JP6310711B2 - Release sheet and transfer sheet - Google Patents

Description

  The present invention relates to a transfer sheet capable of forming a coating layer for printing on a print layer transferred to an adherend, and a release sheet used for the transfer sheet.

  Conventionally, as a caution mark label or the like, a transfer type, particularly a thermal transfer type printing label is sometimes used. In this thermal transfer type print label, a print layer and a heat-sensitive adhesive layer are sequentially laminated on a release agent layer of a release sheet comprising a substrate and a release agent layer.

  In order to use the thermal transfer type print label, the release label is peeled off after the print label is thermally bonded to the adherend through the heat-sensitive adhesive layer. Thereby, the printing label which consists of a heat-sensitive adhesive layer and a printing layer is transcribe | transferred on a to-be-adhered body.

  However, since the printing layer in the transferred printing label is exposed on the outermost surface of the printing label, there arises a problem that it is rubbed and scratched or dropped.

  In order to prevent the above problems, it is conceivable to apply a coat film on the printed layer. However, an application step is required and the cost is increased.

  Although the configuration is significantly different from the print label as described above, Patent Document 1 discloses a heat transfer film for thermally transferring an image formed on a print surface to a transfer target, A thermal transfer film having a release layer on one surface of the material and having a print forming layer made of a thermoadhesive resin on the release layer is disclosed. When this thermal transfer film is transferred to the transfer target, the release layer is transferred to the transfer target together with the print formation layer and the image, thereby forming a protective layer on the surface of the print formation layer.

Japanese Patent Laid-Open No. 9-300893

  The release layer of the thermal transfer film of Patent Document 1 is made of a release agent that can be peeled off from the heat-resistant film substrate. Even if a protective layer is formed on the surface of the print forming layer with such a release agent, it is difficult to exhibit sufficient scratch resistance with the protective layer.

  The present invention has been made in view of such a situation, and a release sheet and a transfer sheet that can form a coating layer for printing excellent in scratch resistance on a printed layer transferred to an adherend. The purpose is to provide.

  In order to achieve the above object, first, the present invention provides a base material, a release agent layer laminated on one surface side of the base material, and a side opposite to the base material side of the release agent layer. A release sheet comprising a laminate and a printing coat layer containing a resin having a glass transition temperature of 10 to 80 ° C., wherein a printing layer is laminated on the printing coat layer, and the printing layer is used for the printing At least an adhesive layer is laminated on the opposite side of the coating layer, and when the release sheet is peeled off after the adhesive layer is bonded to the adherend, the interface between the release agent layer and the printing coat layer. A release sheet is provided in which peeling occurs and the coating layer for printing remains on the adherend side (Invention 1).

  According to the release sheet according to the invention (Invention 1), when the release sheet is peeled off as described above, the printing coat layer can be formed on the print layer transferred to the adherend. This coating layer for printing is excellent in scratch resistance by containing a resin having a glass transition temperature of 10 to 80 ° C. That is, according to the release sheet according to the invention (Invention 1), it is possible to form a coating layer for printing having excellent scratch resistance on the printing layer transferred to the adherend.

  In the said invention (invention 1), it is preferable that the said coating layer for printing contains a polymer fine particle further (invention 2).

  In the above invention (Invention 2), the polymer fine particles are preferably polyethylene fine particles (Invention 3).

  In the said invention (invention 2 and 3), it is preferable that the average particle diameter of the said polymer fine particle is 1-10 micrometers (invention 4).

  In the said invention (invention 2-4), it is preferable that content of the said polymer fine particle in the said coating layer for printing is 40-90 mass parts with respect to 100 mass parts of said resin (invention 5).

  In the said invention (invention 1-5), it is preferable that the said resin is crosslinked resin (invention 6).

  In the said invention (invention 1-6), it is preferable that the said resin is a polyester urethane resin (invention 7).

  In the said invention (invention 1-7), the thickness of the said coating layer for printing is 1.2-15 micrometers, and the peeling force with respect to the said coating layer of the said release agent layer is 200-1800 mN / 25mm. It is preferable (Invention 8).

  In the said invention (invention 1-8), it is preferable that the surface roughness (Ra) by the side of the said coating layer for printing of the said release agent layer is 0.1-2.0 micrometers (invention 9).

  2ndly, this invention is laminated | stacked on the opposite side to the said coating layer for printing of the said peeling sheet (invention 1-9), the printing layer laminated | stacked on the said coating layer for printing in the said peeling sheet. A transfer sheet comprising the adhesive layer thus formed is provided (Invention 10).

  In the said invention (invention 10), it is preferable that the said adhesive bond layer is comprised from the adhesive agent which has heat adhesiveness (invention 11).

  According to the release sheet and the transfer sheet according to the present invention, it is possible to form a print coat layer having excellent scratch resistance on the print layer transferred to the adherend.

It is sectional drawing of the peeling sheet which concerns on one Embodiment of this invention. It is sectional drawing of the transfer sheet which concerns on one Embodiment of this invention. It is explanatory drawing which shows the usage method of the transfer sheet which concerns on one Embodiment of this invention.

Hereinafter, embodiments of the present invention will be described.
[Peeling sheet]
As shown in FIG. 1, a release sheet 1 according to this embodiment includes a base material 11, a release agent layer 12 formed on one surface side of the base material 11 (upper side in FIG. 1), and a release agent layer 12. It is comprised from the coating layer 13 for printing formed in the other side (upper side in FIG. 1) of the base material 11 side.

  In the release sheet 1 according to the present embodiment, as shown in FIG. 2, the printing layer 2 is laminated on the surface opposite to the release agent layer 12 side of the printing coat layer 13 (upper surface in FIG. 1). Then, at least the adhesive layer 3 is laminated on the opposite side of the printing layer 2 to the printing coat layer 13. This laminated body corresponds to the transfer sheet 4 according to the present embodiment. When the release sheet 1 is peeled after the adhesive layer 3 of the transfer sheet 4 is adhered to the adherend, peeling occurs at the interface between the release agent layer 12 and the printing coat layer 13 (see FIG. 3). Thereby, the coating layer 13 for printing can be formed in the printing layer 2 transcribe | transferred to a to-be-adhered body.

(1) Base Material The base material 11 of the release sheet 1 according to the present embodiment is not particularly limited, and any one of conventionally known materials can be appropriately selected and used. Examples of such a substrate 11 include paper substrates such as glassine paper, coated paper, cast coated paper, dust-free paper, and high-quality paper; laminated paper obtained by laminating a thermoplastic resin such as polyethylene on these paper substrates; Or polyester films such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyolefin films such as polyethylene and polypropylene, plastic films such as polycarbonate films and cellulose acetate films; non-woven fabrics; metal foils; or laminated sheets containing these It is done.

  Among these, a plastic film that can give the printing coat layer 13 a desired texture, for example, a matte feeling and a glossy feeling is preferable, a polyester film is particularly preferable, and a polyethylene terephthalate film is more preferable.

  In the base material 11 made of the above plastic film, for the purpose of improving the adhesiveness with the release agent layer 12 provided on the surface, a surface treatment by an oxidation method, a concavo-convex method, or the like on one or both sides as desired, or Primer treatment can be applied. Examples of the oxidation method include corona discharge treatment, plasma discharge treatment, chromium oxidation treatment (wet), flame treatment, hot air treatment, ozone, ultraviolet irradiation treatment, and the like. Examples include a thermal spraying method. These surface treatment methods are appropriately selected according to the type of the base film, but generally, a corona discharge treatment method is preferably used from the viewpoints of effects and operability.

  The thickness of the base material 11 should just be 10-300 micrometers normally, Preferably it is 15-200 micrometers, Especially preferably, it is 20-125 micrometers.

(2) Release agent layer There is no restriction | limiting in particular as release agent which comprises the release agent layer 12 of the release sheet 1 which concerns on this embodiment, Arbitrary things can be suitably selected and used from a conventionally well-known thing. . Examples of such release agents include silicone resin-based, fluororesin-based, alkyd resin-based, olefin resin-based, acrylic-based, long-chain alkyl group-containing compound-based, and rubber-based release agents. From the viewpoint of release properties, silicone resin-based release agents are preferred.

  The thickness of the release agent layer 12 is not particularly limited, but is preferably 0.01 to 3 μm, and particularly preferably 0.03 to 1 μm. When the thickness of the release agent layer 12 is 0.01 μm or more, the function as the release agent layer 12 can be sufficiently exerted. On the other hand, when the release agent layer 12 has a thickness of 3 μm or less, blocking can be prevented from occurring when the release sheet 1 is rolled up.

  When a matte texture is imparted to the printing coat layer 13, the surface roughness (arithmetic average roughness Ra) of the release agent layer 12 on the printing coating layer 13 side is 0.1 to 2.0 μm. It is particularly preferable that the thickness is 0.2 to 1.0 μm. In order to make the surface roughness of the release agent layer 12 on the printing coat layer 13 side within the above range, the surface roughness (arithmetic average roughness Ra) on the release agent layer 12 side as the base material 11 is equivalent to the above. A range of ones may be used. In addition, the surface roughness (arithmetic average roughness Ra) in this specification was measured at a measurement speed of 1.0 mm / s and a measurement length of 10.525 mm using a surface roughness measuring instrument SV-3000 manufactured by Mitutoyo Corporation. Value.

(3) Print coat layer The print coat layer 13 of the release sheet 1 according to the present embodiment coats and protects the print layer 2 transferred to the adherend. The coating layer 13 for printing in the present embodiment contains a resin having a glass transition temperature (Tg) of 10 to 80 ° C. (hereinafter sometimes referred to as “resin R”). The coating layer 13 for printing becomes excellent in abrasion resistance by containing the resin R. That is, if the glass transition temperature of the resin contained in the printing coat layer 13 is less than 10 ° C., the printing coat layer 13 becomes too soft and the scratch resistance becomes poor. On the other hand, if the glass transition temperature of the resin contained in the printing coat layer 13 exceeds 80 ° C., the printing coating layer 13 becomes too hard, and the scratch resistance is also poor.

  From said viewpoint, the glass transition temperature of resin R is 10-80 degreeC, Preferably it is 15-70 degreeC, Most preferably, it is 20-65 degreeC.

  The resin R may be any resin that satisfies the above glass transition temperature, and may be a thermoplastic resin or a curable resin such as a thermosetting resin or an ultraviolet curable resin. Specifically, for example, polyolefin resin, acrylic resin, polyester resin, styrene resin, ABS resin, vinyl chloride resin, fluorine resin, polycarbonate resin, polyester urethane resin, urethane resin, phenol resin, urea resin, melamine resin, unsaturated It can be appropriately selected from polyester resin, epoxy resin, silicon resin and the like. These resins may be used alone or in combination of two or more. In the latter case, the glass transition temperature of the resin obtained by mixing may be in the above range.

  Among the above, the resin R is preferably a cross-linked resin. The cross-linked resin has a high coating strength, and the printing coat layer 13 is more excellent in scratch resistance. Examples of the cross-linked resin include urethane cross-linked resins, isocyanate cross-linked resins, melamine cross-linked resins, and the like. Among them, urethane cross-linked resins are preferable.

  The resin R is particularly preferably a polyester urethane resin. The polyester urethane resin has a very high coating strength, and the printing coat layer 13 is remarkably excellent in scratch resistance and has excellent adhesion to the printing layer 2.

  The polyester urethane resin is a copolymer polyester urethane resin obtained by a polyaddition reaction of the following polyester diol (a), polyalkylene ether glycol (b), aliphatic polyhydric alcohol (c), and diisocyanate compound (d). Is particularly preferred.

（但し、Ｒ^１は炭素数１又は２のアルキル基である）
一般式（２）：

（但し、Ｒ^２は炭素数１又は２のアルキル基、Ｒ^３は水素原子又は炭素数１〜４のアルキル基である） [Polyester diol (a)]
The polyester diol (a) contains 80 mol% or more of an aromatic dicarboxylic acid component when the total acid component is 100 mol%, and the fat represented by the general formula (1) when the total glycol component is 100 mol%. The aliphatic glycol component and / or the aliphatic glycol component represented by the general formula (2) is contained in an amount of 40 mol% or more, and the number average molecular weight is preferably 1500 or more and 3000 or less.
General formula (1):

(However, R ¹ is an alkyl group having 1 or 2 carbon atoms.)
General formula (2):

(However, R ² is an alkyl group having 1 or 2 carbon atoms, and R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

  The above-mentioned polyester diol (a) has a moderate compatibility with the polyalkylene ether glycol component (b) described later which is copolymerized by a urethane bond because 80 mol% or more of the total acid component is an aromatic dibasic acid. The segments derived from both components (a) and (b) are aggregated to form a microphase separation structure, thereby improving the adhesion and blocking resistance of the printing ink (printing layer 2).

  When the total glycol component in the component (a) is 100 mol%, the aliphatic glycol component represented by the general formula (1) and / or the aliphatic glycol component represented by the general formula (2) is 40 mol%. By containing in the above, the solubility to a general purpose solvent improves, and it becomes easy to superpose | polymerize in a general purpose organic solvent.

  The number average molecular weight of the component (a) is preferably 1500 or more and 3000 or less. When the number average molecular weight is less than 1500, the compatibility with the segment derived from the component (b) is improved, and the microphase separation of the segments derived from the components (a) and (b) does not occur, and thus the copolymer obtained In the polyester urethane resin, the affinity with the printing ink, which is the effect of the aggregation structure of the segment derived from the component (b), does not appear, and the printing ink adhesion tends to be impaired. The anti-blocking performance, which is the effect of the aggregated structure of the derived segments, tends to be impaired. On the other hand, when the number average molecular weight exceeds 3000, the incompatibility with the segment derived from the component (b) is excessively increased, and the resin containing the component (a) at a high concentration in the polymerization process of the copolymerized polyester urethane resin; b) It tends to be difficult to obtain a uniform resin by phase-separating into two phases of a resin containing a high concentration of the component. In addition, the said number average molecular weight is the value of standard polystyrene conversion measured by the gel permeation chromatography (GPC) method.

  Examples of the acid component constituting the component (a) include aromatic dibasic acids such as terephthalic acid, isophthalic acid and orthophthalic acid, and ester derivatives thereof, but the incompatibility with the component (b) For expression, terephthalic acid, isophthalic acid, dimethyl terephthalate, dimethyl isophthalate, and dimethyl sodium 5-sulfoisophthalate are more preferred. In addition, dibasic acids other than aromatic dibasic acids used in combination with these aromatic dibasic acids and used in less than 20 mol% of the total acid content include aliphatic dibasic acids such as adipic acid and sebacic acid, 1 And cycloaliphatic dibasic acids such as 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,2-cyclohexanedicarboxylic acid.

  The glycol component used in combination with the dibasic acid in the component (a) is a fat represented by the general formula (1) or the general formula (2) that is copolymerized in an amount of 40 mol% or more in the total glycol component. Examples of the group glycol component include 2-methyl-1,3-propanediol, neopentyl glycol, 1,2-propylene glycol, 2-ethyl-2-butyl-1,3-propanediol, and the like. Among these, neopentyl glycol is preferable from the viewpoint of more effectively increasing the solubility in a general-purpose solvent. Other glycol components copolymerized with these aliphatic glycols include linear chains such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol. An aliphatic glycol component is preferably used. Among these, it is preferable to use ethylene glycol because the polymerization reaction is more likely to proceed.

[Polyalkylene ether glycol (b)]
The polyalkylene ether glycol (b) has a structure obtained by dehydration condensation of an aliphatic glycol having 2 to 4 carbon atoms, and preferably has a number average molecular weight of 1000 or more and 3000 or less.

  Specific examples of the component (b) include polyether diols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Among these, polypropylene glycol is more preferable in order to develop moderate incompatibility with the segment derived from the component (a).

  The number average molecular weight of the component (b) is preferably 1000 to 3000. If the number average molecular weight is less than 1000, the compatibility with the segment derived from the component (a) is improved (a), and the microphase separation of the segment derived from both components (b) does not occur. There is a tendency that the affinity with the printing ink, which is the effect of the aggregation structure of the segments derived from the component (b) in the polymerized polyester urethane resin, is difficult to be exhibited, and the adhesion of the printing ink tends to be impaired. Furthermore, the component (a) The anti-blocking performance, which is the effect of the aggregate structure of the segments derived from, tends not to be exhibited. On the other hand, when the number average molecular weight exceeds 3000, the incompatibility with the component (a) is too high, and the resin containing the component (a) at a high concentration in the polymerization process of the copolymer polyester urethane resin and the component (b) Phase separation occurs in the two phases of the resin contained at a high concentration, and it tends to be difficult to obtain a uniform resin.

  The copolymerization ratio of the component (a) and the component (b) is preferably 40 to 80 parts by mass of the component (b) with respect to 100 parts by mass of the component (a). When the component (b) is less than 40 parts by mass, the affinity with the printing ink, which is the effect of the aggregate structure of the segments derived from the component (b), is not sufficiently exhibited, and thus the printing ink adhesion tends to be impaired. . On the other hand, when the component (b) exceeds 80 parts by mass, the glass transition temperature of the entire copolymer polyester urethane resin is lowered, and the blocking resistance tends to be impaired.

[Aliphatic polyhydric alcohol (c)]
The aliphatic polyhydric alcohol (c) is used as a chain extender in the copolymerized polyester urethane resin, and preferably has 4 to 6 carbon atoms. Specific examples of the component (c) include linear aliphatic glycols such as 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol, and 2-methyl-1,3-propane. Examples thereof include branched glycols such as diol, neopentyl glycol, and 1,2-propylene glycol. Further, for the purpose of improving the reactivity with the crosslinking agent, a trifunctional or higher polyhydric alcohol may be used, and examples thereof include triols such as trimethylolpropane and glycerin, and tetraols such as pentaerythritol. Of these polyhydric alcohol compounds, branched glycols are preferred, and neopentyl glycol is most preferred from the viewpoint of improving the solubility of the resulting copolymerized polyester urethane resin.

  By copolymerizing these aliphatic polyhydric alcohols (c) having 4 to 6 carbon atoms, the urethane bond group concentration in the copolymerized polyester urethane resin is adjusted, and the physical properties such as the glass transition temperature of the copolymerized polyester urethane resin. Can be controlled.

  The aliphatic polyhydric alcohol (c) component can be copolymerized in an amount of preferably 8 parts by mass or less, more preferably 6 parts by mass or less, relative to 100 parts by mass of the component (a). When the amount exceeds 8 parts by mass, a diisocyanate compound (d) component described later and an oligomer having a specific structure are easily produced, and the produced oligomer tends to precipitate in the polyurethane solution in some cases. (C) Although a component is not an essential component, when using, since an effect will not be exhibited if the usage-amount is too small, it is preferable that it is 0.2 mass part or more with respect to 100 mass parts of (a) component. 0.6 parts by mass or more is more preferable, and 1.6 parts by mass or more is more preferable.

[Diisocyanate compound (d)]
As the diisocyanate compound (d) component, any of aromatic, aliphatic and alicyclic diisocyanate compounds may be used. Diphenylmethane diisocyanate, tolylene diisocyanate, 1,3-xylylene diisocyanate, isophorone diisocyanate, 1,6-hexane diisocyanate However, diphenylmethane diisocyanate is preferable because of its good reactivity.

  The copolymerization amount of these diisocyanate compounds is preferably 20 to 50 parts by mass in the copolymerized polyester urethane resin. If it is less than 20 parts by mass, the toughness peculiar to the copolymerized polyester urethane resin hardly appears, and if it exceeds 50 parts by mass, the solubility of the copolymerized polyesterurethane resin produced in a general-purpose solvent tends to decrease.

[Properties of copolymer polyester urethane resin]
The copolymer polyester urethane resin preferably has a number average molecular weight of 10,000 to 100,000. If the number average molecular weight is lower than this, the adhesion of the printing ink tends to be insufficient, and if the number average molecular weight is higher than this, the viscosity of the polyurethane resin solution tends to be high and handling workability tends to be poor. .

  The temperature at which the loss tangent tan δ in the dynamic viscoelasticity measurement of the copolymerized polyester urethane resin is maximized is preferably 40 ° C. or higher, more preferably 50 to 75 ° C. When tan δ is lower than 40 ° C., the anti-blocking property becomes insufficient, and when it exceeds 75 ° C., the print adhesion tends to be lowered.

[Polymerization of copolyester urethane resin]
The copolymerized polyester urethane resin is, for example, in a ketone solvent such as methyl ethyl ketone, methyl isobutyl ketone, or cyclohexanone, or in a mixed solvent of an aromatic hydrocarbon solvent such as toluene or xylene and the ketone solvent. Polymerization is preferably performed by a polyaddition reaction of the component (b), the component (b), the component (c), and the component (d). As the polymerization catalyst, for example, an organic tin complex such as dibutyltin laurate or an amine catalyst such as triethylenediamine can be used.

  Resin R may consist of one kind of resin alone, or a mixture of two or more kinds of resins. For example, the glass transition temperature of the resin R may be within the above range by mixing two or more kinds of resins.

  The printing coat layer 13 preferably contains a crosslinking agent capable of crosslinking the resin R. By cross-linking the resin R with a cross-linking agent, the scratch resistance of the printing coat layer 13 can be further improved.

  Any crosslinking agent may be used as long as it has reactivity with the functional group of the resin R. For example, an isocyanate crosslinking agent, an epoxy crosslinking agent, an amine crosslinking agent, a melamine crosslinking agent, an aziridine crosslinking agent. Hydrazine crosslinking agent, aldehyde crosslinking agent, oxazoline crosslinking agent, metal alkoxide crosslinking agent, metal chelate crosslinking agent, metal salt crosslinking agent, ammonium salt crosslinking agent and the like. Among these, it is preferable to use an isocyanate-based crosslinking agent. A crosslinking agent can be used individually by 1 type or in combination of 2 or more types.

  The isocyanate-based crosslinking agent contains at least a polyisocyanate compound. Examples of the polyisocyanate compound include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate and xylylene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, alicyclic polyisocyanates such as isophorone diisocyanate and hydrogenated diphenylmethane diisocyanate, and the like. , And their biuret bodies, isocyanurate bodies, and adduct bodies that are a reaction product with low molecular active hydrogen-containing compounds such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, and castor oil.

  Examples of the epoxy crosslinking agent include ethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, diglycidyl aniline, diglycidyl amine, N, N, N ′, N′— Examples include tetraglycidyl-m-xylenediamine, N, N-diglycidylaminocyclohexane, diglycidylcyclohexanedicarboxylate, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, and the like.

  Examples of the aziridine-based crosslinking agent include 2,2-bishydroxymethylbutanol-tris [3- (1-aziridinyl) pronate], 4,4-bis (ethyleneiminocarboxyamino) diphenylmethane, tris-2,4,6. -(1-aziridinyl) -1,3,5-triazine, tris [1- (2-methyl) aziridinyl] phosphine oxide, hexa [1- (2-methyl) aziridinyl] triphosphatriazine, trimethylolpropane-β- Aziridinylpropionate, tetramethylolmethane tri-β-aziridinylpropionate, trimethylolpropane tri-β- (2-methylaziridine) propionate, N, N′-hexamethylene-1,6-bis ( 1-aziridinecarboxylate) and the like.

  Examples of the metal chelate compound include those having a metal atom of aluminum, zirconium, titanium, zinc, iron, tin, and the like, but an aluminum chelate compound is preferable from the viewpoint of performance. Examples of the aluminum chelate compound include diisopropoxy aluminum monooleyl acetoacetate, monoisopropoxy aluminum bis oleyl acetoacetate, monoisopropoxy aluminum monooleate monoethyl acetoacetate, diisopropoxy aluminum monolauryl acetoacetate, diisopropoxy Aluminum monostearyl acetoacetate, diisopropoxy aluminum monoisostearyl acetoacetate, monoisopropoxy aluminum mono-N-lauroyl-β-alanate monolauryl acetoacetate, aluminum trisacetylacetonate, monoacetylacetonate aluminum bis (isobutylacetate Acetate) chelate, monoacetylacetonate aluminum (2-ethylhexyl acetoacetate) chelate, monoacetylacetonate aluminum bis (dodecylacetoacetate) chelate, monoacetylacetonate aluminum bis (oleyl acetoacetate) chelate, and the like.

  Examples of other metal chelate compounds include titanium tetrapropionate, titanium tetra-n-butyrate, titanium tetra-2-ethyl hexanoate, zirconium-sec-butyrate, zirconium diethoxy-tert-butyrate, and triethanolamine. Examples thereof include titanium dipropionate, ammonium lactate ammonium salt, and tetraoctylene glycol titanate.

  It is preferable that the compounding quantity of the crosslinking agent with respect to 100 mass parts (solid content) of resin R is 0.1-30 mass parts, and it is especially preferable that it is 0.25-25 mass parts. When the blending amount of the crosslinking agent is 0.1 parts by mass or more, the effect of improving the scratch resistance of the printing coat layer 13 is obtained, and when the blending amount of the crosslinking agent is 30 parts by mass or less, the coating layer 13 for printing. It is possible to suppress the surface hardness of the resin from becoming excessively high and the abrasion resistance from decreasing.

  When the coating layer 13 for printing contains the said crosslinking agent, it is preferable to contain a crosslinking accelerator further. What is necessary is just to select suitably as a crosslinking accelerator according to the kind etc. of a crosslinking agent. For example, when the crosslinking agent is an isocyanate crosslinking agent, dibutyltin dilaurate as a metal salt catalyst, cobalt naphthenate, etc., triethylenediamine, monoethanolamine, etc. as an amine catalyst, lead naphthenate as a carboxylate catalyst, etc. Further, triethylphosphine as a trialkylphosphine catalyst such as potassium acetate can be used. When the crosslinking agent is an epoxy-based crosslinking agent, diazabicycloundecene, diazabicyclononene, tris (dimethylaminomethyl) phenol as a tertiary amine / tertiary amine salt, and 1- as an imidazole series. Cyanoethyl-2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazole, triphenylphosphine as a phosphine / phosphonium salt, tetraphenylphosphonium, tetraphenylborate, other 3-phenyl-1,1-dimethyl Urea, sulfonium salts and the like can be used. A crosslinking accelerator can be used individually by 1 type or in combination of 2 or more types.

  It is preferable that the compounding quantity of the crosslinking accelerator with respect to 100 mass parts of resin R is 1-20 mass parts, It is especially preferable that it is 2-15 mass parts, Furthermore, it is preferable that it is 3-10 mass parts.

  The coating layer 13 for printing preferably contains fine particles in addition to the above components. By containing the fine particles, moderate unevenness is imparted to the surface of the printing coat layer 13 (particularly the surface on the release agent layer 12 side), and a matte feeling can be obtained. Thereby, reflection of light on the surface of the printing coat layer 13 is suppressed, and printing of the printing layer 2 becomes easy to see regardless of the viewing angle. Such an effect is particularly excellent when the surface roughness (Ra) of the base material 11 on the release agent layer 12 side is set to the above-described range.

  When the printing coat layer 13 contains fine particles as described above, the resin R can function as a binder resin.

  Examples of the fine particles include organic fine particles such as polymer fine particles and inorganic fine particles, and polymer fine particles are particularly preferable. When the printing coat layer 13 contains polymer fine particles, the surface of the printing coat layer 13 has excellent antifouling properties. Examples of the polymer fine particles include polyolefin fine particles such as polyethylene fine particles and polypropylene fine particles, acrylic resin fine particles, crosslinked silicone particles, polyethersulfone fine particles, epoxy resin particles, urethane resin particles, melamine resin particles, benzoguanamine resin particles, and phenol resin particles. Etc., and the surface may be modified or may not be modified. These fine particles can be used alone or in combination of two or more.

  Among the above, polyolefin fine particles are preferable, and polyethylene fine particles are particularly preferable. According to the polyethylene fine particles, the surface of the printing coat layer 13 is very excellent in antifouling property.

  The average particle size of the polymer fine particles is preferably 1 to 10 μm, particularly preferably 1.5 to 7 μm, and more preferably 2 to 5 μm. When the average particle size of the polymer fine particles is 1 μm or more, a desired mat feeling can be obtained and good antifouling properties can be obtained. Moreover, when the average particle diameter of the polymer fine particles is 10 μm or less, it is possible to prevent the unevenness on the surface of the printing coat layer 13 from becoming excessively large. In addition, the average particle diameter of the fine particles in the present specification is obtained by measuring the average particle diameter by a centrifugal sedimentation light transmission method.

  The content of the polymer fine particles in the printing coat layer 13 is preferably 30 to 90 parts by mass, and particularly preferably 40 to 80 parts by mass with respect to 100 parts by mass of the resin R. When the content of the polymer fine particles is 30 parts by mass or more, a desired mat feeling can be obtained and good antifouling properties can be obtained. Further, when the content of the polymer fine particles is 90 parts by mass or less, the coating strength of the printing coat layer 13 can be sufficiently ensured.

  The coating layer 13 for printing includes other components such as coloring materials such as dyes and pigments, antioxidants such as anilides and phenols, UV absorbers such as benzophenones and benzotriazoles, plasticizers, and antioxidants. Agents, light stabilizers, dispersants, leveling agents and the like. Although content of these components is arbitrary, it is preferable that these components do not exceed 10 mass% with respect to the whole coating layer 13 for printing.

  The thickness of the printing coat layer 13 is preferably 1.2 to 15 μm, and the peeling force of the release agent layer 12 on the printing coating layer 13 is preferably 200 to 1800 mN / 25 mm. In addition, the peeling force in this specification shall be the value measured based on JISK6854. By satisfying the above conditions, when the release sheet 1 is peeled off after the adhesive layer 3 of the transfer sheet 4 is adhered to the adherend, as shown in FIG. 2 is cut at the boundary between the portion where 2 is laminated and the portion where it is not laminated, and the portion where the printing layer 2 is laminated in the printing coating layer 13 remains on the printing layer 2, and the printing coating layer A portion where the printing layer 2 is not laminated at 13 is peeled off together with the base material 11 and the release agent layer 12 while being attached to the release agent layer 12. Thereby, the printing coat layer 13 having the same size and shape as the printing layer 2 can be formed on the printing layer 2 transferred to the adherend. That is, there is no printing coat layer 13 protruding from the printing layer 2, and a transfer product excellent in appearance can be obtained very simply.

  When the thickness of the coating layer 13 for printing exceeds 15 μm or the peeling force is less than 200 mN / 25 mm, the cutting property of the coating layer 13 for printing is inferior, and when the release sheet 1 is peeled off, the coating layer 13 for printing May be cut off along the outer periphery of the printing layer 2 and the printing coat layer 13 may be in an irregular shape.

  When the thickness of the printing coat layer 13 is 1.2 μm or more, the coating strength as the printing coat layer 13 can be ensured. Moreover, the peeling sheet 1 can be peeled favorably as the peeling force is 1800 mN / 25 mm or less.

  From the above viewpoint, the thickness of the coating layer 13 for printing is preferably 1.2 to 15 μm, particularly preferably 2 to 8 μm, and further preferably 2.5 to 5 μm. Moreover, it is preferable that the peeling force with respect to the coating layer 13 for printing of the release agent layer 12 is 200-1800 mN / 25mm, and it is especially preferable that it is 1000-1500mN / 25mm.

(4) Production of Release Sheet The release sheet 1 can be produced by a conventional method. For example, the release agent layer 12 may be formed on one surface of the substrate 11 and the printing coat layer 13 may be formed on the release agent layer 12. The release agent layer 12 can be formed by applying a release agent and a release agent coating solution containing a solvent or the like, if desired, and then heating and drying as necessary. Further, the coating layer for printing 13 can be formed by applying a coating agent containing a material constituting the coating layer for printing 13 and, if desired, a solvent, and then heating and drying as necessary.

  As a method for applying the release agent solution and the coating agent, for example, a gravure coating method, a bar coating method, a spray coating method, a spin coating method, a knife coating method, a roll coating method, a die coating method and the like can be used.

[Transfer sheet]
As shown in FIG. 2, the transfer sheet 4 according to the present embodiment is a print layered on the surface of the release sheet 1 described above and the surface of the release sheet 1 opposite to the release agent layer 12 side of the printing coat layer 13. It is comprised from the layer 2 and the adhesive bond layer 3 laminated | stacked on the opposite side (upper side in FIG. 2) of the peeling layer 1 side of the printing layer 2. As shown in FIG.

  The printing layer 2 and the adhesive layer 3 in the present embodiment are formed in the same size and shape and are smaller in the planar direction than the release sheet 1, but are not limited thereto. . Moreover, in this embodiment, although the printing layer 2 and the adhesive bond layer 3 are laminated | stacked directly, this invention is not limited to this, A base material etc. may interpose both.

(1) Print layer The print layer 2 displays desired characters, designs, colors, and the like, and is formed by printing ink. The printing ink constituting the printing layer 2 is not particularly limited. For example, gravure printing ink, screen printing ink, relief printing ink, lithographic printing ink, special ink (such as ultraviolet curable ink), etc. Various inks can be used.

  The material of the printing ink is not particularly limited. For example, vinyl-based, polyester-based, acrylic-based, polycarbonate-based, ABS-based, polystyrene-based, urethane-based, polyolefin-based, and epoxy-based inks can be used. .

  The thickness of the printing layer 2 is not particularly limited, but is usually preferably 0.1 to 25 μm, particularly preferably 0.5 to 20 μm, and more preferably 1 to 15 μm. Is preferred.

(2) Adhesive layer The adhesive layer 3 may be any layer that can adhere the print layer 2 to a desired adherend. As an adhesive which comprises the adhesive bond layer 3, a pressure sensitive adhesive (adhesive) may be sufficient and a heat sensitive adhesive may be sufficient. When the adhesive layer 3 is composed of a heat-sensitive adhesive, the printing layer 2 with the printing coat layer 13 can be strongly bonded (thermal transfer) to the adherend by heating, preferably by heating and pressing. . Therefore, it is suitable when the transfer sheet 4 is used for, for example, a caution label.

  The type of pressure-sensitive adhesive may be any of acrylic, polyester, urethane, rubber, silicone, etc., and may be a so-called adhesive. The type of heat-sensitive adhesive may be any of a hot melt type, an organic solvent solution type, an aqueous emulsion type, an aqueous solution type, and the like. For example, a polyurethane adhesive, a polyester adhesive, a polyamide adhesive ( Nylon adhesive), polyolefin adhesive (ethylene vinyl acetate copolymer, etc.), acrylic resin adhesive, silicone resin adhesive, synthetic rubber adhesive (styrene butadiene copolymer rubber, etc.) and the like.

  Although the thickness of the adhesive bond layer 3 is not specifically limited, Usually, it is preferable that it is 5-100 micrometers, and it is especially preferable that it is 10-60 micrometers.

(3) Production of transfer sheet The transfer sheet 4 can be produced by a conventional method. For example, printing may be performed on the exposed surface of the printing coat layer 13 of the release sheet 1 to form the printing layer 2, and the adhesive layer 3 may be formed on the printing layer 2. The printing method of the printing layer 2 is not particularly limited, and examples thereof include gravure printing, screen printing, relief printing, and lithographic printing.

  The formation of the adhesive layer 3 may be appropriately performed according to the type of adhesive. For example, in the case of an adhesive that can be applied, an adhesive coating solution containing an adhesive and optionally a solvent or the like is applied onto the printing layer 2 and then heated and dried as necessary to form the adhesive layer. 3 can be formed. Moreover, after apply | coating an adhesive coating liquid on the peeling surface (surface which has peelability) of another peeling sheet, after forming the adhesive bond layer 3 by heating as needed and drying, the said adhesive agent Layer 3 may be transferred to printing layer 2. On the other hand, in the case of a heat-sensitive adhesive that is difficult to apply, the adhesive layer 3 can be formed by an extrusion coating method, a heat laminating method, or the like.

(4) Use of Transfer Sheet To use the transfer sheet 4 according to this embodiment, first, the adhesive layer 3 of the transfer sheet 4 is bonded to the adherend 5 (see FIG. 3). When the adhesive layer 3 is a heat-sensitive adhesive, it may be heated at a desired temperature and pressurized. Thereafter, the release sheet 1 is peeled off. At this time, as shown in FIG. 3, peeling occurs at the interface between the release agent layer 12 and the printing coat layer 13, and the printing coat layer 13 remains on the printing layer 2. Thereby, the coating layer 13 for printing can be formed in the printing layer 2 transferred to the adherend 5.

  Here, when the thickness of the printing coat layer 13 and the peeling force of the release agent layer 12 with respect to the printing coat layer 13 are set within the above-described range, as shown in FIG. A print coat layer 13 having the same size and shape as the print layer 2 is formed on the print layer 2 by cutting along the outer periphery of the print layer 2. Thereby, there is no coating layer 13 for printing which protruded from the printing layer 2, and the transfer material excellent in the external appearance is obtained.

  Since the printing coat layer 13 according to this embodiment is excellent in scratch resistance, the printing layer 2 transferred to the adherend 5 is hardly damaged. When the printing coat layer 13 contains fine particles (and the surface roughness of the substrate 11 is within a predetermined range), the surface of the printing coat layer 13 has a matte texture, and the printing layer The printing of No. 2 becomes easy to see. Further, when the fine particles are polymer fine particles, they are excellent in antifouling properties and are difficult to stain.

  The embodiment described above is described for facilitating understanding of the present invention, and is not described for limiting the present invention. Therefore, each element disclosed in the above embodiment is intended to include all design changes and equivalents belonging to the technical scope of the present invention.

  For example, between the base material 11 and the release agent layer 12 in the release sheet 1, between the release agent layer 12 and the print coat layer 13, or between the print coat layer 13 and the print layer 2 in the transfer sheet 4. Alternatively, another layer may be provided between the printing layer 2 and the adhesive layer 3.

  EXAMPLES Hereinafter, although an Example etc. demonstrate this invention further more concretely, the scope of the present invention is not limited to these Examples etc.

[Example 1]
Polyester urethane resin (resin R; manufactured by Toyobo Co., Ltd., UR-4125) having a glass transition temperature of 68 ° C. (solid content; the same applies hereinafter) and a polyisocyanate modified product (manufactured by Nippon Polyurethane Industry Co., Ltd., 3 parts by weight of Coronate HL), 2 parts by weight of a tin-based compound (manufactured by Toyo Ink Co., Ltd., BXX3778G) as a crosslinking accelerator, and polyethylene fine particles (manufactured by Koyo Chemical Co., Ltd., micro flat UN-8, average particle size: The mixture was mixed with 40 parts by mass (2.6 μm, no surface modification) and used as a coating agent (containing ethyl acetate as a solvent).

  A laminate in which a release agent layer made of a silicone release agent is formed on one side of a base material made of polyethylene terephthalate (made by Kaisei Kogyo Co., Ltd., Matt PET Type D, thickness: 75 μm, surface roughness (Ra): 0.43 μm) ( Thickness: 75 μm and surface roughness (Ra): 0.43 μm) were prepared. On the release agent layer of this laminate, the coating agent is applied with an applicator, heated at 105 ° C. for 2 minutes, dried and cured, and a cured coating layer having a thickness of 3 μm is formed. A release sheet was obtained.

[Example 2]
A release sheet was produced in the same manner as in Example 1 except that the blending amount of the polyethylene fine particles was changed to 60 parts by mass.

Example 3
A release sheet was produced in the same manner as in Example 1 except that the blending amount of the polyethylene fine particles was changed to 80 parts by mass.

Example 4
A release sheet was prepared in the same manner as in Example 1 except that a polyester urethane resin having a glass transition temperature of 46 ° C. (manufactured by Toyobo Co., Ltd., UR-1350) was used as the resin R.

Example 5
A release sheet was produced in the same manner as in Example 4 except that the blending amount of the polyethylene fine particles was changed to 60 parts by mass.

Example 6
A release sheet was produced in the same manner as in Example 4 except that the thickness of the printing coat layer after curing was changed to 7 μm.

Example 7
A release sheet was produced in the same manner as in Example 4 except that the thickness after curing of the printing coat layer was changed to 10 μm.

Example 8
A release sheet was produced in the same manner as in Example 4 except that the blending amount of the polyethylene fine particles was changed to 80 parts by mass.

Example 9
A release sheet was produced in the same manner as in Example 1, except that a polyester urethane resin (manufactured by Toyobo Co., Ltd., UR-8300) having a glass transition temperature of 23 ° C. was used as the resin R.

Example 10
A release sheet was produced in the same manner as in Example 9 except that the blending amount of the polyethylene fine particles was changed to 60 parts by mass.

Example 11
A release sheet was produced in the same manner as in Example 9 except that the blending amount of the polyethylene fine particles was changed to 80 parts by mass.

Example 12
As a laminate of a base material and a release agent layer, a silicone base material made of polyethylene terephthalate (manufactured by Mitsubishi Plastics, smooth PET50 T-100, thickness: 50 μm, surface roughness (Ra): 0.033 μm) is used on one side. A release sheet was prepared in the same manner as in Example 1 except that a laminate (thickness: 50 μm, surface roughness (Ra): 0.033 μm) formed with a release agent layer made of a release agent was used.

Example 13
Instead of polyethylene fine particles (manufactured by Koyo Chemical Co., Ltd., micro flat UN-8, average particle size: 2.6 μm, no surface modification), polyethylene fine particles (manufactured by Koyo Chemical Co., Ltd., micro flat flat PT-260, average) Peeling is performed in the same manner as in Example 1, except that the particle size is 4.2 μm, no surface modification is used, the blending amount is 60 parts by mass, and the thickness of the printing coat layer after curing is changed to 20 μm. A sheet was produced.

[Comparative Example 1]
100 parts by mass of a polyester urethane resin having a glass transition temperature of 83 ° C (manufactured by Toyobo Co., Ltd., UR-3200), 3 parts by mass of a polyisocyanate-modified product (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate HL), and a crosslinking accelerator 2 parts by mass of a tin-based compound (manufactured by Toyo Ink Manufacturing Co., Ltd., BXX3778G) and 60 parts by mass of polyethylene fine particles (manufactured by Koyo Chemical Co., Ltd., micro-flat UN-8, average particle size: 2.6 μm, no surface modification) Were mixed to prepare a coating agent (containing ethyl acetate as a solvent).

  A release sheet was produced in the same manner as in Example 1 except that the above coating agent was used as the coating agent.

[Comparative Example 2]
100 parts by mass of a polyester urethane resin (manufactured by Toyobo Co., Ltd., UR-1400) having a glass transition temperature of −3 ° C., 3 parts by mass of a polyisocyanate modified product (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate HL) as a crosslinking agent, and crosslinking promotion 2 parts by mass of a tin-based compound (manufactured by Toyo Ink Mfg. Co., Ltd., BXX3778G) and polyethylene fine particles (manufactured by Koyo Chemical Co., Ltd., micro flat UN-8, average particle size: 2.6 μm, no surface modification) A mass part was mixed and used as a coating agent (containing ethyl acetate as a solvent).

  A release sheet was produced in the same manner as in Example 1 except that the above coating agent was used as the coating agent.

[Comparative Example 3]
A release sheet was produced in the same manner as in Example 1 except that an acrylic resin having a glass transition temperature of 100 ° C. (manufactured by Mitsubishi Rayon Co., Ltd., Dianar RB-73) was used instead of the resin R.

  Table 1 shows the types and glass transition temperatures (Tg) of the substrates and the composition and thickness of the coating layer for printing in the above Examples and Comparative Examples. The glass transition temperature (Tg) is a value measured at a temperature rising / falling rate of 20 ° C./min with a differential scanning calorimeter (DS Instruments Q2000, manufactured by T.A. Instruments Japan).

[Production example]
Ink for printing (Seiko Advance, SG700710BLACK, vinyl one-component evaporation drying type) was diluted with a diluting solvent (Seiko Advance, T-912, standard drying speed solvent) to a solid content concentration of 20% by mass. The thing was apply | coated with the applicator on the coating layer for printing of the peeling sheet obtained by the Example and the comparative example. And it heated at 70 degreeC for 24 hours, and formed the printing layer about 15 micrometers thick. The following test examples tested and evaluated about this peeling sheet with a printing layer.

[Test Example 1] (Abrasion resistance evaluation)
After the release sheet with a printed layer obtained above is cut into a width of 30 mm and a length of 250 mm, the release sheet (base material + release agent layer) is peeled off, and the laminate of the print layer and the coating layer for printing is used as a test piece. (The test piece surface was a coating layer for printing). This test piece was attached to a test stand of a Gakushin Tester (manufactured by Daiei Scientific Instruments Co., Ltd., RT-200), and a white cotton cloth of 50 mm × 50 mm was placed on the contact surface of the friction element and fixed. Then, the weight of the friction element was 0.5 N, and the friction element was reciprocated 1000 times at a speed of 30 reciprocations per 100 mm between the test pieces. From the degree of contamination of the white cotton cloth and the degree of scratches on the surface of the test piece, the scratch resistance was evaluated according to the following criteria. The results are shown in Table 2.
5: No scratches or contamination is observed 4: Slight scratches are seen but not noticeable 3 ... Slight but obvious scratches 2 ... Scratches and contamination are slightly 1 1 Scratches and contamination are considerable Remarkable

[Test Example 2] (Peeling force measurement)
The release sheet with a printing layer obtained above was cut into a length of 200 mm and a width of 25 mm, and the laminate of the printing layer and the coating layer for printing in the obtained test piece was tested with a testing machine (Shimazu Seisakusho, Tensilon AGS-20NX). ), And according to JIS K6854, the force when the release sheet (base material + release agent layer) was peeled 150 mm in length at a tensile rate of 0.1 m / min in the 180 ° direction was measured. The peeling force (mN / 25 mm) was used. The results are shown in Table 2.

[Test Example 3] (Anti-fouling evaluation)
The release sheet (base material + release agent layer) was peeled from the release sheet with a print layer obtained above, and a laminate of the print layer and the coat layer for printing was used as a test piece. The exposed surface of the printing coat layer was reciprocated 10 times with a finger, and the antifouling property was evaluated from the degree of contamination at that time according to the following criteria. The results are shown in Table 2.
5 ... No contamination at all 3 ... Slight but obvious contamination 1 ... Contamination is quite significant

[Test Example 4] (Cutability evaluation)
An adhesive tape (manufactured by Nitto Denko Corporation, 31B tape, 20 mm width) was applied to the printed layer of the release sheet with a printed layer obtained above by reciprocating 5 times with a 5 kg roller, and left for 30 minutes. Thereafter, the pressure-sensitive adhesive tape was peeled off at 180 ° peeling with a peeling speed of 0.3 m / min using a testing machine (Shimadzu Corporation, Tensilon AGS-20NX). evaluated. In any of the test pieces, the printing coat layer was peeled off from the release agent layer, and there was no problem in the adhesion of the printing layer to the printing coat layer. The results are shown in Table 2.
5 ... The print coat layer peels along the outer edge of the adhesive tape, and the end of the print coat layer remains on the release agent layer side (the end remains), or the print coat layer peels larger than the outer edge of the adhesive tape. 4 ... Slightly remaining edge or removed, but almost inconspicuous 3 ... Slightly but clearly left edge or removed 2 ... End Remaining and removed are a little noticeable.

[Test Example 5] (Texture evaluation)
The release sheet (base material + release agent layer) was peeled from the release sheet with a print layer obtained above, and a laminate of the print layer and the coat layer for printing was used as a test piece. The exposed surface of the printing coat layer was reciprocated 10 times with a finger, and the texture was evaluated according to the criteria shown below from the resistance at that time and the antiglare property of the exposed surface of the printing coating layer. The results are shown in Table 2.
5: There is no sense of resistance on the finger, and there is no reflection of light when viewed at any angle. 4 ... Almost no sense of resistance and little reflection of light. 2 ... Resistivity and light reflection are remarkably 1 ... Resistance and light reflection are remarkably remarkable

  As can be seen from Table 2, all of the print coat layers of the release sheets produced in the examples were excellent in scratch resistance. In particular, the printing coat layers of the release sheets of Examples 1 to 11 and 13 were excellent in antifouling property and texture. Furthermore, in particular, the release sheets of Examples 1 to 12 were excellent in the cutting properties of the coating layer for printing.

  The release sheet and transfer sheet of the present invention are suitably used for, for example, a transfer type print label, particularly a thermal transfer type print label.

DESCRIPTION OF SYMBOLS 1 ... Release sheet 11 ... Base material 12 ... Release agent layer 13 ... Print coat layer 2 ... Print layer 3 ... Adhesive layer 4 ... Transfer sheet 5 ... Adhering body

Claims (9)

A substrate;
A release agent layer laminated on one side of the substrate;
A release sheet provided with a coating layer for printing containing a resin having a glass transition temperature of 10 to 80 ° C., which is laminated on the side opposite to the substrate side of the release agent layer,
The resin is a cross-linked resin and a polyester urethane resin,
A printing layer is laminated on the printing coat layer, and at least an adhesive layer is laminated on the opposite side of the printing coating layer of the printing layer,
After the adhesive layer is bonded to the adherend, when the release sheet is peeled off, peeling occurs at the interface between the release agent layer and the printing coat layer, and the printing coat layer is on the adherend side. A release sheet characterized by remaining in the film.   The release sheet according to claim 1, wherein the coating layer for printing further contains fine polymer particles.   The release sheet according to claim 2, wherein the polymer fine particles are polyethylene fine particles.   The release sheet according to claim 2 or 3, wherein the polymer fine particles have an average particle size of 1 to 10 µm.   The peeling according to any one of claims 2 to 4, wherein the content of the polymer fine particles in the printing coat layer is 40 to 90 parts by mass with respect to 100 parts by mass of the resin. Sheet. The thickness of the coating layer for printing is 1.2 to 15 μm,
The release sheet according to any one of claims 1 to 5 , wherein the release force of the release agent layer to the coating layer for printing is 200 to 1800 mN / 25 mm. The release sheet according to any one of claims 1 to 6 , wherein a surface roughness (Ra) of the release agent layer on the printing coat layer side is 0.1 to 2.0 µm. The release sheet according to any one of claims 1 to 7 ,
A printing layer laminated on the printing coat layer in the release sheet;
A transfer sheet comprising: an adhesive layer laminated on a side opposite to the printing coat layer of the printing layer. The transfer sheet according to claim 8 , wherein the adhesive layer is composed of an adhesive having thermal adhesiveness.

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