JP2009262337A - Composition for acceptance layer of heat transfer image receiving sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for an acceptance layer constituting an acceptance layer of a heat transfer image receiving sheet which shows excellent dyeing properties of dye and releasability of a heat transfer image receiving sheet and excellent light resistance during heat transfer. <P>SOLUTION: This composition for the acceptance layer for the heat transfer image receiving sheet contains: a resin containing a polyester obtained by condensation polymerizing an alcohol component containing not less than 50 mol.% of an alkylene oxide adduct of bisphenol A and a carboxylic acid component containing more than 50 mol.% of alicyclic carboxylic acid and a polyether-modified silicone with an oxyethylene group and/or an oxypropylene group. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a thermal transfer image receiving sheet, a receiving layer for the thermal transfer image receiving sheet, and a composition for the receiving layer.

There has been proposed a method of forming a color image on a thermal transfer image-receiving sheet that can be dyed with a sublimation dye, using a sublimation dye as a recording agent and a thermal transfer sheet carried on a substrate. In this method, a thermal head of a printer is used as a heating means, and a dye is transferred to an image receiving sheet by heating to obtain a color image. The image formed in this way is very clear because it uses a dye, and is excellent in transparency. Therefore, it is excellent in reproducibility of intermediate colors and gradation, and a high-quality image can be expected.
From the viewpoint of releasability, the dye-receiving layer of the thermal transfer image-receiving sheet is required to have a dyeing property on the image-receiving sheet at the time of thermal transfer, or a releasability associated with heat fusion between the image-receiving sheet and the transfer sheet. , A receiving layer composition containing a heat-visible resin that is not polyester and a specific modified polyether silicone as a release agent is disclosed (Patent Document 1), and contains a small amount of an alicyclic carboxylic acid or alicyclic diol. A receiving layer made of a polyester resin is disclosed (Patent Document 2). Further, from the viewpoint of dyeability, a receiving layer composition comprising a polyester obtained by polycondensation of an aromatic alcohol and a carboxylic acid containing an aliphatic carboxylic acid and a small amount of an alicyclic carboxylic acid, and a modified polyether silicone The thing is disclosed (patent document 3, patent document 4).

JP 2003-11528 A Japanese Patent Laying-Open No. 2005-103804 JP 2006-347148 A JP 2006-88396 A

However, in any of the above-mentioned patent documents, a receiving layer composition excellent in both dyeing property and releasability and having excellent light resistance has not yet been found.
The present invention relates to a thermal transfer image-receiving sheet excellent in dyeability during thermal transfer and releasability of a thermal transfer image-receiving sheet, and excellent in light resistance, a receiving layer used in the image-receiving sheet, and a receiving layer constituting the receiving layer A composition is provided.

The present invention
(1) a resin containing a polyester obtained by condensation polymerization of an alcohol component containing 50 mol% or more of an alkylene oxide adduct of bisphenol A and a carboxylic acid component containing more than 50 mol% of an alicyclic carboxylic acid; A composition for a receiving layer of a thermal transfer image-receiving sheet containing an ether-modified silicone;
(2) The receptor layer for a thermal transfer image-receiving sheet, comprising the receptor layer composition described in (1) above, and (3) the substrate, and the receptor described in (2) above on at least one surface of the substrate. A thermal transfer image-receiving sheet comprising a layer;
About.

  According to the present invention, a thermal transfer image-receiving sheet that is excellent in dyeing property at the time of thermal transfer and releasability of the heat-receiving image transfer sheet, and excellent in light resistance, a receiving layer constituting the image-receiving sheet, and the receiving layer are configured. The composition for receiving layers can be provided.

[Composition for receiving layer of thermal transfer image-receiving sheet]
In the receiving layer composition containing a release agent and a resin containing polyester, the present invention uses a specific release agent and a specific polyester, that is, 50 mol% or more of an alkylene oxide adduct of bisphenol A. A polyester obtained by polycondensation of an alcohol component and a carboxylic acid component containing more than 50 mol% of an alicyclic carboxylic acid, and a polyether-modified silicone having an oxyethylene group and / or an oxypropylene group A composition for a receiving layer of a thermal transfer image-receiving sheet.
In the polyester used for the receiving layer of the thermal transfer image-receiving sheet, bisphenol A, an aromatic alcohol, has a high dyeing property, but has a light-absorbing portion, and is easily decomposed, and aromatic carboxylic acids are more easily decomposed. . On the other hand, alicyclic alcohols and aliphatic alcohols that are difficult to decompose structurally are not sufficiently dyeable, and light resistance is inferior when the amount of alicyclic carboxylic acid is increased. In the present invention, by using a specific polyether-modified silicone as a release agent and using a polyester composed of specific raw material components, all of dyeing property, release property with a transfer sheet, and light resistance The performance of can be satisfied. This is a reduction of an alcohol component containing 50 mol% or more of the above-mentioned polyether-modified silicone and bisphenol A alkylene oxide adduct as a release agent and a carboxylic acid component containing more than 50 mol% of an alicyclic carboxylic acid. Because the compatibility with the polyester obtained by polymerization is increased by using a compound having a similar functional group, the cohesive force between the polymers is weakened, and the dye is likely to penetrate into the polymer. Seem.

In the present invention, the polyester is obtained by polycondensing an alcohol component containing 50 mol% or more of an alkylene oxide adduct of bisphenol A and a carboxylic acid component containing more than 50 mol% of an alicyclic carboxylic acid. As the alkylene oxide adduct of bisphenol A, one having a structure represented by the following formula (1) is preferably used.

In the general formula (1), RO is an oxyalkylene group, and R represents an ethylene group or a propylene group. x and y represent the number of moles of alkylene oxide added and each is a positive number. Each R may be the same or different. The average value of the sum of x and y is 2-7 from a reactive viewpoint with carboxylic acid, Preferably it is 2-5, More preferably, it is 2-4.
As the alkylene oxide adduct of 2,2-bis (4-hydroxyphenyl) propane represented by the above formula (1), specifically, polyoxypropylene-2,2-bis ( 4-hydroxyphenyl) propane, polyoxyethylene-2,2-bis (4-hydroxyphenyl) propane and the like.

In particular, from the viewpoint of releasability of the thermal transfer image-receiving sheet, the alkylene oxide adduct of 2,2-bis (4-hydroxyphenyl) propane represented by the above formula (1) is an ethylene oxide adduct or a propylene oxide adduct. The content ratio (ethylene oxide adduct / propylene oxide adduct) is preferably 50/50 to 0/100, more preferably 40/60 to 0/100, still more preferably 30/70 to 0/100 in terms of molar ratio. And even more preferably 0/100.
The alkylene oxide adduct of 2,2-bis (4-hydroxyphenyl) propane represented by the above formula (1) is included in the raw alcohol component from the viewpoint of releasability of the thermal transfer image-receiving sheet and dyeing property. The content is 50 mol% or more, preferably 70 mol% or more, more preferably 80 mol% or more, and still more preferably 100 mol%.

  In the present invention, other known alcohol components can be used together with the alkylene oxide adduct of bisphenol A as the alcohol component which is a raw material component. For example, ethylene glycol, propylene glycol (1,2-propanediol), glycerin, pentaerythritol, trimethylolpropane, hydrogenated bisphenol A, sorbitol, or alkylene (2 to 4 carbon atoms) oxide (average added mole number 1) -16) Additives and the like. From the viewpoint of releasability of the thermal transfer image-receiving sheet, it is preferable to use a trihydric or higher alcohol as the alcohol component, and more specifically, it is more preferable to use glycerin or pentaerythritol. The said alcohol component may be used individually by 1 type, and may be used in combination of 2 or more type.

  The carboxylic acid component as a raw material monomer for forming polyester contains alicyclic carboxylic acid in excess of 50 mol%. As the alicyclic carboxylic acid, alicyclic dicarboxylic acids or anhydrides of these acids and alkyl esters thereof are preferable, and cyclohexane is more preferable from the viewpoint of reactivity with alcohol during polyester synthesis and heat resistance of the polyester. Dicarboxylic acids, decalin dicarboxylic acids, or anhydrides of these acids.

  Specifically, 1,4-cyclohexanedicarboxylic acid, 2-methyl-1,4-cyclohexanedicarboxylic acid, 2-ethyl-1,4-cyclohexanedicarboxylic acid, 2-propyl-1,4-cyclohexanedicarboxylic acid, 2 -Butyl-1,4-cyclohexanedicarboxylic acid, 2-t-butyl-1,4-cyclohexanedicarboxylic acid, 2,3-dimethyl-1,4-cyclohexanedicarboxylic acid, 2,3-diethyl-1,4-cyclohexane Dicarboxylic acid, 2,3-dipropyl-1,4-cyclohexanedicarboxylic acid, 2,3-dibutyl-1,4-cyclohexanedicarboxylic acid, 2-methyl-3-ethyl-1,4-cyclohexanedicarboxylic acid, 2-methyl -3-propyl-1,4-cyclohexanedicarboxylic acid, 2-methyl-3-butyl-1,4- Chlohexanedicarboxylic acid, 2-ethyl-3-propyl-1,4-cyclohexanedicarboxylic acid, 2-ethyl-3-butyl-1,4-cyclohexanedicarboxylic acid, 2-methyl-3-t-butyl-1,4 -Cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 2,6-decalindicarboxylic acid, 3-methyl-2,6-decalindicarboxylic acid, 3-ethyl-2,6-decalindicarboxylic acid, 3-propyl-2 , 6-decalin dicarboxylic acid, 3-butyl-2,6-decalin dicarboxylic acid, 3,4-dimethyl-2,6-decalin dicarboxylic acid, 3,4-diethyl-2,6-decalin dicarboxylic acid, 3,4 -Dipropyl-2,6-decalin dicarboxylic acid, 3,4-dibutyl-2,6-decalin dicarboxylic acid, 3,8-dimethyl-2, -Decalin dicarboxylic acid, 3,8-diethyl-2,6-decalin dicarboxylic acid, 3,8-dipropyl-2,6-decalin dicarboxylic acid, 3,8-dibutyl-2,6-decalin dicarboxylic acid, 3-methyl -4-ethyl-2,6-decalin dicarboxylic acid, 3-methyl-4-propyl-2,6-decalin dicarboxylic acid, 3-methyl-4-butyl-2,6-decalin dicarboxylic acid, 3-ethyl-4 -Butyl-2,6-decalin dicarboxylic acid and the like, or anhydrides of these acids. Among these, 1,2-cyclohexanedicarboxylic acid and its anhydride, hexahydrophthalic anhydride, 1,4-cyclohexanedicarboxylic acid are preferable, and 1,4-cyclohexanedicarboxylic acid is preferable from the viewpoint of releasability of the thermal transfer image-receiving sheet. More preferred.

  The alicyclic carboxylic acid is contained in the raw material carboxylic acid component in an amount of more than 50 mol% from the viewpoint of the light resistance of the thermal transfer image-receiving sheet, but is preferably 70 mol% or more, more preferably 80 mol% or more. Preferably it is 100 mol%. Here, “more than 50 mol%” means that it does not contain 50 mol% and is greater than 50 mol%. In the present invention, excellent light resistance can be obtained even when the amount of the alicyclic carboxylic acid is large.

  In the present invention, other known carboxylic acid components can be used together with the alicyclic carboxylic acid as the raw carboxylic acid component. Specifically, dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, maleic acid, adipic acid, and succinic acid, alkyl groups having 1 to 20 carbon atoms such as dodecenyl succinic acid, octenyl succinic acid, etc. Divalent carboxylic acids such as succinic acid substituted with 20 alkenyl groups; Trivalent or higher polyvalent carboxylic acids such as trimellitic acid and pyromellitic acid, anhydrides of these acids, and alkyls thereof (1 carbon number) -3) An ester etc. are mentioned. The said carboxylic acid component may be used individually by 1 type, and may be used in combination of 2 or more type.

In the present invention, from the viewpoint of releasability of the thermal transfer image-receiving sheet, it is preferable to use a trivalent or higher carboxylic acid as the carboxylic acid component other than the alicyclic carboxylic acid, specifically, trimellitic acid, It is more preferable to use pyromellitic acid, and trimellitic acid is more preferable.
The polyester can be produced, for example, by subjecting the alcohol component and the carboxylic acid component to condensation polymerization at a temperature of 180 to 250 ° C. in an inert gas atmosphere, using an esterification catalyst as necessary. From the viewpoint of dyeability of the dye and releasability of the thermal transfer image-receiving sheet, the raw material polyester preferably has a broad molecular weight distribution, and is preferably subjected to polycondensation using an esterification catalyst. Examples of the esterification catalyst include metal compounds such as tin catalyst, titanium catalyst, antimony trioxide, zinc acetate, and germanium oxide.

From the viewpoint of dyeing properties and releasability of the thermal transfer image-receiving sheet, the softening point of the polyester is preferably 80 to 250 ° C, more preferably 80 to 200 ° C. The glass transition point is preferably 50 to 85 ° C. The acid value is preferably 1 to 35 mgKOH / g, more preferably 5 to 35 mgKOH / g, from the viewpoint of dispersibility of the resin containing polyester in an aqueous medium, that is, emulsifying properties. The glass transition point, softening point, and acid value can all be obtained by appropriately adjusting the type of monomer used, the blending ratio, the temperature of condensation polymerization, and the reaction time.
In addition, from the viewpoint of film forming properties when obtaining a thermal transfer image-receiving sheet, the number average molecular weight of the polyester is preferably 1,000 to 10,000, more preferably 2,000 to 8,000, and 2,000 to 7,000. Is more preferable.

  In the present invention, the polyester includes a polyester modified within such a range that does not substantially impair the characteristics. Examples of the modified polyester include grafting and blocking with phenol, urethane, epoxy and the like by the methods described in JP-A-11-133668, JP-A-10-239903, JP-A-8-20636, and the like. And a composite resin having two or more kinds of resin units including a polyester unit.

In the present invention, other resins can be used together with the polyester. Resins that can be used include known resins used as the receiving layer of thermal transfer image-receiving sheets, for example, polyolefin resins such as polypropylene, halogenated polymers such as polyvinyl chloride and polyvinylidene chloride, polyvinyl acetate, and polyacrylic esters. And vinyl polymers such as polyvinyl acetal, polystyrene resins, polyamide resins, copolymers of olefins such as ethylene and propylene and other vinyl monomers, cellulose resins such as ionomers and cellulose diacetates, polycarbonates, etc. Polyvinyl chloride and polycarbonate are preferred from the viewpoints of dyeability and release properties of the thermal transfer image-receiving sheet.
In the present invention, the resin used for the receiving layer preferably contains 70% by weight or more, more preferably 80% by weight or more, from the viewpoint of dyeing property of the dye to the thermal transfer image-receiving sheet, Preferably it is 100 weight%.
Accordingly, the softening point, glass transition point, acid value, and number average molecular weight of the resin containing the polyester of the present invention are preferably the same as those of the polyester of the present invention.

Polyether-modified silicone The polyether-modified silicone used in the present invention has an oxyethylene group and / or an oxypropylene group. From the viewpoint of compatibility with the polyester constituting the receiving layer and releasability of the thermal transfer image-receiving sheet, those having an oxyethylene group and an oxypropylene group are preferred. Examples of commercially available products include KF615A (manufactured by Shin-Etsu Chemical Co., Ltd., Polyether-modified silicone).
The polyether-modified silicone used in the present invention has an oxyethylene group and / or an oxypropylene group, and preferably includes those having a structure represented by the following formula (2).

（式中、Ｒは-Ｃ₃Ｈ₆-(Ｃ₂Ｈ₄Ｏ)_a-(Ｃ₃Ｈ₆Ｏ)_bＲ'を表わし、Ｒ'は水素原子、またはアリール基もしくはシクロアルキル基で置換されていてもよい直鎖または分岐のアルキル基を示し、ｍ及びｎは各々２，０００以下の整数を示し、ａ及びｂは各々１〜３０の整数である。）

Wherein R represents —C ₃ H ₆ — (C ₂ H ₄ O) _a — (C ₃ H ₆ O) _b R ′, wherein R ′ is substituted with a hydrogen atom, an aryl group or a cycloalkyl group. A linear or branched alkyl group that may be present, m and n each represent an integer of 2,000 or less, and a and b are each an integer of 1 to 30.)

  The polyether-modified silicone is a graft type, and in the formula (2), the linear or branched alkyl group represented by R ′ has 1 carbon atom from the viewpoint of compatibility with the polyester constituting the receptor layer. -18 linear or branched alkyl group is mentioned preferably, More preferably, a C1-C12 linear or branched alkyl group is mentioned. Examples of the aryl group or cycloalkyl group that the linear or branched alkyl group may have include a phenyl group and a cyclohexyl group. a and b are each an integer of 1 to 30, but are preferably an integer of 5 to 25 from the viewpoint of compatibility with the polyester constituting the receptor layer. M and n are each an integer of 2,000 or less, and m / n = 5/5 to 9/1 from the viewpoint of compatibility with polyester constituting the receiving layer and releasability of the thermal transfer image-receiving sheet. It is preferable that m / n = 6/4 to 8/2 is more preferable.

From the viewpoint of compatibility with the polyester constituting the receptor layer, the polyether-modified silicone of the present invention preferably has an HLB value of 5 to 15, more preferably 10 to 15, and still more preferably 10 to 13. When the polyether-modified silicone has such an HLB value, the compatibility with the polyester constituting the receiving layer is increased, the cohesive force between the polymers is weakened, the dyeing property of the dye, and the release property of the thermal transfer image-receiving sheet. It is considered that light resistance and the like are improved.
From the viewpoint of a good releasability of the solubility and the thermal transfer image-receiving sheet of a solvent, the kinematic viscosity of the polyether-modified silicone is preferably 500~3,000mm ² / s, more preferably 500~2,000mm ² / s, More preferably, it is 500-1500 mm < ² > / s. This kinematic viscosity can be measured with a capillary viscometer.

  In addition, the polyether-modified silicone having an oxyethylene group and / or an oxypropylene group is a resin component 100 in the composition for a receiving layer of the present invention from the viewpoint of dyeability of a dye and releasability of a thermal transfer image-receiving sheet. It is preferable to contain 1-20 weight part with respect to a weight part, More preferably, it contains 1-15 weight part, More preferably, 1-10 weight part is contained.

Release Agent The receiving layer composition of the present invention may contain other release agents in addition to the polyether-modified silicone having an oxyethylene group and / or an oxypropylene group. Examples of the release agent that can be used include modified silicone oils other than the above-described polyether-modified silicone having an oxyethylene group and / or an oxypropylene group, polyethylene, polypropylene, and the like. The polyether-modified silicone having an oxypropylene group is contained in an amount of 80% by weight or more, more preferably 90% by weight or more, and still more preferably, from the viewpoints of dyeing property and releasability of the thermal transfer image-receiving sheet. 100% by weight.
The release agent may be contained in an amount of 0.1 to 20 parts by weight with respect to 100 parts by weight of the resin in the composition for a receiving layer of the present invention, from the viewpoints of dyeing property and release property of the thermal transfer image-receiving sheet. Preferably, it can contain 0.5-10 weight part more preferably.

Composition for Receiving Layer The composition for the receiving layer of the thermal transfer image-receiving sheet of the present invention is a carboxylic acid containing at least 50 mol% of an alcohol component containing 50 mol% or more of an alkylene oxide adduct of bisphenol A and more than 50 mol% of an alicyclic carboxylic acid. It contains a polyester-containing resin obtained by condensation polymerization with an acid component and a polyether-modified silicone having an oxyethylene group and / or an oxypropylene group.
In addition, the composition for receiving layer of the present invention includes pigments such as titanium oxide, zinc oxide, kaolin clay, calcium carbonate, fine powdered silica and the like from the viewpoint of improving the whiteness of the receiving layer and increasing the sharpness of the transferred image. And a filler. From the viewpoint of the whiteness of the thermal transfer image-receiving sheet, these pigments and fillers are preferably 0.1 to 20 parts by weight, more preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the resin containing polyester in the receiving layer composition. 1 to 10 parts by weight can be contained.
The receiving layer composition of the present invention may further contain additives such as a crosslinking agent, a curing agent, and a catalyst, if necessary.

[Receptive layer for thermal transfer image-receiving sheet]
The receiving layer for the thermal transfer image-receiving sheet of the present invention is prepared by dissolving the receiving layer composition of the present invention in an organic solvent or dispersing it in an organic solvent or water on at least one surface of the base material of the thermal transfer image-receiving sheet. It can be formed by applying and drying by a gravure printing method, a screen printing method, a reverse roll coating method using a gravure plate, or the like.
In addition, after mixing the composition for receiving layers with a mixer etc. previously, you may melt | dissolve in an organic solvent or make it disperse | distribute to an organic solvent or water.
Examples of the organic solvent for dissolving the receptor layer composition include ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, methyl isobutyl ketone, and methyl isopropyl ketone, and hydrocarbon solvents tetrahydrofuran such as toluene and xylene. And ether solvents such as dioxane. Among these, methyl ethyl ketone (MEK) and toluene are preferable from the viewpoint of resin solubility and volatility during drying, and a methyl ethyl ketone (MEK) / toluene mixed solvent is more preferable.

Examples of the method for dissolving the receiving layer composition in an organic solvent include a method in which the receiving layer composition and the organic solvent are mixed and dissolved by stirring at room temperature or in a heated state. From the viewpoint of operability and productivity, the solid content concentration in the resulting coating liquid is preferably 10 to 45% by weight, and more preferably 20 to 40% by weight.
The thickness of the dye-receiving layer formed as described above is generally 1 to 50 μm, and preferably 3 to 15 μm from the viewpoint of image quality and productivity. Further, the solid content after drying is preferably ³ to 15 g / m ² per 1 m ² of the receiving layer.

[Thermal transfer image-receiving sheet]
The thermal transfer image-receiving sheet of the present invention comprises the above-mentioned receiving layer formed on at least one surface of a substrate, and the receiving layer contains at least 50 mol% of an alkylene oxide adduct of bisphenol A and an alicyclic ring. Receptive layer containing a resin containing a polyester obtained by condensation polymerization with a carboxylic acid component containing more than 50 mol% of an aromatic carboxylic acid, and a polyether-modified silicone having a oxyethylene group and / or an oxypropylene group It consists of a composition.

Examples of the base material include synthetic paper (polyolefin type, polystyrene type, etc.), fine paper, art paper, coated paper, cast coated paper, wallpaper, backing paper, synthetic resin or emulsion impregnated paper, synthetic rubber latex impregnated paper, synthetic paper Various resin films or sheets such as resin-added paper, paperboard, cellulose fiber paper, polyolefin, polyvinyl chloride, polyethylene terephthalate, polystyrene, polymethacrylate, polycarbonate, etc. can be used. A white opaque film formed by adding a filler or a foamed foam sheet can also be used. Moreover, the laminated body which combined the said base material can also be used.
As for the thickness of these base materials, about 10-300 micrometers is common, for example. From the viewpoint of improving the adhesion to the dye-receiving layer, it is preferable to subject the surface of the substrate to primer treatment or corona discharge treatment.

The transfer sheet used when performing thermal transfer using the thermal transfer image-receiving sheet of the present invention is usually a paper or polyester film provided with a dye layer containing a sublimation dye. Can also be used.
Examples of sublimable dyes that can be suitably used for the thermal transfer image-receiving sheet of the present invention include pyridoneazo series, dicyanostyryl series, quinophthalone series, merocyanine series for yellow dyes; benzeneazo series, pyrazolone azomethine series, isothiazole series for magenta dyes, Pyrazolotriazole series: As cyan dyes, anthraquinone series, cyanomethylene series, indophenol series, and indonaphthol series are listed.
As the means for applying thermal energy at the time of thermal transfer, any conventionally known means for applying can be used. For example, by controlling the recording time with a recording device such as a thermal printer, it is about 5 to 100 mJ / mm ² . This can be done by applying thermal energy.

Hereinafter, the present invention will be described more specifically with reference to examples and the like. In the following examples and the like, each property value was measured and evaluated by the following method.
[Acid value of resin]
Measured according to JIS K0070. However, as a measurement solvent, a mixed solvent of ethanol and ether was a mixed solvent of acetone and toluene (acetone: toluene = 1: 1 (volume ratio)).

[Softening point and glass transition point of polyester]
(1) Using a flow tester (manufactured by Shimadzu Corporation, “CFT-500D”), a 1 g sample was heated at a rate of temperature increase of 6 ° C./min, a load of 1.96 MPa was applied by a plunger, a diameter of 1 mm, a length Extrude from a 1 mm nozzle. Plot the flow tester drop by the flow tester against the temperature, and let the softening point be the temperature at which half the sample flowed out.
(2) Glass transition point Using a differential scanning calorimeter (Perkin Elmer, Pyris6DSC), the temperature was raised to 200 ° C., and the sample cooled to 0 ° C. at a temperature lowering rate of 10 ° C./min from that temperature was heated to 10 ° C. The temperature is increased at a rate of 1 min / min, and the temperature is defined as the intersection of a base line extension below the maximum peak temperature of endotherm and a tangent line indicating the maximum slope from the peak rising portion to the peak apex.

[Number average molecular weight of resin]
The molecular weight distribution is measured by gel permeation chromatography and the number average molecular weight is calculated by the following method.
(1) Preparation of sample solution The resin is dissolved in tetrahydrofuran (THF) so that the concentration is 0.5 g / 100 ml. Subsequently, this solution is filtered using a fluororesin filter having a pore size of 2 μm [manufactured by Sumitomo Electric Industries, Ltd., “FP-200”] to remove insoluble components to obtain a sample solution.
(2) Molecular weight distribution measurement Using the following apparatus, THF is flowed at a flow rate of 1 ml per minute, and the column is stabilized in a constant temperature bath at 40 ° C. 100 μl of the sample solution is injected therein and measurement is performed. The molecular weight of the sample is calculated based on a calibration curve prepared in advance. The calibration curve at this time includes several types of monodisperse polystyrene (2.63 × 10 ³ , 2.06 × 10 ⁴ , 1.02 × 10 ⁵ manufactured by Tosoh Corporation, and 2.10 × 10 ³ manufactured by GL Sciences, Inc. , 7.00 × 10 ³ , 5.04 × 10 ⁴ ) are used as standard samples.
Measuring device: CO-8010 (manufactured by Tosoh Corporation)
Analysis column: GMHLX + G3000HXL (manufactured by Tosoh Corporation)

[Kinematic viscosity of polyether-modified silicone]
According to JIS K2283, it measures at 25 degreeC with an Ubbelohde viscometer.

Production of polyester a 2859 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 1462 g of 1,4-cyclohexanedicarboxylic acid and 22 g of tin dioctylate were introduced into a nitrogen introduction tube, dehydration tube and stirrer. And put into a four-necked flask equipped with a thermocouple, allowed to react at 200 ° C. under normal pressure for 8 hours under a nitrogen atmosphere, and further reacted under reduced pressure (8.3 kPa). The polyester a was obtained by reacting until the softening point measured according to ASTM D36-86 reached 90 ° C. Polyester a obtained had a softening point of 88 ° C., a glass transition point of 51 ° C., an acid value of 6 mgKOH / g, and a number average molecular weight of 3559.

Manufacture of polyester b 3285 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 1419 g of hexahydrophthalic anhydride, and 24 g of tin dioctylate were introduced into a nitrogen introduction tube, dehydration tube, stirrer and thermocouple Was placed in a four-necked flask equipped with a reaction under a nitrogen atmosphere at 200 ° C. under normal pressure for 8 hours, and further under reduced pressure (8.3 kPa). The polyester b was obtained by reacting until the softening point measured according to ASTM D36-86 reached 90 ° C. Polyester b obtained had a softening point of 92 ° C., a glass transition point of 52 ° C., an acid value of 11 mgKOH / g, and a number average molecular weight of 3106.

Production of polyester c 2100 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 456 g of 1,2-propanediol, 2126 g of 1,4-cyclohexanedicarboxylic acid and 23 g of tin dioctylate were nitrogenated The mixture was placed in a four-necked flask equipped with an introduction tube, a dehydration tube, a stirrer, and a thermocouple, and allowed to react at 200 ° C. under normal pressure for 8 hours under a nitrogen atmosphere, and further reacted under reduced pressure (8.3 kPa). The polyester c was obtained by reacting until the softening point measured according to ASTM D36-86 reached 95 ° C. The obtained polyester c had a softening point of 95 ° C., a glass transition point of 51 ° C., an acid value of 25 mgKOH / g, and a number average molecular weight of 4,617.

Manufacture of polyester d 1768 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 66 g of glycerol, 1169 g of 1,4-cyclohexanedicarboxylic acid, and 15 g of tin dioctylate were introduced into a nitrogen inlet tube and dehydration tube The mixture was placed in a four-necked flask equipped with a stirrer and a thermocouple, allowed to react at 200 ° C. under normal pressure for 8 hours under a nitrogen atmosphere, and further reacted under reduced pressure (8.3 kPa). The polyester d was obtained by reacting until the softening point measured according to ASTM D36-86 reached 120 ° C. The obtained polyester d had a softening point of 123 ° C., a glass transition point of 61 ° C., an acid value of 32 mgKOH / g, and a number average molecular weight of 4568.

Production of polyester e 1750 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 1625 g of polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, During the introduction of nitrogen, 1145 g of terephthalic acid, 161 g of dodecenyl succinic anhydride, 480 g of trimellitic anhydride and 25 g of tin dioctylate were placed in a four-necked flask equipped with a dehydrating tube, a stirrer and a thermocouple, and were heated at 220 ° C. under a nitrogen atmosphere. And reacted until the softening point measured according to ASTM D36-86 reaches 120 ° C. to obtain polyester e. Polyester e obtained had a softening point of 125 ° C., a glass transition point of 65 ° C., an acid value of 19 mgKOH / g, and a number average molecular weight of 3,580.

Production of polyester f 3150 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 1065 g of fumaric acid, 3 g of hydroquinone and 21 g of tin dioctylate were introduced into a nitrogen introduction tube, dehydration tube, The mixture was placed in a four-necked flask equipped with a stirrer and a thermocouple, and reacted at 210 ° C. for 5 hours under a nitrogen atmosphere under normal pressure. Polyester f was obtained by reacting at 210 ° C. under reduced pressure (8.3 kPa) until the softening point measured according to ASTM D36-86 reached 100 ° C. Polyester f obtained had a softening point of 100 ° C., a glass transition point of 59 ° C., an acid value of 21 KOH mg / g, and a number average molecular weight of 4280.

Production of polyester g 1520 g of 1,2-propanediol, 2490 g of terephthalic acid, and 22 g of tin dioctylate were placed in a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, and under a nitrogen atmosphere and normal pressure 200 The reaction was carried out at 5 ° C. for 5 hours, and further under reduced pressure (8.3 kPa). 384 g of trimellitic anhydride was added and reacted until the softening point measured according to ASTM D36-86 reached 130 ° C. to obtain polyester g. Polyester g obtained had a softening point of 131 ° C., a glass transition point of 61 ° C., an acid value of 13 mgKOH / g, and a number average molecular weight of 2638.

The raw material composition and properties of each polyester thus obtained are summarized in Table 1.

Examples 1-4 and Comparative Examples 1-5
Production of Thermal Transfer Image Receiving Sheet Polyester, solvent and release agent were mixed at 25 ° C. in the types and blends shown in Table 2 to prepare coating liquids A to I. Each of the coating liquids A to I is applied to a synthetic paper YUPO FGS-250 (thickness 250 μm, basis weight 200 g / m ² ) by a wire bar so that the coating liquid is 5.0 g / m ² and dried. A thermal transfer image-receiving sheet was obtained. Each color (black (K), yellow (Y), magenta (M), cyan (C), green (G), red (R) is obtained by using a commercially available sublimation printer (SELPHY, manufactured by Canon Inc.) on the thermal transfer image receiving sheet. ), Blue (B)) gradation pattern. The evaluation items were dyeing property (printing sensitivity, maximum density), thermal fusing property with an ink ribbon at the time of printing, and light resistance, which were measured and evaluated as follows. The results are shown in Table 2.

Evaluation method (dyeability-printing sensitivity)
The transfer color density in a black low density print (9th gradation) was measured with Gretag.
(Dyeing property-maximum concentration)
The transfer color density in a black high density print (18th gradation) was measured with Gretag.

(Heat fusion)
The presence or absence of heat-fusibility was judged from the peeling sound between the ink ribbon and the thermal transfer image-receiving sheet at the time of gradation pattern printing.
A: There is no abnormal noise at the time of peeling, and there is no problem caused by thermal fusion between the thermal transfer image receiving sheet and the ink ribbon.
B: Although some abnormal noise is heard at the time of peeling, there is no problem caused by heat fusion.
C: It is heat-sealed and peeling is difficult.

(Light resistance)
A light resistance test was conducted using a xenon weather meter under the following conditions.
・ Irradiation tester: SX75 manufactured by Suga Test Instruments Co., Ltd.
Light source: Xenon lamp Filter: Inside = quartz filter, outside = # 275
・ Panel temperature: 50 ℃
-Humidity in the tank: 35-50% RH
・ Irradiation intensity: 50 (W / m 2) …… Measured value at 300 to 400 (nm) ・ Integrated illuminance: 10000 (kJ / m 2) …… Integrated value at 300 to 400 (nm) ・ Hue change: optical Using a densitometer (measured with Gretag), black (K), yellow (Y), magenta (M), cyan (C), green (G), red (R), blue (B) of the gradation pattern print The optical reflection density was measured using a color difference meter (measured with Gretag) before and after irradiation for a step where the optical reflection density before irradiation was around 1.0. The amount of hue change was calculated. The light fastness is the amount of change in hue of a black (K) printed material, and black (K), yellow (Y), magenta (M), cyan (C), green (G), red (R), blue (B ) And the total value of the hue change amount of the printed matter. A smaller hue change indicates better light resistance.
Hue variation _{^{= √ ((a * 1 -a}} * 2) 2 + (b * 1 -b * 2) 2)
L ^* a ^* b ^* value before irradiation: L ^* ₁ , a ^* ₁ , b ^* ₁
L ^* a ^* b ^* value after irradiation: L * ₂ , a ^* ₂ , b ^* ₂

  The receiving layer comprising the composition of the present invention is excellent in dyeing property, excellent in releasability of the thermal transfer image-receiving sheet, and excellent in light resistance, and therefore can be suitably used as a thermal transfer image-receiving sheet. .

Claims (6)

  A resin containing a polyester obtained by condensation polymerization of an alcohol component containing 50 mol% or more of an alkylene oxide adduct of bisphenol A and a carboxylic acid component containing more than 50 mol% of an alicyclic carboxylic acid, and an oxyethylene group And / or a composition for a receiving layer of a thermal transfer image-receiving sheet comprising a polyether-modified silicone having an oxypropylene group.   The composition for receiving layers of Claim 1 which contains the polyether modified silicone which has an oxyethylene group and / or an oxypropylene group with respect to 100 weight part of resin components which comprise a receiving layer. The composition for receiving layers of Claim 1 or 2 whose kinematic viscosity in 25 degreeC of the polyether modified silicone which has an oxyethylene group and / or an oxypropylene group is 500-3,000 mm < ² > / s.   The alkylene oxide adduct of bisphenol A has a content ratio of ethylene oxide adduct and propylene oxide adduct (ethylene oxide adduct / propylene oxide adduct) in a molar ratio of 50/50 to 0/100. The composition for receiving layers in any one of -3.   A receiving layer for a thermal transfer image receiving sheet, comprising the receiving layer composition according to claim 1.   A thermal transfer image-receiving sheet comprising a substrate and the receptor layer according to claim 5 on at least one surface of the substrate.