JP2005205694A - Thermal transfer receiving sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermal transfer receiving sheet which is suitable for a dye thermal transfer printer, has no possibility of double transfer and clogging of a paper sheet caused by static electricity during feeding and discharging the paper sheet under various environments, is excellent in printing adaptability, and is excellent in water resistance of the end face and a half cut part of the receiving sheet even when it is processed into labels. <P>SOLUTION: The thermal transfer receiving sheet has a sheet-like substrate with an antistatic layer on at least one face, and an image receiving layer formed on at least one face of this sheet-like substrate and comprising a dye-receptive resin as a main component. In this thermal transfer receiving sheet, the antistatic layer comprises a di-cationic acrylic polymer resin. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a dye thermal transfer receiving sheet (hereinafter simply referred to as a receiving sheet). More specifically, the thermal transfer image can be recorded on the receiving sheet portion with a high color density and good image quality, and is excellent in antistatic properties under various environments, and can be double-fed by static electricity (a plurality of receiving sheets). The present invention relates to a receiving sheet that is not fed simultaneously), does not cause a malfunction of the printer due to static electricity, and has excellent water resistance on the surface of the receiving layer.

  In a dye thermal transfer printer, an image receiving layer (hereinafter simply referred to as a receiving layer) containing a dye-staining resin of a receiving sheet is superimposed on a dye ink layer of a dye ink sheet (hereinafter simply referred to as an ink ribbon). In accordance with the desired transfer image, a predetermined amount of dye at a required portion of the dye ink layer is transferred onto the receiving layer by heat supplied from a thermal head or the like to form an image. As the ink ribbon, three colors of yellow, magenta, and cyan, or four colors of ink ribbon with black added thereto are used. A full-color image is formed by sequentially transferring the dyes of each color on the ink ribbon to the receiving sheet and superimposing the transferred dyes.

  In recent years, printing systems with higher speed and higher sensitivity have been demanded, and how to efficiently use the heat generated by the thermal head for image formation has become an important technical issue. Therefore, in order to reduce heat loss, a plastic film composed mainly of a thermoplastic polymer that is smooth, has good cushioning and adhesion properties, and has high heat insulating properties is used for the support of the receiving sheet. The ink ribbon base is usually made of a thermoplastic polymer, and resin is also used for the receiving layer for forming an image. Therefore, the media used in the dye thermal transfer method is generally highly charged, and is supplied and discharged in the printer. The static electricity generated by the paper operation often causes double feeding, paper jams, etc., which hinders running performance. In addition, there is a problem that the printer malfunctions due to static electricity generated when the ink ribbon and the receiving sheet are peeled off during printing, and prevention of static electricity is an important issue for the dye thermal transfer printing system.

  In order to solve running troubles such as double feeding of paper sheets and paper jams due to static electricity, either side of the ink ribbon is treated with an antistatic agent, or either side of the receiving sheet is charged. A method of applying an inhibitor was taken. However, when the receiving sheet is supplied in the form of a single sheet, the charge generated between the receiving sheets cannot be prevented only by processing only the ink ribbon, and thus problems such as double feeding have not been solved. It is generally known to provide a layer containing an antistatic agent on the surface of the receiving sheet on which the receiving layer is formed and the back surface of another receiving sheet superimposed on the receiving sheet (for example, Patent Document 1). However, such a measure is not sufficient to prevent the double feed actually occurring.

  Also known are a method of incorporating an antistatic layer in the receiving layer and a method of coating on the surface of the receiving layer (see, for example, Patent Documents 9 to 12). There have been problems such as having an adverse effect on the wearability, or that it is difficult to maintain the antistatic effect over a long period of time. In order to prevent double feeding of the receiving sheet due to static electricity, it is effective to provide an antistatic layer on both the front surface and the back surface of the receiving layer of the receiving sheet (see, for example, Patent Documents 13 to 16). ).

  For example, Patent Documents 17 and 18 describe a method of providing an intermediate layer containing an antistatic agent between a support and a receiving layer. Further, in Patent Document 19, an intermediate layer containing an antistatic agent mainly composed of a cationic acrylic resin is provided on one surface of a support of the receiving sheet, and a receiving layer is laminated thereon, whereby An invention for preventing the generation of static electricity has been proposed. In these inventions, when an intermediate layer containing an antistatic agent is provided between the support and the receptor layer, the surface electrical resistivity is reduced without adversely affecting the dyeing property of the dye, and the electrostatic load is reduced. It is claimed that the problem of sending is resolved.

  However, in general, the antistatic agent has a hygroscopic property, so that the resulting antistatic layer has poor water resistance and has a problem that it becomes sticky in a high humidity environment. In addition, the receiving sheet provided with an antistatic layer between the support and the receiving layer is significantly deteriorated in the adhesion between the antistatic layer and the support in a high humidity environment and when moisture adheres after printing. Problems such as wrinkling of the receiving layer together with the antistatic layer or peeling of the receiving layer from the support arise.

  Furthermore, a label-type receiving sheet (hereinafter simply referred to as a label-type receiving sheet) is known in which a desired dye image is thermally transferred and recorded on a receiving sheet and then the receiving sheet can be freely attached to various articles. . The label-type receiving sheet has a structure in which a release layer, an adhesive layer, a support for receiving sheet, and a receiving layer are sequentially laminated on a release sheet base material. The release sheet part that can be peeled and peeled between the release sheet part composed of the above-mentioned release sheet substrate / release layer and the above-mentioned adhesive layer / receptor sheet support / receptor sheet part. Can be attached to various articles.

  Compared to a general receiving sheet, the label type receiving sheet as described above is used after being subjected to a punching process (half-cut process) in which only the receiving sheet portion is punched, and moisture tends to easily enter from the half-cut portion. . Therefore, when the label type receiving sheet is stored after being printed or carried, for example, in an environment where it gets wet with water, the coating layer such as an antistatic layer having poor water resistance may fall off from the half-cut portion. There is a problem that it is more likely to occur and the image becomes ugly.

JP 62-51490 A JP-A-63-91286 JP-A-1-241491 JP-A-2-95892 JP-A-3-184894 JP-A-4-232788 Japanese Patent Laid-Open No. 5-16551 JP-A-5-58064 JP 63-56489 A JP-A-3-128291 Japanese Patent Laid-Open No. 5-16544 JP-A-5-64979 JP-A-1-259986 JP-A-3-82597 Japanese Patent Laid-Open No. 3-128289 Japanese Patent Laid-Open No. 11-235879 JP-A-3-82597 (page 1-2) Japanese Patent Laid-Open No. 5-16544 (first page) JP-A-4-33894 (2nd page)

  High-quality color hard copy printing systems using the dye thermal transfer system are used in various environments, including the outdoors, as represented by the print club. Various environments such as getting wet are assumed. The present invention is free from double feeding or paper jam due to static electricity at the time of paper feeding / discharging in any environment, and is excellent in printability with a printer, and even when label processing is performed, the end face of the receiving sheet and the half-cut portion An object of the present invention is to provide a receiving sheet having excellent water resistance.

The present invention includes the following inventions.
(1) Thermal transfer receiving sheet having a sheet-like support having an antistatic layer on at least one surface and an image receiving layer formed on at least one surface of the sheet-like support and containing a dye-dyeable resin as a main component The thermal transfer receiving sheet according to claim 1, wherein the antistatic layer contains a dicationic acrylic polymer resin.
(2) The thermal transfer receiving sheet according to item (1), wherein the antistatic layer is provided between the sheet-like support and the image receiving layer.
(3) The thermal transfer receiving sheet according to item (1) or (2), wherein the content of the dicationic acrylic polymer resin is 5 to 30% by mass based on the total solids of the antistatic layer.
(4) The surface electrical resistance of the image receiving layer is 1.0 × 10 ¹² Ω / □ or less in an environment of a temperature of 5 ° C. and a humidity of 30%, and any one of items (1) to (3) The thermal transfer receiving sheet according to Item.
(5) The thermal transfer receiving sheet according to any one of items (1) to (4) has an adhesive layer on the opposite surface of the image receiving layer, the adhesive layer, and a release sheet having a release layer. A label type thermal transfer receiving sheet, wherein the release layer surface is laminated so as to face each other, and the sheet-like support part including the image receiving layer and the adhesive layer is half-cut.

  The receiving sheet of the present invention has no problems such as double feeding due to static electricity in various environments, and wrinkles are generated in the receiving layer or when the moisture is applied to the surface of the receiving sheet. Is highly reliable without peeling from the support.

  As a result of earnestly examining the formation of an antistatic layer in order to prevent the occurrence of poor running such as double feeding of the receiving sheet due to static electricity in the printer, the present inventors have found that the sheet-like support used for the receiving sheet It has been found that by providing an antistatic layer containing a dicationic acrylic polymer resin on at least one surface of the body, the generation of static electricity can be suppressed very efficiently. Preferably, by providing an antistatic layer (also referred to as an intermediate layer) between the receiving layer and the sheet-like support, the intermediate layer becomes a sheet due to moisture absorption of the antistatic agent when exposed to high humidity or in contact with water. A receiving sheet that does not peel off the receiving layer even if water droplets adhere to the end face of the receiving sheet or the half-cut portion of the label-type receiving sheet is obtained without peeling from the support. .

1 and 2 show examples of the layer structure of the receiving sheet of the present invention, but the receiving sheet of the present invention is not limited to these. As shown in FIG. 1, as the antistatic layer, an antistatic layer (intermediate layer 2) may be provided between the sheet-like support 1 and the receiving layer 3, or a sheet-like support that does not form a receiving layer. 1 may be provided with an antistatic layer (back surface layer 4).
In the case of a label-type receiving sheet as shown in FIG. 2, an antistatic layer (back surface layer 9) may be provided on the opposite surface of the release sheet substrate 7 to the release layer 8. In general, as a sealing application, the receiving sheet portion 5 is punched (half-cut 11), and after forming a recorded image, the half-cut portion of the receiving sheet is peeled off.

As the support for the receiving sheet, a plastic sheet mainly composed of a thermoplastic polymer having a smooth surface, good cushioning and adhesion, and high heat insulation is preferably used. Such a sheet is obtained by adding an inorganic pigment to polypropylene, forming it into a sheet shape and stretching it uniaxially or biaxially, and a film comprising a plurality of layers containing a large number of voids ( Synthetic paper), polyethylene terephthalate, or a void-containing film obtained by foaming or stretching polyethylene terephthalate, and these films, or one or more of these films and other films and / or paper, etc. A composite sheet obtained by laminating and sticking is used. In any case, a plastic sheet layer is preferably present on the surface of the support on the receiving layer forming side. These plastic sheets are usually subjected to antistatic surface treatment, and the surface specific electrical resistance is generally about 1.0 × 10 ^{10 to} 1.0 × 10 ¹³ Ω / □.

As the resin used as the main component in the receiving layer, a polyester resin, a polycarbonate resin, a vinyl chloride-vinyl acetate copolymer resin, an acetate butyrate-based resin, or the like with high dyeability is used. Further, a release agent or a crosslinking agent is added to the receiving layer in order to prevent fusion with the ink ribbon. Various reactive silicone oils, surfactants, lubricants such as alkaline soaps are used as the release agent, and isocyanate is used as the crosslinking agent.
When such a material for the receiving layer is applied to a plastic film substrate that has been subjected to a normal antistatic surface treatment, and its surface specific electrical resistance is measured, it is generally about 1.0 × 10 ¹³ Ω / □ or more. A film base that exhibits a high value and is subjected to a general antistatic treatment is insufficient as a support for a receiving sheet of the present invention.

  Various methods for preventing static electricity on the receiving sheet have been proposed, but the most effective means is to use an antistatic agent. Among antistatic agents, it is more effective to use a polymeric surfactant that does not change over time or due to friction or the like. Antistatic agents include anions (carboxylic acids, polyester derivatives, sulfonic acids, phosphorus compounds, etc.), cations (acrylic ester derivatives, acrylic amide derivatives, vinyl ether derivatives, vinyl nitrogen derivatives, polyamine resins), and nonionic (acrylic). Various antistatic agents such as acid esters, ethylene oxide derivatives, amides) are known. In general, cationic polymer antistatic agents exhibit a superior antistatic effect compared to anionic and nonionic antistatic agents.

  By using the conventional antistatic agent as described above and forming an antistatic layer on the surface of the plastic sheet, it is possible to sufficiently reduce the surface specific electrical resistance, and further to accept it on the antistatic layer. Even when the layer is provided as a receiving sheet, the effect of sufficiently suppressing the generation of static electricity on the receiving layer side can be exhibited. However, conventional antistatic agents are generally hygroscopic and therefore have poor water resistance and cause stickiness in a high humidity environment. In particular, a receiving sheet provided with a conventional antistatic layer (intermediate layer) between a support and a receiving layer is used in a high-humidity environment or when moisture adheres after printing. The adhesion between the layers is significantly reduced, and the receiving layer is wrinkled together with the antistatic layer, and in some cases, the receiving layer peels off from the support.

  In the present invention, by providing an antistatic layer containing a dicationic acrylic polymer resin on at least one surface of the sheet-like support, the electrical resistance of the receiving sheet surface is efficiently reduced. Examples of the dicationic acrylic polymer resin used in the present invention include a quaternary ammonium salt type polymer resin whose main component is a structural unit represented by the following general formula (I). By having a substituent containing a dication in the chain portion, excellent antistatic performance is exhibited. The dicationic type only needs to have two cation moieties in one side chain substituent, and may have three or more.

（上記一般式（Ｉ）において、Ｒ^１；水素原子もしくはメチル基、Ｒ^２；１〜４個の炭素原子を有するアルキレン基もしくは−ＣＨ_２−ＣＨ（ＯＨ）−ＣＨ_２−基、Ｒ^３、Ｒ^４、Ｒ^５及びＲ^６；それぞれ１〜４個の炭素原子を有するアルキル基、但し、これらは同一であっても、異なっていてもよい、Ｒ^７；１〜１０個の炭素原子を有するアルキル基もしくは７〜１０個炭素原子を有するアラルキル基、Ａ；−Ｏ−基もしくは−ＮＨ−基、ｎ；１以上の整数を示す。）。
上記式一般式（Ｉ）において、ｎが１〜３の整数であり、Ｘが塩素原子、臭素原子等のハロゲン原子であることが好ましい。
上記式一般式（Ｉ）において、Ｒ^２が、−ＣＨ_２ＣＨ_２−基であることが好ましい。
上記式一般式（Ｉ）において、Ｒ^７が、１〜８個の炭素原子を有するアルキル基もしくはベンジル基であることが好ましい。
上記式一般式（Ｉ）において、Ａが、−Ｏ−基であることが好ましい。
さらに、上記式一般式（Ｉ）において、Ｒ^１、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６及びＲ^７が、メチル基であり、Ａが−Ｏ−基であり、かつＲ^２が−ＣＨ_２ＣＨ_２−基であることが好ましい。

(In the general formula (I), R ¹ ; a hydrogen atom or a methyl group, R ² ; an alkylene group having 1 to 4 carbon atoms, or a —CH ₂ —CH (OH) —CH ₂ — group, R ³ , R ⁴ , R ⁵ and R ⁶ ; each alkyl group having 1 to 4 carbon atoms, provided that these may be the same or different, R ⁷ ; having 1 to 10 carbon atoms An alkyl group or an aralkyl group having 7 to 10 carbon atoms, A: —O— group or —NH— group, n: an integer of 1 or more.
In the general formula (I), n is an integer of 1 to 3, and X is preferably a halogen atom such as a chlorine atom or a bromine atom.
In the above general formula (I), R ² is preferably a —CH ₂ CH ₂ — group.
In the above general formula (I), R ⁷ is preferably an alkyl group having 1 to 8 carbon atoms or a benzyl group.
In the above general formula (I), A is preferably an —O— group.
Further, in the general formula (I), R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are methyl groups, A is an —O— group, and R ² is —CH. ₂ CH ₂ - is preferably a group.

  The dicationic acrylic polymer resin of the present invention can be synthesized by a known method (for example, see JP-A-63-49478). Specific examples include Saftomer ST3300 and ST3700 manufactured by Mitsubishi Chemical Corporation. (Product name). The molecular weight of the dicationic acrylic polymer resin varies depending on the amount used and cannot be generally specified, but the number average molecular weight is preferably 20,000 or more, and more preferably 60,000 or more. When the number average molecular weight is less than 20,000, water resistance may be insufficient.

  In the present invention, the dicationic acrylic polymer resin can provide an excellent antistatic effect even in a relatively small amount, and can form a good antistatic layer even in water resistance. In particular, it is possible to improve water resistance in a configuration in which an antistatic layer (intermediate layer) is provided between the sheet-like support and the receiving layer. The dicationic acrylic polymer resin is preferably contained in the total solid content of the antistatic layer such as the intermediate layer in an amount of 5 to 30% by mass, more preferably 5 to 20% by mass. If the content of the dicationic acrylic polymer resin is less than 5% by mass, the desired antistatic performance may not be obtained. On the other hand, if the content exceeds 30% by mass, the water resistance of the surface of the receiving layer may be reduced. It may be insufficient.

In the present invention, the static electricity generated by the paper feeding and discharging motion in the printer and the static electricity generated when the ink ribbon and the receiving sheet are peeled off during printing cause problems such as poor running performance of the receiving sheet and malfunction of the printer. In order to reduce the level to a low level, the surface specific electric resistance value on the receiving layer side is preferably set to 1.0 × 10 ¹³ Ω / □ or less, more preferably 1.0 × 10 ¹² Ω / □ or less. .

  In the present invention, for the purpose of improving the adhesiveness between the acrylic polymer resin and the plastic film as the substrate for the support, the water resistance of the receiving layer, etc., a generally known crosslinking agent may be used in combination. For example, an epoxy resin, a polyvalent isocyanate compound, and the like can be mentioned. In the case of an aqueous coating material, an epoxy resin is preferably used. Moreover, after coating and drying an acrylic ester resin in an aqueous system, a polyvalent isocyanate compound dissolved in a solvent such as toluene or methyl ethyl ketone (MEK) may be applied thereon. Generally, the addition amount of the crosslinking agent is preferably about 1 to 100% by mass and more preferably 1 to 30% by mass with respect to the acrylic ester resin.

As the epoxy resin, generally known epoxy resins are used. For example, bisphenol type epoxy resin, linear type epoxy resin, methyl-substituted type epoxy resin, side chain type epoxy resin, novolac type epoxy resin, phenol novolac type epoxy resin, Examples include cresol type epoxy resins, polyphenol type epoxy resins, aliphatic type epoxy resins, aromatic type epoxy resins, ether / ester type epoxy resins, and cyclic aliphatic type epoxy resins.
Specific examples include, but are not limited to, bisphenol-A-diglycidyl ether, bisphenol-F-diglycidyl ether, bisphenol-S-diglycidyl ether, bisphenol-A-di-β-methylglycidyl ether, bisphenol- Examples include epoxy resins such as A-hexafluoroacetone diglycidyl ether, tetraphenyl diglycidyl ether, trimethylolpropane triglycidyl ether, resorcinol diglycidyl ether, hydrogenated bisphenol-A-diglycidyl ether.

  Moreover, as a polyvalent isocyanate type compound, what contains 2 or more, preferably 3 or 4 isocyanate groups in the molecule can be used. Specifically, 2,4-tolylene diisocyanate (2,4-TDI), 2,6-TDI, diphenylmethane-4,4′-diisocyanate (MDI), hydrogenated MDI, 1,5-naphthalene diisocyanate, xylylene diene Aromatic isocyanate compounds such as isocyanate (XDI), hydrogenated XDI, metaxylylene diisocyanate (MXDI), 3,3′-dimethyl-4,4′-diphenylylene diisocyanate (TODI), isophorone diisocyanate (IPDI) ), Aliphatic isocyanate compounds such as trimethylhexamethylene diisocyanate (TMDI) and hexamethylene diisocyanate (HDI), and adducts, biurets and isocyanurates of these are preferably used. In general, the molecular weight of the polyfunctional isocyanate compound is preferably about 500 to 1,000.

Of course, a known antistatic agent can be used in combination as long as the effects of the present invention are not impaired. For example, as a cationic antistatic agent, an acrylic acid ester such as a quaternary ammonium salt obtained by quaternizing a methacrylic acid ester of an alcohol having a tertiary amino group with dimethyl sulfate (for example, US Pat. No. 2,946,688) Quaternary ammonium salts, amino groups, water-soluble polyvinyl derivatives containing quaternary ammonium groups, salts quaternized with vinylpyridine copolymers, salts quaternized with polyethylene glycol polyamine, etc. Examples thereof include acrylic acid amide derivatives.

Solid coating amount of the intermediate layer of the present invention is preferably 0.1-5 g / ^{m 2,} more preferably 0.1-2 g / ^{m 2.} If the thickness of the intermediate layer is less than 0.1 g / m ^2, it is difficult to form a uniform coated surface. If coating unevenness occurs in the intermediate layer, the escape route of static electricity is cut off and sufficient antistatic effect is not exhibited. In addition, the hardness of the intermediate layer is often soft, and when the coating thickness exceeds 5 g / m ² , not only is the scratch formed easily when the receiving layer formed thereon is coated, but also the surface strength is reduced. , Troubles such as peeling off of the receiving layer may occur.

  When the crosslinking agent is reacted in the intermediate layer of the present invention, it is preferable to heat after coating and drying. The heating method may be terminated after the intermediate layer is applied and before the receiving layer is applied, or may be heated after the receiving layer is applied.

(Receptive layer)
In the receiving sheet of the present invention, the receiving layer is provided on the stretched porous polyester film surface of the support for the receiving sheet via an intermediate layer. As the receiving layer, a known thermal transfer receiving layer is used as described above. As the resin for forming the receiving layer, a resin having a high affinity for the dye transferred from the ink ribbon and a good dye dyeing property is used. As such a dye dyeing resin, polyester resin, polycarbonate resin, vinyl chloride copolymer, polyvinyl acetal resin, cellulose derivative resin, acrylic resin, and the like can be used.

  In order to prevent the receiving layer from fusing with the ink ribbon due to heating of the thermal head during printing, one or more of a crosslinking agent, a slipping agent, a release agent, and the like are added to the resin. It is preferable. Moreover, you may add 1 or more types, such as a fluorescent dye, a plasticizer, antioxidant, a ultraviolet absorber, a light stabilizer, a pigment, an antistatic agent, in the said resin as needed. These additives may be applied by mixing with a component for forming the receiving layer, or may be applied on and / or below the receiving layer as a coating layer separate from the receiving layer.

The solid content coating amount of the receiving layer is preferably 1 to 15 g / m ² , more preferably 3 to 10 g / m ² . When the coating amount of the receiving layer is less than 1 g / m ² , the receiving layer cannot completely cover the surface of the support, resulting in a decrease in image quality, and the thermal ribbon is heated to bond the ink ribbon and the receiving layer. May cause a fusing trouble. On the other hand, when the solid content coating amount exceeds 15 g / m ² , not only is the effect saturated and uneconomical, but also the strength of the receiving layer coating film is insufficient and the thickness of the receiving layer increases, thereby supporting the support. The heat insulation effect cannot be sufficiently exhibited, and the print density may be lowered.

  Coating layers such as a receiving layer and an intermediate layer of the present invention are known as bar coaters, gravure coaters, comma coaters, blade coaters, air knife coaters, gate roll coaters, curtain coaters, die coaters, lip coaters, and slide bead coaters. Using a coater, a predetermined coating solution can be applied and dried according to a conventional method.

(Back layer)
The receiving sheet of this invention may provide the back surface layer containing an antistatic agent on the surface on the opposite side to the surface which provided the peeling layer of the base material for peeling sheets. With such a configuration, the receiving sheet can be supplied to the printer, run inside the printer, and sent out from the printer more smoothly. As the antistatic agent used for the back layer, the dicationic acrylic polymer resin of the present invention is preferably used, but generally known antistatic agents can be used as long as the effects of the present invention are not impaired. is there. For example, polyethyleneimine, cationic monomer-containing acrylic resin, cation-modified acrylamide resin, various cationic antistatic agents such as cation-modified starch, or anionic and nonionic antistatic agents, etc. What is necessary is just to make it contain in a layer.

In addition, as a binder for forming the back layer, water-soluble resins such as polyvinyl alcohol, or acrylic resins, epoxy resins, polyester resins, phenol resins, alkyd resins, urethane resins, melamine resins, and reaction cured products of these resins are used. be able to. Moreover, fillers, such as an inorganic pigment and an organic pigment, can also be mix | blended as a friction coefficient modifier as needed. The coating amount as the solid content of the backside layer is preferably in a range of from 0.3 to 10 / ^{m 2,} more preferably in the range of 1 to 5 g / ^{m 2.} When the coating amount of the solid content is less than 0.3 g / m ² , the receiving layer surface may not be sufficiently damaged when the receiving sheets are rubbed, resulting in a coating film defect and an increase in surface electrical resistance. Sometimes. If the solid content coating amount exceeds 10 g / m ² , the effect is saturated and uneconomical.

(Adhesive layer)
In the receiving sheet of the present invention, an adhesive layer containing an adhesive as a main component may be provided on the side opposite to the receiving layer coating surface of the receiving sheet support, and used as a label type receiving sheet.
Examples of the resin constituting the adhesive include known adhesive resins such as acrylic, synthetic rubber, natural rubber, and silicone. Examples of the resin for the adhesive include rubbers such as natural rubber, isoprene rubber, styrene-butadiene block copolymer, styrene-isoprene-styrene block copolymer, polyisobutylene, butyl rubber, chloroprene rubber, nitrile rubber, and the like. Is exemplified.

  An acrylic resin is most preferably used as the adhesive resin. Acrylic resins used as adhesives are mainly composed of 2-ethylhexyl acrylate, butyl acrylate, ethyl acrylate, etc., and other (meth) acrylic acid esters (non-functional and having various functional groups (meth) It is a resin obtained by copolymerizing one or more acrylates) or other copolymerizable monomers.

  For the above adhesive resin, rosin, modified rosin, rosin and modified rosin derivative, polyterpene resin, aliphatic hydrocarbon resin, cyclopentadiene resin, aromatic petroleum resin, phenol resin, coumarone-indene Various tackifiers such as resins, cross-linking agents such as isocyanates, epoxies, metal chelates, microcapsule-shaped or foamed or unfoamed hollow particles, anti-aging agents, stabilizers, softeners such as oil, filling Agents, pigments, colorants and the like can be added as necessary. These may be used in combination of two or more as required.

The solid coating amount of the adhesive layer is preferably from 5 to 30 g / ^{m 2,} and more preferably 7~25g / ^{m 2.} When the solid content coating amount of the pressure-sensitive adhesive layer is less than 5 g / m ² , the pressure-sensitive adhesive layer cannot completely cover the support, and the adhesiveness of the receiving sheet may be insufficient. On the other hand, if the solid content coating amount exceeds 30 g / m ² , it is not preferable from the viewpoint of economical efficiency, and the pressure-sensitive adhesive may protrude from the periphery of the pressure-sensitive adhesive layer.

  The adhesive layer uses, for example, a coater selected from a bar coater, gravure coater, comma coater, blade coater, air knife coater, die coater, curtain coater, lip coater, etc. It can be formed by coating and drying. The pressure-sensitive adhesive layer may be formed by coating and drying on the surface of the release layer of the release sheet portion, and then bonded to the opposite side of the receiving layer coating surface of the receiving sheet portion having the receiving layer on the surface. After the adhesive layer is formed by coating and drying on the surface opposite to the receiving layer coated surface of the sheet support, the adhesive layer and the release layer of the release sheet portion may be bonded together.

(Base material for release sheet)
In the case of a label-type receiving sheet, the release sheet portion has a configuration in which a release layer is provided on one side of the release sheet substrate and a back layer is provided on the other side. The base material for the release sheet is a sealing paper in which a resin or the like is coated on a base paper mainly composed of cellulose pulp, a polylaminated paper in which a polyethylene resin is laminated on at least one side of a base paper mainly composed of cellulose pulp, polyolefin A monolayer or multilayer film such as polyethylene terephthalate is used. These films may be stretched or may be stretched and have a porous structure as described in the section of forming a stretched porous polyester film.

  The support for the receiving sheet in the receiving sheet portion and the base material for the release sheet in the release sheet portion can be used in any combination. For example, a laminate composed of a stretched porous polyester film / inorganic pigment-containing stretched porous polypropylene synthetic paper is used as the support for the receiving sheet, and a base material for the release sheet is used as the inorganic sheet-containing stretched porous polypropylene-based synthetic paper. It can be used in various combinations such as a stretched porous polyester film, a stretched polyolefin film or a stretched polyester film.

(Peeling layer)
The release layer provided on one surface of the release sheet substrate contains a known release agent. As the release agent, an emulsion type, solvent type, or solventless type silicone resin, fluorine resin, or the like is preferably used. In this case, the release sheet base material is peeled so that the solid coating amount of the release layer is 0.1 to 3 g / m ² , more preferably 0.3 to 1.5 g / m ^2. The coating solution for layer is applied and dried, and then cured by thermal curing, electron beam or ultraviolet curing to form a release layer. When the solid coating amount of the release layer is less than 0.1 g / m ² , the variation in the peeling performance is large, and when the solid coating amount exceeds 3 g / m ² , the practicality is poor from the economical aspect.

  In the label-type receiving sheet, the peeling force (T-shaped peeling) of the adhesive layer is preferably 50 mN / 25 mm or more, and more preferably 50 to 400 mN / 25 mm. When the peeling force is less than 50 mN / 25 mm, seal floating may occur. If the peeling force of the adhesive layer exceeds 400 mN / 25 mm, peeling between the receiving sheet portion and the peeling sheet portion after printing becomes heavy, and it may be difficult to peel off. Further, the coating method of the release layer coating liquid to the release sheet substrate is not particularly limited, and for example, a bar coater, a direct gravure coater, an offset gravure coater, an air knife coater, etc. can be used as appropriate. .

  The thickness of the entire receiving sheet is preferably 100 to 300 μm. When the thickness is less than 100 μm, the mechanical strength is insufficient, and the receiving sheet has insufficient rigidity, and the curling of the receiving sheet that occurs during printing may not be sufficiently prevented. Also, if the thickness exceeds 300 μm, the number of receiving sheets that can be accommodated in the printer will be reduced, or if a predetermined number of sheets is to be accommodated, the capacity of the receiving sheet accommodating portion will need to be increased, resulting in a compact printer. Such as making it difficult.

  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. In the examples, “parts” and “%” indicate “parts by mass” and “% by mass”, respectively, unless otherwise specified, and “parts” are all solid contents except for those relating to solvents.

Example 1
As a sheet-like support, a white foam PET film (trade name: Lumirror E60L, manufactured by Toray Industries, Inc.) having a thickness of 188 μm was used, and a coating solution for back layer 1 having the following composition was applied to one surface thereof as a solid component. The back layer was formed by coating and drying by a bar coating method so that the amount was 3.0 g / m ² .
Next, on the opposite surface of the back surface layer of the sheet-like support, using the intermediate layer coating liquid-1 having the following composition, coating is performed so that the solid content coating amount is 0.5 g / m ² . After drying to form an intermediate layer, the receiving layer coating liquid-1 having the following composition was applied onto the intermediate layer so that the solid content coating amount was 6 g / m ² and dried to form the receiving layer. After that, it was held for 5 days in an environment of a temperature of 50 ° C. and a relative humidity of 15%, and the receiving layer was thermally crosslinked to prepare a receiving sheet.

Coating liquid for back layer-1
Polyvinyl acetal resin (trade name: ESREC KX-1,
Solid content concentration 8%, manufactured by Sekisui Chemical Co., Ltd. 20 parts polyacrylic ester resin solution (trade name: Jurimer AT613,
Solid content concentration 25%, manufactured by Nippon Pure Chemical Co., Ltd. 28 parts nylon resin particles (trade name: MW300, manufactured by Shinto Fine) 15 parts zinc stearate dispersion (trade name: Z-8-36,
Solid content concentration 36%, manufactured by Chukyo Yushi Co., Ltd.) 43 parts dication type acrylic polymer resin (trade name: Saftomer ST3700,
Solid content concentration 35%, number average molecular weight 100,000, manufactured by Mitsubishi Chemical) 18 parts isopropyl alcohol / water = 6/4 (mass ratio) In a mixed solution, the solid content concentration was adjusted to 14%.

Intermediate layer coating solution-1
Acrylic modified resin (trade name: Rikabond SAR-615A,
Solid content 41%, manufactured by Chuo Rika Kogyo Co., Ltd. 70 parts epoxy resin (trade name: Rikabond SAR-615B,
Solid content concentration 100%, manufactured by Chuo Rika Kogyo Co., Ltd. 15 parts dication type acrylic polymer resin (trade name: Saftomer ST3700,
Solid content concentration 35%, number average molecular weight 100,000, manufactured by Mitsubishi Chemical Co., Ltd.) 11 parts Ethanol / water = 8/2 (mass ratio) In a mixed solution, the solid content concentration was adjusted to 10%.

Receiving layer coating solution-1
Polyester resin (trade name: Byron 200, manufactured by Toyobo) 100 parts silicone oil (trade name: KF393, manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts isocyanate (trade name: Takenate D-110N, manufactured by Takeda Pharmaceutical) 5 parts Toluene / Methyl ethyl ketone = 1 / 1 (mass ratio) mixture so that the solid concentration was 26%.

Example 2
A receiving sheet was prepared in the same manner as in Example 1 except that the following intermediate layer coating solution-2 was used instead of the intermediate layer coating solution-1.
Intermediate layer coating liquid-2
Acrylic modified resin (trade name: Rikabond SAR-615A,
Solid content 41%, manufactured by Chuo Rika Kogyo Co., Ltd. 70 parts epoxy resin (trade name: Rikabond SAR-615B,
Solid content concentration 100%, manufactured by Chuo Rika Kogyo Co., Ltd. 15 parts dication type acrylic polymer resin (trade name: Saftomer ST3700,
Solid content concentration 35%, number average molecular weight 100,000, manufactured by Mitsubishi Chemical) 18 parts ethanol / water = 8/2 (mass ratio) In a mixed solution, the solid content concentration was adjusted to 10%.

Example 3
(Formation of receiving sheet)
In the same manner as in the receiving sheet of Example 1, except that a stretched porous polyester film (trade name: 50E63S, manufactured by Toray Industries, Inc.) having a thickness of 50 μm and containing polyethylene terephthalate as a main component was used as the sheet-like support. A sheet portion was formed.
Hereinafter, a receiving sheet was prepared according to the following procedure.

(Formation of release sheet)
As a release sheet substrate for the release sheet portion, a biaxially stretched transparent polyester film having a thickness of 100 μm (trade name: Emblet, manufactured by Unitika) is used, and a silicon-based release agent (trade name: trade name: KS830 (manufactured by Shin-Etsu Chemical Co., Ltd.) was coated with a bar coating method so as to have a solid content of 0.5 g / m ² and dried to form a release layer. The layer coating liquid-2 was applied by a bar coating method so that the solid coating amount was 3.0 g / m ² and dried to form a back surface layer, thereby forming a release sheet portion.

Back layer coating liquid-2
Polyvinyl acetal resin (trade name: ESREC KX-1,
Solid content concentration 8%, manufactured by Sekisui Chemical Co., Ltd. 20 parts polyacrylic ester resin solution (trade name: Jurimer AT613,
Solid content concentration 25%, manufactured by Nippon Pure Chemical Co., Ltd. 28 parts nylon resin particles (trade name: MW300, manufactured by Shinto Fine) 15 parts zinc stearate dispersion (trade name: Z-8-36,
Solid content concentration 36%, manufactured by Chukyo Yushi Co., Ltd.) 43 parts anionic conductive agent (trade name: Chemistat 6120,
Solid content concentration 30%, manufactured by Sanyo Chemical Co., Ltd.) 15 parts isopropyl alcohol / water = 6/4 (mass ratio) In a mixed solution, the solid content concentration was adjusted to 14%.

(Formation of adhesive layer and formation of receiving sheet)
On the release layer of the release sheet part, an adhesive layer coating solution-1 having the following composition is applied and dried by a gravure coating method so that the solid content coating amount is 15 g / m ² to form an adhesive layer. did. Next, the adhesive layer surface and the receiving layer non-coated surface of the receiving sheet portion provided with the receiving layer were overlapped and laminated to form a receiving sheet.
Adhesive layer coating solution-1
Acrylic adhesive (trade name: PE-115E,
Solid content concentration 40%, manufactured by Nippon Carbide) 100 parts isocyanate curing agent (trade name: CK101,
(Solid content concentration 45%, manufactured by Nippon Carbide) Prepared with 2 parts ethyl acetate so that the solid content concentration was 30%.
(Label processing)
The receiving sheet portion of the obtained receiving sheet was punched (half cut) to prepare a label-type receiving sheet.

Example 4
A receiving sheet was prepared in the same manner as in Example 1 except that the following intermediate layer coating solution-3 was used instead of the intermediate layer coating solution-1.
Intermediate layer coating solution-3
Acrylic modified resin (trade name: Rikabond SAR-615A,
Solid content 41%, manufactured by Chuo Rika Kogyo Co., Ltd. 70 parts epoxy resin (trade name: Rikabond SAR-615B,
Solid content concentration 100%, manufactured by Chuo Rika Kogyo Co., Ltd. 15 parts dication type acrylic polymer resin (trade name: Saftomer ST3700,
Solid content concentration 35%, number average molecular weight 100,000, manufactured by Mitsubishi Chemical) 30 parts ethanol / water = 8/2 (mass ratio) In a mixed solution, the solid content concentration was adjusted to 10%.

Example 5
A receiving sheet was prepared in the same manner as in Example 1 except that the following intermediate layer coating solution-4 was used instead of the intermediate layer coating solution-1.
Intermediate layer coating solution-4
Acrylic modified resin (trade name: Rikabond SAR-615A,
Solid content 41%, manufactured by Chuo Rika Kogyo Co., Ltd. 70 parts epoxy resin (trade name: Rikabond SAR-615B,
Solid content concentration 100%, manufactured by Chuo Rika Kogyo Co., Ltd. 15 parts dicationic acrylic polymer resin (trade name: Saftomer ST3300,
Solid content concentration 35%, number average molecular weight 40,000, manufactured by Mitsubishi Chemical Co., Ltd. 5 parts Ethanol / water = 8/2 (mass ratio) In a mixed solution, the solid content concentration was adjusted to 10%.

Comparative Example 1
A receiving sheet was prepared in the same manner as in Example 1 except that the receiving layer was formed directly on the surface of the sheet-like support without forming the intermediate layer.

Comparative Example 2
A receiving sheet was prepared in the same manner as in Example 1 except that the following intermediate layer coating solution-5 was used instead of the intermediate layer coating solution-1.
Intermediate layer coating solution-5
Acrylic modified resin (trade name: Rikabond SAR-615A,
Solid content 41%, manufactured by Chuo Rika Kogyo Co., Ltd. 70 parts epoxy resin (trade name: Rikabond SAR-615B,
Solid content concentration 100%, manufactured by Chuo Rika Kogyo Co., Ltd. 15 parts cationic acrylic polymer (trade name: Saftomer ST2000H,
Solid content concentration: 34%, manufactured by Mitsubishi Chemical) 5 parts ethanol / water = 8/2 (mass ratio) In a mixed solution, the solid content concentration was adjusted to 10%.

Comparative Example 3
A receiving sheet was prepared in the same manner as in Example 3, except that the intermediate layer coating composition of Example 3 was changed to the following intermediate layer coating solution-6.
Intermediate layer coating solution-6
Acrylic modified resin (trade name: Rikabond SAR-615A,
Solid content concentration 41%, manufactured by Chuo Rika Kogyo Co., Ltd. 30 parts epoxy resin (trade name: Rikabond SAR-615B,
Solid content concentration 100%, manufactured by Chuo Rika Kogyo Co., Ltd. 15 parts cationic acrylic polymer resin (trade name: Saftomer ST2000H,
Solid content concentration: 34%, manufactured by Mitsubishi Chemical) 50 parts ethanol / water = 8/2 (mass ratio) In a mixed solution, the solid content concentration was adjusted to 10%.

Evaluation Using the receiving sheets prepared in the above Examples and Comparative Examples, the surface specific electrical resistance on the receiving layer side, the recording running property, and the water resistance of the receiving layer were evaluated by the methods described below, and the results are shown in Table 1. Summarized.

[Surface specific electrical resistance on the receiving layer side]
The surface specific electric resistance (Ω / □) was measured with a surface resistance meter: Hiresta high resistance measuring instrument manufactured by Mitsubishi Chemical under an environment of a temperature of 5 ° C. and a humidity of 30% RH.

[Recordability]
Using a sublimation color video printer (trade name: UP1850, manufactured by Sony), 100 sheets of each receiving sheet were printed in an environment of 20 to 30% RH at 5 ° C., and the presence or absence of double feeding was evaluated.

〔water resistant〕
Using a sublimation color video printer (trade name: DPP SVM-55, manufactured by Sony), black printing is performed on the entire surface, and then the photographic paper is immersed in warm water at 60 ° C. for 10 minutes. After taking out from warm water, the end face of the photographic paper was rubbed with a cotton swab, and the presence or absence of peeling of the receiving layer was visually confirmed. In addition, about the label type | mold receiving sheet, the half cut part was rubbed and peeling of the receiving layer was evaluated visually according to the following reference | standard.
○: No peeling of the receiving layer even after rubbing 50 times or more.
(Triangle | delta): Although receiving layer peeling generate | occur | produces by rubbing 30-50 times, there is no problem practically.
X: The rubbing layer is peeled off by rubbing 10 times or less, which causes a practical problem.

  The thermal transfer receiving sheet of the present invention is free from problems such as double feeding due to static electricity in various environments, and when receiving moisture under high humidity or the receiving sheet surface, the receiving layer may be wrinkled or supported. It is a highly reliable receiving sheet in which the receiving layer does not peel off from the body, is highly usable as a receiving sheet for a dye thermal transfer printer, and is practically excellent.

It is sectional drawing which shows an example of the laminated constitution of the receiving sheet in this invention. It is sectional drawing which shows an example of the laminated constitution of the label type | mold receiving sheet in this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Sheet-like support body 2 Intermediate | middle layer (antistatic layer)
3 Image receiving layer 4 Back layer (antistatic layer)
5 Receiving Sheet 6 Adhesive Layer 7 Release Sheet Substrate 8 Release Layer 9 Back Layer (Antistatic Layer)
10 Release sheet 11 Half cut

Claims (5)

  In a thermal transfer receiving sheet having a sheet-like support having an antistatic layer on at least one surface, and an image receiving layer formed on at least one surface of the sheet-like support and containing a dye-dyeable resin as a main component, A thermal transfer receiving sheet, wherein the antistatic layer contains a dicationic acrylic polymer resin.   The thermal transfer receiving sheet according to claim 1, wherein the antistatic layer is provided between the sheet-like support and the image receiving layer.   The thermal transfer receiving sheet according to claim 1 or 2, wherein the content of the dicationic acrylic polymer resin is 5 to 30% by mass based on the total solid content of the antistatic layer. The thermal transfer receiving sheet according to claim 1, wherein the image receiving layer has a surface electrical resistance of 1.0 × 10 ¹² Ω / □ or less in an environment of a temperature of 5 ° C. and a humidity of 30%. The thermal transfer receiving sheet according to any one of claims 1 to 4 has an adhesive layer on the opposite surface of the image receiving layer, and the adhesive layer and the release layer surface of the release sheet having the release layer are opposed to each other. A label-type thermal transfer receiving sheet, wherein the sheet-like support portion that is laminated and includes an image receiving layer and an adhesive layer is half-cut.

Images