.

The recording medium of the present invention has a haze value of 7
% Or less, it is necessary to have transparency,
It is preferably 5% or less, more preferably 4% or less. This is because when the haze value exceeds 7%, the transparency of the recording medium is impaired, and the sharpness of the projected image when the information such as the image recorded on the recording medium is projected using the projection device is impaired. Is.

Further, in the present invention, the surface resistance of the slippery coating surface is required to be 1 × 10 ¹⁵ Ω or less, preferably 1 × 10 ¹² Ω or less. This is because when the surface resistance exceeds 1 × 10 ¹⁵ Ω, the recording media set in layers are stuck to each other due to static electricity, making it difficult for them to be fed, and dust and dirt tend to adhere to the recording media. This is because the sharpness of the image may be impaired.

The transparent receiving layer of the recording medium of the present invention is a layer which develops a color by receiving the dye transferred from the thermal transfer sheet, and the material constituting the transparent receiving layer is a dye dyeing property. The material is not particularly limited as long as it is excellent, but a material excellent in dyeing property of a sublimable dye capable of easily performing gradation recording of full color recording is preferable. Such materials include polyester resins, polyacrylic ester resins, polycarbonate resins, polyvinyl acetate resins, styrene acrylate resins, resins having ester bonds such as vinyltoluene acrylate resins, resins having urethane bonds such as polyurethane resins, Resins having amide bonds such as polyamide resins (nylon), resins having urea bonds such as urea resins, polycaprotactic resins, styrene resins, polyvinyl chloride resins, vinyl chloride-vinyl acetate copolymers, polyacrylonitrile resins, etc. Examples of the resin include a resin having a highly polar bond, and a mixture or copolymer thereof.

Further, as the material constituting the transparent receiving layer, a dye receiving resin is cross-linked with a thermosetting crosslinking agent such as amino-modified silicone and epoxy-modified silicone, isocyanate and polyol, and the dye-receiving resin and active material. It is possible to use a composition in which a composition containing a cross-linking agent curable with energy rays is applied on a substrate and then cured with active energy rays, and the like. Above all, it is preferable to use the one cured with active energy rays from the viewpoint of productivity and performance. Specifically, the release agent is added in an amount of 0.01 to 100% by weight with respect to 100% by weight of a mixture composed of 40 to 95% by weight of a polyester resin as a dye receiving resin and 60 to 5% by weight of a crosslinking agent curable by active energy rays. The thing which hardened the composition formed by 30 weight part with an active energy ray is mentioned. The transparent receiving layer comprising these compositions easily dyes a sublimable disperse dye, has excellent stability, and has very good gloss retention after recording.

The polyester resin suitable as the dyeing resin constituting the transparent receiving layer of the present invention is a linear thermoplastic polyester resin obtained by polycondensation of a dicarboxylic acid and a diol, and has a reactive double bond. Examples thereof include unsaturated polyester resins obtained by polycondensation of unsaturated polybasic acids and polyhydric alcohols. Among them, a linear thermoplastic polyester resin obtained by polycondensation of at least one dicarboxylic acid and at least one diol, having a molecular weight of 2000 to 40,000 and a crystallinity of 1% or less is soluble in an organic solvent. In terms of easiness of dyeing and light resistance, it is preferable.

Examples of the dicarboxylic acid constituting the linear thermoplastic polyester resin include terephthalic acid, isophthalic acid,
Naphthalenedicarboxylic acid, diphenyl ether-4,4
-Dicarboxylic acid, glutaric acid, adipic acid, sebacic acid, oxalic acid, succinic acid, or ester-forming derivatives thereof, and the like. Examples of the diol include ethylene glycol, propylene glycol, triethylene glycol, butanediol, diethylene glycol, neopentyl. Examples thereof include glycol, cyclohexanedimethanol, bisphenol A-ethylene oxide adduct, and 2,2-bis (4-hydroxyphenyl) propane.

Specific examples of the linear thermoplastic polyester resin obtained by polycondensation of at least one dicarboxylic acid and at least one diol include terephthalic acid / isophthalic acid / ethylene glycol / neopentyl glycol. Polyester resin, other, terephthalic acid / isophthalic acid / ethylene glycol / bisphenol A-ethylene oxide adduct, terephthalic acid /
Isophthalic acid / ethylene glycol / 1,6-hexanediol, terephthalic acid / isophthalic acid / sebacic acid /
Examples thereof include polyester resins obtained from ethylene glycol / neopentyl glycol, terephthalic acid / sebacic acid / ethylene glycol / neopentyl glycol, terephthalic acid / isophthalic acid / adipic acid / ethylene glycol / neopentyl glycol.
Further, these linear thermoplastic polyester resins may be used alone or in combination of two or more kinds. Particularly when two or more polyester resins are used in combination,
It is preferable for improving the stability against light, heat, water and the like.

Specific examples of the unsaturated polyester resin obtained by polycondensation of an unsaturated polybasic acid having a reactive double bond and a polyhydric alcohol include maleic anhydride / phthalic anhydride / propylene glycol. Obtained from maleic acid / isophthalic acid / propylene glycol, maleic acid / fumaric acid / isophthalic acid / 1,3-butanediol, maleic acid / isophthalic acid / neopentyl glycol, maleic anhydride / tetrahydrophthalic anhydride / dipropylene glycol Unsaturated polyester resins may be mentioned.

In the transparent receiving layer of the present invention, it is preferable to incorporate a crosslinking agent in order to impart sufficient blocking resistance to the receiving layer and cure the dyeing resin composition with active energy rays or the like. In this case, the content of the crosslinking agent is preferably in the range of 5 to 60% by weight, more preferably 6 to 45% by weight, based on the total amount of the dyeing resin. This is because if the content of the crosslinking agent is less than 5% by weight, blocking between the recording medium and the thermal transfer sheet is likely to occur during thermal transfer, and conversely 6
This is because if the amount exceeds 0% by weight, the ratio of the dyeing resin decreases and a sufficient dyeing density cannot be obtained.

The cross-linking agent used in the present invention preferably has at least one polyfunctional monomer in consideration of the curing of the resin composition and the blocking resistance of the recording medium. When ultraviolet rays are used as the rays, monomers having an acryloyloxy group or a methacryloyloxy group as the polymerizable group of the crosslinking agent are preferred.

As the monomer having a (meth) acryloyloxy group, a polyether acrylate or polyether methacrylate type (hereinafter, "acrylate or metal relate" is simply abbreviated as "(meth) acrylate"), polyester (meth). Monomers such as acrylate-based, polyol (meth) acrylate-based, epoxy (meth) acrylate-based, amidourethane (meth) acrylate-based, urethane (meth) acrylate-based, spiroacetal (meth) acrylate-based, polybutadiene (meth) acrylate-based, An oligomer can be mentioned. Specific examples of such monomers and oligomers include 1,2,6-hexanetriol /
Polyether (meth) acrylate synthesized from propylene oxide / acrylic acid, trimethylolpropane / propylene oxide / acrylic acid; adipic acid / 1,
Polyester (meth) acrylate synthesized from 6-hexanediol / acrylic acid, succinic acid / trimethylolethane / acrylic acid; triethylene glycol diacrylate, hexapropylene glycol diacrylate, neopentyl glycol diacrylate, 1,4-
Butanediol dimethacrylate, 2-ethylhexyl acrylate, tetrahydrofurfuryl acrylate,
2-hydroxyethyl methacrylate, ethylcarbitol acrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, 2,2-bis (4-
Acryloyloxydiethoxyphenyl) propane,
(Meth) acrylate or polyol (meth) acrylate such as 2,2-bis (4-acryloyloxypropoxyphenyl) propane; diglycidyl etherified bisphenol A / acrylic acid, diglycidyl etherified polybisphenol A / acrylic acid, triglycidyl Epoxy (meth) acrylates such as etherified glycerin / acrylic acid; γ-butyrolactone / N-methylethanolamine / bis (4-isocyanatocyclohexyl) methane / 2-hydroxyethyl acrylate, γ-
Butyrolactone / N-methylethanolamine / 2,6
Amidourethane (meth) acrylates such as tolylene diisocyanate / tetraethylene glycol / 2-hydroxyethyl acrylate; urethane acrylates such as 2,6-tolylene diisocyanate diacrylate, isophorone diisocyanate diacrylate, hexamethylene diisocyanate diacrylate; Diari Spiroacetal acrylate synthesized from redene pentaerythritol / 2-hydroxyethyl acrylate;
Examples thereof include acrylated polybutadiene synthesized from epoxidized butadiene / 2-hydroxyethyl acrylate. These monomers and oligomers are used alone or as a mixed system of two or more kinds.

In the present invention, the monomer or oligomer as a particularly preferred crosslinking agent is represented by the following general formula (1)

[0027]

[Chemical 1]

[0028] (wherein, m1 is an integer from 1 to 4, X is at least three general _{formula: CH 2 = CH-COO-} R 1 -
(In the formula, R ₁ represents a single bond, an alkylene group having 1 to 8 carbon atoms or a polyoxyalkylene group having an alkylene group having 1 to 8 carbon atoms.), And the remainder is a carbon atom. 1-8C alkyl group, a hydroxyl group, an amino group, the formula :-( OR _{2) m2} -H (wherein, R ₂ is C 1 -C
~ 8 represents an alkylene group, m2 is a positive integer. )
A group represented by the formula: — (OR ₂ ) _{m 2} —OH (in the formula, R ₂ represents an alkylene group having 1 to 8 carbon atoms, and m 2 is a positive integer) or a group represented by the formula: -(OOC
R ₂ ) _{m 2} —H (in the formula, R ₂ represents an alkylene group having 1 to 8 carbon atoms, and m ₂ is a positive integer). ), Such as dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol pentaacrylate, tripentaerythritol hexaacetylate, tripentaerythritol heptaacrylate, the following general formula ( 2)

[0029]

[Chemical 2]

[0030] (wherein, m3 is from 1 to 10 a positive integer, X is optionally -0H or -OCOCH = CH _2.) Poly bisphenol A polyacrylates represented by, for example, diglycidyl ethers of bisphenol A diacrylate, Epicoat # 1001 (Shell: m3 =
Diacrylate of 3) or the following general formula (3)

[0031]

[Chemical 3]

(In the formula, X ₁ , X ₂ , ..., X _m4 are the same or different alkylene groups having 6 or less carbon atoms or those having a structure in which one hydrogen atom thereof is substituted with a hydroxyl group, m4 is an integer of 0 to 5),
For example, 2,2-bis (4-acryloyloxydiethoxyphenyl) propane, 2,2-bis (4-acryloyloxytriethoxyphenyl) propane, 2,2-bis (4-acryloyloxydipropoxyphenyl) propane, etc. Particularly, when ultraviolet rays are used as the active energy rays, they are very preferable because they have very good quick-drying property in the air.

Further, in the present invention, blocking resistance (sticking resistance) between the recording medium and the thermal transfer sheet
In order to further improve the above, it is preferable to add a release agent to the receiving layer or form a release agent layer on the surface of the receiving layer.
Examples of the release agent used include silicon-based surfactants, fluorine-based surfactants, graft polymers having polyorganosiloxane as a trunk or branch, and compounds capable of having a silicon-based or fluorine-containing crosslinked structure. These release agents can be used alone or in combination. The compounding amount of the release agent is in the range of 0.01 to 30 parts by weight, preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the total amount of the dyeing resin and the crosslinking agent. As the silicon-based surfactant, a compound in which polydimethylsiloxane and polyoxyalkylene are blocked (may be slightly modified with other functional groups) is effective, and CH ₃ −
(Si0) 1 / 2-group and -OR- group (R: alkylene residue) in the ratio of 1/10 to 1 / 0.1, preferably in the range of 1/5 to 1 / 0.2 However, it is effective in improving blocking resistance, leveling property and dyeing density.

Specific examples of such a silicon-based surfactant include compounds represented by the following general formulas (4) and (6).

[0035]

[Chemical 4]

(Where P is the following general formula (5)

[0037]

[Chemical 5]

Where n1 and n2 are positive integers, x and y are 0 or positive integers, and the formula: 1/10 ≦
(2n1 + 1) / (n2x + n2y) ≦ 10 is satisfied.
R ₃ represents hydrogen, an alkyl group, an acyl group or an aryl group. )

[0039]

[Chemical 6]

(Where Q is the following general formula (7)

[0041]

[Chemical 7]

Where n3 and n4 are positive integers, x and y are 0 or positive integers, and the formula: 1/10 ≦
(2n3 + n4 + 1) / (n4x + n4y) ≦ 10 is satisfied. z is 0 or an integer of 1 to 5. R ₄ is −
Si (CH ₃ ) ₃ , hydrogen, an alkyl group, an acyl group or an aryl group is represented, and R ₅ is a hydrogen, an alkyl group, an acyl group or an aryl group. ) As the fluorine-based surfactant, any nonionic, anionic, cationic or amphoteric fluorine-based surfactant can be used as long as it is soluble in a mixture of a dyeing resin and a crosslinking agent and exhibits blocking resistance. One or more surfactants can be used. Of these, nonionic surfactants are preferable in view of improving the leveling property and blocking resistance of the recording medium.

Specific examples of the fluorine-containing surfactant used in the present invention include anionic surfactants such as fluoroalkoxy polyfluoroalkyl sulfuric acid ester, fluorocarbon sulfonate, fluorocarbon carboxylate, N-fluoroalkyl. Sulfonamide alkylamine quaternary ammonium salt, N-fluoroalkylsulfonamide alkylamine salt, N-fluoroalkylamide alkylamine quaternary ammonium salt, N-fluoroalkylamide alkylamine salt, N-fluoroalkylsulfonamide alkylhalomethyl ether Cationic surfactants such as quaternary ammonium salts, fluorocarbon sulfonamides, fluorocarbon amino sulfonamides, fluorocarbon carboxy sulfonamides, fluorocarbons Hydroxysulfonamide, Fluorocarbon sulfonamide ethylene oxide adduct, Fluorocarbon hydroxysulfonamide sulfuric acid ester, Fluorocarbon amino acid amide, Fluorocarbon amide, Fluorocarbon hydroxyacid amide, Fluorocarbon amide ethylene oxide addition condensation product, Fluorocarbon hydroxyacid amide sulfate, Fluorocarbon Sulfonic acid, fluorohydrocarbon carboxylic acid, fluorohydrocarbon alkyl ester, fluorohydrocarbon alkyl ether, fluorohydrocarbon carboxyalkyl ester, fluorohydrocarbon hydroxyamide,
Examples thereof include nonionic surfactants such as fluorohydrocarbon alkyl ester sulfuric acid and fluoroalkyldiamine, and amphoteric surfactants such as alkylamine having a betaine-type fluorocarbon sulfonamide bond and alkylamine having a betaine-type fluorocarbon acid amide bond.

As the graft polymer having a polyorganosiloxane as a trunk or a branch, a graft polymer having a polymer or a copolymer obtained by vinyl polymerization, polycondensation, ring-opening polymerization or the like as a trunk and a polyorganosiloxane as a branch is first used. Can be mentioned. Examples of these graft polymers include methacryloyloxy groups at one end,
Alkyl (meth) acrylate, (meth) acrylic acid, derivatives of (meth) acrylic acid having functional groups, vinyl acetate, vinyl chloride, (meth) acrylonitrile to polysiloxane (macromonomer) to which vinyl group or mercapto group is added , At least one of the monomers such as styrene
A graft polymer obtained by polymerizing a seed, a graft polymer obtained by reacting a dicarboxylic acid and a diol with a macromonomer having two hydroxyl groups or carboxyl groups near the end of polysiloxane, and two graft polymers near the end of polysiloxane. Examples thereof include graft polymers obtained by reacting a macromonomer having a hydroxyl group or a carboxyl group with a diepoxy or diisocyanate compound.

Examples of other graft polymers include graft polymers having a polyorganosiloxane as a backbone and a polymer or copolymer obtained by vinyl polymerization, polycondensation, ring-opening polymerization or the like as a branch. Examples of these graft polymers include organosilanes and silanes having a vinyl polymerizable group, such as 3-methacryloxypropyldimethoxymethylsilane, methylvinyldimethoxysilane, and ethylvinyldiethoxysilane, which are condensed to form side chains with methacryloyl. A polysiloxane having an oxy group is synthesized, and then the monomer and alkyl (meth) acrylate, (meth) acrylic acid, a derivative of (meth) acrylic acid having a functional group, vinyl acetate,
Graft polymer obtained by polymerizing at least one kind of monomer such as vinyl chloride, (meth) acrylonitrile and styrene, and glycidyl on a side chain by condensing organosilane and diethoxy-3-glycidoxypropylmethylsilane A graft polymer obtained by synthesizing a polysiloxane having a group, and then reacting this with (meth) acrylic acid to obtain a monomer containing a (meth) acryloyloxy group, and then polymerizing the monomer. A graft polymer obtained by synthesizing a polysiloxane having a hydroxyl group in a side chain by condensing organosilorane and hydroxyethylmethyldimethoxysilane and then polycondensing a dicarboxylic acid and the diol can be mentioned.

When synthesizing the polysiloxane which becomes the trunk or branch of the graft polymer, a cyclic silane, particularly a cyclic dimethylpolysiloxane having 3 to 8 repeating units is used as a main raw material, and trimethylmethoxysilane or trimethylethoxysilane is used as a molecular weight modifier. For example, a silane compound having one alkoxy group in one molecule may be used to polymerize at 70 to 150 ° C. using a functional group-containing silane and a strong acid or strong base as a catalyst.

By blending these graft polymers in the image receiving layer, the blocking resistance with the transfer sheet is improved and the dark fading property of the dyed image receiving layer is also improved. The compounding amount is a mixture 1 of the dyeing resin and the crosslinking agent.
0.01 to 30 parts by weight is preferable with respect to 00 parts by weight,
The range is more preferably 0.05 to 10 parts by weight. This is because if the blending amount is less than 0.01 parts by weight, the improvement in blocking resistance is lessened and the dark discoloration property is not improved. On the contrary, if the blending amount exceeds 30 parts by weight, the image receiving layer cured by active energy rays is opalescent. This is because the dyeing density decreases as the color changes.

The graft polymer containing polyorganosiloxane has a molecular weight of 1,000 from the viewpoint of dark fading.
The above is preferable. Further, the weight ratio of the polyorganosiloxane component and the polymer or copolymer other than polyorganosiloxane is preferably polyorganosiloxane component / polymer or copolymer = 95/5 to 10/90, and more preferably Preferably 90/10 to 20/80
Is the range. If this ratio exceeds 95/5, the dark fading property tends to become poor, and conversely, if it is less than 10/90, the dark fading property tends to become poor as well as the blocking resistance decreases.

As the thermal-crosslinking type or active energy ray-crosslinking type releasing agent capable of forming a silicon type or fluorine-containing type crosslinking structure, in the case of silicon type, a silicon type compound which causes an addition reaction and a silicon type compound which causes a radical reaction are used. ,
Examples include silicon compounds that cause a condensation reaction.
Examples of the silicon compound that causes the addition reaction include a combination of a silicone having a vinyl group and a silicone having a —SiH group, a combination of an amino-modified silicone and an epoxy-modified silicone, and if necessary, a catalyst such as a platinum compound may be used. You may use together. As a silicon compound that causes a radical reaction, there is a combination of a silicone having a vinyl group and a silicone having a methylsilane.
An organic peroxide may be used as a polymerization initiator. Examples of the silicone compound that causes a condensation reaction include a silicone having an alkoxy group, a silicone having a silanol group, a combination of a silicone having an alkoxy group and a silicone having a silanol group, a silicone having a silanol group and a silicone having a -SiH group. And a combination of a silicone having a silanol group and a silicone having an aminooxy group.

In the fluorine-containing system, a combination of an epoxy group-containing fluorine-containing compound and an amino group-containing fluorine-containing compound as a fluorine-containing compound that causes an addition reaction, and a carboxylic acid group-containing fluorine-containing compound as a condensation-containing fluorine-containing compound And a fluorine-containing compound containing an amino group.

In order for these silicon-based or fluorine-containing compounds to form a sufficient cross-linked structure, it is necessary to have at least more than 2 functional groups per molecule of the compound, and 2 or less functional groups per molecule. However, even if a high molecular weight substance is formed, a sufficient crosslinked structure cannot be obtained.

Examples of the active energy ray-crosslinking type silicon-containing or fluorine-containing compound include radically polymerizable compounds such as vinyl group, allyl group, methacryloyl group and acryloyl group. When ultraviolet rays are used as the active energy rays, a compound having an acryloyloxy group, which has good polymerizability by ultraviolet rays, is preferable. In order for these active energy ray crosslinkable compounds to have a sufficient crosslinked structure, it is necessary to have at least one polymerizable group per molecule.

In the present invention, when an active energy ray-crosslinking type releasing agent is used, when the resin composition constituting the image receiving layer is cured with the active energy ray, the releasing agent is also cured at the same time. However, when a heat-crosslinking release agent is used, it is necessary to add a heat-curing step in addition to the curing of the resin composition. Therefore, from the viewpoint of productivity, it is preferable to use the active energy ray-crosslinking type release agent.

When a monomer such as tetrahydrofurfuryl acrylate having a high polymer solubility and a low viscosity is used as a cross-linking agent in the production of the recording medium of the present invention, roll coating, bar coating, It is possible to form a transparent receiving layer by coating the resin composition on the surface of the transparent substrate by coating such as blade coating. However, in order to improve the workability of coating work,
Ethyl alcohol, methyl ethyl ketone, resin composition
It is preferable to add a solvent such as toluene, ethyl acetate or dimethylformamide to adjust the coating viscosity to an appropriate level. Thereby, spray coating, curtain coating, flow coating, dip coating and the like can be easily performed.

In the present invention, active energy rays such as electron rays and ultraviolet rays are used to cure the resin composition constituting the transparent receiving layer, but ultraviolet rays are used in consideration of the control of the radiation source. Is preferred. When ultraviolet rays are used as the active energy rays, the photopolymerization initiator is added in an amount of 0.1 to 1 with respect to 100 parts by weight of the mixture of the dyeing resin and the crosslinking agent.
Add 0 parts by weight.

As the photopolymerization initiator used, benzoin, benzoin isobutyl ether, benzyl dimethyl ketal, ethylphenyl glyoxylate, diethoxyacetophenone, 1,1-dichloroacetophenone, 4'-isopropyl-2-hydroxy-2. -Methyl propiophenone, 1-hydroxycyclohexyl phenyl ketone, benzophenone, benzophenone / diethanolamine, 4,4'-bisdimethylaminobenzophenone, 2-methylthioxanthone, tert-butylanthraquinone, carbonyl compounds such as benzyl, tetramethylthiuram monosulfide Sulfur compounds such as tetramethylthiuram disulfide, azo compounds such as azobisisobutyronitrile and azobis-2,4-dimethylvaleronitrile, Down benzoyl peroxide, di -
Peroxide compounds such as tert-butyl peroxide may be mentioned. These compounds can be used alone or in combination of two or more kinds.

Further, in the present invention, an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, fine silica of several μm or less, fine silica, alumina, talc, titanium oxide, etc. are added to the transparent receiving layer according to the purpose. You may mix | blend an inorganic fine particle etc.
The recording material of the present invention can be produced by applying the above resin composition to the surface of a transparent substrate and irradiating with active energy rays. The transparent receiving layer has a film thickness of 0.5 to 100 μm.
Is preferable, and more preferably 1 to 50 μm. When the film thickness is less than 0.5 μm, the dye diffusion reaches saturation on the way and the dyeing density and stability become insufficient. On the contrary, when it exceeds 100 μm, blocking with the thermal transfer sheet is likely to occur during thermal transfer.

[0058]

EXAMPLES The present invention will be further described below with reference to examples. In the examples, the coefficient of friction was obtained by measuring the coefficient of friction between the image receiving surface and the back surface according to JIS-K7125. The haze value is a direct reading haze computer HG manufactured by Suga Test Instruments Co., Ltd.
Measured by M-2DP. The surface resistance of the slippery coated surface was measured by leaving the sample at 23 ° C. and 50% RH overnight and then taking ULTRA HIGH manufactured by RIKEN CHEMICAL INDUSTRIES, LTD.
Measured by MEGOHM METER TR-42. The printer runnability was evaluated using a full color video printer S340 manufactured by Mitsubishi Electric Corporation. The image quality was evaluated by recording an image using a full color video printer S340 manufactured by Mitsubishi Electric Corporation and visually observing an image projected by an overhead projector. The ash test was carried out under the conditions of 23 ° C. and 50% RH, and the receiving surface of the recording medium and the slippery coating layer were overlapped and rubbed 10 times, and then the slippery coated surface was moved to a distance of 1 cm from the ash of cigarette. It was evaluated by the degree of adhesion of ash when brought close to.

Formation of Receptor Layer The composition shown below and a solvent consisting of 400 parts by weight of methyl ethyl ketone and 100 parts by weight of toluene are mixed and prepared, and uniformly coated on the surface of a substrate by a dipping method. Then, irradiate ultraviolet rays from a high pressure mercury lamp in air to obtain a film thickness of 5 to 6 μm.
m transparent receiving layer.

Receptor layer composition terephthalic acid / isophthalic acid / sebacic acid / ethylene 60 parts by weight Polyester resin produced by condensation polymerization of glycol / neopentyl glycol (molecular weight 20000-25000, glass transition temperature 10 ° C.) terephthalic acid / isophthalic acid / Sebacic acid / Ethylene 20 parts by weight Polyester resin prepared by condensation polymerization of glycol / neopentyl glycol / 1,4-butanediol (molecular weight 20000-25000, glass transition temperature 47 ° C) Dipentaerythritol pentaacrylate 10 parts by weight 2, 2-Bis (4-acryloyloxydiethoxyphen 10 parts by weight phenyl) propane 0.1 parts by weight of a silicon-based surfactant represented by the following general formula (8):

[0061]

[Chemical 8]

(Where n3, n4 and x are expressed by the formula: (2n3
+ N4 + 1) / (n4x) = 1.3 is satisfied. ) 1-Hydroxycyclohexyl phenyl ketone 5 parts by weight Examples 1 to 3 Compositions shown in Table 1 on the treated surface of a polyethylene terephthalate film having a thickness of 125 µm (AS-125 manufactured by Diaphoryl Co., Ltd.) having antistatic treatment on one surface. Object A,
Each of B and C was used as shown in Table 2, coated using a Baker type applicator, and dried to form a transparent easy-slip coating layer. Next, a transparent receptive layer was formed on the untreated surface of the substrate to obtain a recording medium. The evaluation results of the obtained recording medium are shown in Table 2.

Comparative Example 1 A transparent receiving layer was formed on the non-treated surface of a 125 μm thick polyethylene terephthalate film (AS-125 manufactured by Diafoil Co., Ltd.) having one surface subjected to antistatic treatment to obtain a recording medium. The evaluation results of the obtained recording medium are shown in Table 2.

COMPARATIVE EXAMPLE 2 A 125 μm thick polyethylene terephthalate film (AS-125 manufactured by Diafoil Co., Ltd.) having antistatic treatment on one surface was treated with polymethylmetallate solution of polymethylmetallate in which Teflon fine particles were dispersed ( Composition J) was applied and dried to form a slippery coating layer. The coated surface had a slight haze and had an uneven appearance. Next, a transparent receiving layer was formed on the non-treated surface of the substrate to obtain a recording medium. The evaluation results of the obtained recording medium are shown in Table 2.

Comparative Examples 3 to 4 Compositions D and E shown in Table 1 were prepared on the treated surface of a polyethylene terephthalate film (AS-125 manufactured by Diaphoryl Co., Ltd.) having a thickness of 125 μm and having one surface subjected to antistatic treatment.
Each was used as shown in Table 2, coated using a baker type applicator, and dried to form a transparent slippery coating layer. Next, a transparent receptive layer was formed on the untreated surface of the substrate to obtain a recording medium. The evaluation results of the obtained recording medium are shown in Table 2.

Examples 4 to 7 Compositions F, G, H and I shown in Table 1 were used as shown in Table 2 on one side of a surface-treated polyethylene terephthalate film having a thickness of 125 μm. It was applied using a Baker type applicator and dried to form a transparent, easily slipping coating layer. Next, a transparent receptive layer was formed on the untreated surface of the substrate to obtain a recording medium. The evaluation results of the obtained recording medium are shown in Table 2.

Comparative Examples 5 to 7 Compositions A, B and C shown in Table 1 were used as shown in Table 2 on one side of a polyethylene terephthalate film having a thickness of 125 μm which was not surface-treated, and the composition was Baker's type. It was applied using an applicator and dried to form a transparent slippery coating layer. Next, a transparent receptive layer was formed on the untreated surface of the substrate to obtain a recording medium. The evaluation results of the obtained recording medium are shown in Table 2. In Table 1, resin a is a copolymer of 80 mol of vinylidene fluoride and 20 mol of tetrafluoroethylene, Elegan 264 is an antistatic agent manufactured by NOF Corporation, and Resist PE132 is manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. It is an antistatic agent.

[0068]

[Table 1]

[0069]

[Table 2]

[0070]

INDUSTRIAL APPLICABILITY According to the present invention, a transparent easy-sliding coating layer is formed on the surface of the transparent substrate opposite to the surface on which the transparent receiving layer is formed. By using a heat-sensitive recording device or the like, a transmissive recording material of a heat-sensitive transfer recording system having a friction coefficient between the back surface and the back surface of 1 or less and a surface resistance of the slippery coating surface of 1 × 10 ¹⁵ Ω or less can be obtained. It is excellent in the paper feeding property and the traveling property of the recording medium at the time of recording, and when the information such as the image recorded on the recording medium is projected, it is possible to project a clear image free from dust and dirt.

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[Procedure amendment]

[Submission date] October 3, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0013

[Correction method] Change

[Correction content]

On the other hand, when the slippery coating layer is formed after the antistatic treatment is applied to the surface of the transparent substrate, the slippery coating layer is not added or coated with an antistatic agent or the like. It is possible to obtain a recording medium having a low surface resistance on the slippery coating surface. In the present invention,
As the antistatic treatment, for example, a method of kneading an antistatic agent or the like into a transparent substrate, coating the surface of the transparent substrate with an antistatic agent, or performing a treatment such as corona treatment on the transparent substrate surface, etc. Is mentioned. Among these, a material in which an antistatic agent or the like is coated on the surface of a transparent substrate has the most antistatic effect and is preferable. In the present invention, the surface of the transparent base material may be subjected to an antistatic treatment and an easily coating layer containing an antistatic agent may be formed. Further, a releasing agent, a lubricant, a filler and the like may be added to the transparent, slippery coating layer together with the resin for the purpose of further reducing the friction coefficient of the recording medium. further,
The slippery coating layer can also be formed by adding a cross-linking agent described below and curing it with heat or active energy rays.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0017

[Correction method] Change

[Correction content]

The transparent receiving layer of the recording medium of the present invention is a layer which develops a color by receiving the dye transferred from the thermal transfer sheet, and the material constituting the transparent receiving layer is a dye dyeing property. The material is not particularly limited as long as it is excellent, but a material excellent in dyeing property of a sublimable dye capable of easily performing gradation recording of full color recording is preferable. Such materials include polyester resins, polyacrylic ester resins, polycarbonate resins, polyvinyl acetate resins, styrene acrylate resins, resins having ester bonds such as vinyltoluene acrylate resins, resins having urethane bonds such as polyurethane resins, Polyamide resin (nylon) or other amide bond resin, urea resin or other urea bond resin, polycaprolactone resin, styrene resin, polyvinyl chloride resin, vinyl chloride-vinyl acetate copolymer, polyacrylonitrile resin, etc. Examples of the resin include a resin having a high bond and a mixture or copolymer thereof.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0018

[Correction method] Change

[Correction content]

Further, as the material constituting the transparent receiving layer, a dye receiving resin is cross-linked with a thermosetting crosslinking agent such as amino-modified silicone and epoxy-modified silicone, isocyanate and polyol, and the dye-receiving resin and active material. A composition obtained by applying a composition containing a crosslinking agent curable with energy rays onto a substrate and then curing the composition with active energy rays can be used. Above all, it is preferable to use the one cured with active energy rays from the viewpoint of productivity and performance. Specifically, the release agent is added in an amount of 0.01 to 100% by weight with respect to 100% by weight of a mixture of 40 to 95% by weight of a polyester resin as a dye receiving resin and 60 to 5% by weight of a crosslinking agent curable by active energy rays. The thing which hardened the composition formed by 30 weight part with an active energy ray is mentioned. The transparent receiving layer comprising these compositions easily dyes a sublimable disperse dye, has excellent stability, and has very good gloss retention after recording.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0049

[Correction method] Change

[Correction content]

As the thermal-crosslinking type or active energy ray-crosslinking type releasing agent capable of forming a silicon type or fluorine-containing type crosslinking structure, in the case of a silicon type, a silicon type compound which causes an addition reaction and a silicon type compound which causes a radical reaction are used. , A silicon compound that causes a condensation reaction, and the like. Examples of the silicon compound that causes the addition reaction include a combination of a silicone having a vinyl group and a silicone having a —SiH group, a combination of an amino-modified silicone and an epoxy-modified silicone, and if necessary, a catalyst such as a platinum compound may be used. You may use together. Examples of the silicon compound that causes a radical reaction include a combination of a silicone having a vinyl group and a silicone having a methylsilane, and an organic peroxide may be used as a polymerization initiator.
Examples of the silicone compound that causes a condensation reaction include a silicone having an alkoxy group, a silicone having a silanol group, a combination of a silicone having an alkoxy group and a silicone having a silanol group, a silicone having a silanol group and a silicone having a -SiH group. combination,
There is a combination of a silicone having a silanol group and a silicone having an aminooxy group.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Name of item to be corrected] 0058

[Correction method] Change

[Correction content]

[0058]

EXAMPLES The present invention will be further described below with reference to examples. In the examples, the coefficient of friction was obtained by measuring the coefficient of friction between the image receiving surface and the back surface according to JIS-K7125. The haze value is a direct reading haze computer HG manufactured by Suga Test Instruments Co., Ltd.
Measured by M-2DP. The surface resistance of the slippery coated surface was measured by leaving the sample at 23 ° C. and 50% RH overnight and then taking ULTRA HIGH manufactured by RIKEN CHEMICAL INDUSTRIES, LTD.
Measured by MEGOHM METER TR-42. The printer runnability was evaluated using a full color video printer S340 manufactured by Mitsubishi Electric Corporation. The image quality was evaluated by recording an image using a full color video printer S340 manufactured by Mitsubishi Electric Corporation and visually observing an image projected by an overhead projector. The ash test was carried out under the conditions of 23 ° C. and 50% RH, and the receiving surface of the recording medium and the slippery coating surface were overlapped and rubbed 10 times, and then the slippery coating surface was moved to a distance of 1 cm from the ash of the cigarette. It was evaluated by the degree of adhesion of ash when brought close to.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0062

[Correction method] Change

[Correction content]

Examples 1 to 3 Composition A shown in Table 1 was applied to the treated surface of a 125 μm thick polyethylene terephthalate film (AS-125 manufactured by Diafoil Co., Ltd.) having one surface subjected to antistatic treatment.
Each of B and C was used as shown in Table 2, coated using a Baker type applicator, and dried to form a transparent easy-slip coating layer. Next, a transparent receptive layer was formed on the untreated surface of the substrate to obtain a recording medium. The evaluation results of the obtained recording medium are shown in Table 2.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0065

[Correction method] Change

[Correction content]

Comparative Examples 3 to 4 Compositions D and E shown in Table 1 were formed on the treated surface of a polyethylene terephthalate film having a thickness of 125 μm (AS-125 manufactured by Diafoil Co., Ltd.) having one surface subjected to antistatic treatment.
Each was used as shown in Table 2, coated using a baker type applicator, and dried to form a transparent slippery coating layer. Next, a transparent receptive layer was formed on the untreated surface of the substrate to obtain a recording medium. The evaluation results of the obtained recording medium are shown in Table 2.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0069

[Correction method] Change

[Correction content]

[0069]

[Table 2]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazuhiko Sofuku 20-1 Miyukicho, Otake-shi, Hiroshima Mitsubishi Rayon Co., Ltd. Central Research Laboratory

Claims (4)

[Claims] 1. A transparent substrate, a transparent receiving layer provided on one surface of the substrate for receiving a dye transferred from a thermal transfer sheet by heating, and a transparent slippery layer provided on the other surface of the substrate. A coating layer, a haze value of 7% or less, a friction coefficient between the transparent receiving surface and the back surface of 1 or less, and a surface resistance of the slippery coating surface of 1 × 10 ¹⁵ Ω or less. A transmissive recording material of a thermal transfer recording system. 2. The heat-sensitive transfer recording type transmissive recording medium according to claim 1, wherein the transparent slippery coating layer contains at least one of a fluorine resin and a cellulose resin. 3. The heat-sensitive transfer recording type transmissive recording medium according to claim 1, wherein the transparent slipping coating layer contains an antistatic agent. 4. An antistatic treatment is applied to at least one surface of a transparent substrate, a transparent slippery coating layer is formed on one side subjected to the antistatic treatment, and the other surface is transferred from a thermal transfer sheet by heating. A haze value of 7% or less, a coefficient of friction between the transparent receiving surface and the back surface of 1 or less, and a surface resistance of the lubricious coating surface of 1 × 10 ¹⁵ Ω or less are formed. A method for producing a transmissive recording medium of a certain thermal transfer recording system.