JP2007290302A - Thermal transfer receiving sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a receiving sheet which has good transferring properties of a protective layer on a receiving layer face from an ink ribbon, excellent releasing performance of the ink ribbon from the receiving layer face, and high recording density even when high speed printing by a thermal printer is performed. <P>SOLUTION: A thermal transfer receiving sheet comprises a sheet-like substrate and an image receiving layer formed on at least one face of this sheet-like substrate. In the thermal transfer receiving sheet, the image receiving layer comprises a polymer of an acrylate compound expressed by general formula (1). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a thermal transfer receiving sheet (hereinafter simply referred to as “receptive layer”) having an image receiving layer (hereinafter also referred to simply as “receptive layer”) composed mainly of a dye-stainable thermoplastic resin (also simply referred to as “stainable resin”). It is also called a sheet.) More specifically, in the present invention, the peelability of the ink sheet (hereinafter also referred to as an ink ribbon) from the dye layer and the transfer type laminate layer (hereinafter simply referred to as a protective layer) of the ink ribbon even during high-speed printing. ) With a high recording density and high image quality.

  In the dye thermal transfer method, the ink ribbon and the receiving sheet are overlapped, the sublimation dye in the ink ribbon dye layer is transferred onto the receiving layer of the receiving sheet by heat supplied from a thermal head, etc., and then both are released. To form an image. As the dyeing resin used in the receiving layer, vinyl chloride resin, polyester resin, polyvinyl butyral resin, acrylic resin, cellulose resin, etc. are used, and silicone release agents and fluorine release resins are used as release agents. Molding agents, fatty acid release agents, and the like have been proposed.

  In recent years, in order to improve image storability such as light resistance and grease resistance, an “overlaminate” method in which a protective layer is provided after sequentially transferring three-color or four-color dyes on an ink ribbon has become mainstream. . In this method, the receiving layer needs to realize contradictory physical properties such as releasability with respect to the surface of the dye layer of the ink ribbon and adhesion with respect to the surface of the protective layer of the ink ribbon.

  Conventionally, general vinyl chloride resins and cellulose resins have been used as dyeing resins in the receiving layer. With conventional printers, sufficient release properties of the ink ribbon and adhesiveness to the protective layer can be obtained. It was done. However, with recent increases in printer speeds, it is becoming difficult to achieve both releasability and adhesiveness only with these general resins.

  As a modification method of the receiving layer, a method using a vinyl chloride resin and another resin in combination, for example, polyester polyol, polyether polyol, acrylic polyol, polyalkyl vinyl ether, polyvinyl acetate, ethylene-vinyl acetate copolymer, ethylene -Ethylene acrylate copolymer, ethylene-methyl methacrylate copolymer, ketone resin, diallyl phthalate resin, etc.) or the like (see, for example, JP-A-5-4459 (Patent Document 1)) or chlorination. A method of using a vinyl-vinyl acetate copolymer in combination with cellulose acetate butyrate and / or cellulose acetate propionate (for example, see JP-A-5-238166 (Patent Document 2)) and the like are disclosed. .

  A dyeable resin has also been developed, and a copolymer of vinyl chloride and another monomer (see, for example, JP-A-5-262059 (Patent Document 3)) or a main chain of a cellulose compound. A graft polymer obtained by grafting an aromatic-containing (meth) acrylate compound on the surface (for example, see JP-A No. 2004-122522 (Patent Document 4)) is disclosed.

  However, the method as described above is effective in improving the storage stability of the receiving sheet printed matter and the surface writing property, but has contributed much to improving the adhesiveness of the protective layer in the latest high-speed printer. In addition to this, there was a problem that depending on the resin used in combination, the transferability of the dye was impaired and the printing density was lowered.

  Further, as a receiving layer having good protective layer transferability, a receiving layer containing a copolymer of phenoxypolyethylene glycol methacrylate and another monomer is disclosed (for example, JP-A-8-224967 (Patent Document 5). However, it is insufficient for transfer of the protective layer under high-speed printing conditions, resulting in transfer failure.

Japanese Patent Laid-Open No. 5-4459 (page 2) JP-A-5-238166 (2nd page) JP-A-5-262059 (2nd page) Japanese Unexamined Patent Publication No. 2004-122522 (second page) JP-A-8-224967 (2nd page)

  The object of the present invention is to improve the above-mentioned drawbacks of the prior art, have good transferability of the protective layer from the ink ribbon to the receiving layer surface even during high-speed printing, and have excellent ink ribbon peeling performance from the receiving layer surface, and An object is to provide a receiving sheet having a high recording density.

The present invention includes the following inventions.
(1) In a thermal transfer receiving sheet having a sheet-like support and an image receiving layer formed on at least one surface of the sheet-like support, the image receiving layer is an acrylate compound represented by the general formula (1) A thermal transfer receiving sheet comprising:

（式中、ｎは１〜３から選ばれる整数。Ｒ^１、Ｒ^２はそれぞれ独立して、水素原子、メチル基、またはエチル基を表し、Ｒ^３は、水素原子またはメチル基を表す。）
（２）前記画像受容層が、塩化ビニル−酢酸ビニル系共重合体を含有する（１）項に記載の熱転写受容シート。

(In the formula, n is an integer selected from 1 to ^3. R ¹ and R ² each independently represents a hydrogen atom, a methyl group, or an ethyl group, and R ³ represents a hydrogen atom or a methyl group.)
(2) The thermal transfer receiving sheet according to item (1), wherein the image receiving layer contains a vinyl chloride-vinyl acetate copolymer.

(3) The thermal transfer receiving sheet according to (2), wherein the image receiving layer contains 5 to 50 parts by mass of the polymer of the acrylate compound with respect to 100 parts by mass of the vinyl chloride-vinyl acetate copolymer. .
(4) The thermal transfer receiving sheet according to any one of (1) to (3), wherein the image receiving layer further contains a polyester plasticizer.
(5) The thermal transfer receiving sheet according to any one of (1) to (4), wherein the image receiving layer further contains an epoxy-modified silicone and / or an epoxy polyether-modified silicone.

  The receiving sheet of the present invention is a receiving sheet that has a high printing density, good image quality, excellent transferability of the ink ribbon protective layer, and excellent releasability between the receiving layer and the ink ribbon even during high-speed printing. is there.

(Receptive layer)
The receiving sheet of the present invention has at least a sheet-like support and a receiving layer formed on at least one surface of the sheet-like support, and the receiving layer is represented by the general formula (1) as a dyeing resin. It contains a polymer of the acrylate compound represented. In the general formula (1), n is any integer of 1 to 3, and 1 is particularly preferable. R ¹ and R ² each independently represent a hydrogen atom, a methyl group, or an ethyl group, and R ³ represents a hydrogen atom or a methyl group.

  Specific examples of the acrylate compound include 2-hydroxy-3-phenoxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 4-hydroxy-5-phenoxypentyl acrylate, and 3-hydroxy-4- (m-ethylphenoxy). Monomers such as butyl acrylate, 3-hydroxy-4- (p-methylphenoxy) butyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate are exemplified, and these polymers are preferably used.

Although the molecular weight of the acrylate compound polymer used by this invention is not specifically limited, The number average molecular weights 3000-30000 measured by gel permeation chromatography (GPC) are preferable, and 5000-20000 are more preferable. When the number average molecular weight is less than 3000, fusion between the receiving layer and the ink ribbon may occur. On the other hand, when the number average molecular weight exceeds 30000, other dyeing resins (for example, vinyl chloride-acetic acid). When used in combination with a vinyl copolymer) or the like, the compatibility may deteriorate and the uniformity of the coated surface may be lost.
In addition, the acrylate compound represented by the general formula (1) is a vinyl chloride, vinyl acetate, polyester, cellulose acetate butyrate, cellulose acetate propionate, polycarbonate, other acrylics, etc., as long as the effects of the present invention are not impaired. It can also be used after being copolymerized with a monomer or resin.

  In the receiving layer of the present invention, a vinyl chloride-vinyl acetate copolymer is preferably used together with the polymer of the specific acrylate compound, the light fastness of the image is good, and the blur of the image in a high humidity environment is small. The amount of the acrylate compound polymer is preferably 5 to 50 parts by mass, and more preferably 10 to 45 parts by mass with respect to 100 parts by mass of the vinyl chloride-vinyl acetate copolymer. If the content of the acrylate compound polymer is less than 5 parts by mass, the transferability of the protective layer from the ink ribbon may be deteriorated. On the other hand, if it exceeds 50 parts by mass, the light resistance may be reduced and the image may be blurred. is there.

  The vinyl chloride-vinyl acetate copolymer used preferably has a (vinyl chloride component / vinyl acetate component) mass ratio of 75/25 to 90/10. The heat resistance may decrease and the ribbon and the receiving sheet may be fused at the time of printing, and if it exceeds 90/10, the printing density may decrease and the quality may be impaired. The vinyl chloride-vinyl acetate copolymer preferably has a number average molecular weight measured by gel permeation chromatography (GPC) in the range of 10,000 to 50,000, more preferably 20,000 to 35,000. When the number average molecular weight is less than 10,000, fusion between the receiving layer and the ink ribbon may occur. On the other hand, when the number average molecular weight exceeds 50,000, a coating solution containing a vinyl chloride-vinyl acetate copolymer is contained. The viscosity of the coating increases, and the smoothness of the coated surface may be inferior.

  The vinyl chloride-vinyl acetate copolymer may include a comonomer component other than a vinyl chloride component and a vinyl acetate component, such as vinyl propionate, acrylic acid, methacrylic acid, methyl acrylate, ethyl methacrylate, Acrylic acid or methacrylic acid such as butyl acrylate, methacrylic acid-2-hydroxyethyl, -2-ethylhexyl acrylate and alkyl esters thereof, maleic acid such as maleic acid and diethyl maleate and alkyl esters thereof, methyl vinyl ether, Examples include alkyl vinyl ethers such as 2-ethylhexyl vinyl ether. Furthermore, examples of the comonomer include ethylene, propylene, acrylonitrile, methacrylonitrile, and styrene. The vinyl chloride-vinyl acetate copolymer may be any of a block copolymer, a graft copolymer, an alternating copolymer, and a random copolymer. Furthermore, a hydroxyl group or a carboxyl group may be introduced. Good.

  Further, a polyester plasticizer is preferably used in the receiving layer of the present invention, and the polyester plasticizer has an effect of increasing the printing density by promoting the penetration of the dye into the receiving layer. For example, when the acrylate compound polymer of the present invention and a vinyl chloride-vinyl acetate copolymer are used in combination, the compatibility can be improved and a uniform receiving layer can be formed. 3-50 mass parts is preferable with respect to 100 mass parts of all the polymer components of a receiving layer, and, as for the compounding quantity of a polyester plasticizer, More preferably, it is 5-40 mass parts. When the blending amount of the polyester plasticizer is less than 3 parts by mass, the effect of improving the printing density may be small, and when it exceeds 50 parts by mass, the structural strength of the receiving layer decreases and the surface of the printed product is easily peeled off. May occur.

  The polyester plasticizer used in the present invention preferably has a viscosity specified by JIS K 7117-1 of 500 mPas or less, more preferably in the range of 30 to 500 mPas. When the viscosity exceeds 500 mPas, the compatibility with the vinyl chloride-vinyl acetate copolymer is deteriorated, the uniformity of the coated surface is lost, and the image quality of the printed matter may be deteriorated. On the other hand, when the viscosity of the polyester plasticizer is too low, bleeding out from the receiving layer occurs in a high-temperature environment, which may reduce image storage stability. Although the kind of polyester plasticizer is not specifically limited, For example, the condensate of adipic acid and dihydric alcohol or dicarboxylic acid and dihydric alcohol is mentioned. Specific examples include a condensate of phthalic acid and 1,2-butanediol, a condensate of adipic acid and 1,4-butanediol, and the like.

  The receptor layer of the present invention preferably contains an epoxy-modified silicone oil and / or an epoxy polyether-modified silicone oil. By including an epoxy-modified silicone oil or an epoxy-polyether-modified silicone oil, the releasability between the ink ribbon and the receiving layer can be improved, and when transferring the protective layer, an acrylic resin or butyral which is a protective layer component The resin and the epoxy group are bonded to each other, and good protective layer transfer suitability is obtained. The blending amount of these silicone oils is not particularly limited, but it is preferably blended in the range of 0.5 to 20 parts by mass with respect to 100 parts by mass of all polymer components used in the receiving layer. . When the ratio of these silicone oils to 100 parts by mass of the total polymer components used in the receptor layer is less than 0.5 parts by mass, the adhesion between the receptor layer and the protective layer may be significantly reduced, while 20 parts by mass. If it exceeds, the peelability of the receiving layer and the ink ribbon may decrease.

  In addition, it is possible to use a known releasable substance in a compounding amount that does not impair the performance of the present invention. Although not particularly limited, specifically, dimethyl silicone oil, alcohol-modified silicone oil, amino-modified silicone oil, carboxyl-modified silicone oil, modified silicone oil such as methacrylic acid-modified silicone oil, paraffin wax, polyethylene, Examples of the releasable substance include hydrocarbons such as fluorocarbons, fatty acids such as stearic acid, aliphatic amides, esters, alcohols, metal soaps, and natural waxes. These releasable substances are preferably blended in the range of 0.1 to 20 parts by mass with respect to 100 parts by mass of all polymer components of the receiving layer, and are not particularly limited.

  In order to improve the releasability, it is also possible to crosslink the dyeable resin with a crosslinking agent such as a polyvalent isocyanate compound, epoxy, or organometallic compound. These crosslinking agents are preferably blended so that the number of functional groups of the crosslinking agent is about 0.1 to 1,000 with respect to the number of functional groups of the dyeable resin.

  In addition, a known dyeing resin may be used in combination as appropriate, as long as the effects of the present invention are not impaired. Although not particularly limited, for example, polyacetal resins such as polyester resin, cellulose acetate butyrate, polyvinyl formal, polyacetal, polyvinyl butyral, bisphenol A (hereinafter also referred to as BIS-A) type epoxy resin, hydrogenated BIS-A. Type epoxy resin, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polystyrene, styrene-acrylonitrile copolymer, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, polymethyl methacrylate, methyl methacrylate-styrene copolymer, polyamide In addition, one or two or more of resins such as ethyl cellulose, cellulose acetate, propyl cellulose, cellulose nitrate, polycarbonate resin, phenoxy resin, and polyurethane can be used in combination.

  In addition, for the purpose of controlling dyeability, a plasticizer other than the polyester-based plasticizer can be used in combination as long as the effects of the present invention are not impaired. As the plasticizer other than the polyester plasticizer, known ones such as phthalate ester, aliphatic dibasic ester, trimellitic ester, phosphate ester, and epoxy can be used.

  In order to further improve the light resistance, an ultraviolet absorber (hereinafter referred to as UVA), a hindered amine light stabilizer (hereinafter referred to as HALS), or an antioxidant can be used alone or in combination. As UVA, benzotriazole UVA, triazine UVA, oxalic anilide UVA, and benzophenone UVA are generally known, but especially benzotriazole has a wider absorption wavelength range than other UVAs, Since it has a maximum absorption peak on the high wavelength side and has a large absorbance, a particularly excellent effect is obtained when used in combination with HALS, and it is preferably used. As a compounding quantity, 1-70 mass parts is mix | blended with respect to 100 mass parts of all the polymer components of a receiving layer, and the mixing | blending of 1-40 mass parts is used preferably from the balance of UVA input amount and an effect especially. . HALS is a compound having a 2,2,6,6-tetramethylpiperidine skeleton, and is not particularly limited as long as it has this skeleton. HALS is blended in an amount of 1 to 70 parts by weight with respect to 100 parts by weight of the total polymer components in the receiving layer, and a blending amount of 1 to 40 parts by weight is particularly preferred because of the balance between the HALS input and the effect.

The solid coating amount of the receiving layer is preferably about 1 to 12 g / m ² , more preferably ² to 10 g / m ² . Incidentally, when the solid coating amount of the receiving layer is less than 1 g / m ² , the receiving layer can completely cover the support surface (an intermediate layer, a barrier layer, etc. may be formed on the surface). In some cases, the image quality may be degraded, and a fusing problem may occur in which the receiving layer and the ink ribbon adhere to each other due to heating of the thermal head. On the other hand, if the solid content coating amount of the receiving layer exceeds 12 g / m ² , not only is the effect saturated and uneconomical, but the strength of the receiving layer is insufficient, or the thickness of the receiving layer is increased and supported. The heat insulation effect of the body is not sufficiently exhibited, and the image density may be lowered.

(Sheet support)
As the support of the receiving sheet in the present invention, papers mainly composed of cellulose pulp, synthetic resin films and the like are used. For example, paper such as high-quality paper (acidic paper, neutral paper), medium-quality paper, coated paper, art paper, glassine paper, resin-laminated paper, or polyolefin such as polyethylene or polypropylene, polyester such as polyethylene terephthalate, polyamide Films or sheets based on synthetic resins such as polyvinyl chloride, polystyrene, polycarbonate, polyvinyl alcohol, polyvinyl chloride, or porous single layer stretched films or porous materials based on thermoplastic resins such as polyolefin or polyester A multi-layer stretched film (for example, synthetic paper, porous polyester film) and the like, and a laminate obtained by laminating and sticking these films to each other and another film and / or paper are appropriately used.

The substrate surface layer (substrate on the receiving layer side) of the support is not particularly limited, but a thermoplastic resin such as polyolefin or polyester is used from the viewpoint of the uniformity and gradation of the printed image. A porous single layer stretched film or a porous multilayer stretched film (for example, synthetic paper or porous polyester film) as a main component is preferably used.
Furthermore, in order to prevent static electricity and improve whiteness, it is also possible to provide a coating layer containing various known conductive agents, white pigments, fluorescent dyes, etc. between the sheet-like support and the receiving layer. .

(Middle layer)
In the present invention, among the above sheet-like supports, papers mainly composed of cellulose pulp are advantageous in terms of cost, and are preferably used because the texture of the resulting receiving sheet is close to photographic paper. The When using a paper support, it is preferable to provide an intermediate layer containing hollow particles on the paper support.

  The material and manufacturing method of the hollow particles used in the intermediate layer are not particularly limited. Specifically, the material for forming the walls of the hollow particles may be acrylonitrile, vinylidene chloride, styrene, acrylate, or the like. Homopolymers, copolymers thereof, and mixtures of these homopolymers can be mentioned. As a method for producing these hollow particles, for example, a method of encapsulating butane gas in resin particles and heating and foaming, an emulsion polymerization method or the like can be mentioned.

  The adhesive resin used in the intermediate layer is not particularly limited. For example, hydrophilic polymer resins such as polyvinyl alcohol resins, cellulose resins and derivatives thereof, casein, starch derivatives, and the like have film-forming properties, heat resistance, and flexibility. It is preferably used from the viewpoint of sex. Also, emulsions of various resins such as (meth) acrylic acid ester resins, styrene-butadiene copolymer resins, urethane resins, polyester resins, ethylene-vinyl acetate copolymer resins are used as low-viscosity and high-solids aqueous resins. . The adhesive resin used in the low density layer is more preferably used in combination with the above hydrophilic polymer resin and emulsions of various resins from the viewpoints of coating strength, adhesion, and coatability of the low density layer.

(Barrier layer)
A barrier layer is preferably provided between the intermediate layer and the receiving layer. Generally, as the solvent of the coating solution for the receiving layer, an organic solvent such as toluene or methyl ethyl ketone is used. Therefore, the barrier layer is formed by deformation of the hollow particles due to swelling and dissolution of the hollow particles in the intermediate layer due to penetration of the organic solvent. It is effective as a barrier to prevent destruction.

  As the resin used for the barrier layer, a resin having excellent film forming ability, preventing penetration of an organic solvent, and having elasticity and flexibility is used. Specifically, starch, modified starch, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, gum arabic, fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, carboxy modified polyvinyl alcohol, acetoacetyl group modified polyvinyl alcohol, silanol Modified polyvinyl alcohol, diisobutylene-maleic anhydride copolymer salt, styrene-maleic anhydride copolymer salt, styrene-acrylic acid copolymer salt, ethylene-acrylic acid copolymer salt, urea resin, urethane resin, melamine Water-soluble resins such as resins and amide resins are used. Water dispersible resins such as styrene-butadiene copolymer latex, acrylic ester resin latex, methacrylic ester copolymer latex, ethylene-vinyl acetate copolymer latex, polyester polyurethane ionomer, polyether polyurethane ionomer, etc. Can be used. Among the above resins, water-soluble resins are preferably used. Moreover, said resin may be used individually or may use 2 or more types together.

  Furthermore, the barrier layer may contain various pigments, preferably a swellable inorganic layered compound is used, which is excellent not only in preventing penetration of the coating solvent but also in preventing blurring of the thermal transfer dyed image. An effect is obtained. Examples of the swellable inorganic layered compound include synthetic mica such as fluorine phlogopite, potassium tetrasilicon mica, sodium tetrasilicon mica, sodium teniolite, lithium teniolite, or sodium hectorite, lithium hectorite, saponite, etc. Smectite is more preferably used. Among these, sodium tetrasilicon mica is particularly preferable, and a desired particle size, aspect ratio, and crystallinity can be obtained by a fusion synthesis method.

(Back layer)
In the receiving sheet of the present invention, on the surface (back surface) opposite to the receiving layer, the running property is improved, the static electricity is prevented, the receiving layer is prevented from being damaged due to rubbing between the receiving sheets, and the printed receiving sheet is stacked. Then, the back layer may be formed for the purpose of preventing dye transfer from the receiving layer to the back surface of the receiving sheet adjacent to and in contact with the receiving layer. A resin as an adhesive component and various conductive agents can be added to the back layer for antistatic treatment. As the conductive agent, it is preferable to use a cationic polymer. As the cationic polymer, polyethyleneimine, an acrylic polymer containing a cationic monomer, a cation-modified acrylamide polymer, a cationic starch, or the like can be generally used.

  In the present invention, each coating layer such as a receiving layer, a back layer, an intermediate layer or a barrier layer is formed in accordance with a conventional method, and a coating solution containing required components is prepared for each bar coater, gravure coater, comma coater. After coating and drying on a predetermined surface of a sheet-like support using a known coater such as a blade coater, air knife coater, gate roll coater, die coater, curtain coater, lip coater, and slide bead coater If necessary, it can be formed by heat curing.

  Furthermore, the receiving sheet may be calendered, and the unevenness of the receiving layer surface can be reduced and smoothed. For example, when paper is used as the support, the calendering process may be performed at any stage after coating the intermediate layer, the barrier layer, or the receiving layer. There are no particular limitations on the calendar device used for the calendar process, the nip pressure, the number of nips, the surface temperature of the metal roll, etc., but the pressure condition when performing the calendar process is preferably 0.5 to 50 MPa. More preferably, it is 1-30 MPa. The temperature condition is preferably 20 to 150 ° C, more preferably 30 to 130 ° C. As the calendar device, for example, a calendar device generally used in the paper industry such as a super calendar, a soft calendar, a gloss calendar, a clearance calendar, and the like can be appropriately used.

  The present invention will be described in more detail with reference to the following examples, but the present invention is of course not limited thereto. Unless otherwise specified, “parts” and “%” in the examples all represent “parts by mass” and “% by mass”, and are solid amounts except for those relating to solvents.

"Synthesis of acrylate polymers"
Each acrylate polymer was synthesized by a known method using acrylate monomers as shown in Table 1. The number average molecular weight of the obtained resin is also shown in Table 1.

Example 1
"Formation of an intermediate layer"
As a sheet-like support, art paper (trade name: OK Kanto N, 174.4 g / m ² , made by Oji Paper Co., Ltd.) having a thickness of 150 μm is used, and an intermediate layer coating liquid-1 having the following composition is applied on one side thereof. The intermediate layer was formed by coating and drying so that the film thickness after drying was 51 μm.
Intermediate layer coating solution-1
Pre-expanded hollow particles (average particle size 3.2 μm, volume hollow ratio 76%) made of a copolymer mainly composed of acrylonitrile and methacrylonitrile 50 parts polyvinyl alcohol (trade name: PVA205, manufactured by Kuraray Co., Ltd.) 10 parts styrene Butadiene latex (trade name: PT1004, manufactured by Nippon Zeon) 40 parts Water 250 parts

"Formation of barrier and receptor layers"
On the formed intermediate layer, the barrier layer coating solution-1 having the following composition is applied and dried so that the solid content coating amount is 2 g / m ² to form a barrier layer. On the layer, the receiving layer coating liquid-1 having the following composition was applied and dried so that the solid content coating amount was 5 g / m ² to form a receiving layer.
Coating liquid for barrier layer-1
Swellable inorganic layered compound (sodium 4 silicon mica,
Particle average major axis 6.3 μm, aspect ratio 2700) 30 parts polyvinyl alcohol (trade name: PVA105, manufactured by Kuraray) 50 parts styrene-butadiene latex (trade name: L-1537, manufactured by Asahi Kasei) 20 parts water 1100 parts

Receiving layer coating solution-1
Vinyl chloride-vinyl acetate copolymer (trade name: Solvain C, manufactured by Nissin Chemical Industry, composition ratio:
Vinyl chloride / vinyl acetate = 87/13, number average molecular weight 31000) 100 parts acrylate polymer A 30 parts polyester plasticizer (trade name: K3220, manufactured by Mitsubishi Chemical,
30 parts epoxy polyether-modified silicone oil (trade name: SF8421)
10 parts alcohol-modified silicone oil (trade name: SF8427, manufactured by Toray Dow Corning Silicone)
Toray Dow Corning Silicone Co., Ltd.) 2 parts isocyanate compound (trade name: NY-710A, manufactured by Mitsubishi Chemical Corporation) 5 parts Toluene / methyl ethyl ketone = 1/1 (mass ratio) 200 parts

"Formation of back layer"
Next, on the other surface of the sheet-like support (the surface opposite to the receiving layer-forming surface), the back layer coating solution-1 having the following composition is 3 g in solid content after drying. / M ² was applied and dried to form a back layer, followed by heat treatment at 50 ° C. for 4 days. Furthermore, in order to smooth the surface of the receiving sheet, calendar processing (roll surface temperature 78 ° C., nip pressure 2.5 MPa) was performed to prepare a receiving sheet.

Back layer coating solution-1
Polyvinyl acetal resin (trade name: ESREC KX-1, manufactured by Sekisui Chemical Co., Ltd.) 40 parts Polyacrylate resin (trade name: Jurimer AT613, manufactured by Nippon Pure Chemicals) 20 parts nylon resin particles (trade name: MW330, Shinto Paint) 10 parts zinc stearate (trade name: Z-7-30, manufactured by Chukyo Yushi) 10 parts cationic conductive resin (trade name: Chemistat 9800, manufactured by Sanyo Kasei) 20 parts water / isopropyl alcohol = 2/3 ( (Mass ratio) 400 parts

Example 2
A receiving sheet was prepared in the same manner as in Example 1 except that the following receiving layer coating solution-2 was used instead of the receiving layer coating solution-1.
Receiving layer coating solution-2
Vinyl chloride-vinyl acetate copolymer (trade name: Solvine CL, manufactured by Nissin Chemical Industry, composition ratio:
Vinyl chloride / vinyl acetate = 86/14, number average molecular weight 25000) 100 parts acrylate polymer B 30 parts polyester plasticizer (trade name: D670, manufactured by JPLUS,
30 parts epoxy polyether-modified silicone oil (trade name: SF8421)
10 parts alcohol-modified silicone oil (trade name: SF8427, manufactured by Toray Dow Corning Silicone)
Toray Dow Corning Silicone) 2 parts isocyanate compound (trade name: NY-710A, manufactured by Mitsubishi Chemical Corporation) 5 parts Toluene / methyl ethyl ketone = 1/1 (mass ratio) 200 parts

Example 3
A receiving sheet was prepared in the same manner as in Example 1 except that the following receiving layer coating solution-3 was used instead of the receiving layer coating solution-1.
Receiving layer coating solution-3
Vinyl chloride-vinyl acetate copolymer (trade name: Solvain C, manufactured by Nissin Chemical Industry, composition ratio:
Vinyl chloride / vinyl acetate = 87/13, number average molecular weight 31000) 100 parts acrylate polymer C 30 parts polyester plasticizer (trade name: D670, manufactured by JPLUS,
30 parts epoxy polyether-modified silicone oil (trade name: SF8421)
10 parts alcohol-modified silicone oil (trade name: SF8427, manufactured by Toray Dow Corning Silicone)
Toray Dow Corning Silicone) 2 parts isocyanate compound (trade name: NY-710A, manufactured by Mitsubishi Chemical Corporation) 5 parts Toluene / methyl ethyl ketone = 1/1 (mass ratio) 200 parts

Example 4
A receiving sheet was prepared in the same manner as in Example 1 except that the following receiving layer coating solution-4 was used instead of the receiving layer coating solution-1.
Receiving layer coating solution-4
Vinyl chloride-vinyl acetate copolymer (trade name: Solvain C, manufactured by Nissin Chemical Industry, composition ratio:
Vinyl chloride / vinyl acetate = 87/13, number average molecular weight 31000) 100 parts acrylate polymer D 30 parts polyester plasticizer (trade name: D670, manufactured by JPLUS,
30 parts epoxy polyether-modified silicone oil (trade name: SF8421)
10 parts alcohol-modified silicone oil (trade name: SF8427, manufactured by Toray Dow Corning Silicone)
Toray Dow Corning Silicone) 2 parts isocyanate compound (trade name: NY-710A, manufactured by Mitsubishi Chemical Corporation) 5 parts Toluene / methyl ethyl ketone = 1/1 (mass ratio) 200 parts

Example 5
A receiving sheet was prepared in the same manner as in Example 1 except that the following receiving layer coating solution-5 was used instead of the receiving layer coating solution-1.
Receptive layer coating solution-5
Vinyl chloride-vinyl acetate copolymer (trade name: Solvain C, manufactured by Nissin Chemical Industry, composition ratio:
Vinyl chloride / vinyl acetate = 87/13, number average molecular weight 31000) 100 parts acrylate polymer E 30 parts polyester plasticizer (trade name: D670, manufactured by JPLUS,
30 parts epoxy-modified silicone oil (trade name: KF105, viscosity 300 mPas)
10 parts alcohol-modified silicone oil (trade name: SF8427, manufactured by Shin-Etsu Chemical Co., Ltd.)
Toray Dow Corning Silicone) 2 parts isocyanate compound (trade name: NY-710A, manufactured by Mitsubishi Chemical Corporation) 5 parts Toluene / methyl ethyl ketone = 1/1 (mass ratio) 200 parts

Example 6
A receiving sheet was prepared in the same manner as in Example 1 except that the following receiving layer coating solution-6 was used instead of the receiving layer coating solution-1.
Receptive layer coating solution-6
Vinyl chloride-vinyl acetate copolymer (trade name: Solvain C, manufactured by Nissin Chemical Industry, composition ratio:
Vinyl chloride / vinyl acetate = 87/13, number average molecular weight 31000) 100 parts acrylate polymer F 30 parts polyester plasticizer (trade name: D670, manufactured by JPLUS,
30 parts epoxy polyether-modified silicone oil (trade name: SF8421)
10 parts alcohol-modified silicone oil (trade name: SF8427, manufactured by Toray Dow Corning Silicone)
Toray Dow Corning Silicone) 2 parts isocyanate compound (trade name: NY-710A, manufactured by Mitsubishi Chemical Corporation) 5 parts Toluene / methyl ethyl ketone = 1/1 (mass ratio) 200 parts

Example 7
A receiving sheet was prepared in the same manner as in Example 1 except that the following receiving layer coating solution-7 was used instead of the receiving layer coating solution-1.
Receiving layer coating solution -7
Vinyl chloride-vinyl acetate copolymer (trade name: Solvain C, manufactured by Nissin Chemical Industry, composition ratio:
Vinyl chloride / vinyl acetate = 87/13, number average molecular weight 31000) 100 parts acrylate polymer A 40 parts polyester plasticizer (trade name: K3220, manufactured by Mitsubishi Chemical,
Viscosity 100 mPas) 10 parts epoxy polyether modified silicone oil (trade name: SF8421,
10 parts alcohol-modified silicone oil (trade name: SF8427, manufactured by Toray Dow Corning Silicone)
Toray Dow Corning Silicone Co., Ltd.) 2 parts isocyanate compound (trade name: NY-710A, manufactured by Mitsubishi Chemical Corporation) 5 parts Toluene / methyl ethyl ketone = 1/1 (mass ratio) 200 parts

Example 8
A receiving sheet was prepared in the same manner as in Example 1 except that the following receiving layer coating solution-8 was used instead of the receiving layer coating solution-1.
Receptive layer coating solution-8
Vinyl chloride-vinyl acetate copolymer (trade name: Solvain C, manufactured by Nissin Chemical Industry, composition ratio:
Vinyl chloride / vinyl acetate = 87/13, number average molecular weight 31000) 100 parts acrylate polymer A 10 parts polyester plasticizer (trade name: K3220, manufactured by Mitsubishi Chemical,
Viscosity 100 mPas) 40 parts epoxy polyether modified silicone oil (trade name: SF8421)
10 parts alcohol-modified silicone oil (trade name: SF8427, manufactured by Toray Dow Corning Silicone)
Toray Dow Corning Silicone Co., Ltd.) 2 parts isocyanate compound (trade name: NY-710A, manufactured by Mitsubishi Chemical Corporation) 5 parts Toluene / methyl ethyl ketone = 1/1 (mass ratio) 200 parts

Comparative Example 1
A receiving sheet was prepared in the same manner as in Example 1 except that the following receiving layer coating solution-9 was used instead of the receiving layer coating solution-1.
Receiving layer coating solution-9
Vinyl chloride-vinyl acetate copolymer (trade name: Solvain C, manufactured by Nissin Chemical Industry, composition ratio:
Vinyl chloride / vinyl acetate = 87/13, number average molecular weight 31000) 100 parts alcohol-modified silicone oil (trade name: SF8427,
Toray Dow Corning Silicone Co., Ltd.) 0.8 parts isocyanate compound (trade name: NY-710A, manufactured by Mitsubishi Chemical Corporation) 3 parts Toluene / methyl ethyl ketone = 1/1 (mass ratio) 200 parts

Comparative Example 2
A receiving sheet was prepared in the same manner as in Example 1 except that the following receiving layer coating solution-10 was used instead of the receiving layer coating solution-1.
Receiving layer coating solution-10
100 parts polyester plasticizer (trade name: K3220, manufactured by Mitsubishi Chemical Co., Ltd.)
Viscosity 100 mPas) 30 parts alcohol-modified silicone oil (trade name: SF8427,
Toray Dow Corning Silicone Co., Ltd.) 0.8 parts isocyanate compound (trade name: NY-710A, manufactured by Mitsubishi Chemical Corporation) 5 parts Toluene / methyl ethyl ketone = 1/1 (mass ratio) 200 parts

Evaluation The receiving sheets obtained in the above Examples and Comparative Examples were evaluated by the following methods. The obtained results are shown in Table 2.

[Print density test]
Using a commercially available thermal transfer video printer (trade name: 6800, manufactured by KODAK) equipped with a sublimation ink ribbon (trade name: 6800-4R, manufactured by KODAK), a solid black image on the receiving sheet in an environment of 20 ° C. The print density was measured using a reflection densitometer (trade name: Macbeth RD-914, manufactured by Gretag). When the print density is measured at five points and the average value thereof is a density of 2.0 or more, there is no practical problem.

[Image quality evaluation test]
Using a commercially available thermal transfer video printer (trade name: 6800, manufactured by KODAK) equipped with a sublimation ink ribbon (trade name: 6800-4R, manufactured by KODAK) for evaluation of image quality on a receiving sheet in a 20 ° C environment. A gradation pattern was printed and visually evaluated according to the following criteria.
○: The printed image has no color loss or color unevenness and is practical.
Δ: Color loss and color unevenness are slightly observed in the printed image, and there is no problem in practical use.
X: Color loss and color unevenness are observed in the printed image, which is not suitable for practical use.

[Protective layer transferability test]
Using a thermal transfer tester (trade name: TH-PMI2, manufactured by Okura Electric Co., Ltd.), the applied energy was varied, and the protective layer portion of the sublimation ink ribbon (trade name: 6800-4R, manufactured by KODAK) was The minimum energy that can be transferred onto the receiving layer of the receiving sheet and transferred by the protective layer was determined. In this protective layer transferability test, if the minimum protective layer transfer energy is 1 mj / dot or less, the transferability level has no practical problem.

[Ribbon releasability test]
Using a commercially available thermal transfer video printer (trade name: 6800, manufactured by KODAK) equipped with a sublimation ink ribbon (trade name: 6800-4R, manufactured by KODAK), a solid black image on the receiving sheet in an environment of 50 ° C. 10 were printed continuously. At that time, the fusing condition between the receiving sheet and the ribbon and the discharge property of the receiving sheet from the printer were evaluated based on the following criteria as printing suitability.
○: There is no fusion between the receiving sheet and the ribbon, and 10 sheets are normally discharged continuously, and there is no problem in practical use.
Δ: Some noise is caused by light fusion between the receiving sheet and the ribbon, but all 10 sheets are discharged and practical.
X: The receiving sheet and the ribbon are fused, and there is a sheet that is not normally discharged, which is not suitable for practical use.

The receiving sheet of the present invention has a high printing density, good image quality, excellent ink ribbon protective layer transferability, releasability between the receiving layer and the ink ribbon, etc., even during high-speed printing. It is useful for various thermal transfer type full-color printers such as, and contributes greatly to the industry.

Claims (5)

In a thermal transfer receiving sheet having a sheet-like support and an image receiving layer formed on at least one surface of the sheet-like support, the image receiving layer is a polymer of an acrylate compound represented by the general formula (1) A thermal transfer receiving sheet comprising:

(In the formula, n is an integer selected from 1 to ^3. R ¹ and R ² each independently represents a hydrogen atom, a methyl group, or an ethyl group, and R ³ represents a hydrogen atom or a methyl group.)   The thermal transfer receiving sheet according to claim 1, wherein the image receiving layer contains a vinyl chloride-vinyl acetate copolymer.   The thermal transfer receiving sheet according to claim 2, wherein the image receiving layer contains 5 to 50 parts by mass of the polymer of the acrylate compound with respect to 100 parts by mass of the vinyl chloride-vinyl acetate copolymer.   The thermal transfer receiving sheet according to claim 1, wherein the image receiving layer further contains a polyester plasticizer. The thermal transfer receiving sheet according to claim 1, wherein the image receiving layer further contains an epoxy-modified silicone and / or an epoxy polyether-modified silicone.