JP3181631B2 - Sublimation type thermal transfer recording system - 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 medium used in a sublimation type thermal transfer recording system, and more particularly, to a recording medium having a high degree of whiteness.

[0002]

2. Description of the Related Art A sublimation-type thermal transfer recording system has features such as quiet sound, compact and inexpensive apparatus, easy maintenance, and short output time. Since it is used, high gradation recording can be easily performed by continuously changing the amount of heat generation energy, and high density and high resolution can be obtained. Therefore, it is particularly advantageous for obtaining a full-color hard copy as compared with other recording methods, and is widely used as a recording method for a color printer, a video printer, and the like.

Conventionally, an image receiving layer of a recording medium of this recording system is cured by a cross-linking agent which can cure a dyeing resin mainly composed of a polyester resin with an active energy ray as disclosed in JP-A-1-42284. What has been used has been used. In this, a benzotriazole-based ultraviolet absorber is added to the image receiving layer in order to improve the light fastness of the recorded image, but in this case, the image receiving layer becomes yellowish and the substrate has a high whiteness. Even when paper, synthetic paper, plastic film, or the like is used, the completed recording medium has a disadvantage that the whiteness is low.

[0004] At present, consumer video printers are becoming widespread in the market, and users prefer image receiving paper having a high degree of whiteness of the background as compared with photographs. As means for increasing the whiteness of a recording medium, Japanese Patent Application Laid-Open No. Sho.
As disclosed in JP-A No. 3 (KOKAI) No. 3, a method of kneading a white pigment such as titanium oxide into an image receiving layer or adding a fluorescent whitening agent is known, but the method is cured with an active energy ray such as ultraviolet rays. In the case of the image receiving layer, the white pigment is yellowed by strong energy or the fluorescent whitening agent is decomposed, so that the image receiving layer is yellowed.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to improve the above-mentioned disadvantages of the prior art, and to provide a sublimation having a high whiteness even after the image receiving layer is cured by an active energy ray and having excellent light fastness of a recorded image. The object of the present invention is to obtain a recording medium of the thermal transfer recording type.

[0006]

The object of the present invention is to solve the problem of the substrate surface.
100 parts by weight of a mixture comprising 40 to 95% by weight of a polyester resin and 60 to 5% by weight of a crosslinking agent curable by active energy rays, and at least one kind of a release agent of 0.01 to 50% by weight.
30 parts by weight and represented by the following chemical formula (8) or (9)
At least one benzophenone UV absorber
The problem is solved by an image receiving layer coated with a resin composition comprising 0 parts by weight and 1 to 10 parts by weight of at least one kind of hindered amine light stabilizer , and cured by an active energy ray.

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Hereinafter, the present invention will be described in detail. Examples of the polyester resin used in the present invention include a linear thermoplastic polyester resin obtained by polycondensation of a dicarboxylic acid and a diol or / and an unsaturated polybasic acid having a reactive double bond and a polyhydric alcohol. There is an unsaturated polyester resin obtained by the condensation polymerization of, among others, a molecular weight of 2,000 obtained by the condensation polymerization of at least one or more dicarboxylic acids and at least one or more diols.
A linear thermoplastic polyester resin having a crystallinity of 1% or less, which is a linear thermoplastic polyester resin having a crystallinity of 1% or less, is preferable in terms of solubility in an organic solvent, ease of dyeing, and excellent light resistance.

The blending amount of the polyester resin is 40 to 95% by weight of the total amount with the crosslinking agent. If the amount is less than 40% by weight, the dyeing concentration of the sublimable disperse dye does not become high under low energy conditions. When the compounding amount exceeds 95% by weight, the amount of the crosslinking agent decreases, the non-blocking property with the color sheet (transfer paper) coated with the sublimable disperse dye becomes poor, and the sublimable disperse dye easily dyeable resin composition is used. The recording medium and the color sheet that have been applied and cured with the active energy ray cause blocking (sticking) during thermal transfer. The preferred amount is in the range of 55% to 94% by weight.

Specific examples of the linear thermoplastic polyester resin obtained by condensation polymerization of at least one or more dicarboxylic acids and at least one or more diols include terephthalic acid / isophthalic acid / ethylene glycol / neopentyl glycol. Obtained 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 / ethylene glycol / neopentyl glycol,
Examples include polyester resins obtained from terephthalic acid / sebacic acid / ethylene glycol / neopentyl glycol, terephthalic acid / isophthalic acid / adipic acid / ethylene glycol / neopentyl glycol, and these may be used in combination of two or more. I can do it. In particular,
From the viewpoint of stability to light, heat, water, and the like, it is preferable to use at least two of these polyesters in combination in order to improve stability. For example, when two types of polymers A and B are used in combination, the preferred use range of the polymers is 20 to 80% by weight of A and 80 to 20% by weight of B.

It is also possible to use esterified dimethyl terephthalate, dimethyl isophthalate or the like instead of terephthalic acid or isophthalic acid as a raw material for polycondensation.

The unsaturated polyester resin obtained by condensation polymerization of an unsaturated polybasic acid having a reactive double bond with a polyhydric alcohol includes maleic anhydride / phthalic anhydride / propylene glycol, maleic anhydride / Isophthalic acid / propylene glycol, maleic acid / fumaric acid /
Isophthalic acid / 1,3-butanediol, maleic acid /
Examples include resins obtained from isophthalic acid / neopentyl glycol, maleic anhydride / tetrahydrophthalic anhydride / dipropylene glycol, and the like.

The crosslinking agent is necessary for curing the resin composition used in the image receiving layer of the recording medium of the present invention with active energy rays and for obtaining the blocking resistance of the cured resin composition. The compounding amount is in the range of 5 to 60% by weight, preferably 6 to 45% by weight of the total amount with the polyester resin. If the compounding amount of the crosslinking agent is less than 5% by weight, blocking tends to occur. Conversely, if it exceeds 60% by weight, the blocking resistance is improved, but the ratio of the polyester resin is reduced, and a sufficient dyeing concentration is obtained. It becomes difficult to be.

In consideration of the curing of the resin composition by the crosslinking agent and the blocking resistance of the recording medium, the crosslinking agent preferably has at least one kind of polyfunctional monomer or polyfunctional oligomer. When ultraviolet rays that are easy to handle are used as the line, the polymerizable group of these crosslinking agents is preferably a monomer or oligomer having an acryloyloxy group or a methacryloyloxy group.

As an example of the monomer or oligomer having a (meth) acryloyloxy group, polyether acrylate or polyether methacrylate (hereinafter, "acrylate or methacrylate" is simply abbreviated to "(meth) acrylate") polyester (meth) Monomers such as acrylate, polyol (meth) acrylate, epoxy (meth) acrylate, amido urethane (meth) acrylate, urethane (meth) acrylate, spiro acetal (meth) acrylate and polybutadiene (meth) acrylate; Oligomer can be mentioned.

Specific examples of such a monomer or oligomer include polyether (meth) acrylate synthesized from 1,2,6-hexanetriol / propylene oxide / acrylic acid and trimethylolpropane / propylene oxide / acrylic acid; adipine Acid / 1,6-
Polyester (meth) acrylate synthesized from hexanediol / acrylic acid, succinic acid / trimethylolethane / acrylic acid, etc .; triethylene glycol diacrylate, hexapropylene glycol diacrylate, neopentyl glycol diacrylate, 1,4-
Butanediol dimethacrylate, 2-ethylhexyl acrylate, tetrahydrofurfuryl acrylate,
2-hydroxyethyl methacrylate, ethyl carbitol acrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, 2,2-bis (4-
Acryloyloxydiethoxyphenyl) propane,
(Meth) acrylates such as 2,2-bis (4-acryloyloxypropoxyphenyl) propane or polyol (meth) acrylates;

Diglycidyl etherified bisphenol A
/ Acrylic acid, diglycidyl etherified polybisphenol A / acrylic acid, triglycidyl etherified glycerin / epoxy (meth) acrylate such as acrylic acid;
γ-butyrolactone / N-methylethanolamine / bis (4-isocyanatocyclohexyl) methane / 2-hydroxyethyl acrylate, γ-butyrolactone / N
Amidourethane (meth) acrylates such as -methylethanolamine / 2,6-tolylene diisocyanate / tetraethylene glycol / 2-hydroxyethyl acrylate;

Urethane acrylates such as 2,6-tolylene diisocyanate diacrylate, isophorone diisocyanate diacrylate, hexamethylene diisocyanate diacrylate; spiro acetal acrylate synthesized from diarylidenepentaerythritol / 2-hydroxyethyl acrylate; epoxidized butadiene Acrylated polybutadiene synthesized from / 2-hydroxyethyl acrylate, etc., and these monomers and oligomers are used alone or in a mixture of two or more.

Among the above monomers and oligomers, the following general formula (1):

[0019]

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[In the formula, n is an integer of 1 to 4, and at least 3 Xs are represented by the general formula: CH ₂ ＣＨCH—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.)
The remainder is an alkyl group having 1 to 8 carbon atoms, a hydroxyl group, an amino group, and a formula:-(CR ₂ ) _m -H (wherein R ₂ represents an alkylene group having 1 to 8 carbon atoms, and m is a positive integer. And a group represented by the formula:-(OR ₂ ) _m -OH (wherein R ₂ and m are as defined above). Such as dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol pentaacrylate, tripentaerythritol hexaacrylate, tripentaerythritol heptaacrylate, etc., or a compound represented by the following general formula ( 2),

[0021]

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[0022] (wherein, n 1 to 10 a positive integer, X 'is optionally -OH or -OCOCH = CH _2.) Poly bisphenol A polyacrylates represented by, for example, diglycidyl ether Bisacrylate A diacrylate, diacrylate of Epicoat # 1001 (n = 3, manufactured by Shell), etc., or the following general formula (3):

[0023]

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(Wherein X ₁ , X ₂ ,..., X _n have 6 carbon atoms)
The following structures having the same or different alkylene group or a structure in which one hydrogen atom is substituted with a hydroxyl group, and n is 0
Which is an integer of from 5 to 5, for example, 2,2-
Bis (4-acryloyloxydiethoxyphenyl) propane, 2,2-bis (4-acryloyloxytriethoxyphenyl) propane, 2,2-bis (4-acryloyloxydipropoxyphenyl) propane and the like are used as active energy rays. When ultraviolet light is used, the quick-drying property in air is very good, and it is a particularly preferred crosslinking agent.

In the present invention, a release agent is added to the image receiving layer in order to further improve the blocking resistance (sticking resistance) between the recording medium and the transfer sheet.
Examples of the release agent to be used include a silicon-based surfactant, a fluorine-based surfactant, a graft polymer having a polyorganosiloxane as a trunk or a branch, and a compound capable of forming a silicon-based or fluorine-containing crosslinked structure. These release agents can be used alone or in combination. The amount of the release agent is 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. CH ₃ — (SiO) 1 / 2-group and -O
The ratio of the R-group (R: alkylene residue) is 1/10 to 1/1 /
0.1, preferably in the range of 1/5 to 1 / 0.2 is effective for improving the 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).

[0028]

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(Where P is the following general formula (5)

[0030]

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

[0032]

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(Where Q is the following general formula (7)

[0034]

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Wherein n3 and n4 each represent a positive integer, x and y each represent 0 or a positive integer, and the formula:
.Ltoreq. (2n3 + n4 + 1) / (n4x + n4y) .ltoreq.10. z is 0 or an integer of 1 to 5. Also, R
₄ -Si (CH _{3) 3,} represent hydrogen, an alkyl group, an acyl group or an aryl group, R ₅ represents hydrogen, an alkyl group, an acyl group or an aryl group. )

As the fluorine-based surfactant, any of nonionic, anionic, cationic and amphoteric surfactants can be used as long as they are soluble in a mixture of a dyeing resin and a crosslinking agent and exhibit blocking resistance. 1 fluorinated surfactant
More than one species can be used. Above all, a nonionic surfactant is preferable in consideration of the improvement in the leveling property and the blocking resistance of the recording medium.

Specific examples of the fluorine-based surfactant used in the present invention include anionic surfactants such as fluoroalkoxypolyfluoroalkyl sulfate, fluorocarbon sulfonate and fluorocarbon carboxylate, and N-fluoroalkyl Sulfonamidoalkylamine quaternary ammonium salt, N-fluoroalkylsulfonamidoalkylamine salt, N-fluoroalkylamidoalkylamine quaternary ammonium salt, N-fluoroalkylamidoalkylamine salt, N-fluoroalkylsulfonamidoalkylhalomethyl ether Cationic surfactants such as quaternary ammonium salts,

Fluorocarbon sulfonamide, fluorocarbon aminosulfonamide, fluorocarbon carboxysulfonamide, fluorocarbon hydroxysulfonamide, fluorocarbon sulfonamide ethylene oxide adduct, fluorocarbon hydroxysulfonamide sulfate, fluorocarbon amino acid amide, fluorocarbon acid amide, fluorocarbon hydroxyamide, Ethylene oxide addition condensate of fluorocarbon amide, fluorocarbon hydroxyamide sulphate, fluorocarbon sulfonic acid, fluorohydrocarbon carboxylic acid, fluorohydrocarbon alkyl ester, fluorohydrocarbon alkyl ether, fluorohydrocarbon carboxyalkyl ester Ether, fluorohydrocarbons hydroxyamide, fluorohydrocarbon alkyl esters sulfates, nonionic surfactants such as fluoroalkyl diamine,

Examples of the amphoteric surfactant include an alkylamine having a betaine-type fluorocarbon sulfonamide bond and an alkylamine having a betaine-type fluorocarbonamide bond.

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

Other examples of the graft polymer include a graft polymer having a polyorganosiloxane as a base 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 methacryloyl on the side chain by condensation of an organosilane and a silane having a vinyl polymerizable group, such as 3-methacryloxypropyldimethoxymethylsilane, methylvinyldimethoxysilane, and ethylvinyldiethoxysilane. A polysiloxane having an oxy group is synthesized, and then the monomer and a derivative of an alkyl (meth) acrylate, (meth) acrylic acid, a functional group-containing (meth) acrylic acid,

A graft polymer obtained by polymerizing at least one kind of monomer such as vinyl acetate, vinyl chloride, (meth) acrylonitrile, styrene, etc., and organosilane and diethoxy-3-glycidoxypropylmethylsilane are condensed. Thus, a polysiloxane having a glycidyl group in the side chain is synthesized, and then reacted with (meth) acrylic acid to obtain a monomer containing a (meth) acryloyloxy group, and then the monomer is polymerized. A graft polymer obtained by condensing an organosilane with hydroxyethylmethyldimethoxysilane to synthesize a polysiloxane having a hydroxyl group in a side chain, and then a polypolymer obtained by polycondensing a dicarboxylic acid and the diol. Can be mentioned.

In synthesizing the polysiloxane that forms 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 regulator. For example, a silane compound having one alkoxy group per molecule may be used and polymerized at 70 to 150 ° C. using a functional group-containing silane and a strong acid or base as a catalyst.

By incorporating these graft polymers into the image receiving layer, the blocking resistance to the transfer sheet is improved and the dye fading 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,
More preferably, it is in the range of 0.05 to 10 parts by weight. This is because if the amount is less than 0.01 part by weight, the improvement in blocking resistance is reduced and the dark fading property is not improved. The reason for this is that the dyeing concentration also decreases as the color changes.

The graft polymer containing a polyorganosiloxane has a molecular weight of 1000 from the viewpoint of dark fading.
The above are preferred. Further, the weight ratio of the polyorganosiloxane component to the polymer or copolymer other than the polyorganosiloxane is preferably polyorganosiloxane component / polymer or copolymer = 95/5 to 10/90, more preferably Preferably 90/10 to 20/80
Range. If this ratio exceeds 95/5, the dark fading tends to be poor, and if it is less than 10/90, the blocking resistance decreases and the dark fading tends to be poor.

As a thermal crosslinking type or active energy ray crosslinking type releasing agent capable of forming a silicon-based or fluorine-containing crosslinking structure, a silicon-based compound that causes an addition reaction or a silicon-based compound that causes a radical reaction ,
Silicon-based compounds that cause a condensation reaction are exemplified.
Examples of the silicon-based 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 a catalyst such as a platinum compound, if necessary. You may use together.

Examples of the silicon-based compound that causes a radical reaction include a combination of silicone having a vinyl group and silicone having methylsilane, and an organic peroxide may be used as a polymerization initiator. Examples of the silicon compound that causes a condensation reaction include silicone having an alkoxy group, silicone having a silanol group, a combination of silicone having an alkoxy group and silicone having a silanol group, silicone having a silanol group and -SiH
There are a combination with a silicone having a group, a combination of a silicone having a silanol group and a silicone having an aminooxy group, and the like.

In the fluorinated compound, a combination of an epoxy group-containing fluorinated compound and an amino group-containing fluorinated compound as a fluorinated compound causing an addition reaction, and a carboxylic acid group-containing fluorinated compound as a fluorinated compound causing a condensation reaction And amino group-containing fluorine-containing compounds.

In order for these silicon-based or fluorine-containing compounds to form a sufficient crosslinked structure, the compound must have at least two functional groups per molecule, and the number of functional groups per molecule is two or less. However, even if a high molecular weight product is formed, a sufficient crosslinked structure cannot be obtained.

Examples of the active energy ray cross-linkable silicon-based or fluorine-containing compounds include compounds having radical polymerizability such as vinyl group, allyl group, methacryloyl group and acryloxy group. When an ultraviolet ray is used as the active energy ray, a compound having an acryloyloxy group having good polymerizability by the ultraviolet ray 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 cross-linking type release agent is used, when the resin composition constituting the image receiving layer is cured with the active energy ray, the release agent can be simultaneously cured. However, when a heat-crosslinking release agent is used, it is necessary to add a heat curing step separately from the curing of the resin composition. Therefore, from the viewpoint of productivity, it is preferable to use an active energy ray cross-linking release agent.

The benzophenone ultraviolet absorber and the hindered amine light stabilizer are compounded for the purpose of improving the light fastness of a recording medium dyed with a sublimable disperse dye.

The ultraviolet absorber and the light stabilizer improve the light fastness and the dyeing sensitivity of the recording medium. As the ultraviolet absorber, at least one benzophenone-based ultraviolet light selected from the following general formulas (8) and (9) is used. When the absorber and the hindered amine light stabilizer are used in combination, yellowing of the image receiving layer cured by the active energy ray can be prevented, and an image receiving paper having high whiteness can be manufactured.

[0054]

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[0055]

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Specific examples of the benzophenone-based ultraviolet absorber represented by the general formulas (8) and (9) include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2-hydroxy-4-octoxy. Benzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,
4'-Dioctoxybenzophenone, 2,2'-dihydroxy-4,4'-didodecyloxybenzophenone and the like.

It is necessary to use one or more of these in an amount of 1 to 10 parts by weight based on 100 parts by weight of the total of the polyester resin and the crosslinking agent. When the amount is less than 1 part by weight, the light resistance is not sufficient. On the other hand, when the amount exceeds 10 parts by weight, the curability due to the active energy becomes poor. The preferred range of the amount is 2 to 8 parts by weight.

As the hindered amine light stabilizer, bis (2,2,6,6-tetramethyl-4-piperidyl)
Sebacate [SANOL (registered trademark) LS770, Sankyo], bis (1,2,2,6,6-pentamethyl-4-)
Piperidyl) sebacate [SANOL (registered trademark) LS
765, Sankyo], dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine succinate [SANOL (registered trademark)
LS622LD, Sankyo], poly [[6- (1,1,3,3
3-tetrabutyl) imino-1,3,5-triazine-
2,4-diyl] [(2,2,6,6-tetramethyl-
4-piperidyl) imino] hexamethylene [(2,2,
6,6-tetramethyl-4-piperidyl) imino]]
[SANOL (registered trademark) LS944LD, Sankyo], 1
-[2- [3- (3,5-Di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4-
[3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] 2,2,6,6-tetramethylpiperidine [SANOL (registered trademark) LS262
6, Sankyo].

It is necessary to use one or more of these in the range of 1 to 10 parts by weight based on 100 parts by weight of the total of the polyester resin and the crosslinking agent. If the amount is less than 1 part by weight, the effect of improving the dyeing density, light stability and dark discoloration is not sufficient, and if it exceeds 10 parts by weight, the curability by active energy rays will be poor.

The resin composition composed of the above components is
When using tetrahydrofurfuryl acrylate, which has high polymer solubility and low viscosity, as a component of the cross-linking agent, coating such as roll coating, bar coating, and blade coating is possible, but improves coating workability. In order to use a solvent for these resin compositions, for example, ethyl alcohol, methyl ethyl ketone, toluene,
It is better to mix ethyl acetate, dimethylformamide and the like to adjust the coating viscosity to an appropriate value. Thereby, spray coating, curtain coating, flow coating, dip coating and the like can be easily performed.

The above resin composition may further contain fine inorganic fine particles of several μm or less, for example, silica, depending on the purpose of use.
Alumina, talc, titanium oxide and the like may be blended.

The resin composition for producing the image receiving layer of the recording medium according to the present invention is cured by an active energy ray such as an electron beam or an ultraviolet ray. . When ultraviolet rays are used as the active energy rays, the photopolymerization initiator is used in an amount of 0.1 to 10.0 with respect to 100 parts by weight of the total of the polyester resin and the crosslinking agent.
It is preferable to add parts by weight. Specific examples of the photopolymerization initiator include benzoin, benzoin isobutyl ether,
Benzyldimethyl ketal, ethylphenylglyoxylate, diethoxyacetophenone, 1,1-dichloroacetophenone, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenylketone, benzophenone, benzophenone / diethanolamine, 4,4'-bisdimethylaminobenzophenone, 2-methylthiooxanthone, t
carbonyl compounds such as tert-butylanthraquinone and benzyl;

Sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; azo compounds such as azobisisobutyronitrile and azobis-2,4-dimethylvaleronitrile; benzoyl peroxide and di-tert-butyl peroxide And these compounds are used in one kind or in a mixture of two or more kinds.

Films or papers are suitable as a substrate for applying the above resin composition and irradiating with an active energy ray to obtain a recording medium, such as a polyester film, a polypropylene film, a nylon film and a vinyl chloride. Plastic film such as film; coated paper, baryta paper, art paper mainly composed of wood fiber; acrylic paper, PP paper, polyester paper mainly composed of plastic fiber,
Laminated paper in which a plastic film or a synthetic paper is laminated on one or both sides of plain paper may be used.

These papers or films may be used as they are, or may be used after being subjected to pretreatment such as washing, etching, corona discharge, irradiation with active energy rays, dyeing, printing, etc., if necessary. May be.

These substrates are uniformly coated with the dye sublimable dyeable composition by the above-mentioned coating method so that the film thickness after curing is 0.5 to 100 μm, preferably 1 to 50 μm. Then, it is cured with an active energy ray to form an image receiving layer. When the film thickness is less than 0.5 μm, the diffusion of the dye reaches saturation on the way, and it is not possible to dye a deep color. On the other hand, if the thickness exceeds 100 μm, blocking tends to occur during heating.

When the dyed film or paper is stacked, it is preferable to apply the resin composition to only one side of the base material in order to prevent the transfer of the disperse dye. In order to prevent dyeing, it is more preferable to provide a non-migrating layer on the surface opposite to the coated surface of the sublimable disperse dye dyeable resin composition.

The composition for forming the non-migration layer includes 100 parts by weight of a monomer / oligomer mixture of the above-mentioned polyfunctional monomer and / or monofunctional monomer, and if necessary, the above-mentioned photopolymerization initiator 0.1 A coating agent consisting of １００100 parts by weight can be used, but in order to sufficiently prevent transfer by a disperse dye, the average number of polymerizable groups in the monomer / oligomer mixture is 1.5 or more per molecule. It is necessary. These coating agents can also adjust the viscosity with a solvent, apply to a substrate, and cure as in the case of the sublimable disperse dye dyeable composition.

Hereinafter, embodiments of the present invention will be described in more detail. In the Examples and Comparative Examples,
Indicates "parts by weight".

Preparation of base material A milky white polyester film (W-900 made by Diafoil) having a thickness of 38 μm was laminated on one side of art paper (85 μm in thickness), and a white polypropylene paper (Yupo FPG made by Oji Yuka) on the other side. A thickness of 60 μm was laminated. The adhesive used was AD-577-1 and CAT-52 manufactured by Toyo Morton Co. The coating amount was 5 g / m ² between the milky white polyester film and the coated paper when dry, and 3 g / m ² between the coated paper and the white polypropylene paper when dry. ^{It was set to 2} . Drying was performed at 80 ° C. for about 30 seconds and aged at 40 ° C. for 2 days.

Preparation of Image-Receiving Layer The coating solutions shown in Table 1 were prepared, uniformly applied on a milky white polyester film as a base material by a dipping method, and further irradiated with ultraviolet light from a high-pressure mercury lamp in the air to form a film. 5-6μ
An image receiving layer having m was prepared. Table 2 shows the evaluation results.

[0072]

[Table 1]

The "notes" in Table 1 are as follows. 1) dipentaerythritol hexaacrylate 2) dipentaerythritol pentaacrylate 3) dipentaerythritol tetraacrylate 4) 2,2-bis (4-acryloyloxydiethoxyphenyl) propane 5) terephthalic acid / isophthalic acid / sebacic acid / ethylene Glycol / neopentyl glycol polycondensed resin (molecular weight 20000-25000, Tg10 ° C.) 6) Resin polycondensed with ethylene oxide adduct of terephthalic acid / isophthalic acid / sebacic acid / ethylene glycol / bisphenol A (molecular weight 20000-2500)
0, Tg 77 ° C.) 7) 2,4-dihydroxybenzophenone 8) 2-hydroxy-4-methoxybenzophenone 9) 2-hydroxy-4-methoxybenzophenone-5
-Sulfonic acid 10) 2,2'-dihydroxy-4,4'-dimethoxybenzophenone 11) 2,2 ', 4,4'-tetrahydroxybenzophenone 12) 2- (2'-hydroxy-3', 5 ' -Di-t-
Butylphenyl) benzotriazole 13) 1-hydroxycyclohexylphenyl ketone 14) a silicone compound represented by the following general formula (10)

[0074]

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[0075]

[Table 2]

The evaluation of the whiteness in Table 2 was visually conducted under sunlight, and ○: high whiteness. Δ: Slightly yellowish. ×:
yellow. Indicated by

[0077]

As described above in detail, according to the present invention, in a recording medium of a sublimation type thermal transfer recording system having an image receiving layer cured by an active energy ray, a high white color without yellowing even after curing. It is possible to obtain a recording medium having a high degree of light resistance and excellent light resistance of a recorded image. Further, the recording medium has a high-grade feeling due to the high whiteness of the background, and the recorded image is very clear, which greatly contributes to the spread of video printers and the like.

──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Kazuhiko Sufuku 20-1 Miyukicho, Otake City, Hiroshima Prefecture Inside Mitsubishi Rayon Co., Ltd. (72) Inventor Masaki Nimoto 4-1-1 Sunadabashi, Higashi-ku, Nagoya City, Aichi Prefecture No. 60 Mitsubishi Rayon Co., Ltd. Product Development Laboratory (56) References JP-A-2-57388 (JP, A) JP-A-3-128961 (JP, A) JP-A-62-189195 (JP, A) JP-A-2-67193 (JP, A) JP-A-4-211995 (JP, A) JP-A-5-77564 (JP, A) JP-A-5-77565 (JP, A) Int.Cl. ⁷ , DB name) B41M 5/38-5/40

Claims (1)

(57) [Claims] 1. A polyester resin having a thickness of 40 to 9 on a surface of a base material.
Crosslinking agent 60 curable with 5% by weight and active energy rays
And 100 parts by weight of the mixture consisting of 5 wt%, and at least one release agent 0.01 to 30 parts by weight, the following chemical formula
(8) or 1 to 10 parts by weight of at least one benzophenone-based ultraviolet absorber represented by (9), and at least 1
A sublimation type thermal transfer recording type recording medium provided with an image receiving layer obtained by applying a resin composition comprising 1 to 10 parts by weight of a kind of hindered amine light stabilizer and curing with an active energy ray. Embedded image Embedded image