JP2007223291A - Transfer sheet and forming method of recording image using the said transfer sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To offer a transfer sheet which can perform cutting process smoothly. <P>SOLUTION: The sheet is composed of a substrate and a transfer layer which is peelable from this substrate. The transfer layer is formed on the substrate containing a releasing agent, and has a Young's modulus of 210 MPa or more (for example 250 to 1,000 MPa) and makes up the transfer sheet with its absorbance of a wave length corresponding to the releasing agent being 0.95 or less (for example 0.8 to 0.9) over on top of the peeled-off surface of the transfer layer after the exfoliation of the substrate. The exfoliation strength between the transfer sheet and the substrate can be 200 to 750 mN/25 mm. The transfer sheet can be composed of the adhesion layer formed on the substrate and the image receiving layer formed on this adhesion layer. The releasing agent is a silicone compound and the adhesion layer can be formed with the solution or emulsion containing a solvent which can dissolve a silicone compound. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a transfer sheet for forming a recorded image on various transfer objects such as clothing, and a method for forming a recorded image using the sheet. More specifically, the present invention relates to a cutting plotter after an image is recorded by an inkjet recording method. The present invention relates to a transfer sheet suitable for the purpose of cutting the sheet and the like, and a recording image forming method using the sheet.

  Marks, logos, and image printing on the surface of fabrics such as T-shirts, ceramics, and plastic products are usually performed by various printing methods, mainly screen printing. However, in these printing methods, it is necessary to produce an expensive printing original plate. For this reason, printing of a small number of copies is not only unsuitable from the viewpoint of cost, but it also takes a long time to produce an original plate, so that it is difficult to print quickly. In order to solve these problems, recently, using an ink jet printer or a color copying machine, an image is recorded in advance on a transfer sheet having a support layer and a transfer layer, and the recorded image on the transfer sheet is transferred to clothing or the like. Methods are known for thermal transfer to the body.

  For example, in Japanese Patent Application Laid-Open No. 2004-223802 (Patent Document 1), in a laminate film having a protective film layer that is detachably provided on a heat-resistant substrate, the protective film is used for image protection of printed matter. It is peeled and transferred onto the image surface of the printed matter by thermocompression bonding, and the peel strength F from the heat resistant substrate of the protective film layer in the laminate film is 200 ° C. from the surface opposite to the protective film layer of the heat resistant substrate. In the case where the heat treatment is performed, a laminate film characterized by 1 to 50 N / m is disclosed.

  However, this laminate film has low releasability and low flexibility of the protective film layer. Therefore, after forming an image with an inkjet printer, etc., it can be cut cleanly even if it is cut to the desired size with a cutting plotter. Can not. Further, even in the thermal transfer after cutting, the transfer layer is stretched or deformed.

  Japanese Patent Laying-Open No. 2005-201989 (Patent Document 2) discloses a transfer sheet composed of a base material and a transfer layer that can be peeled off from the base material. The transfer layer is composed of an adhesive layer formed on the surface, and a concealing layer formed on the adhesive layer and containing a concealing agent and a binder resin which may have a crosslinkable group. A transfer sheet having an elongation of 30% or more is disclosed.

However, even in this transfer sheet, there is no description or suggestion about the relationship between the release agent and the releasability, and the releasability is not sufficient.
JP-A-2004-223802 (Claim 1) Japanese Patent Laying-Open No. 2005-201989 (Claim 1)

  Accordingly, an object of the present invention is to provide a transfer sheet and a method for forming a recorded image, which can smoothly perform a cutting process.

  Another object of the present invention is to suppress peeling and uncut portions between the substrate and the transfer layer even when cut with a cutting plotter or the like, and to stretch or deform even when peeling between the substrate and the transfer layer before transfer. Another object of the present invention is to provide a transfer sheet and a method for forming a recorded image that can suppress the above-described problem.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventor uses a transfer layer having a specific Young's modulus and adjusts the amount of release agent transferred from the substrate on the surface of the transfer layer after peeling. The present inventors have found that the cutting process can be performed smoothly and completed the present invention.

  That is, the transfer sheet of the present invention is a sheet composed of a base material and a transfer layer that can be peeled off from the base material, and the transfer layer is formed on the base material containing a release agent. It is formed and has a Young's modulus of 210 MPa or more, and the absorbance at a wavelength corresponding to the release agent is 0.95 or less on the release surface of the transfer layer after peeling the substrate. About 0.8 to 0.9 may be sufficient as the light absorbency of the wavelength corresponding to the said mold release agent. The peel strength between the transfer layer and the substrate may be about 200 to 750 mN / 25 mm. The Young's modulus of the transfer layer may be about 250 to 1000 MPa. The transfer layer may be composed of an adhesive layer formed on the surface of the substrate and an image receiving layer formed on the adhesive layer. The release agent may be a silicone compound, and the adhesive layer may be formed of a solution or emulsion containing a solvent capable of dissolving the silicone compound. The image receiving layer may be composed of at least one selected from a transparent layer and a non-transparent layer. Such a transfer sheet may be used for applications that require a cutting process. Further, it may be used for forming an image by an ink jet recording method.

  The present invention provides a transfer sheet manufacturing method comprising a coating step of applying a dope solution containing a component constituting the transfer layer on a substrate, and a step of drying the applied dope solution, And a method for producing the transfer sheet by controlling the kind of the solvent constituting the dope liquid of the transfer layer forming the release surface and / or the drying temperature of the dope liquid. This method may be a transfer sheet manufacturing method in which an adhesive layer is formed on the surface of the substrate, and then an image receiving layer is formed on the adhesive layer. In this method, a solvent capable of swelling or dissolving the release agent is used as a solvent constituting the dope liquid of the adhesive layer, and the dope liquid may be dried at a temperature 0 to 30 ° C. lower than the boiling point of the solvent. .

  Further, in the present invention, an image is recorded on the transfer layer of the transfer sheet, cut to a desired size, the substrate is peeled off from the transfer layer, and the transfer layer and the transfer target are contacted and heated. A method of forming a recorded image by transferring the image onto a transfer medium is also included.

  Furthermore, the present invention includes a method for improving the release characteristics of the transfer sheet by transferring a release agent contained in the base material to the transfer layer.

  In the present invention, by controlling the Young's modulus of the transfer layer and the transfer amount of the release agent from the substrate on the release surface of the transfer layer, the transfer layer has appropriate elasticity, and the substrate and the transfer layer Therefore, it is possible to smoothly perform the cutting process (particularly, the cutting process using a plotter after image formation). Furthermore, even if it is cut with a cutting plotter or the like, it is possible to suppress peeling and uncut portions of the base material and the transfer layer, and it is possible to suppress elongation and deformation even when the base material and the transfer layer before transfer are peeled off.

  The transfer sheet of the present invention comprises a substrate and a transfer layer that can be peeled off from the substrate.

[Base material]
As the substrate, an opaque, translucent or transparent substrate can be used as long as it contains a release agent and can be peeled off from the transfer layer. Examples of such a releasable substrate include a release treated paper (release paper), a release treated synthetic paper, a chemical fiber paper, and a plastic film.

  Examples of the paper constituting the release processing paper (release paper) include paper (printing paper, packaging paper, thin paper, etc.). The papers may be subjected to various types of processing such as laminating and surface coating with polypropylene and polystyrene.

  Examples of synthetic paper include various synthetic papers using polypropylene, polystyrene, and the like.

  Examples of the chemical fiber paper include various chemical fiber papers made from chemical fibers such as polyamide fibers, acrylic fibers, polyester fibers, and polypropylene fibers.

As the polymer constituting the plastic film, various resins (thermoplastic resin and thermosetting resin) can be used, and a thermoplastic resin is usually used. Examples of the thermoplastic resin include polyolefin resins (poly C _2-4 olefin resins such as polypropylene), cellulose derivatives (cellulose esters such as cellulose acetate), polyester resins (polyethylene terephthalate, polybutylene terephthalate, etc.). Polyalkylene naphthalates such as polyalkylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, or copolyesters thereof), polyamide resins (polyamide 6, polyamide 6/6, etc.), vinyl alcohol resins (polyvinyl alcohol, ethylene) -Vinyl alcohol copolymer etc.). Of these films, olefin-based resins, polyester-based resins, polyamide-based resins and the like are usually used, and polyesters (especially polyethylene terephthalate) are particularly preferable in terms of mechanical strength, heat resistance, workability, and the like.

  The thickness of a base material can be selected according to a use, and is 10-250 micrometers normally, Preferably it is 15-200 micrometers, More preferably, it is about 20-150 micrometers.

  The releasability can be imparted by a conventional method, for example, by treating the base material with a release agent, or allowing the base material to contain a release agent. Examples of the release agent include silicone compounds, fluorine resins (vinylidene fluoride resins, fluorinated ethylene-propylene resins, fluorine oligomers, etc.), waxes (waxes, higher fatty acid salts, higher fatty acid esters, higher fatty acid amides). Etc.). Of these release agents, silicone compounds can be particularly preferably used.

Examples of the silicone compound include compounds containing polyorganosiloxane. The polyorganosiloxane is a linear, branched or network compound having a Si—O bond (siloxane bond), and is composed of units represented by the formula: R _a SiO _{(4-a) / 2} Has been.

In the above formula, R is, for example, a halogenated group such as a C _1-10 alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group, a 3-chloropropyl group, or a 3,3,3-trifluoropropyl group. C _1-10 alkyl group, a vinyl group, an allyl group, _{C 2-10} alkenyl groups such as butenyl group, a phenyl group, a tolyl group, _{C 6-20} aryl group such as a naphthyl group, a cyclopentyl group, _{C 3,} such as a cyclohexyl group C- _10-12 aryl- _C1-4 alkyl groups, such as _-10 cycloalkyl group, a benzyl group, a phenethyl group, etc. are mentioned. R is preferably a methyl group, a phenyl group, an alkenyl group (such as a vinyl group), or a fluoro C _1-6 alkyl group. The coefficient a is a number from 0 to 3.

Examples of the polyorganosiloxane include polydialkylsiloxanes such as polydimethylsiloxane (preferably polydiC _1-10 alkylsiloxane) and polyalkylalkenylsiloxanes such as polymethylvinylsiloxane (preferably _{polyC 1-10} alkyl C _{2− 10} alkenyl siloxane), polyalkylaryl siloxanes such as polymethylphenyl siloxane (preferably poly C _1-10 alkyl C _6-20 aryl siloxane), polydiaryl siloxanes such as polydiphenyl siloxane (preferably polydi C _6-20 aryl siloxane) ), A copolymer composed of the polyorganosiloxane unit [dimethylsiloxane-methylvinylsiloxane copolymer, dimethylsiloxane-methylphenylsiloxane copolymer , Dimethylsiloxane - methyl (3,3,3-trifluoropropyl) siloxane copolymer, dimethylsiloxane - methylvinylsiloxane - methylphenylsiloxane copolymer, etc.], and others.

The silicone compound has an epoxy group, a hydroxyl group, an alkoxy group, a carboxyl group, an amino group or a substituted amino group (such as a dialkylamino group), an ether group, ( It may be a polyorganosiloxane having a substituent such as a (meth) acryloyl group. Further, both ends of the silicone compound may be, for example, a trimethylsilyl group, a dimethylvinylsilyl group, a silanol group, or a tri- _C1-2 alkoxysilyl group.

  Specific examples of silicone compounds that can be used industrially include silicone oil, silicone rubber, and silicone resin.

  Silicone oil is a compound mainly composed of a linear polymer having a low degree of polymerization. For example, the viscosity at 25 ° C. is 5 to 1,000,000 mPa · s, preferably 10 to 500,000 mPa · s, more preferably 100. ˜100,000 mPa · s. Examples of the silicone oil include silicone oils corresponding to the polyorganosiloxane, such as dimethyl silicone oil, methylphenyl silicone oil, methylhydrogen silicone oil, cyclic polydimethylsiloxane, alkyl-modified silicone oil, amino-modified silicone oil, and silicone polyether. Examples thereof include polymers, fatty acid-modified silicone oils, epoxy-modified silicone oils, and fluorosilicone oils.

  Silicone rubber is usually a compound obtained by vulcanizing a linear polymer having a high degree of polymerization. Examples of the silicone rubber include methyl silicone rubber, vinyl silicone rubber, phenyl silicone rubber, phenyl vinyl silicone rubber, and fluorinated silicone rubber.

  Silicone resins have a cross-linked three-dimensional structure. Examples of the silicone resin include silicone varnish, silicone-modified varnish (alkyd-modified product, polyester-modified product, epoxy-modified product, acrylic-modified product, urethane-modified product, etc.), silicone molding compound containing an inorganic filler, and the like.

  Of these silicone compounds, silicone oil is preferable from the viewpoint of releasability. These silicone compounds can be used alone or in combination of two or more.

  In the case of paper, for example, after carrying out a sealing treatment (for example, clay coat), the release property can be imparted by coating with a release agent (for example, silicone oil).

[Transfer layer]
The transfer layer is formed on a base material containing a release agent and can be peeled from the base material, and has a Young's modulus of 210 MPa or more (for example, about 225 to 1200 MPa). In the present invention, the transfer layer exhibits such a Young's modulus, so that the cutting process can be performed smoothly, and the occurrence of uncut portions is suppressed even when cut. The Young's modulus is preferably 250 MPa or more (for example, 250 to 1000 MPa), more preferably 300 MPa or more (for example, 300 to 700 MPa), and particularly about 350 to 500 MPa. When the Young's modulus is within this range, not only the effect in the cutting process (suppression of peeling at the time of cutting and the uncut portion of the film resulting therefrom), but also the elongation and deformation of the transfer layer in the thermal transfer after cutting can be suppressed.

In the present invention, it is necessary that the release agent contained in the base material is transferred (moved or permeated) in an appropriate amount to the transfer layer. Therefore, uncut residue after cutting by a cutting plotter can be suppressed. The migration of the release agent can be evaluated by measuring the absorbance of the wavelength corresponding to the release agent on the release surface of the transfer layer after peeling the substrate. Specifically, this absorbance needs to be 0.95 or less, preferably 0.1 to 0.94 (eg 0.5 to 0.93), especially 0.7 to 0.92 (especially 0. 8 to 0.9). In the present invention, the wavelength of the release agent can be evaluated by measuring an infrared absorption spectrum. For example, when the release agent is a silicone compound, it is evaluated by measuring the absorbance around a wavelength of 1500 cm ^−1. it can. As described later, the method for appropriately transferring the release agent includes adding a solvent capable of dissolving the release agent to the coating liquid for forming the transfer layer (for example, the adhesive layer), or manufacturing conditions of the transfer layer. And a method of adjusting

  The peel strength between the transfer layer and the substrate can be selected from a range of about 100 to 1000 mN / 25 mm (for example, 130 to 900 mN / 25 mm), but from the point that the elongation and deformation of the transfer layer peeled from the substrate can be suppressed. Preferably it is about 200-750 mN / 25 mm, More preferably, it is about 300-600 mN / 25 mm (especially 350-550 mN / 25 mm).

  As a specific embodiment, the transfer layer is not particularly limited as long as it can be peeled off from the base material, and is composed of a single layer structure (for example, a hot-melt adhesive resin, which can be bonded to a transfer object, It may be a layer capable of forming an image, etc.) or may be a laminated structure. Further, in the transfer layer, the surface of the transfer layer may be brought into contact with the transfer target, or the peeling surface of the transfer layer may be brought into contact with the transfer target.

  In particular, the transfer layer has at least one surface of the base material (particularly, one surface of the base material) from the viewpoint of high adhesiveness to the transfer target and easy transfer of an image previously formed on the recording sheet. And an adhesive layer that can be peeled from the substrate and an image receiving layer formed on the adhesive layer.

(Adhesive layer)
The adhesive layer is made of a resin that can be peeled off from the substrate and can be transferred to the transfer target. Further, the adhesive layer is not particularly limited as long as the transfer layer is a soft resin having the Young's modulus, and is composed of, for example, at least a soft hot melt adhesive resin.

  The soft hot melt adhesive resin is not particularly limited as long as it is a resin having thermal adhesiveness, and examples thereof include urethane resins, polyamide resins, olefin resins, and polyester resins.

(1) Urethane-based resin Examples of the heat-adhesive urethane-based resin include thermoplastic urethane-based resins obtained by a reaction between a diisocyanate component and a diol component.

  Examples of the diisocyanate component include aromatic diisocyanates (eg, phenylene diisocyanate, tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, toluidine diisocyanate, diphenyl ether diisocyanate, naphthalene diisocyanate, etc.), and aromatic aliphatic diisocyanates (eg, xylylene diisocyanate, etc.). Alicyclic diisocyanates (eg, isophorone diisocyanate), aliphatic diisocyanates (eg, propylene diisocyanate, trimethylene diisocyanate, butylene diisocyanate, pentamethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate Over preparative etc.), and others. A diisocyanate component can be used individually or in combination of 2 or more types. The diisocyanate component may be an adduct or may be used in combination with a polyisocyanate component such as triphenylmethane triisocyanate as necessary.

Examples of the diol component include aliphatic diols (for example, C _2-10 such as ethylene glycol, trimethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, neopentyl glycol, etc. Alkanediol, etc.), alicyclic diol (eg, hydrogenated bisphenol A, hydrogenated xylylene glycol, cyclohexanediol, cyclohexanedimethanol, etc.), aromatic diol (eg, bisphenol A, catechol, resorcin, hydroquinone, xylylene glycol) other low molecular weight diols etc.), polyether diols (e.g., diethylene glycol, triethylene glycol, polyoxy C _2-4 alkylene such as polytetramethylene ether glycol Glycol)), polyester diol [the reaction product of the diol component or polyether diol and dicarboxylic acid or a reactive derivative thereof (lower alkyl ester, acid anhydride), a derivative from lactone, etc.], polycarbonate diol [ For example, a reaction product of the low molecular weight diol and a dialkyl carbonate (such as a di-C _1-6 alkyl carbonate such as dimethyl carbonate) can be exemplified.

In the polyester diol, dicarboxylic acids include, for example, aliphatic dicarboxylic acids (for example, C _4-14 aliphatic dicarboxylic acids such as adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, etc.), and alicyclic dicarboxylic acids. Acid, aromatic dicarboxylic acid (for example, phthalic acid, terephthalic acid, isophthalic acid, etc.) are included. These dicarboxylic acids can be used alone or in combination of two or more. If necessary, the dicarboxylic acid may be used in combination with a polyvalent carboxylic acid such as trimellitic acid. Lactones include, for example, butyrolactone, valerolactone, caprolactone, laurolactone and the like. These lactones can be used alone or in combination of two or more.

  These diol components can be used alone or in combination of two or more. The diol component may be used in combination with polyols such as trimethylolpropane and pentaerythritol as necessary.

  The urethane-based resin may be cross-linked or modified with a chain extender or a cross-linking agent such as a polyvalent amine if necessary. For example, a polyurethaneurea resin modified with the polyvalent amines may be used, and the polyamines may be used as a chain extender, and the urethane resin may be a thermoplastic elastomer. Examples of the thermoplastic urethane-based elastomer include an elastomer having an aliphatic polyether or polyester as a soft segment and a short-chain glycol polyurethane unit as a hard segment.

  Examples of polyvalent amines include hydrazine, aliphatic diamines (for example, ethylene diamine, trimethylene diamine, tetramethylene diamine, hexamethylene diamine, trimethyl hexamethylene diamine, octamethylene diamine, etc.), aromatic diamines (for example, phenylene diamine). , Xylylenediamine, diphenylmethanediamine, etc.), alicyclic diamines [for example, hydrogenated xylylenediamine, bis (4-aminocyclohexyl) methane, isophoronediamine, etc.]. These polyvalent amines can be used alone or in combination of two or more.

  These urethane resins can be used alone or in combination of two or more.

  Examples of urethane resins include urethane resins such as polyester type urethane resins, polycarbonate type urethane resins, and polyether type urethane resins, and polyurethane urea resins. Among these urethane resins, in particular, yellowing The polyester type urethane resin and the polycarbonate type urethane resin are preferable from the point that there are few, and especially the aliphatic polyester type urethane resin, the aliphatic polycarbonate type urethane resin, or a combination thereof is preferable.

Furthermore, from the viewpoint of flexibility and the like, a polyester-type urethane resin (for example, 1,4-butanediol, etc.) obtained by using a diol component containing 50% by weight or more (for example, 75% by weight or more) of an aliphatic polyester diol. An isophorone diisocyanate using a polyester diol derived from a reaction of a C _2-6 alkanediol of the above with a C _4-12 aliphatic dicarboxylic acid such as adipic acid, isophthalic acid or phthalic acid, or the lactone And polyurethane urea resins corresponding to these polyester-type urethane resins are preferred.

  Among these, urethane resins (such as polyester-type urethane resins and polycarbonate-type urethane resins) are particularly preferable because they exhibit a high elongation with a small tensile strength.

  The urethane resin may be used as an organic solvent solution, an aqueous solution, or an aqueous emulsion. An aqueous solution or aqueous emulsion of a urethane-based resin may be prepared by dissolving or emulsifying and dispersing a urethane-based resin using an emulsifier, such as a free carboxyl group or a tertiary amino group in the molecule of the urethane-based resin. You may prepare by introduce | transducing an ionic functional group and dissolving or disperse | distributing a urethane type resin using an alkali or an acid. Urethane resin in which a free carboxyl group or tertiary amino group is introduced into such a molecule is a reaction between a diisocyanate component and a diol (particularly a high molecular diol) component having a free carboxyl group or tertiary amino group. It is comprised with the urethane type resin obtained by these. The diol having a free carboxyl group (particularly a polymer diol) is, for example, a diol component and a polyvalent carboxylic acid having 3 or more carboxyl groups or an anhydride thereof (for example, 4 bases such as pyromellitic anhydride). Acid anhydride, etc.), a polycarboxylic acid having a sulfonic acid group (such as sulfoisophthalic acid), a method of ring-opening polymerization of a lactone using dimethylolpropionic acid or the like as an initiator.

(2) Polyamide resin As the polyamide resin with heat adhesion, polyamide 6, polyamide 46, polyamide 66, polyamide 610, polyamide 612, polyamide 11, polyamide 12, polyamide resin formed by reaction of dimer acid and diamine, Examples thereof include polyamide-based elastomers (for example, polyamide using polyoxyalkylene diamine as a soft segment). These polyamide resins can be used alone or in combination of two or more. Among these, preferred polyamide-based resins include polyamides having at least one unit selected from units constituting polyamide 11 and units constituting polyamide 12 (for example, homopolyamides such as polyamide 11 and polyamide 12, polyamide 6). / 11, polyamide 6/12, polyamide 66/12, copolyamides such as copolymers of dimer acid and diamine and laurolactam or aminoundecanoic acid), polyamide resins produced by reaction of dimer acid and diamine, etc. It is.

(3) Olefin-based resin Examples of the heat-adhesive olefin-based resin include α such as ethylene, propylene, 1-butene, 3-methyl-1-pentene, 4-methyl-1-butene, 1-hexene, and 1-octene. Examples thereof include olefins (particularly α-C _2-10 olefins) or copolymers and olefin elastomers.

  Examples of the α-olefin homopolymer or copolymer include polyolefin (polyethylene such as low density polyethylene and linear low density polyethylene, ethylene-propylene copolymer, atactic polypropylene, etc.), modified polyolefin [ethylene-butene- 1 copolymer, ethylene- (4-methylpentene-1) copolymer, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer or its ionomer, ethylene-ethyl acrylate copolymer, etc. Ethylene- (meth) acrylate copolymer, propylene-butene-1 copolymer, ethylene-propylene-butene-1 copolymer, maleic anhydride grafted polypropylene, etc.]. Examples of the olefin-based elastomer include elastomers having polyethylene or polypropylene as a hard segment and ethylene-propylene rubber (EPR) or ethylene-propylene-diene rubber (EPDM) as a soft segment.

  These olefin resins can be used alone or in combination of two or more. Among these olefin resins, modified polyolefins, particularly modified ethylene resins (for example, ethylene copolymers such as ethylene-vinyl acetate copolymer and ethylene-ethyl acrylate copolymer) from the viewpoint of thermal adhesion. Is preferred.

(4) Polyester resin Examples of the heat-adhesive polyester resin include a homopolyester resin or a copolyester resin using at least an aliphatic diol or an aliphatic dicarboxylic acid, and a polyester elastomer.

Examples of the homopolyester resin include aliphatic diols (C _2-10 alkanediol and polyoxy C _2-4 alkylene glycol described in the section of the urethane resin) and aliphatic dicarboxylic acids (the C _4-14 fatty acids). A saturated aliphatic polyester resin produced by a reaction of a lactone with a lactone if necessary.

In the copolyester resin, a part of components (diol and / or terephthalic acid) of polyethylene terephthalate or polybutylene terephthalate is replaced with other diols (C _2-6 such as ethylene glycol, propylene glycol, 1,4-butanediol). Polyoxyalkylene glycols such as alkylene glycol, diethylene glycol and triethylene glycol, cyclohexanedimethanol and the like) or dicarboxylic acids (such as the above-mentioned aliphatic dicarboxylic acid, phthalic acid, isophthalic acid and other asymmetric aromatic dicarboxylic acids) or lactones (butyrolactone, Saturated polyester resins substituted with valerolactone, caprolactone, laurolactone, etc.).

Examples of the polyester-based elastomer include elastomers having _C2-4 alkylene arylate (ethylene terephthalate, butylene terephthalate, etc.) as a hard segment and (poly) oxyalkylene glycol as a soft segment.

  As the polyester resin, a polyester resin containing a urethane bond, for example, a resin obtained by increasing the molecular weight of a polyester resin with the diisocyanate may be used.

  These polyester resins can be used alone or in combination of two or more.

  These soft hot melt adhesive resins can be used alone or in combination of two or more. Hot melt adhesive resins are usually water insoluble. The hot melt adhesive resin may be a reactive hot melt adhesive resin having a reactive group (carboxyl group, hydroxyl group, amino group, isocyanate group, silyl group, etc.) at the terminal.

  The softening point of these soft hot melt adhesive resins is, for example, about 70 to 180 ° C., preferably 80 to 170 ° C., more preferably about 90 to 160 ° C. (particularly 90 to 150 ° C.). In particular, it is preferable to combine a plurality of resins having different softening points from the viewpoint of exhibiting a sufficient adhesive force to the transfer target and the concealing layer and suppressing penetration of the fabric or the like into the transfer target. A resin having a point of about 70 to 120 ° C. (for example, 80 to 110 ° C.) and a resin having a softening point of 120 ° C. or more and 180 ° C. or less (for example, 130 to 160 ° C.) may be combined.

  The melting point of the soft hot melt adhesive resin can be selected from the range of about 50 to 250 ° C., for example, about 60 to 200 ° C., preferably 70 to 150 ° C., more preferably about 70 to 130 ° C. (especially 80 to 120 ° C.). It may be.

  Among these soft hot-melt adhesive resins, when the material to be transferred is a fabric such as clothing, a urethane resin (for example, a urethane resin having a softening point of 70 to 180 ° C. is used from the viewpoint of adhesion, flexibility, and texture. Etc.), polyamide resins (for example, polyamide resins having a melting point of 70 to 180 ° C.), olefin resins [for example, olefin resins having a melting point of 70 to 120 ° C. (especially ethylene copolymers)], particularly urethane resins (For example, a polyester type urethane resin having a softening point of 70 to 180 ° C.) is preferable. In particular, urethane resin having a softening point of 70 to 180 ° C. and / or ethylene resin having a melting point of 70 to 120 ° C. is 50% by weight or more, preferably 60% by weight or more, more preferably 70% by weight in the resin component constituting the adhesive layer. It is preferable to contain it by weight% or more.

In order for the release agent contained in the base material to migrate, the dope liquid (coating solution) for producing the adhesive layer preferably contains a solvent capable of swelling or dissolving the release agent. The dope solution may be either a solution or an emulsion. The ratio of the resin component in the dope liquid is, for example, about 1 to 90% by weight, preferably about 5 to 80% by weight, and more preferably about 10 to 60% by weight (particularly 20 to 50% by weight). Examples of the solvent include aliphatic hydrocarbons (pentane, hexane, etc.), alicyclic hydrocarbons (cyclohexane, etc.), aromatic hydrocarbons (toluene, xylene, etc.), halogenated hydrocarbons (methylene chloride, chloroform, etc.). , Ethylene chloride, etc.), ethers (1,4-dioxane, tetrahydrofuran, etc.), esters (methyl acetate, ethyl acetate, etc.), ketones (acetone, methyl ethyl ketone, etc.), alcohols (ethanol, isopropanol, butanol, hexanol, etc.) Amides (acylamides such as formamide and acetamide, mono- or di-C _1-4 alkyl-acylamides such as N-methylformamide, N-methylacetamide, N, N-dimethylformamide, N, N-dimethylacetamide), Sulfoxide (Dialkyl sulfoxides such as dimethyl sulfoxide), nitriles (alkyl nitriles such as acetonitrile, chloroacetonitrile, propionitrile, butyronitrile, benzonitrile, etc.). These solvents can be used alone or in combination of two or more. Among these solvents, for example, when the release agent is a silicone compound, alcohols such as isopropanol, ketones such as methyl ethyl ketone, amides such as dimethylformamide, or a mixed solvent thereof is generally used.

  The adhesive layer may contain various additives as necessary, for example, stabilizers (antioxidants, ultraviolet absorbers, heat stabilizers, etc.), antistatic agents, flame retardants, lubricants, antiblocking agents, fillers, colorants. Further, it may contain an antifoaming agent, a coating property improving agent, a thickener and the like.

  The thickness of the adhesive layer is, for example, about 5 to 300 μm, preferably about 10 to 200 μm, more preferably about 20 to 100 μm (particularly about 20 to 60 μm).

(Image receiving layer)
The image receiving layer is not particularly limited as long as it can form an image and the transfer layer exhibits the Young's modulus so long as it does not impair the softness of the transfer layer. Transparent layer or opaque layer), and in particular, the non-transparent layer may be a concealing layer.

  The transparent layer and the non-transparent layer may contain at least a soft resin from the viewpoint of imparting flexibility to the transfer layer. Examples of the soft resin include olefin resin, styrene resin, vinyl resin (vinyl chloride resin, polyvinyl acetate resin, polyvinyl butyral resin, etc.), acrylic resin, thermoplastic elastomer, polyamide resin, polyester. Thermoplastic resins such as urethane resins and urethane resins, and thermosetting resins such as urethane resins and epoxy resins. These soft resins can be used alone or in combination of two or more. Moreover, even if it is hard resin, it can be used as a soft resin composition by mixing with a rubber component, a plasticizer (mineral oil, paraffin oil, etc.), etc. Of these soft resins, vinyl chloride resins, polyester resins, and urethane resins are preferable.

Examples of the vinyl chloride resin include polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-C _2-4 olefin copolymer (vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, etc. ), Vinyl chloride- (meth) acrylic acid ester copolymers (vinyl chloride-methyl methacrylate, etc.), vinyl chloride-acrylonitrile copolymers, ethylene-vinyl acetate copolymers and copolymers obtained by graft polymerization of vinyl chloride on polyurethane Examples include coalescence. These vinyl chloride resins may be soft resins containing a conventional plasticizer. Examples of the plasticizer include phthalate ester plasticizers [dibutyl phthalate (DBP), dioctyl phthalate (DOP), etc.], phosphate ester plasticizers [tricresyl phosphate (TCP), trioctyl phosphate (TOP), etc.] And aliphatic polycarboxylic acid esters [dioctyl adipate (DOA), dioctyl sebacate (DOS), etc.], epoxy plasticizers (alkyl epoxy stearate, epoxidized soybean oil, etc.) and the like. The proportion of the plasticizer is, for example, 1 to 100 parts by weight, preferably 3 to 75 parts by weight, and more preferably about 5 to 50 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.

  Examples of the polyester resin include the polyester resins exemplified in the section of the adhesive layer. Of the polyester resins, aliphatic polyester resins, polyester elastomers, polyester resins containing urethane bonds, and the like are preferable.

  As the urethane resin, the urethane resin exemplified in the section of the adhesive layer can be used. Among urethane resins, polyester-type urethane resins, polycarbonate-type urethane resins (for example, non-yellowing aliphatic polycarbonate-type urethane resins, etc.), in particular, diol components containing 50% by weight or more of aliphatic polyester diols. The polyester type urethane resin obtained by using is preferable.

  The softening point of the soft resin can be selected from the range of 70 to 180 ° C, and is, for example, about 70 to 150 ° C, preferably 70 to 120 ° C, and more preferably about 80 to 110 ° C.

  Of these soft resins, urethane resins are particularly preferable from the viewpoint of adhesive strength and flexibility.

  In the case of forming a concealing layer, among the soft resins, a soft resin having adhesive strength and film-forming properties, for example, a soft resin that may have a crosslinkable group (for example, a vinyl chloride resin, a polyester resin) Resin, urethane resin, etc.). Examples of the crosslinkable group include an isocyanate group, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, a methylol group, and an alkoxysilyl group. In the concealing layer, a soft resin that may have such a crosslinkable group may be used as a binder resin in combination with a concealing agent. Among these binder resins, urethane resins that may have an isocyanate group are preferable from the viewpoint of adhesive strength and flexibility.

  The concealing agent (or concealing property improving agent) is not limited as long as the transfer target can be concealed by whitening or the like, and examples thereof include at least a white pigment and a white concealing agent such as a microcapsule that can be whitened by thermal expansion. These masking agents can be used alone or in combination of two or more.

  The white pigment is not limited to a pigment composed of a white pigment alone, but resin particles containing a white pigment (for example, particles coated with a binder resin, particles in which a plurality of white pigments are dispersed in binder resin particles, etc. ).

  White pigments include titanium-based white pigments (such as titanium oxide (titanium white)), zinc-based white pigments (such as zinc oxide and zinc sulfide), composite white pigments (such as lithopone), and extender pigments (magnesium silicate, magnesium oxide, Examples include calcium carbonate, barium sulfate, aluminum extender pigments (alumina, aluminum hydroxide, aluminum silicate, etc.), silica, mica, bentonite, and the like. Of these white pigments, titanium-based white pigments, particularly titanium oxide, are preferred.

  The crystal form of titanium oxide may be an anatase type, but the rutile type is preferred because it has a high refractive index and excellent hiding power.

  The average particle diameter of the white pigment is preferably 3 μm or less, for example, 0.01 to 3 μm, preferably 0.05 to 2 μm (for example, 0.05 to 1 μm), and more preferably 0.1 to 1 μm (for example, 0.1 μm). 1 to 0.5 μm). If the average particle size of the white pigment is too small, the white hiding power is not sufficient, and if it is too large, the texture and adhesiveness are impaired.

  The microcapsule contains a low-boiling solvent that is vaporized by heating in thermal transfer as a core material, and the boiling point of the solvent as the core material is 200 ° C. or less, preferably 50 to 180 ° C., more preferably about 50 to 150 ° C. It is. Examples of such solvents include aliphatic hydrocarbons (pentane, hexane, etc.), alicyclic hydrocarbons (cyclohexane, etc.), aromatic hydrocarbons (toluene, xylene, etc.), ethers (1,4-dioxane, tetrahydrofuran). Etc.), esters (methyl acetate, ethyl acetate etc.), ketones (acetone, methyl ethyl ketone etc.), alcohols (methanol, ethanol, isopropanol etc.), especially hydrocarbon solvents (eg hexane etc.) are preferred.

  As the wall material constituting the microcapsule, a thermoplastic resin having a high gas barrier property and softening by heating in thermal transfer, for example, a vinylidene chloride polymer [for example, vinylidene chloride-acrylonitrile copolymer, vinylidene chloride- (meth) acrylic] Acid copolymer, vinylidene chloride- (meth) acrylate copolymer, vinylidene chloride-vinyl acetate copolymer, etc.], polyacrylonitrile polymer, vinyl alcohol polymer (for example, polyvinyl alcohol, ethylene-vinyl alcohol copolymer) For example, polyamide 6, polyamide 66, polyamide 610, polyamide 11, polyamide 12, etc.).

  The average particle size of the microcapsules is preferably 50 μm or less, for example, 0.1 to 50 μm, preferably 0.5 to 20 μm, and more preferably about 1 to 10 μm.

  When heated at 150 ° C. for 1 minute, the volume of the microcapsules preferably expands 3 times or more (for example, 5 to 1000 times, preferably 10 to 100 times, more preferably about 10 to 50 times).

  These masking agents can be used alone or in combination of two or more. Of these masking agents, white pigments such as titanium oxide are preferred.

  In the present invention, it is preferable that a hiding agent such as titanium oxide is sufficiently dispersed in the hiding layer from the viewpoint of the mechanical strength of the hiding layer. That is, the masking agent is preferably dispersed in the form of primary particles without agglomeration. Even when the particles are aggregated, the dispersed particles preferably have a small particle size (secondary particle size), for example, a secondary particle size of 10 μm or less (for example, 0.1 to 10 μm), preferably 0.1 to 0.1 μm. It is about 7 μm, more preferably about 0.1 to 5 μm. The method for sufficiently dispersing the masking agent is not particularly limited, but a conventional method such as a disperser such as a disper, a homomixer, a bead mill, a ball mill, a roll mill, a colloid mill, a sand mill, an attritor, or a paint conditioner was used. The method etc. are mentioned.

  Further, in order to improve the dispersibility of the concealing agent, the concealing agent (particularly a white pigment) is previously dispersed in a resin (for example, a resin that may have a crosslinkable group of the same system as the binder resin) or a resin solution. May be used. The ratio (weight ratio) between the concealing agent and the resin dispersed in advance is, for example, about 50/50 to 99/1, preferably about 60/40 to 97/3, and more preferably about 70/30 to 95/5.

  The ratio (weight ratio) between the masking agent and the binder resin is, for example, the former / the latter = 30/70 to 90/10, preferably 35/65 to 80/20, more preferably 40/60 to 75/25 (particularly 45/55 to 70/30). In the present invention, since the ratio of the concealing agent can be increased without reducing various properties such as elongation and strength, the transfer sheet has a high concealing property (particularly white concealing property). And the durability of the transfer layer transferred to the transfer medium is also excellent. In addition, since the masking layer contains a pigment component as a masking agent, it is excellent in releasability.

  The masking layer may further contain a crosslinking agent. The crosslinking agent can be appropriately selected according to the type of the binder resin, and is a compound having two or more reactive functional groups with respect to the functional group of the binder resin (for example, a polyfunctional compound having the crosslinkable group or Multivalent metal ions, etc.). Specifically, polyisocyanate, polyamine, polyvalent carboxylic acid, silane coupling agent, polyethyleneimine, urea resin, melamine resin, magnesium ion (compound capable of generating magnesium ion) and the like can be mentioned. When the binder resin is a urethane resin, it is preferable to use a polyisocyanate (for example, a diisocyanate component or a polyisocyanate component exemplified in the section of the adhesive layer) as a crosslinking agent. By using the cross-linking agent, the strength and the adhesive force with the adhesive layer can be further improved.

  The ratio of the crosslinking agent is, for example, about 0.1 to 30 parts by weight, preferably about 0.5 to 20 parts by weight, and more preferably about 1 to 10 parts by weight with respect to 100 parts by weight of the binder resin.

  The thickness of the concealing layer is, for example, about 3 to 500 μm, preferably about 5 to 300 μm, and more preferably about 10 to 100 μm (particularly 15 to 50 μm).

  The transparent layer and the non-transparent layer may contain various additives, for example, dye fixing agents, stabilizers (antioxidants, ultraviolet absorbers, heat stabilizers, etc.), antistatic agents, flame retardants, lubricants, It may contain an antiblocking agent, a filler, a colorant, a color former, an antifoaming agent, a coating property improving agent, a thickener and the like.

  Both the transparent layer and the non-transparent layer (particularly the hiding layer) can be used as a layer for forming an image. Both layers may be used alone or in combination. For example, a transparent layer as an ink receiving layer may be formed on the masking layer as a layer for forming an image.

  Such an ink receiving layer is not particularly limited as long as an image can be formed, and is a conventional ink receiving layer, for example, a porous layer (a layer composed of organic or inorganic particles and a binder resin, a porous organic layer). Alternatively, a layer containing inorganic particles, a layer obtained by a phase separation method in which a polymer is microphase-separated using a good solvent and a poor solvent, or a layer made of an ink fixing resin can be used.

  Of these ink receiving layers, an image receiving layer composed of at least a particle component such as organic or inorganic particles and a binder resin is preferable. Such an image receiving layer is suitable for forming an image by an ink jet recording method.

  Although various organic or inorganic particles can be used as the particle component, organic particles are preferable from the viewpoint of the mechanical properties of the sheet and the texture of the transferred material after transfer. In particular, particles composed of the hot melt adhesive resin (urethane resin, polyamide resin, olefin resin, polyester resin, etc.) exemplified in the section of the adhesive layer are particularly preferable. These hot melt adhesive resins can be used alone or in combination of two or more. Among these hot melt adhesive resins, urethane resin particles (such as particles composed of the urethane resin exemplified in the above-mentioned adhesive layer) and / or polyamide resin particles (exemplified in the above-mentioned adhesive layer). A combination of a urethane resin particle and a polyamide resin particle is particularly preferable. Further, the hot melt adhesive particles may be porous particles.

  The average particle diameter of the particle component is, for example, about 0.2 to 150 μm, preferably 1 to 130 μm, and more preferably about 3 to 120 μm.

  The binder resin is not particularly limited as long as it has film-forming properties. In addition to the binder resin, hydrophilic polymers (polyoxyalkylene glycol resins such as polyethylene glycol, vinyl alcohol resins such as polyvinyl alcohol, acetic acid, etc. Cellulose derivatives such as cellulose) and the like can be used. These binder resins can be used alone or in combination of two or more. Of these, urethane resins and polyester resins are preferred. The binder resin may be a cationic resin in which a tertiary amino group or a quaternary ammonium salt is introduced into the resin molecule.

  The ratio of the particle component can be selected from a range of about 10 to 5000 parts by weight, preferably 200 to 5000 parts by weight, more preferably 300 to 3000 parts by weight (particularly 500 parts by weight) in terms of solid content with respect to 100 parts by weight of the binder resin. ~ 2000 parts by weight).

  In the ink receiving layer, a dye fixing agent (for example, a cationic compound such as an aliphatic quaternary ammonium salt or an aromatic quaternary ammonium salt, or a polymer dye such as a polycationic compound is used in order to improve the fixing property of the ink. A fixing agent, etc.) may be included. The proportion of the dye fixing agent is 1 to 200 parts by weight, preferably 5 to 150 parts by weight, more preferably 10 to 100 parts by weight (especially 10 to 60 parts by weight) based on 100 parts by weight of the binder resin in terms of solid content. Degree.

  The thickness of the ink receiving layer is, for example, about 5 to 150 μm, preferably about 10 to 100 μm, more preferably about 20 to 80 μm (particularly about 20 to 70 μm).

  An anchor layer made of a resin component may be further formed between the hiding layer and the ink receiving layer in order to improve the adhesion between the two layers. As the resin component, various thermoplastic resins and thermosetting resins can be used. From the viewpoint of effectively improving the adhesive force, the resin component contained in both the hiding layer and the ink receiving layer is the same or the same type. It is preferable to use the above resin (resin having affinity for the resin component contained in both). Further, the anchor layer is preferably a cationic resin into which a tertiary amino group or a quaternary ammonium salt is introduced from the viewpoint of fixing the ink that has oozed from the ink receiving layer. For example, when the binder resin of the concealing layer is a urethane resin, from the viewpoint of adhesive strength and flexibility, the resin component constituting the anchor layer is preferably a urethane resin (for example, the thermoplastic urethane resin), In particular, a cationic thermoplastic urethane resin is preferable from the viewpoint that the adhesive force between layers can be improved and the ink fixing property of the ink receiving layer can be supplementarily improved.

  As the urethane resin, the urethane resin exemplified in the paragraph of the adhesive layer can be used. For example, an aliphatic polyester type urethane resin using at least an aliphatic polyester diol as a diol component, or a polycarbonate type urethane resin ( For example, a non-yellowing aliphatic polycarbonate type urethane resin) is preferable. Examples of the cationic resin include the cationic urethane resins exemplified in the section of the image receiving layer.

  The thickness of the anchor layer is, for example, about 0.1 to 30 μm, preferably about 0.5 to 20 μm, more preferably about 1 to 10 μm (particularly 1 to 5 μm).

  Furthermore, an anti-blocking layer, a slipping layer, an antistatic layer, etc. may be formed on the transparent layer and / or the non-transparent layer, if necessary.

  The thickness of the transfer layer is, for example, about 3 to 1000 μm, preferably 5 to 500 μm, more preferably 10 to 300 μm (particularly 15 to 100 μm).

[Transfer sheet manufacturing method]
The transfer sheet of the present invention can be produced by forming a transfer layer on the surface of the substrate. That is, when the transfer layer is composed of a plurality of layers, the transfer layer can be produced by sequentially forming each layer constituting the transfer layer. For example, it can be produced by forming an adhesive layer that can be peeled from the substrate on the releasable surface of the substrate, and then forming a concealing layer on the adhesive layer. In the case of forming other layers, an ink receiving layer or the like may be further formed on the masking layer.

  Specifically, according to the layer structure of the transfer sheet, it can be formed by applying a coating agent composed of the above components to the releasable surface of the substrate. The binder resin and adhesive resin contained in the coating agent can usually be used in the form of a solution or an emulsion. Therefore, you may prepare the coating agent for transfer layers by mixing the solution or emulsion containing binder resin or adhesive resin, and another component. When the solvent of the solution or emulsion is aqueous, a solvent containing water is usually used, water alone may be used, and a hydrophilic organic solvent such as alcohols may be contained as necessary. In the case of an organic solvent, for example, the solvent exemplified in the section of the adhesive layer can be used. Therefore, after apply | coating the coating agent for each layer and making it dry, you may apply | coat the following coating agent repeatedly.

  The coating agent can be applied to at least one surface of the substrate by a conventional method such as a roll coater, an air knife coater, a blade coater, a rod coater, a bar coater, a comma coater, or a gravure coater. The coating film can be formed by drying at a temperature of about 50 to 150 ° C. (preferably 80 to 120 ° C.).

  Here, in the present invention, the drying condition of the adhesive layer has an important meaning in order to transfer the release agent of the base material. What is necessary is just to select drying conditions (temperature, time, etc.) suitably so that it can transfer to an adhesion layer by the appropriate quantity (range of the said light absorbency) of the mold release agent of a base material. For example, it can be selected according to the boiling point of the solvent contained in the dope liquid of the adhesive layer. For example, it may be a temperature near the boiling point of the solvent, for example, a temperature lower by about 0 to 30 ° C. (particularly 0 to 10 ° C.) than the boiling point. Specifically, in the case of an equal mixture of dimethylformamide and methyl ethyl ketone, the drying temperature is, for example, 90 to 120 ° C, preferably 100 to 117 ° C, more preferably about 105 to 115 ° C. In addition, after forming the adhesive layer, in the step of forming another layer such as an image receiving layer, the release agent of the substrate may be transferred to the adhesive layer by performing drying or the like under such conditions.

  The transfer layer formed in this manner is subjected to an appropriate temperature (for example, about 140 to 250 ° C., preferably about 140 to 200 ° C.) and pressure (500 to 50, Thermal transfer can be performed by thermocompression bonding at an appropriate time (for example, about 5 seconds to 1 minute) at about 000 Pa). Specifically, after peeling the base material from the transfer sheet, the peeled surface of the adhesive layer and the transfer target are brought into contact with each other and heated. If necessary, the transfer body containing the transfer image may be heated for crosslinking. The heating method may be a method in which the transfer layer is pressurized and heated with a heating sliding member such as an iron via a release paper as necessary.

  An image may be formed on the transfer layer by the recording method or the like. Specifically, after recording an image on a transfer layer (for example, a concealing layer or an ink receiving layer) of the transfer sheet, the substrate may be peeled off from the transfer sheet, or the substrate may be peeled off from the transfer sheet. Thereafter, an image may be recorded on a transfer layer (eg, a concealing layer). These recording methods can be properly used according to the application. When an apparatus such as an ink jet recording method or an electrophotographic method is used, an image is usually recorded before transfer.

[Image forming method]
In the case of forming an image using the transfer sheet of the present invention, the substrate may be peeled off from the transfer sheet and then recorded on a transfer layer (for example, an image receiving layer). After recording the image, the substrate is peeled from the transfer sheet.

  Therefore, as an image forming method of the present invention, for example, an image is recorded on the transfer layer of the transfer sheet, cut to a desired size, the substrate is peeled off from the transfer layer, and the transfer layer and the transfer object are separated. A method of forming a recorded image by bringing it into contact and heating and transferring it to a transfer medium can be mentioned.

  As a method for recording an image on the transfer layer, in addition to a method for forming an image on the transfer layer with a writing instrument such as an oil-based or water-based ink pen, an ink jet recording method (such as an ink jet method in which ink droplets are ejected from a nozzle toward a sheet). Examples thereof include a method of forming an image on an image receiving layer before transfer by a recording method such as a hot melt transfer method, a sublimation type heat transfer method, an electrophotographic method (color copying machine, color laser printer, etc.). An image can be formed by a similar method on a film or sheet to be attached to the concealing layer. Among these, it is preferable to form an image by an ink jet recording method using a water-based or oil-based ink or a solvent ink from the viewpoints of image clarity and simplicity.

  Examples of the method of cutting to a desired size include a mechanical method such as a cutting plotter, and a method of cutting using a cutter or scissors. In the present invention, since the transfer layer has a specific elasticity and has an appropriate peeling property with respect to the substrate, the cutting layer (especially when cut by a mechanical method such as a cutting plotter). ) Also does not occur between the substrate and the transfer layer, and the occurrence of uncut portions is also suppressed.

The method for transferring the transfer layer of the transfer sheet to the transfer target may be a method in which the transfer layer is contacted with the transfer target with the transfer layer as a contact surface and heated, and then the substrate is peeled off. After peeling off, a method is preferred in which the peeled surface (particularly the adhesive layer) of the transfer layer is brought into contact with the transfer object and heated. When the transfer layer is composed of, for example, an image receiving layer and an adhesive layer, the release surface is an adhesive layer. Further, the transfer body containing the transfer image may be heated and cross-linked if necessary. The heating method may be a method of heating and pressurizing the transfer layer with a heating member (for example, a heating sliding member such as an iron or a heat press machine) via a release paper as necessary. The heating temperature can be selected according to the type of resin constituting the transfer layer (for example, the adhesive layer), and is, for example, about 80 to 250 ° C, preferably about 100 to 200 ° C, and more preferably about 120 to 180 ° C. The heating time is, for example, about 5 seconds to 1 minute, preferably about 10 seconds to 1 minute. The pressure is, for example, about 0.05 to 10 N / cm ² , preferably about 0.1 to 5 N / cm ² . In the present invention, even if thermal transfer is performed in this way, elongation and deformation of the transfer layer after cutting can be suppressed.

[Transfer]
Since the transfer sheet of the present invention has both flexibility and strength, it can be transferred to various transfer materials with a strong adhesive force. As the transfer target, a two-dimensional or three-dimensional structure formed of various materials such as fiber, paper, wood, plastic, ceramics, and metal can be used. Furthermore, since the transfer sheet of the present invention is excellent in flexibility, a fabric (for example, a T-shirt or the like), a plastic film sheet, paper, or the like may be used as a transfer target. In particular, a transfer sheet on which a concealing layer is formed is excellent in concealing property (particularly white concealing property), so that a clear image can be formed on the concealing layer regardless of the color of the transfer object. Therefore, among the above-mentioned transferred objects, it is preferably used for a dark-colored transferred object. The dark transfer object may be either a transfer object having a color unique to the transfer object, or a transfer object dyed or colored in a dark color. The dark color includes colors such as black, gray, dark blue, and blue (for example, lightness of 0 to 5, preferably about 0 to 3).

  INDUSTRIAL APPLICABILITY The present invention is effective as a transfer sheet for transferring to a transfer target such as a two-dimensional or three-dimensional structure formed of various materials such as fibers, paper, wood, plastic, ceramics, and metal. In particular, the transfer sheet of the present invention can be smoothly cut with a cutting plotter or the like, and is therefore suitable for applications that require a cutting process.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In the text, “parts” are based on weight unless otherwise specified. The contents of each component of each layer of the transfer sheet obtained in Examples and Comparative Examples, and the evaluation methods for various properties of the transfer sheet are as follows.

[Content of each component]
(Base material)
Silicone-coated paper: manufactured by Lintec Corporation, SGP85OKT-TP (LB), basis weight 110 g / m ²
(Adhesive layer)
Polyester urethane resin solution A: manufactured by Dainichi Seika Kogyo Co., Ltd., Resamine UD1305, solvent: dimethylformamide / methylethylketone = 40/60 (weight ratio), solid content 50% by weight, softening temperature 95 ° C.
Polyester urethane resin solution B: manufactured by Dainichi Seika Kogyo Co., Ltd., Resamine ME3119LP, solvent: dimethylformamide / methyl ethyl ketone = 35/65 (weight ratio), solid content 34% by weight, softening temperature 135 ° C.
Dimethylformamide: Diluting solvent.

(Hidden layer)
Polyester urethane resin solution B: manufactured by Dainichi Seika Kogyo Co., Ltd., Resamine ME3119LP, solvent: dimethylformamide / methyl ethyl ketone = 35/65 (weight ratio), solid content 34% by weight, softening temperature 135 ° C.
Titanium oxide-containing carbonate-based urethane resin solution C: manufactured by Dainichi Seika Kogyo Co., Ltd., Seika Seven BS012 (S) white, dispersed particle size of titanium oxide 0.2 μm, urethane-based resin / titanium oxide = 9/1 (weight ratio) ), Solvent: dimethylformamide, solid content 55% by weight
(Anchor layer)
Cationic carbonate-based urethane emulsion D: F-8559D manufactured by Daiichi Kogyo Seiyaku Co., Ltd., solid content: 26% by weight.

(Ink receiving layer)
Polyamide 12 particles E: manufactured by Daicel Degussa Co., Ltd., Vestamelt 430-P06, oil absorption 45 ml / 100 g, melting point 110 ° C., average particle size 60 μm
Polyamide 6/12 particles F: manufactured by Atofina Japan Co., Ltd., ORGASOL 3501EX D NAT-1, oil absorption 212 ml / 100 g, melting point 142 ° C., average particle size 10 μm
Polyamide 12 particles G: Daicel Degussa Co., Ltd., Vestamelt 640-P1, melting point 76 ° C., average particle size 100 μm
Polyurethane resin emulsion H: manufactured by Shin-Nakamura Chemical Co., Ltd., SP Resin ME-307
Polyethylene glycol I: manufactured by Sanyo Chemical Industries, PEG4000S
Dye fixing agent J: manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Kachiogen L
Polyurethane resin particles K: manufactured by Dainippon Ink & Chemicals, Inc., Bernock CFB-100, glass transition temperature-12 ° C., softening point 135 ° C., average particle size 20 μm.

[Absorbance]
The obtained transfer sheet was peeled from the release paper (base material), the infrared absorption light spectrum of the surface of the peeled adhesive layer was measured, and the absorbance at the wavelength (1500 cm ⁻¹ ) corresponding to the release agent was measured.

[Peel strength and Young's modulus]
In accordance with JIS K7161, the peel strength of the sheet (strength per 25 mm width of the sheet) and Young's modulus were measured in the MD direction of the sheet (sheet flow direction).

[Membrane deformability]
The transfer sheet was cut to a width of 10 mm × 15 cm, and a part of the transfer layer (a part from one end of the sheet up to 5 cm in the length direction) was peeled from the substrate. The base material and the transfer layer at the peeled portion of the sheet are fixed by being sandwiched between upper and lower clamps of a tensile tester, pulled at a constant speed (30 cm / min), and then peeled off by T-type to remove the sheet. After peeling the base material and the transfer layer for the portion (length 10 cm), the length after peeling of the unpeeled portion (10 cm) of the transfer layer was measured and evaluated according to the following criteria.

○: 10 cm or more and less than 10.5 cm Δ: 10.5 cm or more to less than 11 cm ×: 11 cm or more.

[Uncut]
Using a plotter (SP-300, manufactured by Roland DG), the transfer sheet is cut into 5 cm regular triangles at a blade pressure of 390 mN / cm ² and a speed of 10 cm / sec, and the degree of cutting at the apex is visually confirmed.

◯: There is no uncut portion at all three vertex portions. Δ: There is a left uncut portion at one vertex portion. ×: There are uncut portions at two or more vertex portions.

Examples 1-4 and Comparative Examples 1-5
On the silicone-coated paper, the adhesive layer coating solution shown in Table 1 (dry coating amount 35 g / m ² ) was applied and dried under the conditions shown in Table 1 to obtain a sheet having an adhesive layer. Next, a coating solution for concealing layer (dry coating amount 40 g / m ² ) shown in Table 1 was applied on this adhesive layer and dried under the conditions shown in Table 1 to form a concealing layer. The evaluation results of the obtained transfer sheet are also shown in Table 1.

  As is clear from the results in Table 1, film deformation of the transfer sheets of Examples 1 to 4 is suppressed. In particular, the transfer sheets of Example 2 and Example 4 are not left uncut after being cut with a plotter. On the other hand, the transfer sheets of Comparative Examples 1 to 5 have large film deformation and low practicality.

Example 5
On the concealing layer of the transfer sheet obtained in Example 2, the following anchor layer coating solution (dry coating amount 5 g / m ² ) was applied and dried at 110 ° C. for 3 minutes to have an anchor layer. A sheet was obtained. Next, the following ink receiving layer coating solution (dry coating amount 30 g / m ² ) was applied on the anchor layer, and dried at 100 ° C. for 3 minutes to form an ink receiving layer. As a result of evaluating the deformability of the film and the uncut portion of the obtained transfer sheet, both were good.

(Anchor layer coating solution)
Cationic carbonate urethane emulsion D: 92 parts Isopropanol: 8 parts (ink receiving layer coating solution)
Polyamide 12 particles E: 36 parts Polyamide 6/12 particles F: 13 parts Polyamide 12 particles G: 2 parts Polyurethane resin emulsion H: 3 parts Polyethylene glycol I: 6 parts Dye fixing agent J: 5 parts Polyurethane resin particles K: 35 Department.

Claims (13)

  A sheet composed of a base material and a transfer layer that can be peeled from the base material, wherein the transfer layer is formed on a base material containing a release agent and has a Young's modulus of 210 MPa or more. And a transfer sheet having an absorbance at a wavelength corresponding to the release agent of 0.95 or less on the release surface of the transfer layer after peeling the substrate.   The transfer sheet according to claim 1, wherein the absorbance at a wavelength corresponding to the release agent is 0.8 to 0.9.   The transfer sheet according to claim 1, wherein the peel strength between the transfer layer and the substrate is 200 to 750 mN / 25 mm.   The transfer sheet according to claim 1, wherein the transfer layer has a Young's modulus of 250 to 1000 MPa.   The transfer sheet according to claim 1, wherein the transfer layer comprises an adhesive layer formed on the surface of the substrate and an image receiving layer formed on the adhesive layer.   The transfer sheet according to claim 5, wherein the release agent is a silicone compound, and the adhesive layer is formed of a solution or emulsion containing a solvent capable of dissolving the silicone compound.   6. The transfer sheet according to claim 5, wherein the image receiving layer is composed of at least one selected from a transparent layer and a non-transparent layer.   The transfer sheet according to claim 1, which is used for an application requiring a cutting process.   2. The transfer sheet according to claim 1, which is used for forming an image by an ink jet recording method.   A method for producing a transfer sheet, comprising: a coating step of applying a dope solution containing a component constituting the transfer layer on a substrate; and a step of drying the applied dope solution, wherein the release surface from the substrate is The method for producing a transfer sheet according to claim 1, wherein the kind of solvent constituting the dope liquid of the transfer layer to be formed and / or the drying temperature of the dope liquid is controlled.   A method for producing a transfer sheet in which an adhesive layer is formed on the surface of a substrate and then an image receiving layer is formed on the adhesive layer, and a release agent can be swollen or dissolved as a solvent constituting the dope liquid of the adhesive layer The method according to claim 10, wherein the solvent is used and the dope solution is dried at a temperature lower by 0 to 30 ° C than the boiling point of the solvent.   An image is recorded on the transfer layer of the transfer sheet according to claim 1 and cut into a desired size, and then the substrate is peeled from the transfer layer, and the transfer layer and the transfer target are contacted and heated to be transferred. To form a recorded image.   The method for improving the peeling characteristics of the transfer sheet according to claim 1, by transferring a release agent contained in the substrate to the transfer layer.