TW201245297A - Polyvinyl alcohol-based film, production method of polyvinyl alcohol-based film, and heat transfer laminate by using the same - Google Patents

Abstract

The present invention provides a polyvinyl alcohol-based resin film which has excellent mold releasing property and is more suitable for use in the base film of a heat transfer film, a production method of a polyvinyl alcohol-based film and a heat transfer laminate byusing the polyvinyl alcohol-based film. The polyvinyl alcohol-based film of this invention contains 1-20 parts by weight of a non-ionic surfactant (B) containing oxyethylene group or oxypropylene group, relative to 100 parts by weight of polyethylene alcohol-based resin (A).

Description

201245297 VI. Description of the Invention: [Technical Field] The present invention relates to a polyvinyl alcohol-based film excellent in mold release property, and more particularly to a substrate which can be preferably used as a laminate for heat transfer. A polyvinyl alcohol-based film having a release property of a film, a method for producing the polyvinyl alcohol-based film, and a laminate for heat transfer using the polyvinyl alcohol-based film. [Prior Art] A method of adding a molded article includes a method of transferring a transfer layer of a film for transfer using a film for transfer. The film for transfer is a layer in which a transfer layer is laminated on the base film, and the transfer layer also includes a resin layer which serves as a protective layer for protecting the surface of the transferred material after transfer, and a pattern layer, an adhesive layer, and the like which are further included on the resin layer. The transfer method is roughly divided into a hydraulic transfer method and a heat transfer method. The hydraulic transfer method is a method in which a transfer layer such as a molded article is mortgaged on a transfer layer by superimposing a surface on the transfer layer side of the film for hydraulic transfer on the surface of the transfer layer and floating on the water surface. After transferring to the object to be transferred, the object to be transferred is taken out, washed with water to dissolve and remove the base film, and the pattern or the like is transferred to the object to be transferred. In such a hydraulic transfer method, a method of using a polyethylene film which is excellent in water solubility as a base film is known (for example, Patent Documents 1 and 2). On the other hand, the film for thermal transfer used in the heat transfer method is used for a film for heat transfer in which a transfer layer is laminated in a peelable state by a film of a thermoplastic resin film or the like. The resin layer which accounts for & ax ^ is a protective layer, and is usually composed of a surface material such as hardness or solvent resistance, and a composition of 14 | s + πι_ is superior to the known composition. A heat transfer method using a transfer film having such a configuration of 201245297 is a method in which a transfer layer is removed by peeling off a base film from a transfer layer by pressing a surface on the transfer layer side of the transfer film to a surface of the transfer target. Transfer to the surface of the object to be transferred. A polyester resin film such as a polyethylene terephthalate film has been used for the base film of the film for thermal transfer. However, the polyester resin film usually has high affinity with the transfer layer, so that the melamine resin is used. A release agent layer such as a polysiloxane or a fluorine is interposed between the transfer layer and the base film to ensure mold release property. However, such a release agent treatment is disadvantageous in terms of environment and cost, and therefore a base film which does not require a release agent treatment is sought. In this case, in recent years, a method of using a polyvinyl alcohol-based film in a base film of a laminate for heat transfer has been studied. For example, in Patent Document 3, a film for decoration (heat transfer film) provided with one (4) (corresponding to a transfer layer) on one surface of a transparent film (corresponding to a base film) is disclosed, and polyethylene is disclosed as a transparent film. An alcohol resin film. Further, in Patent Document 4, a resin film containing a polyvinyl alcohol-based resin as a main component in which a peeling layer, a pattern layer, and a binder layer are laminated on one surface of a base film is used as the base film.曰本特开2007- 152622 曰本特开 201 1 — 1154 曰 曰 特 特 7 7 7 7 7 7 7 7 7 — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — [Invention] The polyvinyl alcohol-based film is known as a detachable mold. Although it is known as a film which is excellent in use, it is used as a titanium wire which does not use a release agent, ", and a base film for a laminated film for transfer. In the case of 201245297, 'there is much better release than the previous one. Actually, the commercially available polyethylene film does not have such high mold release property, even if the base film of the film for hydraulic transfer is used. The base film of the film for thermal transfer can not satisfy the mold release property 0, and thus there is a demand for the application of the release film in recent years or the improvement of the productivity of the decorative jewelry in the heat transfer printing, and the design of high precision From the viewpoint of formability, excellent mold release property is also required, but the polyvinyl alcohol-based film specifically used in the above patent documents is not sufficient. The object of the present invention is to provide a very excellent one in this context. Demolding The polyvinyl alcohol-based film, in particular, a polyvinyl alcohol-based film having excellent mold release property, which is preferably used for a base film of a laminate for heat transfer, and a method for producing the polyvinyl alcohol-based film, and use thereof The laminated body for transfer of a polyvinyl alcohol-based film, the laminated system for heat transfer is used in a decorative method using a heat transfer method. The polyvinyl alcohol-based film of the present invention is based on a polyvinyl alcohol-based resin (A). 100 parts by weight, containing 1 to 20 parts by weight of a nonionic surfactant (B) containing an oxyethylene group and an oxypropylene group. Previously, it was known that a polyvinyl alcohol-based film usually contains a surfactant. In the production site of the polyvinyl alcohol-based film, it is ensured that the film-formed polyvinyl alcohol-based film is wound up on the drum or the tape of the substrate at the time of film formation, and the grain is peeled off from the substrate, thereby preventing self-rolling. The surfactant is added to reduce the adhesion from the viewpoint of the adhesion at the time of the extraction of the film. For example, in the above Patent Documents 1 and 2, the surfactant may be a polyoxyethylene sorbitan. Monolaurate, polyoxyethylene 201245297. However, the "release of the base film of the film for thermal transfer" which is desired in the present invention is "the mold layer which can be easily peeled off without the release agent". The degree of release of the layer of the body is much higher than the release property required at the manufacturing site of the polyethylene film. The content of the surfactant (a nonionic surfactant containing only a polyoxyethylene group as a polyoxyalkylene group) which is usually used is not sufficient. In the present invention, when a polyvinyl alcohol-based film is actually produced, it has characteristics such as: a general content of a surfactant which is often used for the purpose of improving film formability, and contains more nonionic interfacial groups. The surfactant also has an oxypropylene group that is not used. The present invention also provides a method for producing a polyethylene glycol-based film: a polyethylene glycol-based resin (A) 1. . The method of casting and forming a film of a polyacetal-based resin aqueous solution of a non-ionic interface of a wide-oxyethylene group and an oxypropylene group. It is also known to provide a laminate for transfer, which is characterized in that: the base layer [II] composed of the above polyvinyl alcohol-based film, and the printing layer [the amount of the alcohol-based film of the hardened/green tree-shaped sputum contains the additive as before Containing the active agent, it has excellent release properties. The mold releaser or the protective film or the like is required to have mold release properties and can be used as a heat transfer without a release agent layer. [Embodiment] 6 201245297 [Polyvinyl alcohol-based film] First, the polyvinyl alcohol-based film of the present invention will be described. The polyvinyl alcohol-based film of the present invention is based on polyvinyl alcohol. The resin (A) contains a nonionic surfactant (B) having an oxyethylene group and an oxypropylene group. (1) Polyethylenic alcohol resin (A) Polyethyl propylene glycol used in the present invention The resin (A) is obtained by polymerizing a vinyl ester compound according to a conventional method and then saponifying it. In the present invention, the polyvinyl alcohol resin (A) may be used alone or in combination as needed. The vinyl ester-based compound may, for example, be vinyl phthalate, vinyl acetate, vinyl difluoroacetate, vinyl propionate, vinyl butyrate, vinyl phthalate, vinyl laurate or koheic acid. Vinyl acetate (vinylversatate), ethyl succinate, ethylene stearate 6|, etc. The materials may be used alone or in combination of two or more. Practically, vinyl acetate may be preferably used. Polyvinyl alcohol resin (A), It is generally preferred to use an unmodified polyvinyl alcohol resin, but a partially modified modified polyvinyl alcohol resin may also be used. The modified polyvinyl alcohol resin may be exemplified by an ethylene brewing compound and a small amount. In the case of other monomer copolymerizers, the ratio of the monomers in this case is such that the range of the benefits of the present invention is not hindered, such as 10 mol% or less, preferably 7 m. The following: A six TO early: Xindan ... dodecene ... eighteen rare and other dilute hydrocarbons; acrylic acid, methyl acrylic acid, butyric acid, cis-succinic acid, cis-butyl diacid bismuth, clothing An acid such as 201245297, such as an unsaturated acid or a salt thereof, or a mono- or dialkyl ester; a nitrile such as acrylonitrile or methacrylonitrile; a guanamine such as acrylamide or methacrylamide; a vinyl sulfonic acid; An olefin sulfonic acid such as allyl sulfonic acid or methallyl sulfonic acid or a salt thereof, an alkyl vinyl ether; a polyoxyethylene (meth) allyl ether, a polyoxypropylene (meth) allyl group Polyoxyalkylene (meth)allyl ether such as ether; polyoxyalkylene such as polyoxyethylene (meth) acrylate or polyoxypropylene (meth) acrylate a group of (meth)acrylic acid; polyoxyethylene (meth) acrylamide, polyoxypropylene (meth) acrylamide, etc. polyoxyalkylene (meth) acrylamide; Oxyethylene vinyl ^ methyl) propylene amine 1,1 monomethyl propyl] oxime, polyoxyethylene vinyl, polyoxypropylene vinyl ether, polyoxyethylene propylene 16, polyoxypropylene Propylamine, polyoxyethylene ethylene amine, polyoxypropylene vinylamine, dipropylacetone decylamine, gasified N-propylene guanamine methyl trimethyl ammonium, gasified allyl trimethyl ammonium Gasification of dimethyldipropyl propyl, dimethyl propyl vinyl ketone, n-ethylene group, such as slightly (four), 1 ethylene, partial ethylene, etc. These other monomers can be used alone or in combination Further, in the present invention, the term "(meth) propyl group means a propyl group or a methyl propyl group, and the so-called (meth) propyl group means a propyl group or a methyl group. Propylene-based so-called (meth) acrylate means acryl vinegar or methacrylate. Further, 'when the above-mentioned ethylene vinegar-based compound is used for polymerization (or copolymerization)', a known polymerization method can be used without particular limitation, but usually an alcohol such as methanol, ethanol or isopropanol is used as a solvent for solution polymerization. In addition to solution polymerization, emulsion polymerization or suspension polymerization can also be carried out. Further, the polymerization reaction is carried out by using a known radical polymerization catalyst such as azobisisobutyl, epoxide, oxidized, and oxidized laurel, and the like, and the reaction temperature is usually from 35 ° C. ~Boiling point, more preferably 50~8〇<t around the range of choice. Then, when the obtained vinyl ester polymer is saponified, the above vinyl ester polymer is dissolved in an alcohol and carried out in the presence of a basic catalyst. The alcohol may, for example, be decyl alcohol, ethanol or butanol, and the concentration of the vinyl ester copolymer in the above alcohol is appropriately selected within the range of 20 to 50% by weight. The alkaline catalyst used in the above-mentioned four-stage can use an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, sodium decoxide, sodium ethoxide or potassium methoxide or an organic catalyst of an alcohol. The amount of the above-mentioned basic catalyst to be used may be appropriately selected in the range of 1 to 100 mmol equivalents based on the ethylene-based polymer. Further, saponification may be carried out by an acid catalyst as the case may be. Thus, a polyvinyl alcohol-based resin (A) can be obtained. Further, the polyvinyl alcohol-based resin (A) is preferably a polyvinyl alcohol-based resin having a 1,2-diol bond in its side chain, and the above-mentioned polyvinyl alcohol having a fluorene- 2, diol bond in its side chain. The resin can be obtained, for example, by the following method: (丨) a method of saponifying a copolymer of vinyl acetate and 3,4-diethyloxy-1-butene, and (Π) stretching of vinyl acetate and ethylene carbonate a method for saponifying and decoupling a copolymer of ethyl ester, and (iii) saponifying and deketating a copolymer of vinyl acetate with 2,2-dialkyl-4-ethlyl-1,3-dioxolane The method of the method, (iv) a method of saponifying a copolymer of vinyl acetate and glycerol monoallyl ether, and the like. In the present invention, the polyvinyl alcohol-based resin (A) has an average degree of saponification of usually 70 mol. /. Above, for example, pay attention to 〇〇. In the above-mentioned applications where the processing is precise at a high temperature, the average degree of saponification is preferably from 7 〇 to 9 〇 mol%, and on the other hand, the average saponification degree is preferably % 9 201245297 in the application of heat resistance. /. Among them, the average degree of saponification may be from 7 Torr according to processing conditions or purposes. /. Appropriately selected within the above range. In addition, when the average degree of saponification of the polyvinyl alcohol-based resin (4) is too low, there is a tendency that not only the film strength is lowered, but also it is difficult to peel the film from the casting surface at the time of production. Further, the above average degree of saponification is measured in accordance with JIS K 6726. Further, the viscosity of the 4% by weight aqueous solution of the polyvinyl alcohol-based resin (A) in 2 Å is preferably in the range of 5 to 7 GmPa.s, more preferably in the range of 15 to 6 (mpa s). If the viscosity of the 4% by weight aqueous solution is too low, the strength of the film may be lowered. If the viscosity of the 4% by weight aqueous solution is too high, the viscosity tends to be high and the film tends to be difficult to form. Furthermore, the above is in 2〇. The 4% by weight water solution viscosity of the crucible was determined in accordance with jIS κ 6726. (2) Nonionic surfactant (b) The nonionic surfactant (B) used in the present invention is a structural unit containing an oxyethylene group and an oxypropylene group as an oxygen extension base. In general, in order to improve the peeling of the drum or the tape on the substrate when the self-made film is formed, the roll-wound property of the film is often added to the polyethylene-based film to add a surfactant which is blended for such a purpose. An oxyethylene group having excellent hydrophilicity is used as the oxygen-extended alkyl structural unit. The nonionic surfactant (1) used in the present invention is characterized in that it contains an oxyethylene group in the hydrophilic portion and an oxypropylene group in the hydrophobic portion. In general, the hydrophobic portion contains a long-chain alkyl group, and the adjustment of hydrophobicity can be adjusted by the length of the base-bond bond, etc., but in the present invention, the nonionic surfactant (B) and the oxypropyl group are used. Adjusted by the ratio. The nonionic boundary of the structural unit containing both the oxyethylene group and the oxypropylene group is a non-ionic boundary. 201224297 The surfactant (B), for example, an alkyl ether having an aerobic vinyl group and an oxypropylene group added thereto (B1), addition of an aerobic vinyl and oxypropylene based fatty acid ester (B2), addition of an aerobic vinyl and oxypropylene based polyol ether (B3), addition of an aerobic vinyl group and an oxypropylene group At least one selected from the group consisting of alkyl phenyl ethers, polyoxyethylene groups of oxyethylene groups and oxypropylene groups, and the like. Among these, in terms of mold release effect and easy availability, it is preferred to add a mixture of aerobic and oxypropyl groups (B1), addition of aerobic ethylene and oxygen. a propylene-based fatty acid ester (B2), an addition of an aerobic vinyl group and an oxypropylene group of a polyhydric alcohol ether (B3), particularly preferably an alkoxyvinyl group and an oxypropylene group-containing alkyl ether (B1), An aerobic vinyl and oxypropylene based polyol ether (B3) is added. Examples of the alkyl ether (β1) to which the aerobic vinyl group and the oxypropylene group are added include polyoxyethylene polyoxypropylene alkyl ethers, and specific examples thereof include polyethylene polyoxypropylene butyl ether and polyoxyethylene. Polyoxypropylene oxime ether, propylene oxide lauryl ether, polyoxyethylene polyoxypropylene myristyl ether, propylene oxide cetyl ether, polyoxyethylene polyoxypropylene stearyl ether, polyoxyethylene poly, polyoxyethylene Poly, polyoxyethylene polyoxypropylene oleyl ether, and the like. Examples of the above-mentioned fatty acid ester (B2) to which an aerobic vinyl group and an oxypropylene group are added include polyoxyethylene polyoxypropylene alkyl esters, and specific examples thereof include oxyethylene polyoxypropylene laurate. The above addition of aerobic vinyl and oxypropylene groups

Ethylene polyoxypropylene sorbitol ether and the like. Addition of aerobic vinyl and oxypropylene groups

201245297 exemplified polyoxyethylene polyoxypropylene benzophenone benzoate, specific examples can be mentioned: polyethylene polyoxypropylene hexyl benzoquinone, polyoxyethylene polyoxypropylene heptyl phenoxy oxyethylene oxypropylene octane Base benzene and so on. The above-mentioned polyol ester to which an aerobic vinyl group and an oxypropylene group are added may, for example, be a polyoxyethylene polyoxypropylene sorbitan fatty acid vinegar. In the towel of the present invention, the number of structural units of the oxygen B in the nonionic surfactant (B) is preferably from 1 to 2, particularly preferably from 2 to 6 Torr, more preferably from 4 to 5 Å. When the number of the structural units is too large, the viscosity of the polyethylene glycol-based resin water and the liquid tends to increase, and the planar smoothness of the obtained film tends to be lowered. Further, the number of structural units of oxypropylene in the nonionic surfactant (B) is preferably 7 (), more preferably 2 to 6 q, still more preferably 4 to 5 Å. If the number of the structural units is too large, the viscosity of the polyvinyl alcohol-based resin aqueous solution tends to increase, and the planar smoothness of the obtained film tends to decrease. Further, the number of structural units of the oxyethylene group and the number of units of the oxypropylene group are preferably 2 to 1 Å, more preferably 4 to 85, and more preferably: "" 6 to 8 〇 'best For 20~8〇. When the number of the structural units is too large, the viscosity of the aqueous solution of the enol-based resin tends to increase, and the planar smoothness of the obtained film tends to be lowered. = The surfactant (8) contains a plurality of oxygen epoxides and oxypropylene groups. / Any one of the oxyethylene units and oxypropylene units may be copolymerized to form a copolymer, but in order to make oxygen The vinyl group can function as a portion, and the oxypropylene group can sufficiently exhibit hydrophobicity, and preferably exists as a polyoxyethylene moiety and a polyoxypropylene moiety. The surfactant is preferably a block copolymer. 12 201245297 In the invention of the oxyethylene group St, the nonionic surfactant (B) + (the content ratio of the molar ratio of the propylene group (oxyethylene group / oxypropylene group) 2 =: the aspect of the increase in the enthalpy For example, it is preferably 9/7〇1 to 2〇/8°' and further preferably 70/30~30/7〇. Regardless of the oxygen, it is completely prepared. Or too large, the tendency of the homogenizer to reduce the mold release property to the curable resin layer. Aspect 2, in the present invention, in terms of the increase in mold release property or the accuracy of viscosity, §, nonionic surfactant (8) The weight average molecular weight is 10 G 〜1 _ 〇 ', and particularly preferably 2 (10) 〜 8 咖. If the weight average molecular weight is too small, the mold release property tends to decrease, and if it is too large, the polyethylene glycol resin aqueous solution is present. The viscosity is increased to cause a failure in the production of the film; in the present invention, the HLB of the nonionic surfactant 1B) is preferably from 2 to 18, particularly preferably from 2 to 15, in terms of mold releasability. Further preferably, it is 3 to 12. In the present invention, the HLB value is a value calculated by the Gdffin method and is calculated by the following formula. HLB = 2 〇 x (molecular weight of the hydrophilic portion / molecular weight of the whole) Here, the hydrophilic portion means the total molecular weight of the oxyethylene structural unit. Therefore, it is preferred that the HLB value of the ratio of the oxyethylene structural unit to all the molecules of the surfactant (b) is in the above range. The surfactant (B) having an HLB value in the above range means that it has a balance of moderate hydrophobicity in the range of no dispersibility in water. By having such a balance, it is possible to ensure good dispersibility in the polyvinyl alcohol-based resin, and it is easy to be infiltrated from the polyvinyl alcohol-based film by the improved hydrophobicity. The surfactant (b) which bleeds out on the surface of the polyvinyl alcohol-based film can function as one type of release agent. Therefore, it is presumed to be useful for post-transfer hardening when used as a base film for a laminate for heat transfer. The peeling of the resin layer and the base film is improved. In the present invention, the content of the nonionic surfactant (B) is preferably (9) by weight relative to 100 parts by weight of the polyethylene resin (A) in terms of mold release property and film appearance. The portion is further preferably a part by weight 'more preferably 3 to 10 parts by weight, most preferably 5 to 8 parts by weight. In general, the amount of the surfactant added to improve the mold release property of the drum or the tape which becomes the substrate at the time of film formation is less than 1 part by weight of the polyvinyl alcohol-based resin, so the polyethylene of the present invention is used. The alcoholic film is characterized by more than the usual amount. The reason for this is that the non-ionic surfactant (8) of the present invention (4) has an effect of increasing the mold release property by the exudation of the nonionic surfactant (8), and the amount previously contained as an additive is not charged. Ι界二: Surface 'If the content becomes too much, the non-ionic layer that penetrates the surface will increase the amount of other 2 (B)'. The surface of the film tends to become sticky. As a result, in the case of a film or a fat, there is a case where other resins are repelled. For example, when it is used as a base film of a laminate, it is obtained because of the low capacity, and the resulting surface of the transfer layer is lowered.纟 is that the surface gloss of the protective layer of the obtained molded article is lowered (3) Other components The polyethylene glycol-based film of the present invention is not an enol-based resin W and a non-ionic material, and only contains the above-mentioned polyethylene-containing nonionic interface. Composition of Active Agent (B) 14 Polyethylene glycol film manufactured by 201245297. It is also preferably produced by forming a film by using a surfactant such as a surfactant (Β) or a plasticizer other than β). x, non-destructive blending of fillers. '3 (1) Other interface-forming agent (b,): It is used to improve the seam of the film or the tape (such as the film or the tape of the film of the polyethylene film) and the film (9). The surfactant other than the above-mentioned nonionic or /1 (Β) (hereinafter referred to as "other surfactant (")" is added. And other surfactants (for example, a nonionic surfactant other than the above-mentioned nonionic surfactants other than oxygen and a surfactant) may be mentioned, for example, only a vinylidene group or a gas. Polyalkylene alkyl alkyl ethers of polypropylene, polyalkylene alkyl alkyl ether alkyl alkyl esters, sorbitan fatty acid esters, pit-based amines, polyoxyl extension bases Burning amines, polypropylene glycols, glycols, allyl phenyl ethers, etc. Other surfactants (Β') are not limited to nonionic surfactants, anionic interfaces can also be used. Active hydrazine, cationic surfactant, amphoteric surfactant, anionic surfactant, for example, sulphuric acid vinegar type such as sulphuric acid sulphuric acid, and 12-yard benzene sulfonate sulfonic acid anion The surfactant is a surfactant. The cation-based interface activity is, for example, an amine such as laurylamine hydrochloride, a quaternary ammonium salt such as lauryl triammonium chloride, or a pyridyl salt such as vaporized lauryl pyridinium. The amphoteric surfactants can be exemplified by: Ν-烧基_Ν, Ν- Dimethyl money beet 15 201245297 alkali, etc. The other surfactants (B,) may be used alone or in combination of two or more. The content of the other surfactant (B,) is not detrimental to the degree of the invention f. In the case where X is not bleed out, for example, the surface property such as surface whitening may be lowered, and it is usually 1 part by weight or less based on 100 parts by weight of the polyethylene resin. (3 - 2 ) The plasticizer may, for example, be glycerin such as glycerin, diglycerin or triglycerin; or a hospital glycol such as triethylene glycol, polyethylene glycol, polypropylene glycol or dipropylene glycol; or a tris(tetra)propyl plant. Two or more types may be used alone or in combination. The amount of the plasticizer blended in the above polyethylene-based resin (A) is compared with the weight of the polyvinyl alcohol-based resin (A). It is preferably 3 parts by weight or less, and particularly preferably 20 parts by weight or less. If the amount of the plasticizer to be blended is too large, the boring property of the film gradually disappears and becomes difficult to handle. Further, the plasticizer The lower limit is usually 〇5 parts by weight. (3 - 3) Filler The above filler can be, for example, Lift: Palace powder (not only various unprocessed products, but also can be deuterated, oxidized or modified) or polymethyl methacrylate and other organic powders, such as talc, mica, dioxide and other inorganic powders. These may be used alone or in combination of two or more. Among them, the powder of the temple may be preferably used. The blending amount of the filler blended in the above polyvinyl alcohol-based resin (4) is relative to the weight of the polyvinyl alcohol-based resin (4). The portion is preferably at most 15 parts by weight or less. If the blending amount of the filler is too large, the film strength tends to decrease in practical use. 16 201245297 (3 - 4) Other additives and further inventions An oxidizing agent (such as a phenolic amine system), a stabilizer (a phosphate ester or the like), a coloring material, a fragrance, an extender, an antifoaming agent, a rust preventive agent, and an ultraviolet absorber may be appropriately blended in the range of the effect. Can be blended with other water-soluble polymer compounds (polyacrylic acid sodium, polyoxyethylene, polyethylene, slightly bite _, dextrin, polyglucamine, chitin, methyl cellulose, trans-ethyl ethyl cellulose Other additives, etc.) . The polyethylene-based film of the present invention having the above-described structure is excellent in mold release property. Therefore, even when it is used as a heat-transfer film, there is no difference between the curable resin f and the polyethylene film. The release agent layer can also be used to peel off the polyvinyl alcohol film of the curable resin layer transferred to the surface of the molded article and the polyvinyl alcohol film of the base film after heat transfer, and the polyethylene of the present invention. The alcohol-based medium imparts excellent mold release property as described above, but it is also excellent in properties such as affinity, water solubility, organic solvent resistance, gas barrier properties, and the like as properties of the polyethylene glycol film. = It is not limited to the base film of the laminated body for heat transfer, and can also be used as a base film of a hydraulic layered product. Further, it can be used as a polyethylene glycol film for other previously known purposes. [Manufacturing method of the polyethylene-based film] The following describes the method for producing the polyethylene-based film of the present invention. First, the above-mentioned polyvinyl alcohol-based resin (A) and non-agent (8) are optionally required. Other surfactants (B·), plasticizers, other additives The poly 201245297 vinyl alcohol resin aqueous solution β is prepared by mixing and dissolving in a specific blending amount in water. The concentration of the polyethylene glycol resin aqueous solution is usually preferably 1 〇 to 3 〇 by weight, particularly preferably 1 5 . When the concentration is too low, the stability of the film thickness tends to be lowered, and if it is too high, the viscosity tends to be high and the film formation tends to be difficult. Then, the polyvinyl alcohol-based resin aqueous solution is used. The self-forming mold is cast on a film forming belt or a film forming drum and dried to be film-formed, and further heat-treated as needed. Thus, the above-mentioned film forming belt means that it is mounted on a pair of rolls. The moving endless belt 'casts the aqueous solution of the polyethylene glycol resin flowing out of the dies in the endless belt and dries it. The endless belt is preferably made of stainless steel, for example, and the outer peripheral surface is mirror polished. In addition, the above-mentioned film-making drum 'refers to a rotating drum type roll' is a casting drum type roll which is made of a water-soluble pouch of a polyethylene resin which flows out of a butting mold, and is dried. temperature In the use of plastic cavity: male + & +. (d) (four) belt case 'usually preferably ~ 160C' is particularly good for 9 ~ 15 generation. If the drying temperature is too low, there will be insufficient drying, bring it If the peeling tends to be dull, if the moisture content is too high, the moisture content will be too low and the film will become brittle. In the case of using a film forming drum, the film forming drum is usually preferably -100 C'. 82 to 99 ° C 〇 If the drying temperature is too low, the drying tends to be insufficient. The peeling from the drum tends to be delayed, and if it is too high, the moisture content is too low and the film tends to become brittle. The first drum refers to a drum type pro-column which is extended on the most upstream side by the aqueous solution of the polyethylene glycol resin which has flowed out of the mold. After the above drying, heat treatment is carried out as needed, and the heat treatment method may be, for example, Listed: hot rolls (including rolls), hot air, far infrared, dielectric heating and other methods. Further, the surface to be heat-treated is preferably the surface on the opposite side to the surface in contact with the film forming tape or the film forming drum. Further, the moisture content of the film subjected to the heat treatment is preferably 4 to 8 parts by weight. about. Further, the water content of the film after the heat treatment is usually preferably from 2 to 6% by weight. The moisture content of the vinyl alcohol-based film can be measured, for example, by using a card-charge moisture meter (manufactured by Kyoto Electronics Manufacturing Co., Ltd., rMKS_21〇). The heat treatment of the knives by the above heat treatment machine is usually preferably carried out at 5 Torr to 13 Torr, more preferably 60 to 120 °, that is, if the temperature of the heat treatment is too low, there is a contact with the film forming tape or the first film forming film. The tendency of the surface to be curled becomes difficult to handle. If the temperature of the heat treatment is too high, the film becomes soft. Therefore, if the film is wound and stretched without causing pleats, the length is increased and the width is increased. The tendency to shrink. Further, in order to heat-treat: the time required for the above heat treatment depends on the surface temperature thereof, and the kernel is usually set to 0.2 to 15 seconds, preferably 衩. 5 to 12 seconds. The above-mentioned hydrazine treatment is usually carried out after the treatment of each of the rolls for dry film drying, usually by a different ", processing roll or floating dryer, etc." Thus, a polyvinyl alcohol-based film can be obtained. The film of the polyvinyl alcohol-based film of the present invention preferably has a film thickness of 20 to 8 Å Um. The film thickness is preferably a core, particularly the range of the weight % of the polyvinyl alcohol obtained above, and more preferably the moisture content of the 丨6 film. It is preferably % by weight. If the water content is too low 0.5 to 8 ', then 19 201245297 tends to become brittle, and the above-mentioned polyethylene has a tendency to adhere. The method shown below ^ g 1 method, for example The moisture content of the polyvinyl alcohol-based film in the following description can be set as follows: () The moisture content is adjusted by the following method, and the resin water is adjusted (4) Carry out (4) and make 2 degrees of the material: the method of humidifying and dehumidifying the polyethylene glycol film. The second change of the tree:: = according to the temperature, the drying efficiency is affected, so at 70::8. Adjusted. Also, when drying, it is preferably between 150 and 50 c, more preferably on the same day. At least 2 鲂祛 with a temperature gradient are also: in the dryer, & and from the viewpoint of moisture adjustment, drying is performed for 1 to 12 minutes, preferably for flowering #1 to 11 minutes, right above If the gradient of the drying temperature is too large or the drying time is too long, the drying tends to be excessive. On the contrary, if the gradient of the drying temperature is too small or the drying time is too short, the drying tends to be insufficient. 1 50~5 (the relationship between the rc changes the dry coffee) and is usually effective to gradually raise the temperature from the beginning of the drying to the maximum drying temperature of the temporary drying temperature range until the special temperature The moisture content is gradually lowered, and the drying temperature is gradually lowered, whereby the target a water rate is finally achieved. This is for controlling crystallinity, mold release property, productivity, and the like, and examples thereof include 120 ° C - 130. (: 115 °C — lOOt, 130*t 12〇C — 1 l〇°C, 115°C - 120°C _ 110°C — 90°C, etc. Temperature gradient setting' is implemented with appropriate selection. 20 201245297 (ii) Polyethylene glycol The reeling and dehumidification of the polyethylene film is carried out through the humidity control tank to adjust the moisture content. (Because the film is taken before the coiling of the polyethylene film or After the coiling, the heat is removed to dehumidify the polyvinyl alcohol-based film to adjust the moisture content. The 'polyethylene glycol film of the present invention can also be used for the forging surface, the finished pattern, and the enamel. The concave-convex pattern such as the pattern is applied to the embossing roller or the like. The polyephedrine film which is used for the two-purpose enamel can be directly used as an unstretched film for various purposes, and can also be used as a single axis. Stretch or double sleeve stretch film. =: When the film is stretched, the stretching method can be applied to a known method. For example, (1) chuck-type stretching, (7) stretching, (3) tenter stretching, and the like can be cited. (1) Suitable for batch production, (2) suitable for single! Stretch film of type 1, (3) ^ Although the device becomes expensive, it is effective to produce a stretch film on an industrial scale. By -, you can also perform biaxial stretching one by one. The stretching method may be carried out in any one of sequential biaxial stretching and simultaneous biaxial stretching, and in terms of thickness uniformity, it is preferred that the combination (2) is in which the film is stretched. ^) Xing Yu)'s double axis. The film stretched on the surface of the film is preferably 1.5 to 1.5. The total stretching ratio is more than or equal to 12 times, and more preferably 3 to 10 times. The rate is in the longitudinal direction:: In terms of Γ, it can be preferably applied in the direction of the stretched goods by ~(7) times, especially 2~8 °, and stretched in the transverse direction by 1.5~1, especially a 9 ~ times the one. In the case of double-twisting, especially in the case of stretching 2 to 8 times and further 3 to 5, in terms of the uniformity of the surface of the film, 21 201245297 is preferably stretched in the longitudinal direction by "~4 times" In particular, especially when 疋2~3·5 times 'the same magnification as the horizontal side. 疋~3·5 times', and more preferably, the unevenness in the longitudinal and lateral directions is too low, and the stretching ratio is too low. The tendency of residual susceptibility to breakage: in the case where the stretching ratio is too high, there is a film which is allowed to retain the moisture-proof and dilute alcohol-based film. For example, it is preferable to carry out the previously known preservation: the environment of 1 G to 25 t [Layer for thermal transfer] and hardenability The laminate for thermal transfer of the present invention is a resin layer [II] and a printed layer [ΙΠ]. _ (1) Base 臈 [I] as a substrate The film of the above-mentioned polyvinyl alcohol-based film of the present invention can be used. For the polyvinyl alcohol-based film, an unstretched film can be used as it is, and X can also be used as a uniaxially stretched or biaxially stretched film. In the present invention, the thickness of the base film (1) is particularly preferably in the range of 5 to 120, more preferably 1 〇 to 1 〇 () / zm. In terms of surface glossiness, the surface roughness (Ra) of the side of the curable resin layer of the base film [I] is preferably m or less, more preferably 0.001 to 〇m, and still more preferably 〇. 〇1~〇^坩. When the surface roughness (Ra) is too large, the surface glossiness tends to decrease. Further, there is a tendency that even if the surface roughness (Ra) is less than 0.001 // m, no improvement in surface glossiness is observed. tendency. In the base film [I], the surface roughness (Ra) of the [π] side of the curable resin layer is adjusted to 22 201245297, and the method of casting the film at the time of film formation of the base film [i] can be cited. The surface roughness is set to ls or less, or the stretching ratio 〇 at the time of film formation of the base film (1) is at least 1.5 times or more, or a combination of the two. Further, the surface roughness (Ra) was obtained by using a "color 3D laser microscope VK_97〇〇j manufactured by Keyence Co., Ltd., and measuring the arithmetic mean roughness (Ra) in accordance with JIS B 〇6〇1 - 2001. 2) Curable resin layer [π] The curable resin layer [Π] is a layer which is the outermost layer of the decorative molded article by the peeling of the base film [I], and is peeled off or peeled off before the base film (1) is peeled off. After that, it is cured to form a protective layer for protecting the surface of the transferred body. Examples of the material constituting the curable resin layer 聚 include polyacrylic resin, polyester resin, polyethylene resin, cellulose resin, and rubber resin. , P〇lyUrethane resin, thermoplastic resin of polyethylene acetate resin; active energy ray-curable resin composition such as ultraviolet curable resin composition or electron beam curable resin composition; thermosetting resin As a protective layer, it is preferable to use an active energy ray-curable resin composition from the viewpoint of imparting chemical resistance and abrasion resistance. For example, it is preferable to contain an acrylic resin and an (meth)acrylic acid ester-based compound. Examples of the acrylic resin include a homopolymer or a copolymer of an acrylate monomer, or other ethylenic unsaturated. An acrylic copolymer or the like as a copolymerization component. Examples of the acrylate monomer include decyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and fluorenyl. Butyl acrylate, (曱23 201245297) hexyl acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, benzyl (meth)acrylate, cyclomethacrylate Ester, (mercapto) dimethylaminoethyl acrylate, isooctyl (decyl) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, 2-methoxy (meth) acrylate Ethyl acetonate, (butyl) butyloxyethyl acrylate, decyloxytriethylene glycol (methyl) acrylase, etc., wherein an alkyl group having an alkyl group having a carbon number of 1 to 12 is preferred. Ester, particularly preferably (fluorenyl) propylene Acid oxime ester, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate. Other ethylenically unsaturated monomers include, for example, (meth)acrylic acid 2 _ Hydroxyethyl ester, 2-hydroxypropyl (meth)acrylate, 3-mono-2-hydroxypropyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-methyl-based 3-phenyl Hydroxy-containing unsaturated monomers such as oxypropyl ester, diethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, N-hydroxymethyl todenyl (meth) acrylamide; glycidol A glycidyl group-containing unsaturated monomer such as methacrylate or allyl glycidyl acrylate; isocyanate 2 - propylene methoxyethyl ester, 2-methyl propylene methoxyethyl isocyanate An isocyanate group-containing unsaturated monomer; acrylamide, methacrylamide, N-(n-butoxyalkyl) acrylamide, N-(n-butoxyalkyl)decyl acrylamide, etc. An amidino group-containing unsaturated monomer; acrylamide-3-methylbutylmethylamine, diammonium alkyl acrylamide, An amino group-containing unsaturated monomer such as dimethylaminoalkylmethyl acrylamide; an olefin sulfonic acid such as vinyl sulfonic acid, allyl sulfonic acid or methallyl sulfonic acid; 2 - a sulfonic acid group-containing unsaturated monomer such as mercaptopropanesulfonic acid, styrenesulfonic acid or a salt thereof; styrene, vinyl acetate, acrylonitrile, acrylamide or the like. 24 201245297 == content ratio of monomer and other ethylenically unsaturated monomers

Example (copolymerization ratio) Tony 4* σ丨im A and ‘,,, particularly limited, for example, it is preferred to set the monomer to 20 to i. / ^ „ Intraspecies 〜 〜 ί ί ί ί ί ί ί ί , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , % by weight, and other ethylenically unsaturated monoterpenoids are sighed to 0 to 60% by weight, and further preferably acrylate monomer $ & 1 ΛΛ . θ 斤 早 〇 〇 80 80 80 %, the other ethylenically unsaturated monomer is set to 〇~2〇〇晋. / ^ ^ Weight / .. The content ratio of the right acrylate monomer is too small 'The cured material of the curable resin layer (protective layer) The durability of the water-resistance and the moist heat resistance is lowered. The acrylic resin can be easily produced by radical copolymerization of the above-mentioned polymerization component in an organic solvent according to a method known to a person skilled in the art. The acrylic resin used in the linear curable resin composition preferably has a glass transition temperature (Tg) of 20 to 13 (rc, particularly preferably 30 to 12 ° C, and further preferably 40 to 30 if the glass transition point When the (Tg) is too low, the curability of the active energy ray-curable resin composition or the like is present. The adhesive layer has adhesiveness and tends to cause defects during the subsequent processing (also in the steps of curling, poor printing, etc.), and when it is too high, it exists in the active energy ray-curable resin composition. When the curable resin layer is cured to form a protective layer, it tends to become brittle. Further, the weight average molecular weight (Mw) of the acrylic resin is preferably 10,000 to 500,000, more preferably 2 〇〇〇〇 to 1 〇〇〇〇. 〇, particularly preferably 30,000-80,000 » If the weight average molecular weight (Mw) of the acrylic resin is too small, 25 201245297 has a tendency to be softened and adhered to the curable resin layer before curing. When the subsequent processing is carried out on the layer, the cause of the problem (such as curling in the step, poor printing, etc.) is too large, and the following tendency is caused: • It is difficult to obtain the uniformity of the film thickness when the curable resin layer is applied and after drying The hardness of the coating film becomes higher than necessary, and causes a problem (a crack of the coating film, interlayer peeling, etc.) when the subsequent processing is performed. The acid amine ester compound is a (mercapto) acrylate compound having an amine ester bond in the molecule, and can be produced by reacting a hydroxyl group-containing (fluorenyl) acrylic compound with a polyvalent isocyanate compound and, if necessary, a polyol. Examples of the above-mentioned (mercapto)-based acrylic acid-containing compound include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxyl (meth)acrylic acid. Butyl ester, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 2-(methyl)propenyloxyethyl 2-hydroxypropyl phthalate, (A) 2) hydroxy-2-methyl 3-propenyl propyl acrylate, caprolactone modified 2-hydroxyethyl (meth) acrylate, neopentyl alcohol tri (meth) acrylate, dioxane Tetraol penta (meth) acrylate, caprolactone modified dine pentaerythritol penta(indenyl) acrylate, caprolactone modified pentaerythritol tri(meth) acrylate, oxyethylene modification II Neopentyl pentoxide (mercapto) acrylate, oxyethylene modified neopentyl An alcohol tris(mercapto) acrylate or the like, among which a hydroxyl group-containing (meth)acrylic acid compound having three or more acrylonitrile groups can be preferably used. Further, these may be used alone or in combination of two or more. Examples of the above-mentioned polyvalent isocyanuric acid compound include polyaromatic acid brewing such as an aromatic system, and the like. Among them, toluene diisocyanate and diphenyl are mentioned. Methane diisocyanate, hydrogenated diphenylmethane diisocyanate, I stearky methyl polyisocyanate, modified diphenylmethane diisocyanate, hydrogenated dimethyl diisocyanate, benzodimethyl diisocyanate , hexamethylene diisocyanate, tridecyl hexamethylene diisocyanate, tetramethyl dimethyl diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis (isocyanate) a polyisocyanate such as cyclohexane, phenyl diisocyanate, octadecyl diisocyanate, triisocyanate, naphthalene diisocyanate or a trimer compound or a multimeric compound of such polyisocyanates; Polyisocyanate, water-dispersible polyisocyanate (for example, "Aquanate 100", "Aquanate 110", "Aquanate 200", "Aquanat" manufactured by Nippon Polyurethane Industry Co., Ltd. e 210", etc.), or a reaction product of the polyisocyanate and the polyester. Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, and polybutylene glycol. 6 —Hexanediol, neopentyl glycol, cyclohexanedimethanol, hydrogenated bisphenol A, polycaprolactone, trihydroxydecylethane, trimethylolpropane, polydithiopyrene, pentane Polyols such as tetraol, polytetramethylene glycol, sorbitol, mannitol, glycerin, polyglycerol, polydecyl diol; polyoxyethylene, polyoxypropylene' with oxyethylene/oxypropylene block or random a polyether polyol having at least one structure copolymerized; the polyol or polyether polyol with maleic acid needle, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, Polyester polyol of a condensate of a polyacid such as diacid or isophthalic acid; a caprolactone modified polyol such as an ester modified polyether polyol; a polyolefin polyol, a hydrogenated polybutadiene A polybutadiene-based polyol such as a polyhydric alcohol. Further, 'the polyhydric alcohol may, for example, be 2 2 bis(hydroxymethyl)butyric acid, tartaric acid, 2,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2,2-di(hydroxyl) Mercaptoic acid, 2,2-bis(hydroxyethyl)propionic acid, 2,2-bis(hydroxypropyl)propionic acid, dihydroxymethylacetic acid, bis(4-hydroxyphenyl)acetic acid, 4 4 - a carboxy group-containing polyol such as bis(4-hydroxyphenyl)pentanoic acid or uronic acid; or a sulfonic acid group or a sulfonic acid base-containing polyol such as i,4-butanediol sulfonate or the like. In the case of using a reaction product of a polyisocyanate and a polyhydric alcohol, for example, a polyisocyanate having an isocyanate group at the terminal obtained by reacting the above polyol with the above polyisocyanate may be used. In the reaction of the polyisocyanate with the polyol, in order to promote the reaction, it is also preferred to use a metal catalyst such as monobutyltin dilaurate or a diazocyclo[5.4.0]undecene-7. Amine catalysts, etc. The method for producing the above-mentioned (meth) acrylate-based compound may, for example, be a method of mixing a hydroxyl group-containing (meth)acrylic acid compound and a polyvalent isocyanate compound in an inert gas atmosphere, usually at 30 to 80 eC. The reaction is carried out for 2 to 10 hours. In the reaction, an amine esterification catalyst such as tin octenate, monobutyltin dilaurate, octanoic acid, potassium octylate, acetic acid bromine, stannous octoate or triethylenediamine is preferably used. The weight average molecular weight of the (meth)acrylic acid ester ester compound is preferably from 300 to 400 Å and further preferably from 1,000 to 3,500, particularly preferably from 1,200 to 3,000. If the weight average molecular weight is too small, the cohesive force tends to be insufficient after the curing of the curable resin layer, and if it is too large, the viscosity tends to be too high, and 28 201245297 tends to be difficult to manufacture. In addition, the weight average molecular weight is a weight average molecular weight converted from a standard polystyrene molecule, and is used by a high performance liquid chromatography ("Shodex GPC system_u type" manufactured by Showa Denko Co., Ltd.). 3 columns in series: Shodex GPC KF— 8〇6L (Exclusion limit molecular weight: 2xl〇7, separation range: 1〇〇~2xl〇7, theoretical number of plates: 丨〇〇〇〇 plate/root, filler material : styrene-divinylbenzene copolymer, filler particle size: 1 0 // m ). Thus, an active energy ray-curable resin composition containing an acrylic resin and a (meth) acrylate-based compound can be obtained, but when the active energy ray-curable resin composition is an ultraviolet curable resin composition, It is preferred to further contain a photopolymerization initiator. In the case of an electron beam curable resin composition, a photopolymerization initiator is not required. The photopolymerization initiator may, for example, be diethoxyacetophenone, 2-hydroxy-2-methyl-bromopropane-i-one, benzyldidecyl ketal, 4 (2-hydroxyl) Oxy)phenyl-(2-hydroxy-2-hydroxy)one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-cyanoyl (4-thiomethyl) 1-ketone, 2-blockyl-2-dimethylamino-[-(4-cylinylphenyl)butanone, 2-hydroxy-2-indolyl-[4-(1-mercaptoethylene) Phenylacetate such as phenyl] propylene oxime oligomer; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether benzoin isobutyl ether and other benzoin; benzophenone, o-benzidine benzoic acid methyl vinegar , 4-phenyldibenzophenone, 4-phenylindole- 4:methyl-diphenyl sulfide, 3,3,,4,4'~tetra(t-butylperoxycarbonyl) a clumsy Ketone, 2,4,6-dimethyldiphenylhydrazine, 4-phenylindoleyl-N,N- 29 201245297 monomethyl-N-[2-(1-oxo-oxo-2-propenyloxy) Diethyl benzophenones such as ethyl]ethylammonium bromide, chlorinated (4-stanomethyl sulfhydryl)trimethylammonium; Isopropyl thioxanthone, 4-isopropyl thioxanthene, 2,4-diethyl thianonanone, 2,4-dichlorothiazinone, Bu- 4- 4-propoxy a thioxanthone such as a thioxanthone or a 2 (3-methylamino-2-hydroxy-3,4-dimethyl]-9-ketone internal racemic vapor; 4,6-trimethyl benzhydryl-diphenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-indenyl-monopentylphosphine oxide, double 2,4,6-trimethylphenyl fluorenyl oxide, fluorenyl phosphine oxide, etc., etc., etc. Further, these photopolymerization initiators may be used alone or in combination of two or more. These auxiliaries may also be used in combination: triethanolamine, triisopropanolamine, 4,4, diammonium dimethyl ketone (Mitchlerone), 4,4, diethylaminodiphenyl hydrazine Ketone 2-methylaminoethyl benzoic acid, ethyl 4-diguanyl benzoate, 4: dimethylaminobenzoic acid (n-butoxy) acetonate, 4-diammonium benzoate isoamyl Ester, 4-dimethylamino benzoic acid 2-ethylhexyl ester, 2,4-diethyl thioxanthone, 2 4 -diisopropyl 9-oxygen 2,4-diisopropyl thioxanthone, etc. Among these, it is preferred to use benzyl dimethyl ketal, hydrazine hydroxycyclohexyl phenyl ketone, benzoyl isopropyl ketone, 4- (( 2-(Ethyloxy)-phenyl (2-carbyl-2-propyl) ketone, 2-(tetra)-2-methyl-b-phenylpropanol-- in the present invention, wear-resistant hardenability The thickness of the resin layer [II] is preferably #m, and further preferably 2 to 1 Å in m. In terms of chemical resistance, 1 to 15 〇βηι, particularly preferably 2 to 120, if the thickness If it is too thin, there is a tendency that the abrasion resistance and the chemical resistance are lowered when the abrasion resistance is 30, 2012, 297. If the thickness is too large, the release film after the transfer tends to be poor, which tends to cause burrs or the like. When forming the curable resin layer [π], it is only by gravure coating method, roll coating method, bar coating method, doctor blade coating method, lip coating method, gravure coating method, web The raw material resin or the raw material resin composition may be laminated by a printing method such as a printing method. In the case of using the active energy ray-curable resin composition described above, a layer composed of an active energy ray-curable resin composition (curable resin layer [H]) may be laminated from the base film [I] until The printed layer may be cured by irradiating the active energy ray at any stage during the period in which the ruthenium is transferred to the transferred body and the base film (1) is peeled off, or may be formed by peeling the base film (1) and then irradiating the active energy ray to be hardened. Protective layer (hard coating). For example, it can be carried out by (a) laminating an active energy ray-curable resin composition layer on the base film to modulate the active energy ray and hardening it, and (b) building a layer of active energy ray hardenability on the base film. After the resin composition layer, the following printed layer is formed, and then the active energy ray is irradiated from the base film side to be hardened; (c) Further, after the build-up to the subsequent adhesive layer, the active energy ray is irradiated from the base film side. (4) After the transfer layered body of the present invention is applied to the transferred body, the active energy ray is irradiated from the base film side to be hardened; (e) the transfer layer for transfer of the present invention is followed by After the transfer body, the base film is peeled off and irradiated with an active energy ray to be hardened. In terms of the followability of the transferred body at the time of heat transfer, it is preferably a method of hardening (4) or (e) after transfer, and particularly preferably a method of (e). Further, the laminate for transfer of the present invention may be supplied as a laminate in which the 31 201245297 curable resin layer is cured as in the above (1) to (c), but it is preferably supplied as (d) and (e) above. A laminate comprising a curable resin layer before curing. In addition, when the curable resin layer is cured by irradiation with an active energy ray, the active energy ray can be, for example, light such as far ultraviolet ray, ultraviolet ray, near ultraviolet ray, infrared ray, or electromagnetic wave such as X ray or r ray, and other electrons can be used. The beam, the proton ray, the neutron ray, etc., in terms of the hardening speed, the availability of the irradiation device, the price, etc., are advantageously hardened by ultraviolet irradiation. A method of hardening by ultraviolet irradiation, using a high-pressure mercury lamp that emits light in a wavelength region of 15 to 45 nm, an ultra-high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, etc. ~i〇j/cm2 can be around. After UV irradiation, it can be heated as needed to achieve complete hardening. (3) Printed layer [III] The printed layer [III] is printed with a layer such as a pattern, and the material of the printed layer is made of a polyethylene-containing resin, a polyamide resin, a (four) resin, a (iv) acid resin, and a poly Amine vinegar resin 'polyethylene shrinkage resin, polyester vinegar resin, cellulose vinegar resin, acid alcohol resin and other resins as a binder, and contains pigments of appropriate colors to browse the rough seven * bamboo A 枓The coloring ink which is a coloring agent, that is, the printing method of the printing layer [III], can be formed by a usual printing method such as a lithography method, a gravure printing method, or a screen printing method. In particular, in order to perform multicolor printing or gradient display, it is preferred that the rabbit watch f is a plate printing method or a gravure printing method. β (4) Next layer [IV] 32 201245297 The transfer layering system of the present invention has the above-mentioned base film (1) laminated. Hardening! The tree layer of the tree layer [II] #刷层[ΙΠ] is preferably layered on the printed layer [(1)] and then layered [IV]. Next, the layer [IV] is the one in which the above-mentioned laminated body is attached to the transferred body. As long as the MJ layer is formed. It can be formed when the force of σ is weaker. Next, the material of the layer [IV] is used, and a photosensitive or pressure-sensitive resin suitable for the material of the object to be transferred may be suitably used, and examples thereof include a polyester resin, an acrylic resin, a resin, and polyphenylene. A vinyl resin, a polyamide resin, a vaporized polyolefin tree, a gas-diethyl-acetic acid ethyl sulphide copolymer resin, a cyclized rubber knee, a benzo ketone resin, and the like. The method of forming the layer [IV] may, for example, be a gravure printing method, a light coating bar coating method, a coating method such as a knife coating method, or a printing method such as a gravure printing method or a screen printing method. Further, the adhesive layer formed of the above material may be bonded by a lamination method or the like to form an adhesive layer [IV]. Further, the layer [IV] may also serve as a printing layer [HJ]. In terms of the followability of the adherend, the thickness of the subsequent layer [IV] is preferably 0.5 to 5"m, more preferably, more preferably 2 to = μ ni. If the thickness is too thin, then There is a tendency that the followability of the adherend at the time of the transfer is lowered. If the thickness is too thick, there is a tendency that the cost is increased and it is not economical. [The method of using the laminate for heat transfer of the present invention: heat transfer method] The heat transfer method is described by a thermal transfer method of a laminate. (1) A method of decorating a transferred body surface First, a transfer layer of a transfer layer body is used (when the transfer layer has a layer of 33 201245297 layer [IV], For the adhesion layer [IV], the coating layer [III] is adhered to the transferred body surface without the adhesion layer [IV]. Secondly, the roll transfer using a heat-resistant rubber-like elastomer such as Shixia rubber is used. A transfer machine such as a machine or a reversible transfer machine is placed on the base film [I] side of the laminated body for transfer by a heat-resistant rubber-like elastomer set at a temperature of about 80 to 27 (about TC and a pressure of about 490 to 1960 Pa). Apply heat and pressure. Thereby, layer [IV] or printed layer [ ΙΠ] Next to the surface of the transferred body, after the cooling, the curable resin layer [II] is cured by irradiation with an active energy ray or the like to form a protective layer (hard coat layer), and finally the base film (1) is peeled off. The boundary between the base film [I] and the protective layer (cured resin layer [π]: hard coat layer) is peeled off to terminate the transfer. (2) The transfer synchronous transfer method is used as the transfer target. The method of decorating the surface of the resin molded article, the method of decorating the surface of the resin molded article as the object to be transferred by the forming synchronous transfer method by the injection molding using the transfer laminated body of the present invention First, the way the base film becomes the side of the fixed mold (usually the mother mold)

In the case of the shape, the printing layer of the transfer laminated body will be used as the conveying device having the positioning mechanism "1111 奥成.报田松阿处丨 _ Λ» /

If the position of the body is used, the movable mold (mother mold) and the fixed mold (male mold) are fixed. Intermittent 34 201245297 It is convenient to fix the transfer layer. When the laminated resin transfer molding laminate is melted, the position of the printed layer [III] is not always generated, and the positional deviation of the printed layer [III] does not occur. After the molding die is closed, the gate is melted and filled. The transferred body is formed in the mold. The transfer laminated body is conveyed simultaneously with the formation of the transferred body, and then on the surface of the transferred body. Examples of the molding resin to be a material to be transferred include a polystyrene resin, a polyolefin resin, an ABS resin, a general resin such as an AS resin or an AN resin, and a polyphenylene ether-polystyrene resin or a poly A general-purpose engineering resin or polyfluorene resin such as a carbonate resin, a polyacetal resin, an acrylic resin, a polycarbonate modified polyphenylene ether resin, a polybutylene terephthalate resin, or an ultrahigh molecular weight polyethylene resin. A super engineering resin such as a polyphenylene sulfide resin, a polyphenylene ether resin, a polyarylate resin, a polyether quinone resin, a polyimide resin, a liquid crystal polyester resin, or a polyallyl heat resistant resin. Further, a composite resin to which a reinforcing material such as glass fiber or inorganic filler is added may be used. The object to be transferred composed of the resins may be transparent, translucent or opaque. Also, the transferred body may be colored or may not be colored. After cooling the resin molded article as the object to be transferred, the molding die is opened to take out the resin molded article. In the method in which the peeling strength of the base film and the curable resin layer of the laminate for transfer of the present invention is much smaller than the separation strength of the transferred body and the transfer layer, the laminate for heat transfer is continuously conveyed, and the molded article is removed. Peeling of the curable resin layer and the base film occurs at the time of molding. In the case where the film for heat transfer is transported in a single sheet, it is also possible to simply peel off the base film from the molded article taken out. 35 201245297 Thus, a molded article in which the curable resin layer is obtained as the outermost layer can be obtained. When the mold is released and taken out, the hardening of the curable resin layer is not completed, and then the hardening is terminated. The hardened curable resin layer [II] serves as a protective layer for the molded article. The decorative molded article thus obtained is also excellent in surface gloss. Although the reason is not clear, the reason for the glossiness can be obtained by the fine unevenness of the surface of the coating film (specifically, the unevenness of 1 / m or less), because the base film and the hardenability can be considered. The resin layer is interposed between the resin and the exuded surfactant. Therefore, when the base film is peeled off, the curable resin which has not been hardened can be prevented from being stretched by the base film, or the base film can be prevented from being wrinkled when the curable resin is hardened. . [Examples] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the following examples as long as it does not exceed the gist thereof. Furthermore, the "parts" and "%" existing in the examples mean the weight basis. [Measurement and Evaluation Method] (1) Evaluation method of polyvinyl alcohol film 〇 - 1) Peel strength (g/24 mm) After placing the polyvinyl alcohol film in a 23 t, 50% RH atmosphere for 24 hours, in this environment, A scotch tape of 24 mm in width (kUotape (registered trademark) LP_24 manufactured by Nichiban) is cut to a length of i〇cm, by making a roll of 2 kg round-trip! Then, the scotch tape was attached to the air surface of the polyvinyl alcohol film, and the scotch tape was peeled off from the film surface at a speed of 3 〇〇mm/sec in a direction of 90 degrees using a tensile tester, and the peeling was measured at this time. The average load of 3 〇 _ 36 201245297 Λ The weight is the peel strength. (1 - 2) A 100 mm X 1 00 mm sample was cut on the adhesive self-polyethylene glycol film. The surface on the air surface side of the film of the two swatches was placed on the side of the casting surface, and after 24 hours of humidity adjustment at 231 x 60% RH, it was placed directly from the upper portion in a 23 〇c x 6 〇 % rh environment. Hammer 500g, and then placed for 24 hours. Thereafter, the adhesion resistance was evaluated on the basis of the following conditions by peeling off the two swatches by hand. 〇: The swatches were hardly adhered to each other only to the extent that the film was peeled off and the whole was separated. △: If you want to grab and lift the same piece, the degree of separation will fall off in another month. x : The extent to which force is required to peel off the sample, and the swatches are in close contact with each other. (2) Evaluation of the laminated body for transfer <Production of the laminated body for transfer> The polyvinyl alcohol film was used as the base film [I], and the thickness of the base film (1) was 1 60 /zm. The active energy ray-curable resin composition was applied by a coater, and dried at 80 ° C for 15 minutes to prepare a laminate of a curable resin layer [II] having a thickness of 80 / zm on the substrate 貘 [I]. Body (α ). On the surface of the hardened resin layer [II] of the laminate (α), a pattern of a grid is formed by a printing method using a printing ink, and a base film [I] / a curable resin layer [II] is obtained. / Printed layer [III] constitutes a laminate (cold). Further, on the surface of the printed layer [III] of the laminated body (cold), the above-mentioned thermocompression bonding layer coating was applied to the surface of the printed layer [III] of the laminated body (cold) by a bar coater, and the liquid was dried at 80 ° C. 15 minutes, thereby forming a thermocompression bonding layer [iv] ' having a thickness of 2 μm to obtain a laminate composed of the base film (1) / the curable resin layer [π] / the printing layer [III] / the bonding layer [IV] ( r). The laminate (7) and the green glass substrate (thickness: 2.8 mm) were preheated in a dryer heated to 130 ° C for 3 minutes to melt the thermocompression bonding adhesive of the laminate (7). Next, the layer [IV] surface was pressed against a green glass substrate to prepare a bonded sample. With respect to the obtained bonded sample, the curable resin layer [π] is cured by irradiating the base film [I] with ultraviolet rays of 1000 mJ to form a protective layer (hardened curable resin layer: hard coat layer) to form protection. After the layer, the protective layer after the base film was peeled off was evaluated in the following manner. <Evaluation of Protective Layer> (2 - 1 ) The surface glossiness of the protective layer reflects the fluorescent lamp on the surface of the protective layer (cured resin layer), and visually observed and evaluated based on the following criteria. The sharpness of the light. 〇: Clearly see the outline of the fluorescent light. △: The outline of the fluorescent lamp is blurred. x : The outline of the fluorescent lamp cannot be confirmed. (2 - 2 ) The write-up property of the protective layer is measured on the surface of the protective layer (cured resin layer), using the image measuring device ICM_ 1DP of the Suga test machine, and the measurement is performed under the following conditions' and based on the following Benchmarks are evaluated. (Measurement conditions) Measurement method: Reflection 38 201245297 Measurement angle: 45. Incident, 45° light receiving slit: 0.03mm Measuring hole: 20mm Light comb width: 2.0mm Writeability. C = [ ( Μ _ Π1 ) / Γ \/Γ -L \ / η/ \ 1 κ } χ ^ M + m ) ]χ 1〇〇( 〇/〇) c : Writeability (%) at the width of the comb (mm) Μ : The highest amount of light at the width of the comb (mm) 01 : Width of the comb (mm) The minimum amount of light (evaluation basis) S: Grade 90% or more A ··Unreachable grade 70~90% B: Not reached grade 30~70% C: Not up to grade 30%

..., ~〇ι, only J (20. 〇, with the saponification degree as shown in Table 1 and the average viscosity of 4% aqueous solution) and the sputum of polyvinyl alcohol (A) 1 〇 0 parts in 'mixed ❹ 1 Show i the weight of the flat ^ 8 ^ characteristics (oxyethylene and oxypropylene base ratio of the tenth average molecular weight, HLB) of the polyanthracene ... ... as a non-early "Oxygen alkylene alkyl Ether, in addition, added: a non-ionic surfactant (Β,) polyoxyl amine group (10) (~ ... ' as a plasticizer glycerin, part to prepare a solid 18% polyvinyl alcohol Aqueous resin solution (doping). 'To the whole u=Polyvinyl alcohol-based resin solution sprayed to the surface temperature Μ...Polyethylene_film. For the obtained two-meter 39 201245297 the above evaluation method to evaluate the peel strength and adhesion resistance The results are shown in Table 1. β [Production and evaluation of the laminated body No. 1-7 for transfer] The polyvinyl alcohol film No. 1.7 produced as described above was used as the base film [I], and the above-mentioned transfer layer was used. The method for producing a body was used to produce a laminate for transfer, and the surface glossiness and imageability were evaluated based on the above evaluation method. 1. In addition, the active energy ray resin composition constituting the curable resin layer [II], the design printing ink used in the printing layer [III], and the adhesive layer used in the layer [IV] are prepared as follows. (1) Active energy ray-curable resin composition of 40 parts of solid content of urethane amide "UV-3 520" manufactured by Nippon Synthetic Chemical Industry Co., Ltd. and organic chemistry of Osaka by 2-butanone One part of the photopolymerizable monomer "Viscoat #300" manufactured by the Industrial Co., Ltd. is 50% of the solids of the polymethyl methacrylate r MN" manufactured by Kaneka Co., Ltd., and the total solid content concentration is 50%. In the dilute-mixed solution, "Irgacure 819" manufactured by Nagase Industries Co., Ltd. was mixed as a photopolymerization initiator in a ratio of 3 parts to 100 parts by weight of the solid component. (2) Design printing ink was prepared from black pigment 10 An ink for printing a concave plate comprising 5 parts of nitrocellulose, 5 parts of an alkyd resin, 30 parts of toluene, 30 parts of ethyl acetate, and 1 part by weight of isopropyl alcohol. (3) Coating liquid for heating layer for heating layer Under reflux conditions, for day Polyester "SP-185" (polyester resin) manufactured by Synthetic Chemical Industry Co., Ltd. is mixed and dissolved in a manner of 20% relative to "mixture solvent of toluene and 2 201245297 Λ butanone of 4:1 (weight ratio)" 41 201245297 【I ΐ i

00 00 Polyethylene oxypropylene butyl ether 9/10 1000 S 〇«Λ ο r">〇< B (65.4) Ό 00 00 Polyoxypropylene butyl ether 0/17 1000 m 〇ο m 〇< B (66.0) *n 00 00 Polyethylene Vinyl Laurel "20/0 1000 ir" • Τί ν〇s〇00 <N 〇< B (64.0) 00 00 Polyoxyethylene polypropylene glyceryl ether 18/48 3700 Tn ΓΟ — 沄〇〇S (93.3) ΓΛ 00 00 Polyoxyethylene polypropylene propylene lauryl ether 14/8 1200 Bu Bu 〇 Ο ( S (94.1) <N o OS 00 ΓΊ Polyethylene oxypropylene Ether 37/38 4000 to ro οό 沄〇〇S (93.7) 00 00 9/10 I 1000 卜> Ο 1 <1 〇S (94.1) 6 Saponification degree (mole%) 1 Viscosity (mPa_s) ” 1 Type ΕΟ/ΡΟ" ((Morby)) Weight average molecular weight | Blend amount (part 3 1 HLB 1 base film thickness (#m) 1 Peel strength (g / 24mm) Resistance to adhesion l Surface gloss 1 Back to U City w PVA Ling a ^ Fortunately A 屮萑 "ί ® Miscellaneous: ei 铋 two PVA film transfer laminate basement membrane evaluation I - umbrella potential w umbrella 001 遝 琎 琎 〇铋 «- 〇铋 葙 « (8)莸^*«岭供屮 cone*:{ :* (3. 03) target yak 轶 % % % % % % % % U U 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 The peeling strength of the polyvinyl alcohol-based film N〇丨_4 composed of the composition of the surfactant (B), and the non-oxyethylene or oxypropylene group having a blending ratio of 1 part by mass or more The peeling strength of the polyvinyl alcohol-based film Nos. 5 and 6 which are composed of the composition of the ionic surfactant is 1/1 〇 or less, and the mold release property is excellent. Further, it is convenient to use an oxyethylene group and an oxypropylene group. In the case of the nonionic surfactant (B), the decrease in the peel strength was not confirmed in the amount of Ng 7 in which the content was less than 丨f. Therefore, it was found that the ruthenium was damaged by 3 相对 with respect to the polyvinyl alcohol. 1 ff or more of a nonionic surfactant having a t-ethyl group and an acryl-based group is effective for reducing the peel strength. Further, 3 or more parts having an oxyethylene unit and oxypropylene The nonionic surfactant of the dilute unit is in contact with the polyvinyl alcohol film. The resistance to creep deformation off almost no effect. Further, it is known that the transfer layered body has a film thickness of the heat transfer film No. 1-4 having a small peeling strength as compared with the case of using the heat transfer film No. 5-7 having a large peel strength. Excellent writeability. [Industrial Applicability] Since the polyvinyl alcohol-based film of the present invention is excellent in mold release property, it is useful as a base film for a separator film or a film for transfer. [Simple description of the diagram] None [Key component symbol description] 43

Claims (1)

201245297 VII. Patent application scope: 1. A polyacetone-based film which is 100% by weight of the polyvinyl alcohol-based resin (4) and contains 1 to 2 parts by weight of an oxyethylene group and an oxypropylene group. The ion-based surfactant (B) is formed. 2. The polyethylene glycol film according to the patent of claim i, wherein the nonionic surfactant (B) is selected from the group consisting of a pendant ether (B1) having an aerobic vinyl group and an oxypropylene group. At least one of a group consisting of a fatty acid ester of an aerobic vinyl group and an oxypropyl group (B2) and a polyether ether to which an aerobic vinyl group and an oxypropylene group are added. 3. In the case of the polyvinyl alcohol-based film of the third paragraph of the patent application, the number of structural units of the oxyethylene group in the non-ionic surfactant (B) is i~7〇, and the number of structural units of the oxypropylene group i, ". 4. The polyvinyl alcohol film according to claim 1 of the patent scope, wherein the ratio of the oxyethylene group to the oxypropylene group in the nonionic surfactant (B) (oxyethylene/oxygen) The propylene group (mole ratio) is 1 〇 / 9 〇 ~ 9 〇 / 1 〇. 5. The polyvinyl alcohol film according to the first item of the patent application, wherein the weight of the nonionic surfactant (B) The average molecular weight is 1 〇〇 1 〇〇〇 (1). 6. The polyvinyl alcohol-based film according to claim 1, wherein the non-ionic surfactant (B) has an HLB of 2 to 18. For example, in the polyvinyl alcohol-based film of the above-mentioned item, the polyoxyethylene block is used as the hydrophilic portion, and the polyoxypropylene is embedded as the hydrophobic portion. The polyvinyl alcohol-based film of any one of the items 1 to 6 wherein the degree of saponification of the polyvinyl alcohol-based resin (A) is 7 〇 mol% or more. 4 201245297 9. As claimed in the patent scope! The film 'where' the viscosity of the polyvinyl alcohol resin is 5 to 70 mPa. s. The polyvinyl alcohol of any of the 6 items (A) is 4 weights at 2 °C. % aqueous solution. A polyvinyl alcohol-based oxime containing ～2 () parts by weight of a nonionic surfactant containing oxygen and an alkenyl group (B) in an amount of 100 parts by weight based on the polyvinyl alcohol eucalyptus. ▲Oxygen-propion, the non-ionic surfactant (B), the structural unit of the oxyethylene group, the number of structural units of the oxypropylene group is 1 to 7°, and the content ratio of the oxyethylene oxypropylene group (oxygen) Ethyl/oxypropyl) (······························································ The hydrophilic portion of the ionic surfactant (8) is a polyoxyethylene moiety, the hydrophobic portion is a polyoxypropylene block, and the HLB is 2 to 18. 12. A method for producing a polyethylene glycol film, which is a polyethyl hydrazine. The aqueous solution of the alcohol-based resin is cast to form a film, and the aqueous solution of the polyethylene-based resin contains 1 to 2 parts by weight based on 100 parts by weight of the polyvinyl alcohol-based resin. The ethoxylated vinyl group and the oxypropylene group-containing nonionic surfactant (Β). 13. The polyvinyl alcohol film according to claim 12, wherein the concentration of the polyethylene glycol resin aqueous solution is 1 〇 〜 3 〇 〇 0 0 种 种 种 种 种 种 种 种 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 The resin layer [II], the printing layer [III]. The layered body for transfer of the substrate of the substrate 骐[I], the surface roughness (Ra) of the [π] side of the hardened resin layer of the substrate [I]. For 1^m 45 201245297