CN102731946B - The manufacture method of polyvinyl alcohol film and polyvinyl alcohol film and employ its hot transfer printing duplexer - Google Patents

Abstract

The object of the present invention is to provide the manufacture method of polyvinyl alcohol resin film and this polyvinyl alcohol film and employ the hot transfer printing duplexer of this polyvinyl alcohol film, described polyvinyl alcohol resin film has the such excellent release qualities of the basement membrane that is applicable to hot transfer film.Nonionic system tensio-active agent (B) that polyvinyl alcohol film of the present invention contains 1 ~ 20 weight part relative to polyvinyl alcohol resin (A) 100 weight part forms, and this nonionic system tensio-active agent (B) is containing aerobic ethylidene and oxygen propylidene.

Description

The manufacture method of polyvinyl alcohol film and polyvinyl alcohol film and employ its hot transfer printing duplexer

Technical field

The present invention relates to the polyvinyl alcohol film of release property excellence, if be described in further detail, then relate to the manufacture method of polyvinyl alcohol film and this polyvinyl alcohol film and employ the hot transfer printing duplexer of this polyvinyl alcohol film, described polyvinyl alcohol film has the such release property of the basement membrane (basefilm) that is applicable to hot transfer printing duplexer.

Background technology

As the trailing of products formed, exist and use transfer film by the method for the transfer printing layer transfer printing of transfer film.Transfer film is the transfer film of stacked transfer printing layer on basement membrane, and described transfer printing layer to become resin layer and the patterned layer, adhesive linkage etc. on the resin layer that protection is transferred the protective layer of material surface after comprising transfer printing.

Transfer printing is roughly divided into hydraulic-transfer method, thermal transfer.

Hydraulic-transfer method refers to: make it bubble through the water column by the mode being positioned at top with the face of the transfer printing layer side of hydraulic-transfer film, above film, the transferred object such as products formed are pushed on transfer printing layer, transfer printing layer is needed on transferred object, thereafter transferred object is taken out, carry out washing and dissolving removal basement membrane, thus pattern etc. is needed on the method for transferred object.In such hydraulic-transfer method, the polyvinyl alcohol film of the water-soluble excellence of known use is as basement membrane (such as patent documentation 1,2).

On the other hand, the hot transfer film used in thermal transfer can be used in the hot transfer film that the basement membrane that formed by thermoplastic resin membrane etc. obtains with the stacked transfer printing layer of strippable state; Resin layer as protective layer is generally made up of the resin combination of the surface physical property such as hardness, solvent resistance excellence.Use the heat-transferring method with the transfer film of this formation to refer to: after the face of the transfer printing layer side of transfer film is crimped on the surface of transferred object, basement membrane is peeled off from transfer printing layer and removes, thus transfer printing layer is needed on the method on transferred object surface.

As the basement membrane of so hot transfer film, use the polyester based resin films such as pet film all the time, but polyester based resin film affinity that is usual and transfer printing layer is high, be thus to guarantee release property between transfer printing layer and basement membrane by making melamine resin or the releasing agent layer such as silicon-type, fluorine system be situated between.But consider from environment aspect and cost aspect, such releasing agent process is disadvantageous, therefore seeks the basement membrane not needing releasing agent process.

Under such a condition, in recent years, the basement membrane having carried out hot transfer printing duplexer also compatibly uses the research of polyvinyl alcohol film.Such as, Patent Document 3 discloses and be provided with in the decoration film (hot transfer film) of ornament layer (being equivalent to transfer printing layer) in the one side of transparent film (being equivalent to basement membrane), use polyvinyl alcohol resin film as transparent film.In addition, propose at the one side stacked above one another peel ply of basement membrane, patterned layer, bond layer and in the transfer foil obtained in patent documentation 4, using with polyvinyl alcohol resin is that the resin film of main component is as this basement membrane.

Prior art document

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 2007-152622 publication

Patent documentation 2: Japanese Unexamined Patent Publication 2011-11540 publication

Patent documentation 3: Japanese Unexamined Patent Publication 7-40515 publication

Patent documentation 4: Japanese Unexamined Patent Publication 9-277458 publication

Summary of the invention

the problem that invention will solve

Polyvinyl alcohol film is known as the film of release property excellence, but when being used as the basement membrane of hot transfer printing laminate film not using releasing agent, requires to have the release property more than in the past excellent.Practical situation are release properties that commercially available polyvinyl alcohol film does not possess this height usually, even if be the basement membrane of hot transfer film by the basement membrane of hydraulic-transfer film conversion, also cannot meet release property.

And then, there is the requirement of the productivity of the mould release film purposes be applicable in recent years and the ornament improving thermal transfer printing, in addition, also require excellent release property from the viewpoint of the appearance design formative of fine, but in above-mentioned patent documentation, the concrete polyvinyl alcohol film used not exclusively meets.

In this context, the object of the present invention is to provide: have the polyvinyl alcohol film of very excellent release property, be particularly applicable to employ thermal transfer trailing in the basement membrane of hot transfer printing duplexer that uses such, there is the excellent polyvinyl alcohol film of release property and the manufacture method of this polyvinyl alcohol film and employ the transfer printing duplexer of this polyvinyl alcohol film.

for the scheme of dealing with problems

Nonionic system tensio-active agent (B) that polyvinyl alcohol film of the present invention contains 1 ~ 20 weight part relative to polyvinyl alcohol resin (A) 100 weight part forms, and this nonionic system tensio-active agent (B) is containing aerobic ethylidene and oxygen propylidene.

All the time, usually tensio-active agent is contained in known polyvinyl alcohol film.In the manufacture scene of polyvinyl alcohol film, from the viewpoint of guarantee by become during masking substrate, cylinder or bring the polyvinyl alcohol film obtained through masking to batch time and the peeling off easness and prevent from sticking together during pull-out when pulling out film from film winding roller of substrate, add tensio-active agent to alleviate adhesion.Such as, in above-mentioned patent documentation 1,2, use polyoxyethylene 20 sorbitan monolaurate, polyoxyethylene alkyl amine (polyoxyethylenealkylamine) etc. as tensio-active agent.

But, as object of the present invention, hot transfer film basement membrane required by release property be the layer making formation temporarily form duplexer easily can carry out the degree peeled off release property when there is not releasing agent, and far away higher than polyvinyl alcohol film manufacture scene required by release property.Thus, normally used tensio-active agent (only containing the nonionic system tensio-active agent of polyoxyethylene as polyoxy alkylidene) and content thereof are insufficient.

The invention is characterized in, compared to the general content in order to improve masking and normally used tensio-active agent more containing usually do not use in the actual manufacture of polyvinyl alcohol film, the nonionic system tensio-active agent with oxygen propylidene.

The present invention also provides the manufacture method of polyvinyl alcohol film, it makes the polyvinyl alcohol resin aqueous solution containing nonionic system tensio-active agent (B) of 1 ~ 20 weight part relative to polyvinyl alcohol resin (A) 100 weight part carry out curtain coating and masking, and this nonionic system tensio-active agent (B) is containing aerobic ethylidene and oxygen propylidene.

And then the present invention also provides a kind of transfer printing duplexer, it is characterized in that, it is laminated with the basement membrane [I], curable resin layer [II], the printed layers [III] that are formed by aforementioned polyvinyl alcohol film.

the effect of invention

Polyvinyl alcohol film of the present invention not only has oxygen ethylidene also have the tensio-active agent of oxygen propylidene as oxyalkylene to contain more than the current amount contained as additive, thus has very excellent release property.Therefore, can be used for the purposes needing release property every film, protective film etc.And, as the basement membrane of the transfer printing duplexer used in hot transfer printing, can not be situated between releasing agent layer mode and use.

Embodiment

[polyvinyl alcohol film]

First, polyvinyl alcohol film of the present invention is described.

Polyvinyl alcohol film of the present invention is the polyvinyl alcohol film containing nonionic system tensio-active agent (B) in polyvinyl alcohol resin (A), and this nonionic system tensio-active agent (B) is containing aerobic ethylidene and oxygen propylidene.

(1) polyvinyl alcohol resin (A)

The polyvinyl alcohol resin (A) used in the present invention is conventionally polymerized by vinyl ester based compound, then its saponification obtained.In the present invention, polyvinyl alcohol resin (A) not only can be used alone, and also can mix two or more as required and use.

As above-mentioned vinyl ester based compound, vinyl formate, vinyl-acetic ester, vinyl trifluoroacetate, propionate, vinyl butyrate, caprate, vinyl laurate, tertiary ethylene carbonate, vinyl palmitate, stearic acid vinyl ester etc. can be listed.They can be used alone or and with two or more, are applicable in practical using vinyl-acetic ester.

In addition, as the polyvinyl alcohol resin used in the present invention (A), usually preferably use unmodified polyvinyl alcohol resin, but also can use partially modified modified polyvinyl alcohol system resin.As modified polyvinyl alcohol system resin, the resin that a small amount of copolymerization of other monomer of sening as an envoy to obtains in vinyl ester based compound can be enumerated, the ratio of monomer is in the case the scope not hindering effect of the present invention, such as, be less than 10 % by mole, is preferably less than 7 % by mole.

As other monomer above-mentioned, include, for example out: ethene, propylene, iso-butylene, α-octene, α-dodecylene, the olefines such as α-vaccenic acid, vinylformic acid, methacrylic acid, β-crotonic acid, toxilic acid, maleic anhydride, the unsaturated acids such as methylene-succinic acid or its salt or its mono alkyl ester or dialkyl etc., vinyl cyanide, the nitriles such as methacrylonitrile, acrylamide, the amidess such as Methacrylamide, ethylene-sulfonic acid, allyl sulphonic acid, the alkene sulfonic acids such as methallylsulfonic acid or its salt, alkyl vinyl ethers, polyoxyethylene (methyl) allyl ethers, polyoxyalkylene (methyl) allyl etherss such as polyoxypropylene (methyl) allyl ethers, polyoxyethylene (methyl) acrylate, polyoxyalkylene (methyl) acrylate such as polyoxypropylene (methyl) acrylate, polyoxyethylene (methyl) acrylamide, polyoxyalkylene (methyl) acrylamides such as polyoxypropylene (methyl) acrylamide, polyoxyethylene [1-(methyl) acrylamido-1,1-dimethyl propyl] ether, polyoxyethylene vinyl ether, polyoxypropylene vinyl ether, polyoxyethylene allyl amine, polyoxypropylene allyl amine, polyoxyethylene vinyl amine, polyoxypropylene vinyl amine, two acryl pyroracemamides (diacrylacetoneamide), (N acrylamide ylmethyl) trimethyl ammonium chloride, allyl group trimethyl ammonium chloride, dimethyl diallyl ammonium chloride, dimethyl-allyl vinyl ketone, NVP, vinylchlorid, vinylidene chloride etc.These other monomers can be used alone or and use two or more.

Be explained; in the present invention; (methyl) allyl group represents allyl group or methylallyl, and (methyl) acryl represents acryl or methacryloyl, and (methyl) acrylate represents acrylate or methacrylic ester.

And, when using above-mentioned vinyl ester based compound to carry out being polymerized (or copolymerization), can known polymerization process be used with being not particularly limited, usually with alcohol such as methyl alcohol, ethanol or Virahols for solvent carries out solution polymerization.In addition, except solution polymerization, also letex polymerization, suspension polymerization can be carried out.

In addition, polyreaction uses the known catalysts for radical polymerization such as Diisopropyl azodicarboxylate, acetyl peroxide, benzoyl peroxide, lauroyl peroxide and carries out, temperature of reaction is selected from the scope of 35 DEG C ~ boiling point usually, is more preferably selected from the scope of about 50 ~ 80 DEG C.

Then, when by obtained vinyl ester based polymer saponification, above-mentioned vinyl ester based polymer is dissolved in alcohol and carries out under the existence of alkaline catalysts.As above-mentioned alcohol, can list methyl alcohol, ethanol, butanols etc., the concentration of the vinyl ester based copolymer in above-mentioned alcohol suitably can be selected in the scope of 20 ~ 50 % by weight.

As alkaline catalysts during above-mentioned saponification, the alkaline catalysts that the alkali-metal oxyhydroxide such as sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, potassium methylate, alkoxide are such can be used.The consumption of above-mentioned alkaline catalysts suitably can be selected in the scope relative to vinyl ester based polymer being 1 ~ 100 mmole equivalent.Be explained, also can according to circumstances utilize acid catalyst to carry out saponification.

Polyvinyl alcohol resin (A) can be obtained by operating like this.

In addition, as polyvinyl alcohol resin (A), side chain is also preferably used to have the polyvinyl alcohol resin of 1,2-diol bond; Above-mentioned side chain has 1, the polyvinyl alcohol resin of 2-diol bond obtains by following method: such as, i () is by vinyl-acetic ester and 3, the method of the multipolymer saponification of 4-diacetoxy-1-butylene, (ii) by the multipolymer saponification of vinyl-acetic ester and vinylethylene carbonate and the method for decarbonate, (iii) by vinyl-acetic ester and 2,2-dialkyl group-4-vinyl-1, the multipolymer saponification of 3-dioxolane de-ketalization method, (iv) is by the method etc. of the multipolymer saponification of vinyl-acetic ester and allylin.

In the present invention, the mean saponification degree of above-mentioned polyvinyl alcohol resin (A) is generally more than 70 % by mole, such as, the preferred mean saponification degree of purposes paying attention to the processing appropriateness under the high temperature of more than 100 DEG C is 70 ~ 90 % by mole, on the other hand, the preferred mean saponification degree of purposes paying attention to thermotolerance is more than 90 % by mole.Wherein, can be suitably select in the scope of more than 70 % by mole from mean saponification degree according to processing conditions, object.Be explained, when the mean saponification degree of polyvinyl alcohol resin (A) is too low, not only film strength reduces, and deposits the tendency be difficult to during fabrication from curtain coating face stripping film.

Be explained, above-mentioned mean saponification degree measures according to JISK6726.

And then at 20 DEG C of polyvinyl alcohol resin (A), 4 % by weight solution viscosities are preferably the scope of 5 ~ 70mPas, are more preferably the scope of 15 ~ 60mPas.The tendency that thin film strength reduces is there is in 4 % by weight solution viscosities time too low.On the other hand, there is the tendency that viscosity is high, be difficult to masking when 4 % by weight solution viscosities are too high.Be explained, at above-mentioned 20 DEG C, 4 % by weight solution viscosities measure according to JISK6726.

(2) nonionic system tensio-active agent (B)

Nonionic system tensio-active agent (B) used in the present invention containing the structural unit of aerobic ethylidene and oxygen propylidene as oxyalkylene.Generally speaking, in order to from by become during masking base material, cylinder or bring stripping, improve batching property of roller, how in polyvinyl alcohol film, to be added with tensio-active agent.Using such object, compounding tensio-active agent uses the oxygen ethylidene of wetting ability excellence as oxyalkylene structural unit.The feature of nonionic system tensio-active agent (B) used in the present invention is, hydrophilic parts comprises oxygen ethylidene, and hydrophobic parts comprises oxygen propylidene.Comprise chain alkyl usually used as hydrophobic parts, and hydrophobic adjustment is regulated by the length etc. of alkyl chain, but in the present invention, nonionic system tensio-active agent (B) used is regulated containing proportional by oxygen ethylidene and oxygen propylidene.

As the nonionogenic tenside (B) containing aerobic ethylidene and these two kinds of structural units of oxygen propylidene, include, for example out the polyol ester etc. of the alkyl phenyl ether of the polyol ethers (B3) of the fatty acid ester (B2) of the alkyl oxide (B1) of addition aerobic ethylidene and oxygen propylidene, addition aerobic ethylidene and oxygen propylidene, addition aerobic ethylidene and oxygen propylidene, addition aerobic ethylidene and oxygen propylidene, addition aerobic ethylidene and oxygen propylidene, use at least a kind that is selected from them.Among them, from the viewpoint of the easy degree of release property effect and acquisition, the polyol ethers (B3) of the fatty acid ester (B2) of the alkyl oxide (B1) of preferred addition aerobic ethylidene and oxygen propylidene, addition aerobic ethylidene and oxygen propylidene, addition aerobic ethylidene and oxygen propylidene, the more preferably polyol ethers (B3) of the alkyl oxide (B1) of addition aerobic ethylidene and oxygen propylidene, addition aerobic ethylidene and oxygen propylidene.

As the alkyl oxide (B1) of above-mentioned addition aerobic ethylidene and oxygen propylidene, include, for example out polyoxyethylene polyoxy-propylene class, as object lesson, polyoxyethylene polyoxypropylene butyl ether, polyoxyethylene polyoxypropylene decyl ethers, polyoxyethylene polyoxypropylene lauryl ether, polyoxyethylene polyoxypropylene myristyl ether, polyoxyethylene polyoxypropylene cetyl ether, polyoxyethylene polyoxypropylene stearyl ether, polyoxyethylene polyoxypropylene oleyl ether etc. can be listed.

As the fatty acid ester (B2) of above-mentioned addition aerobic ethylidene and oxygen propylidene, include, for example out polyoxyethylene polyoxypropylene alkyl esters, as object lesson, polyoxyethylene polyoxypropylene laurate etc. can be listed.

As the polyol ethers (B3) of above-mentioned addition aerobic ethylidene and oxygen propylidene, include, for example out polyoxyethylene polyoxypropylene polyvalent alcohol ethers, as object lesson, polyoxyethylene polyoxypropylene glyceryl ether, polyoxyethylene polyoxypropylene Glycerol dimer base ether, polyoxyethylene polyoxypropylene sorb alcohol ether etc. can be listed.

As the alkyl phenyl ether of above-mentioned addition aerobic ethylidene and oxygen propylidene, include, for example out polyoxyethylene polyoxypropylene alkyl phenyl ethers, as object lesson, polyoxyethylene polyoxypropylene hexyl phenyl ether, polyoxyethylene polyoxypropylene heptyl phenyl ether, polyoxyethylene polyoxypropylene octyl phenyl ether etc. can be listed.

As the polyol ester of above-mentioned addition aerobic ethylidene and oxygen propylidene, include, for example out polyoxyethylene polyoxypropylene sorbitan fatty acid ester class.

In the present invention, the structural unit number of the oxygen ethylidene in nonionic system tensio-active agent (B) is preferably 1 ~ 70, is more preferably 2 ~ 60, and more preferably 4 ~ 50.The tendency that the viscosity that described structural unit number exists the polyvinyl alcohol resin aqueous solution time too much uprises, the tendency that the plane smooth that there is the film obtained reduces.In addition, the structural unit number of the oxygen propylidene in nonionic system tensio-active agent (B) is preferably 1 ~ 70, is more preferably 2 ~ 60, and more preferably 4 ~ 50.The tendency that the viscosity that described structural unit number exists the polyvinyl alcohol resin aqueous solution time too much uprises, the tendency that the plane smooth that there is the film obtained reduces.And then the total of the structural unit number of oxygen ethylidene and the structural unit number of oxygen propylidene is preferably 2 ~ 100, is more preferably 4 ~ 85, more preferably 6 ~ 80, be especially preferably 20 ~ 80.When described structural unit number is too much, the tendency that the viscosity that there is the polyvinyl alcohol resin aqueous solution uprises, the tendency that the plane smooth that there is the film obtained reduces.

When tensio-active agent (B) comprises multiple oxygen ethylidene and oxygen propylidene, the material that oxygen ethylene units and oxygen propylene unit carry out block copolymerization and obtain and the material carrying out random copolymerization and obtain, as tensio-active agent, working as hydrophilic portion to make oxygen ethylidene, making oxygen propylidene give full play to effect as hydrophobic portion, preferably exist in the mode in polyoxyethylene portion and polyoxypropylene portion, be therefore preferably segmented copolymer.

In addition, in the present invention, 90/10 ~ 10/90 is preferably with molar ratio computing from the viewpoint of contain proportional (the oxygen ethylidene/oxygen propylidene) of the oxygen ethylidene in release property increase nonionic system tensio-active agent (B) and oxygen propylidene, be more preferably 80/20 ~ 20/80, more preferably 70/30 ~ 30/70.Oxygen ethylidene and oxygen propylidene containing proportional too small or excessive, all there is the tendency reduced relative to the release property of curable resin layer.

And then in the present invention, from the viewpoint of increase, the viscosity optimization of release property, the weight-average molecular weight of nonionic system tensio-active agent (B) is preferably 100 ~ 10000, is more preferably 200 ~ 8000.There is the tendency that release property reduces in described weight-average molecular weight, the viscosity that there is the polyvinyl alcohol resin aqueous solution time excessive uprises and causes the tendency of obstruction when manufacturing film time too small.

In the present invention, from the viewpoint of release property, the HLB of nonionic system tensio-active agent (B) is preferably 2 ~ 18, is more preferably 2 ~ 15, and more preferably 3 ~ 12.HLB value described in the present invention refers to the value calculated by lattice Lifei method (Griffinmethod), can be calculated by following formula.

HLB=20 × (molecular weight of the molecular weight/entirety of hydrophilic portion)

Herein, hydrophilic portion mainly refers to the total molecular weight of oxygen ethylidene structural unit.Therefore, represent that the HLB value of the ratio of oxygen ethylidene structural unit in the molecular entities of tensio-active agent (B) is preferably above-mentioned scope.HLB value is that the tensio-active agent (B) of above-mentioned scope refers to: in the scope not damaging dispersiveness in water, have the hydrophobic balance possessing appropriateness.Can thinking, by having such balance, its good dispersion in polyvinyl alcohol resin can be guaranteed, and under the state improved in hydrophobicity, become easily from the state that polyvinyl alcohol film oozes out.Be speculated as, the tensio-active agent (B) oozing out into polyvinyl alcohol film surface works owing to can be used as a kind of releasing agent, therefore, when being used as the basement membrane of hot transfer printing duplexer, after transfer printing, the stripping improving curable resin layer and basement membrane is contributed to.

In the present invention, from the viewpoint of release property and film appearance, the content of above-mentioned nonionic system tensio-active agent (B) is preferably 1 ~ 20 weight part relative to polyvinyl alcohol resin (A) 100 weight part, be more preferably 2 ~ 15 weight parts, more preferably 3 ~ 10 weight parts, are particularly preferably 5 ~ 8 weight parts.Generally for and improve and add tensio-active agent as the cylinder of substrate during masking or the release property between being with, its content is relative to polyvinyl alcohol resin 100 weight part lower than 1 weight part, and therefore the feature of polyvinyl alcohol film of the present invention is more than common amount.This is because, for nonionic system tensio-active agent (B) used in the present invention, in order to be obtained the increase effect of release property by oozing out of nonionic system tensio-active agent (B), the amount in the past contained as additive is insufficient.On the other hand, when content becomes too much, nonionic system tensio-active agent (B) quantitative change of oozing out to surface is many, and film surface is easy to become glutinous greasy.Its result, on film when other resin stacked, repels other resin sometimes.This situation is when being such as used as the basement membrane of hot transfer printing duplexer owing to being easy to repel the reasons such as stacked curable resin, and the reason that reduces occurs for the reason that the superficiality becoming transfer printing layer reduces and then the surface luster of protective layer that becomes obtained products formed.

(3) other composition

Polyvinyl alcohol film of the present invention is not limited to the polyethylene base system alcohol film only manufactured by the composition comprising above-mentioned polyvinyl alcohol resin (A) and nonionic system tensio-active agent (B).Also be filmed preferably by suitably compounding tensio-active agent except above-mentioned nonionic system tensio-active agent (B) (B '), softening agent etc. and manufacture.In addition, also can in the scope not damaging object of the present invention compounding filler.

(3-1) other tensio-active agent (B ')

Compounding for the purpose of release property between the film that tensio-active agent except above-mentioned nonionic system tensio-active agent (B) (hereinafter referred to as " other tensio-active agent (B ') ") goes out using the metallic surface and the masking that improve as the cylinder or band etc. of the film forming apparatus of polyvinyl alcohol film.

As other tensio-active agent (B '), such as, as nonionic system tensio-active agent, the tensio-active agent except the aforesaid nonionic system tensio-active agent containing aerobic ethylidene and oxygen propylidene can be listed, such as, only containing a kind of polyoxyalkylene alkyl ethers class in aerobic ethylidene or oxygen propylidene, polyoxyalkylenes alkyl phenyl ethers, polyoxyalkylenes alkyl esters, sorbitan fatty acid ester class, polyoxyalkylenes alkyl amine, polyoxyalkylenes alkylamide, polypropylene glycol ethers, ethanetetrayl glycol (acetyleneglycol) class, allyl phenyl ethers etc.

In addition, as other tensio-active agent (B '), be not limited to nonionic system tensio-active agent, also can use negatively charged ion system tensio-active agent, positively charged ion system tensio-active agent, amphoterics.As negatively charged ion system tensio-active agent, such as, the negatively charged ion system tensio-active agent of the sulfonic acid types such as sulfuric acid ester type, DBS such as the carboxylic acid types such as potassium laurate, octyl sulfate ester is applicable.As positively charged ion system tensio-active agent, include, for example out the pyridinium salts etc. such as the quaternary ammonium salt such as amine, lauryl trimethyl ammonium chloride, lauryl chloride pyridine such as laurylammonium chloride.As amphoterics, include, for example out N-alkyl-N, N-dimethyl ammonium betaine etc.

Other tensio-active agent (B ') can use a kind or combine two or more and use.

Other tensio-active agent (B ') if content be the degree not damaging object of the present invention, in addition, being exuded to the degree that superficiality such as not having such as surperficial albefaction reduces, is below 1 weight part relative to polyvinyl alcohol resin 100 weight part usually.

(3-2) softening agent

As above-mentioned softening agent, include, for example out the glycerols such as glycerine, Glycerol dimer, triglycerin, the aklylene glycol classes such as triethylene glycol, polyoxyethylene glycol, polypropylene glycol, dipropylene glycol, TriMethylolPropane(TMP) etc.They can be used alone or and use with two or more.

The compounding amount of the compounding softening agent in above-mentioned polyvinyl alcohol resin (A) is preferably below 30 weight parts relative to polyvinyl alcohol resin (A) 100 weight part, is more preferably below 20 weight parts.When the compounding amount of above-mentioned softening agent is too much, the hardness that there is film disappears and becomes reluctant tendency.Be explained, the lower value of softening agent is generally 0.5 weight part.

(3-3) filler

As above-mentioned filler, include, for example out the organic dust of starch (being not only various rough, also can be etherificate product, oxidation product, modification product), polymethylmethacrylate etc., the inorganic powder etc. of talcum, mica, silicon-dioxide etc.They can be used alone or and use with two or more.Wherein compatibly can use starch.

The compounding amount of filler compounding in above-mentioned polyvinyl alcohol resin (A) is preferably below 20 weight parts relative to polyvinyl alcohol resin (A) 100 weight part, is more preferably below 15 weight parts.When the compounding amount of above-mentioned filler is too much, there is the tendency that film strength reduces in practical.

(3-4) other additive

And then, can the scope of effect of the present invention suitably compounding antioxidant (phenol system, amine system etc.), stablizer (phosphoric acid ester etc.), colouring matter, spices, extender, defoamer, rust-preventive agent, UV light absorber do not hindered, also can suitably other other the additive such as water-soluble high-molecular compound (sodium polyacrylate, polyoxyethylene, Polyvinylpyrolidone (PVP), dextrin, chitosan, chitin, methylcellulose gum, Natvosol etc.) compounding.

There is the polyvinyl alcohol film of the present invention of above such technical scheme due to release property excellence; when making hot transfer film; even if be not situated between at releasing agent layer between curable resin layer and polyvinyl alcohol film, also can easily will be transferred to the curable resin layer (protective layer) on products formed surface and peel off as the polyvinyl alcohol film of basement membrane after hot transfer printing.

Be explained, polyvinyl alcohol film of the present invention is not only endowed release property excellent as described above, also maintain the characteristic that existing polyvinyl alcohol film has, namely, maintain wetting ability, water-soluble, the excellent specific property such as organic solvent resistance, barrier properties for gases, therefore be not defined for the basement membrane of hot transfer printing duplexer, can be used for the basement membrane of hydraulic-transfer duplexer yet, also can be used as the purposes of other polyvinyl alcohol film for purposes known at present.

[manufacture method of polyvinyl alcohol film]

Below, the manufacture method of polyvinyl alcohol film of the present invention is described.

First, according to the compounding above-mentioned polyvinyl alcohol resin (A) of compounding amount, nonionic system tensio-active agent (B) of regulation, and as required compounding other tensio-active agent (B '), softening agent, other additive etc., be dissolved in the water, thus prepared the polyvinyl alcohol resin aqueous solution.

As the concentration of the polyvinyl alcohol resin aqueous solution, be usually preferably 10 ~ 30 % by weight, be more preferably 15 ~ 25 % by weight., there is viscosity time too high and uprise and the tendency that is difficult to masking in the tendency that described concentration exists thickness stability time too low reduces.

Then, the polyvinyl alcohol resin aqueous solution is cast to masking band or on masking cylinder from T-shaped mould, makes it dry and film like, heat-treat further as required thus manufacture.

Herein, above-mentioned masking band refers to, has and is set up in endless belt between pair of rolls, that divide a word with a hyphen at the end of a line, and the polyvinyl alcohol resin aqueous solution curtain coating flowed out from T-shaped mould is made the masking band of its drying on endless belt.Above-mentioned endless belt preference is as being made up of stainless steel, and its outer surface implements the band of mirror finish.

In addition, above-mentioned masking cylinder refers to, the masking cylinder of the cylinder forming roll of rotation, and the polyvinyl alcohol resin water solution flow flowed out from T-shaped mould to be extended down on the swing roller forming roll of more than 1 and to make the masking cylinder of its drying by it.

When using masking band, drying temperature is preferably 80 ~ 160 DEG C usually, is more preferably 90 ~ 150 DEG C.There is the dry not enough and tendency of stripping dull from band when drying temperature is too low, time too high, there is the tendency that moisture rate becomes too low, film becomes fragile.

In addition, when using masking cylinder, masking first cylinder is preferably 80 ~ 100 DEG C usually, is more preferably 82 ~ 99 DEG C.Exist when drying temperature is too low dry not enough, from the tendency of the stripping dull of cylinder, time too high, there is the tendency that moisture rate becomes too low, film becomes fragile.Herein, above-mentioned masking first cylinder refers to, be positioned to the polyvinyl alcohol resin aqueous solution flowed out from T-shaped mould carry out curtain coating, the cylinder of the cylinder forming roll of side, most upstream.

After above-mentioned drying, heat-treat as required, as described heat-treating methods, include, for example out the methods such as hot-rolling (comprising stack), hot blast, far infrared rays, induction heating.In addition, the face of the opposition side, face that the face be heat-treated preferably contacts with masking band or masking cylinder.In addition, the water content implementing heat treated film is preferably 4 ~ 8 about % by weight usually.And then the water content of the film after thermal treatment is preferably 2 ~ 6 % by weight usually.

Be explained, the moisture rate of polyvinyl alcohol film such as can use Ka Er Fischer moisture determinator (capital of a country Electronics Industry Company system, " MKS-210 ") and measure.

Thermal treatment based on above-mentioned heat-treating machine is usually preferred to be carried out at 50 ~ 130 DEG C, more preferably carries out at 60 ~ 120 DEG C.That is, when above-mentioned heat treated temperature is too low, there is the face contacted with masking band or masking first cylinder and curling tendency occurs thus becomes not easily to process; When heat treated temperature is too high, because film becomes soft, when stretching to batch with not producing fold, observe the tendency of the orientation grow on long side direction (longitudinaldirection), reduced width.And then the time required for above-mentioned thermal treatment is relevant with its surface temperature when Heat treating roll, is usually set to 0.2 ~ 15 second, is preferably set to 0.5 ~ 12 second.Above-mentioned thermal treatment, normally after the dryer roll process for dry film, is then carried out by other Heat treating roll, floating type moisture eliminator (floatingdryer) etc. usually.

So polyvinyl alcohol film can be obtained.

The thickness of polyvinyl alcohol film of the present invention is preferably 15 ~ 100 μm, is more preferably 20 ~ 80 μm.

As the moisture rate of the polyvinyl alcohol film of above-mentioned gained, be preferably the scope of 0.5 ~ 8 % by weight, be more preferably 1 ~ 6 % by weight.There is the tendency become fragile when moisture rate is too low, when moisture rate is too high, there is the tendency of adhesion.

As the inflation method of the moisture rate of above-mentioned polyvinyl alcohol film, include, for example out following shown method.That is, according to the inflation method of following shown moisture rate, the moisture rate of the polyvinyl alcohol film in above-mentioned scope can be set as.

(i) by adjust up and down to the polyvinyl alcohol resin aqueous solution carry out drying and masking time dryer temperature, carry out the method for the humidification/dehumidifying of polyvinyl alcohol film and moisture rate adjusted.About the temperature of resin aqueous solution, its temperature has an impact to drying efficiency, is therefore adjusted to the scope of 70 ~ 98 DEG C.In addition, preferably, time dry, preferably between 150 ~ 50 DEG C, in the hot air dryer of more than at least 2 more preferably between 145 ~ 60 DEG C with thermograde, carry out drying, and then, preferably carry out the drying of 1 ~ 12 minute from the viewpoint of moisture adjustment, more preferably carry out the drying of 1 ~ 11 minute.

When the gradient scope of above-mentioned drying temperature is excessive or time of drying is long, there is dry excessive tendency, on the contrary the gradient scope of drying temperature too small or time of drying is too short time, there is dry not enough tendency.

Said temperature gradient is the thermograde periodically changing drying temperature between 150 ~ 50 DEG C, typically, slowly temperature is improved from drying starts, the highest drying temperature in the drying temperature scope temporarily set till reaching the water ratio of regulation, it is effective for then slowly reducing drying temperature and finally obtaining target water ratio.This carries out in order to crystallization control, release property, productivity etc., include, for example out 120 DEG C-130 DEG C-115 DEG C-100 DEG C, 130 DEG C-120 DEG C-110 DEG C, 115 DEG C-120 DEG C of-110 DEG C of-90 DEG C of isothermal gradients settings, can suitably select and implement.

(ii) by making polyvinyl alcohol film before batching by damping groove, carrying out the humidification/dehumidifying of polyvinyl alcohol film, carrying out the adjustment of moisture rate.

(iii) by batching polyvinyl alcohol film front or heat-treating after batching, and carry out the dehumidifying of polyvinyl alcohol film, thus carry out the adjustment of moisture rate.

In addition, polyvinyl alcohol film of the present invention, can as required and with the giving pears concavo-convex pattern such as (pearskin) pattern, embossed pattern, silk cloth pattern, and described concavo-convex pattern can use grain roller etc. to carry out.

In addition, polyvinyl alcohol film of the present invention directly can be used for various uses in the mode of unstretching film, in addition, also can the mode of uniaxial extension or biaxially-stretched film use.

When as stretched film, the applicable known method of drawing process, as general method, include, for example out the fixed stretching of (1) chuck, the stretching of (2) roll-type, the stretching of (3) tentering formula etc.(1) be suitable for the making of batch-wise stretched film, (2) are suitable for the stretching of single shaft.Device can become extensive in addition, but (3) are effective making in stretched film with technical scale.Also may be combined with (2) and (3) and successively carry out biaxial stretch-formed.Drawing process can adopt uniaxial extension, successively biaxial stretch-formed (SequentialBiaxialStretching), simultaneously biaxial stretch-formed in any one, biaxial stretch-formed wherein from the viewpoint of the homogeneity preferably combination (2) of thickness and (3).

From the viewpoint of the surface uniformity of film, total stretching ratio of described stretched film is preferably 1.5 ~ 16 times, is more preferably 2 ~ 12 times, more preferably 3 ~ 10 times.Or, be suitable for from the viewpoint of the surface uniformity of film: with stretching ratio for being preferably 1.5 ~ 10 times at longitudinal direction, being more preferably 2 ~ 8 times, more preferably 3 ~ 5 times, be preferably 1.5 ~ 10 times at transverse direction, be more preferably 2 ~ 8 times, more preferably the mode of 3 ~ 5 times stretch.When biaxial stretch-formed, from the viewpoint of the surface uniformity of film to be preferably 1.5 ~ 4 times at longitudinal direction, to be more preferably 2 ~ 3.5 times, be preferably 1.5 ~ 4 times at transverse direction, be more preferably the mode of 2 ~ 3.5 times and stretch, and then be more preferably identical multiplying power in length and breadth.When stretching ratio is too low, easy residual tensile is irregular, when stretching ratio is too high, there is film and becomes the tendency being easy to rupture.

About the preservation of polyvinyl alcohol film, preferably such as carry out the process of known water vapor proof barrier packaging, preserve with vacant state under the atmosphere of 10 ~ 25 DEG C.

[hot transfer printing duplexer]

Hot transfer printing duplexer of the present invention is for being laminated with the hot transfer printing duplexer of basement membrane [I], curable resin layer [II], printed layers [III].

(1) basement membrane [I]

As basement membrane [I], the polyvinyl alcohol film of the invention described above can be used.About described polyvinyl alcohol film, directly unstretching film can be used, also monadic stretching membrane or biaxially-stretched film can be used in addition.

In the present invention, the thickness of basement membrane [I] is particularly preferably set as, in the scope of 5 ~ 120 μm, being more preferably 10 ~ 100 μm.

In addition, in the present invention, the surfaceness (Ra) of curable resin layer [II] side of basement membrane [I] is preferably less than 1 μm from the viewpoint of surface luster property, is more preferably 0.001 ~ 0.7 μm, more preferably 0.01 ~ 0.5 μm.The tendency that surface luster property reduces is there is in described surfaceness (Ra) time excessive.Be explained, even if described surfaceness (Ra) is less than 0.001 μm, also there is the tendency almost not observing effects on surface glossiness and carry out improving.In described basement membrane [I], as the method surfaceness (Ra) of curable resin layer [II] side being adjusted to above-mentioned scope, can list: the method etc. the surfaceness of the casting belt (castingbelt) during the masking of basement membrane [I] being set to below 1S, stretching ratio during basement membrane [I] masking being set to the method for more than at least 1.5 times or both are combined.

Be explained, surfaceness (Ra) uses KEYENCECORPORATION system " colored 3D laser microscope VK-9700 ", is that benchmark measurement profile arithmetic average error (Ra) obtains according to JISB0601-2001.

(2) curable resin layer [II]

Described curable resin layer [II] becomes the layer on the most top layer of decorated molded article by peeling off basement membrane [I], time peeling off to basement membrane [I] or peel off after fixing, becomes the protective layer on the surface for the protection of transfer printing body.

As the material forming curable resin layer [II], include, for example out: these thermoplastic resins of polyacrylics, vibrin, polyvinyl chloride (PVC) RESINS, celluosic resin, rubber resin, urethane resin, vinylite, ultra-violet solidified resin composition, electron(beam)curing resin combination isoreactivity energy ray-curable resin combination, compositions of thermosetting resin etc.As protective layer, from the viewpoint of imparting chemical-resistant, wear resistant, preferably use actinic energy ray curable resion composition.

Described actinic energy ray curable resion composition is such as preferably the actinic energy ray curable resion composition containing acrylic resin and ammonia ester (methyl) acrylate based compound.

As described acrylic resin, include, for example out: the acrylic copolymer etc. being copolymer composition with the homopolymer of acrylic ester monomer or multipolymer, other ethylenically unsaturated monomer.

As acrylic ester monomer, include, for example out (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) Ethyl acrylate, (methyl) 2-EHA, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, (methyl) benzyl acrylate, (methyl) cyclohexyl acrylate, (methyl) acrylate, (methyl) Isooctyl acrylate monomer, (methyl) n-octyl, (methyl) lauryl acrylate, (methyl) vinylformic acid 2-methoxy acrylate, (methyl) acrylate, butoxy ethyl, (methyl) methoxyethyl triglycol ester etc., wherein the carbonatoms of preferred alkyl is the alkyl acrylate of 1 ~ 12, more preferably (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) 2-EHA.

As other ethylenically unsaturated monomer, include, for example out: (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 3-chlorine 2-hydroxypropyl acrylate, (methyl) vinylformic acid tetrahydro furfuryl ester, (methyl) vinylformic acid 2-hydroxyl 3-phenoxy-propyl, (methyl) vinylformic acid binaryglycol ester, (methyl) polyalkylene glycol acrylate ester, the unsaturated monomer of the hydroxyls such as N-methylol (methyl) acrylamide, glycidyl methacrylate, methacrylic acid allyl glycidyls etc. contain the unsaturated monomer of glycidyl, 2-acryloyloxyethyl isocyanate, the unsaturated monomer containing isocyanate group such as 2-methacryloxyethyl isocyanic ester, acrylamide, Methacrylamide, N-(n-butoxy alkyl) acrylamide, the unsaturated monomer of the amide-containings such as N-(n-butoxy alkyl) Methacrylamide, acrylamido-3-methyl butyl methylamine, dimethylamino acrylamide, dimethylamino Methacrylamides etc. contain amino unsaturated monomer, ethylene-sulfonic acid, allyl sulphonic acid, the alkene sulfonic acids such as methallylsulfonic acid, 2-acrylamide-2-methylpro panesulfonic acid, styrene sulfonic acid or its salt etc. contain sulfonic unsaturated monomer, vinylbenzene, vinyl-acetic ester, vinyl cyanide, acrylamide etc.

Contain proportional (copolymerization ratio) of described acrylic ester monomer and other ethylenically unsaturated monomer is not particularly limited, such as, preferred acrylate system monomer is 20 ~ 100 % by weight, other ethylenically unsaturated monomer is 0 ~ 80 % by weight, more preferably acrylic ester monomer is 40 ~ 100 % by weight, other ethylenically unsaturated monomer is 0 ~ 60 % by weight, and further preferred acrylate system monomer is 80 ~ 100 % by weight, other ethylenically unsaturated monomer is 0 ~ 20 % by weight.Acrylic ester monomer containing proportional very few time, there is the tendency that the weather resistance such as the water tolerance/humidity resistance of the cured article (protective layer) of curable resin layer reduces.

Above-mentioned acrylic resin can be as free-radical polymerized in made aforementioned polymeric composition carry out in organic solvent, the method known by those skilled in the art and easily manufacturing.

As the acrylic resin used in actinic energy ray curable resion composition, its second-order transition temperature (Tg) is preferably 20 ~ 130 DEG C, is more preferably 30 ~ 120 DEG C, more preferably 40 ~ 110 DEG C.When second-order transition temperature (Tg) is too low, the curable resin layer that there is actinic energy ray curable resion composition etc. causes occurring when implementing post-treatment the tendency of bad phenomenon (in operation for reel/print bad etc.) with tackiness; Time too high, there is the tendency become fragile when making the curable resin layer of actinic energy ray curable resion composition etc. solidify and become protective layer.

In addition, the weight-average molecular weight (Mw) of acrylic resin is preferably 10000 ~ 500000, is more preferably 20000 ~ 100000, and more preferably 30000 ~ 80000.

When the weight-average molecular weight (Mw) of described acrylic resin is too small,, therefore there is the tendency that bad phenomenon (winding in operation/print bad etc.) occurs when to implement post-treatment on this layer in the curable resin layer softnessization before solidification with tackiness; Time excessive, exist and be inclined to as follows: being difficult to obtain film uniformity and the hardness of dried film when being coated with curable resin layer higher than aequum, bad phenomenon (be full of cracks/splitting etc. of film occurs) occurs when causing implementing post-treatment.

Ammonia ester (methyl) acrylate based compound is (methyl) acrylate based compound in molecule with ammonia ester bond, manufactures by making (methyl) acrylic compounds containing hydroxyl and polyisocyanate compound and polyol reaction as required.

As above-mentioned (methyl) acrylic compounds containing hydroxyl, include, for example out (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 2-hydroxy butyl ester, (methyl) vinylformic acid 4-hydroxy butyl ester, the own ester of (methyl) vinylformic acid 6-hydroxyl, 2-(methyl) acryloyl-oxyethyl-2-hydroxypropylphthalate, 2-hydroxyl-3-(methyl) acryloxy (methyl) propyl acrylate, caprolactone modification 2-hydroxyethyl (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, caprolactone modification Dipentaerythritol five (methyl) acrylate, caprolactone modification tetramethylolmethane three (methyl) acrylate, ethylene oxide denatured Dipentaerythritol five (methyl) acrylate, ethylene oxide denatured tetramethylolmethane three (methyl) acrylate etc., wherein preferably use (methyl) acrylic compounds with the hydroxyl of the acryl of more than 3.In addition, they can use a kind or combine two or more use.

As above-mentioned polyisocyanate compound, include, for example out fragrant family, fat family, the polyisocyanates such as ester ring type system, wherein list: tolylene diisocyanate, diphenylmethanediisocyanate, hydrogenated diphenyl methane diisocyanate, many phenylmethanes polyisocyanates, modified diphenylmethane diisocyanate, the sub-dimethyl vulcabond of hydrogenation of benzene, Xylene Diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, tetramethylxylene diisocyanate, isophorone diisocyanate, norbornylene vulcabond, two (isocyanatomethyl) hexanaphthene of 1,3-, phenylene vulcabond, lysinediisocyanate, Lysine triisocyanate, the trimer compound of the polyisocyanates such as naphthalene diisocyanate or these polyisocyanates or polymer compound, biuret form polyisocyanates, water dispersive polyisocyanate (" Aquanate100 " of such as, NipponPolyurethaneIndustryCo., Ltd., " Aquanate110 ", " Aquanate200 ", " Aquanate210 " etc.), or the reaction product etc. of these polyisocyanates and polyvalent alcohol.

As described polyvalent alcohol, include, for example out: ethylene glycol, Diethylene Glycol, triethylene glycol, TEG, polyoxyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butyleneglycol, polytetramethylene glycol, 1,6-hexylene glycol, neopentyl glycol, cyclohexanedimethanol, Hydrogenated Bisphenol A, polycaprolactone, trimethylolethane, TriMethylolPropane(TMP), many TriMethylolPropane(TMP)s, tetramethylolmethane, many tetramethylolmethanes, sorbyl alcohol, N.F,USP MANNITOL, glycerine, poly-glycerine, the polyvalent alcohols such as polytetramethylene glycol, have polyoxyethylene, polyoxypropylene, the polyether glycol of at least a kind of structure in the block of ethylene oxide/propylene oxide or random copolymerization, this polyvalent alcohol or polyether glycol and maleic anhydride, toxilic acid, fumaric acid, itaconic anhydride, methylene-succinic acid, hexanodioic acid, the polyester polyol of the condenses of the polyprotonic acids such as m-phthalic acid, the caprolactone modification polyvalent alcohols such as caprolactone modification polytetramethylene polyol, polyolefin polyvalent alcohol, the polyhutadiene system polyvalent alcohols etc. such as hydrogenation polybutadiene polyol.

And then, as described polyvalent alcohol, such as also can list: 2,2-two (methylol) butyric acid, tartrate, 2,4-resorcylic acid, 3,5-resorcylic acid, 2, two (methylol) propionic acid, 2 of 2-, two (hydroxyethyl) propionic acid, 2 of 2-, 2-two (hydroxypropyl) propionic acid, dihydroxymethyl acetic acid, two (4-hydroxy phenyl) acetic acid, 4, the two carboxylic polyvalent alcohol such as (4-hydroxy phenyl) valeric acid, homogentisic acid etc. of 4-, BDO sodium sulfonate etc. contain the polyvalent alcohol etc. of sulfonic group or azochlorosulfonate acid alkali.

When using the reaction product of polyisocyanates and polyvalent alcohol, such as, above-mentioned polyvalent alcohol and above-mentioned polyisocyanates is made to carry out reacting and the end that obtains contains the polyisocyanates of isocyanate group.In the reaction of described polyisocyanates and polyvalent alcohol, the amine series catalysts etc. that the metal catalyst also preferably using dibutyl tin laurate such for the purpose of promoting to react, 1,8-diazabicyclo [5.4.0] 11 carbon-7-alkene are such.

As the manufacture method of above-mentioned ammonia ester (methyl) acrylate based compound, include, for example out: by (methyl) acrylic compounds of hydroxyl and polyisocyanate compound mixing under non-active gas atmosphere, usually with 30 ~ 80 DEG C of reactions method of 2 ~ 10 hours.In this reaction, preferably use the polyurethane-reinforcement catalyzer such as octylenic acid tin, di-n-butyltin dilaurate, lead octoate 36, potassium octanoate, Potassium ethanoate, stannous octoate, Triethylene Diamine.

The weight-average molecular weight of ammonia ester (methyl) acrylate based compound is preferably 300 ~ 4000, is more preferably 1000 ~ 3500, and more preferably 1200 ~ 3000.Exist the hypodynamic tendency of cohesion after the solidification of curable resin layer when described weight-average molecular weight is too small, time excessive, there is the tendency that viscosity becomes too high, is difficult to manufacture.

Be explained, above-mentioned weight-average molecular weight refers to the weight-average molecular weight obtained according to the conversion of polystyrene standard molecular weight, the chromatographic column of 3 series connection is used: ShodexGPCKF-806L (exclusion limit molecular weight: 2 × 10 in high performance liquid chromatograph (Showa electrician Inc., " ShodexGPCsystem-11 type ") ⁷, separating ranges: 100 ~ 2 × 10 ⁷, theoretical plate number: 10000 column plates/root, weighting agent material: styrene diethylene benzene copoly mer, weighting agent particle diameter: 10 μm) and to measure.

Thus, the actinic energy ray curable resion composition containing acrylic resin and ammonia ester (methyl) acrylate based compound can be obtained, but when actinic energy ray curable resion composition is ultra-violet solidified resin composition, preferably further containing Photoepolymerizationinitiater initiater.Then Photoepolymerizationinitiater initiater is not needed when electron(beam)curing resin combination.

As described Photoepolymerizationinitiater initiater, include, for example out: diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, benzil dimethyl ketal, 4-(2-hydroxyl-oxethyl) phenyl-(2-hydroxyl-2-propyl group) ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-(4-methylthio group phenyl)-2-morpholine propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl) butanone, the acetophenones such as 2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] acetone oligopolymer, bitter almond oil camphor, benzoin methylether, ethoxybenzoin, benzoin iso-propylether, the bitter almond oil camphor classes such as benzoin isobutyl ether, benzophenone, o-benzoyl yl benzoic acid methyl esters, 4-phenyl benzophenone, 4-benzoyl-4 '-methyl-diphenyl sulfide, 3,3 ', 4,4 '-four (tert-butyl hydroperoxide carbonyl) benzophenone, 2,4,6-tri-methyl benzophenone, 4-benzoyl-N, N-dimethyl-N-[2-(1-oxo-2-propenyl oxygen base) ethyl] xylylene Benzylphosphonium Bromide ammonium, the benzophenones such as (4-benzoylbenzyl) trimethyl ammonium chloride, ITX, ITX, 2,4-diethyl thioxanthone, 2,4-bis-clopenthixal ketone, the chloro-4-propoxythioxanthone of 1-, the thioxanthene ketones such as 2-(3-dimethylamino-2-hydroxyl)-3,4-dimethyl-9H-thioxanthone-9-ketone methochloride, 2,4,6-trimethylbenzoy-dipheny phosphine oxides, two (2,6-Dimethoxybenzoyl)-2,4,4-trimethyl-pentyl phosphine oxide, the acylphosphine oxide classes etc. such as two (2,4,6-trimethylbenzoyl)-phenyl phosphine oxide.Be explained, these Photoepolymerizationinitiater initiaters can only be used alone a kind, also can and use two or more.

In addition, as their auxiliary agent, also can and use: trolamine, tri-isopropanolamine, 4,4 '-dimethylamino benzophenone (michaelis ketone), 4,4 '-diethylamino benzophenone, 2-dimethyl aminoethyl phenylformic acid, EDMAB, 4-dimethylaminobenzoic acid (n-butoxy) ethyl ester, 4-dimethylaminobenzoic acid isopentyl ester, 4-dimethylaminobenzoic acid 2-ethylhexyl, 2,4-diethyl thioxanthone, 2,4-diisopropylthioxanthone etc.

Among them, preferably use benzil dimethyl ketal, 1-hydroxycyclohexylphenylketone, benzoyl isopropyl ether, 4-(2-hydroxyl-oxethyl)-phenyl (2-hydroxyl-2-propyl group) ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone.

In the present invention, the thickness of curable resin layer [II] is preferably 1 ~ 150 μm from the viewpoint of wear resistant, chemical-resistant, is more preferably 2 ~ 120 μm, more preferably 2 ~ 100 μm.There is the tendency that wear resistant reduces, chemical-resistant reduces in described thickness, then tends to the variation of the film breaks after becoming transfer printing, causes the reason of burr etc. time blocked up when crossing thin.

When forming curable resin layer [II], above-mentioned material resin or material resin composition are passed through the coating methods such as photogravure coating method, rolling method, stick coating method, scraper for coating method, lip coating method, and the print process such as gravure processes, silk screen print method is carried out stacked.

When employing above-mentioned actinic energy ray curable resion composition; after the upper stacked layer (curable resin layer [II]) formed by actinic energy ray curable resion composition of basement membrane [I]; printed layers [III] is needed on transfer printing body; can time being stripped to basement membrane [I], any stage irradiates active energy beam and makes it solidify; also can irradiate active energy beam afterwards in stripping basement membrane [I] and make it solidify, thus make protective layer (hard coat).

Such as can carry out as follows: (a) after stacked actinic energy ray curable resion composition layer, irradiates active energy beam and solidify on basement membrane; B () after stacked actinic energy ray curable resion composition layer, forms printed layers described later on basement membrane, irradiate active energy beam thereafter and solidify from basement membrane side; Irradiate active energy beam from basement membrane side c () is laminated to adhesive linkage described later further after and solidify; Irradiate active energy beam from basement membrane side d () makes transfer printing duplexer of the present invention be adhered to transfer printing body after and solidify; E () makes transfer printing duplexer of the present invention be adhered to transfer printing body after, peel off basement membrane and irradiate active energy beam and solidify.From the viewpoint of the followability to transfer printing body during hot transfer printing, preferably make it in the method for (d) or (e) of transfer printing after fixing, more preferably the method for (e).Be explained, transfer printing duplexer of the present invention can supply in the mode of the duplexer after the solidification of curable resin layer as above-mentioned (a) ~ (c), preferably supplies in the mode of the duplexer containing the curable resin layer before solidification as above-mentioned (d) and (e).

Be explained, when curable resin layer being solidified irradiating active energy beam, as active energy beam, such as, the light such as far ultraviolet rays yue, ultraviolet, near-ultraviolet ray, infrared rays can be utilized, the hertzian wave such as X-ray, gamma-rays, electron rays, proton radiation, neutron ray etc. can be utilized in addition, consider the acquisition easness, price etc. of curing speed, irradiating unit, the solidification based on uviolizing is favourable.

The method of solidifying as being made it by uviolizing, as long as use the high pressure mercury vapour lamp, extra-high-pressure mercury vapour lamp, carbon arc lamp, metal halide lamp, xenon lamp, chemical lamp etc. that send the light of 150 ~ 450nm wavelength region may, with 0.01 ~ 10J/cm ²degree carry out irradiating.After uv irradiation, also can carry out as required heating and seeking to solidify completely.

(3) printed layers [III]

Printed layers [III] is for being printed with the layer of pattern etc., as the material of printed layers, can use: containing resins such as polyethylene base system resin, polyamide series resin, polyester based resin, acrylic resin, polyurethane series resin, polyvinyl acetal system resin, polyester-polyurethane system resin, cellulose ester system resin, Synolac as binding agent, the pigment containing appropriate color or dyestuff are as the painted ink of tinting material.

As the formation method of printed layers [III], the common print processes etc. such as flexographic printing process, gravure processes, silk screen print method can be used.Particularly, in order to carry out polychrome printing, tone performance, flexographic printing process, gravure processes are applicable.

(4) adhesive linkage [IV]

Transfer printing duplexer of the present invention for being laminated with the transfer printing duplexer of above-mentioned basement membrane [I], curable resin layer [II], printed layers [III], preferably on upper strata lamination adhesive layer [IV] of printed layers [III].

Adhesive linkage [IV] makes above-mentioned duplexer be adhered to and is transferred dignity.Can be formed when the bonding force of printed layers and products formed is weak.As the material of adhesive linkage [IV], as long as suitably use and be suitable for the raw-material thermo-sensitivity of transfer printing body or the resin of pressure-sensitive, include, for example out polyester based resin, acrylic resin, polystyrene resin, polyamide series resin, chlorinated polyolefin resin, ethylene chloride-vinyl acetate copolymer resin, thermoprene, coumarone indeneresin (coumarone-indeneresin) etc.

As the formation method of adhesive linkage [IV], the coating methods such as photogravure coating method, rolling method, stick coating method, scraper for coating method can be listed, the print process such as gravure processes, silk screen print method.In addition, to fit the sheet material with cementability that formed by above-mentioned material and make adhesive linkage [IV] by laminating etc.In addition, adhesive linkage [IV] also can double as printed layers [III].

The thickness of adhesive linkage [IV] is preferably 0.5 ~ 50 μm from the viewpoint of to the followability of adherend, is more preferably 1 ~ 40 μm, more preferably 2 ~ 30 μm.When described thickness is crossed thin, there is the tendency that cost uprises in the tendency reduced the followability of adherend when there is transfer printing, and uneconomical time blocked up.

[using method of hot transfer printing duplexer of the present invention: thermal transfer]

The heat-transferring method employing hot transfer printing duplexer of the present invention is described.

(1) to the method being transferred dignity and decorating

First, the transfer printing layer of transfer printing duplexer (being adhesive linkage [IV] when transfer printing layer has adhesive linkage [IV], is printed layers [III] when not having adhesive linkage [IV]) is closely attached on is transferred dignity.Then, use possesses the transfer machines such as the elastomeric roller transfer machine of the heat resistant rubber shapes such as silicon rubber, up and down transfer machine, via temperature being set as about 80 ~ 270 DEG C, pressure setting is the heat resistant rubber shape elastomerics of the condition of about 490 ~ 1960Pa, applies heat and pressure from basement membrane [I] side of transfer printing duplexer.By such operation, adhesive linkage [IV] or printed layers [III] is made to be adhered to transfer printing body surface.

After the cooling period; by active energy beam irradiation etc. make curable resin layer [II] solidify and after making protective layer (hard coat); when finally peeling off basement membrane [I]; cause stripping at the interface of basement membrane [I] and protective layer (the curable resin layer [II] after solidification: hard coat), transfer printing terminates.

(2) utilize based on injection molding shaping while the face of transfer printing to the synthetic resin as the transfer printing body method of decorating

The following describes following method: use transfer printing duplexer of the present invention, utilize based on injection molding shaping while the face of transfer printing to the synthetic resin as the transfer printing body method of decorating.

First, be that the mode of fixed mould (being generally former) side is sent in mold for forming with basement membrane by transfer printing duplexer.The feeding of transfer printing duplexer can be sent into a sheet by a sheet by the transfer printing duplexer of monolithic, also can be intermittently sent into by the necessary part of the duplexer of long size.When using the transfer printing duplexer of long size, the transporter with locating mechanism can be used, carrying out the printed layers [III] of transfer printing duplexer and the alignment of orientation (register) of mold for forming.In addition, when transfer printing duplexer is sent into off and on, as long as with moveable die (former) and fixed mould (formpiston) stationary transfer duplexer detect the position of transfer printing duplexer with sensor after, due to often can at same position stationary transfer duplexer, there is not the dislocation of printed layers [III], thus convenient.

After closed moulding mould, from cast gate, the injection of the moulding resin of melting is filled in mould, thus makes transfer printing body shaping.Side by side send into transfer printing duplexer with the shaping of transfer printing body, be adhered to transfer printing body surface.

As the moulding resin of material becoming transfer printing body, the resins for universal use such as polystyrene resin, polyolefin-based resins, ABS resin, AS resin, AN resin can be listed.In addition, also the general engineering resin such as polyphenylene oxide-polystyrene system resin, polycarbonate-based resin, polyacetal system resin, acrylic resin, polycarbonate modified polyphenylene oxide resin, polybutylene terephthalate resin, polyvinyl resin with super-high molecular weight can be used, the special engineered resins such as polysulfone resin, polyphenylene sulfide system resin, Polyphony Ether resin, polyarylate resin, polyetherimide resin, polyimide resin, liquid-crystal polyester resin, polyallyl system heat stable resin.Also can use the compound resin that with the addition of the strongthener such as glass fibre, mineral filler.By the transfer printing body of these resin formation can be transparent, translucent, opaque in any one.In addition, transfer printing body can be painted, also can not be painted.

Using after the synthetic resin cooling of transfer printing body, open mold for forming and take out synthetic resin.The basement membrane of transfer printing duplexer of the present invention and the stripping strength of curable resin layer very little compared to the stripping strength between transfer printing body and transfer printing layer, thus, in the method be continuously fed at hot transfer printing duplexer, the stripping of curable resin layer and basement membrane is caused when the demoulding of products formed.Even if when hot transfer film is sent into single chip mode, also from taken out products formed, only basement membrane can be peeled off simply.

By such operation, the products formed that curable resin layer is most top layer can be obtained.When the solidification of the moment curable resin layer of the demoulding, taking-up does not terminate, it is then made to have solidified.Curable resin layer [II] after solidification becomes the protective layer of products formed.

Such operation and the decorated molded article obtained is also excellent in surface luster.Reason is not yet clear and definite, but in view of fine concavo-convex (be specifically less than 1 μm concavo-convex) of glossiness by film coated surface obtains, can think this is because: can be situated between basement membrane and curable resin layer at oozed out tensio-active agent, thus the curable resin preventing solidification not terminate when basement membrane is peeled off is pullled to basement membrane, or the fold that inhibit basement membrane related during the solidification of being cured property resin while shaping.

Embodiment

Below enumerate embodiment and specifically describe the present invention further, but the present invention only otherwise exceeding its purport is not just limited to following embodiment.

Be explained, in example, " part ", " % " represent weight basis.

[evaluation of measuring method]

(1) evaluation method of polyvinyl alcohol film

(1-1) stripping strength (g/24mm)

By PVA (PVOH) FILM 23 DEG C, place 24 hours under 50%RH environment after, in the present context by the glass ribbon (NichibanCo. of width 24mm, Ltd. Cellotape processed (registered trademark) LP-24) be cut to length 10cm, utilize the roller of 2kg to carry out air surface that described glass ribbon is attached at PVA (PVOH) FILM by 1 back and forth.Then use tensile testing machine, glass ribbon is peelled off from face by the speed to the directions of 90 degree with 300mm/ second, measures using average load when now peelling off 30mm as stripping strength.

(1-2) resistance to blocking

The sample strip of 100mm × 100mm is cut out from PVA (PVOH) FILM.For 2 sample strip, by the face of air surface side during manufacture film and the face overlap of side, curtain coating face, carry out damping in 24 hours under 23 DEG C × 60%RH after, under the environment of 23 DEG C × 60%RH, carry the hammer of 500g as former state from top, placed 24 hours further.Thereafter, according to situation during 2 sample strip overlapping with hand stripping, according to following benchmark, resistance to blocking is evaluated.

Zero: the degree that overall separation only occurs when attempting stripping film, sample strip is not adhered each other substantially.

△: tackiness is the degree that when catching a sample strip upwards to mention, the sample strip of opposite side just falls.

×: the stripping of sample needs the degree of effort, and sample strip is adhered each other.

(2) evaluation of transfer printing duplexer

The making > of < transfer printing duplexer

Using PVA (PVOH) FILM as basement membrane [I], bar coater is utilized to be coated on this basement membrane [I] by actinic energy ray curable resion composition in the mode that thickness is 160 μm, and by it 80 DEG C of dryings 15 minutes, thus produce the duplexer (α) of the curable resin layer [II] being laminated with thickness 80 μm on basement membrane [I].

On curable resin layer [II] face of duplexer (α), use printing ink to form cancellate pattern by gravure processes, obtain the duplexer (β) formed by basement membrane [I]/curable resin layer [II]/printed layers [III].

And then, by bar coater, above-mentioned thermo-compressed adhesive linkage coating fluid is coated on printed layers [III] face of duplexer (β) in the mode of thickness 100 μm, and by it 80 DEG C of dryings 15 minutes, form the thermo-compressed adhesive linkage [IV] of thickness 20 μm, obtain the duplexer (γ) formed by basement membrane [I]/curable resin layer [II]/printed layers [III]/adhesive linkage [IV].

In the drying machine being heated to 130 DEG C, duplexer (γ) and blue or green sheet glass substrate (thickness 2.8mm) are carried out preheating in 3 minutes, the thermo-compressed caking agent of duplexer (γ) is melted, with hand roller (handroller), signature is pressed on blue or green sheet glass substrate in this adhesive linkage [IV] face, thus produce laminating sample.

For obtained laminating sample, irradiate the ultraviolet of 1000mJ across basement membrane [I], make curable resin layer [II] be solidified to form protective layer (the curable resin layer after solidification: hard coat).After forming protective layer, as following, the protective layer after stripping basement membrane is evaluated.

The evaluation > of < protective layer

(2-1) the surface luster property of protective layer

Make the face reflector fluorescent light of protective layer (the curable resin layer after solidification), evaluated according to the clarity of following benchmark to luminescent lamp by visual observation.

Zero: the profile clearly can seeing luminescent lamp.

△: the soft edge of luminescent lamp.

×: the profile that cannot confirm luminescent lamp.

(2-2) image definition (imageclarity) of protective layer

For the face of protective layer (the curable resin layer after solidification), use the image definition determinator ICM-1DP of SugaTestInstrumentsCo., Ltd., measure under the following conditions, evaluate by following benchmark.

(condition determination)

Measuring method: reflection

Measure angle: 45 ° of incidences, 45 ° of reception light

Slit (slit): 0.03mm

Measure hole: 20mm

Light comb width (opticalcombwidth): 2.0mm

Image definition: C=[(M-m)/(M+m)] × 100 (%)

C: the picture boldness (%) during light comb width (mm)

M: the highest light quantity during light comb width (mm)

M: minimum light quantity during light comb width (mm)

(metewand)

More than S:90% rank

A:70 ~ lower than 90% rank

B:30 ~ lower than 70% rank

C: lower than 30% rank

[making of PVA (PVOH) FILM No.1-7 and evaluation]

To in the polyvinyl alcohol (A) 100 parts of average viscosity (20 DEG C) with saponification deg such shown in table 1 and 4% aqueous solution, according to the compounding polyoxyalkylene alkyl with characteristic shown in table 1 (oxygen ethylidene and oxygen propylidene containing proportional, weight-average molecular weight, HLB) of the amount shown in table 1, further interpolation, as 0.3 part, the polyoxy alkylamino ether (B '-1) of nonionic system tensio-active agent (B '), the glycerine 1 part as softening agent, has prepared the polyvinyl alcohol resin aqueous solution (doping) of solid constituent concentration 18%.

This polyvinyl alcohol resin solution is spued to surface temperature from T-shaped mould and is adjusted to the stainless steel endless belt of the rotation of 90 DEG C, carry out casting film, obtain the PVA (PVOH) FILM of thickness shown in table 1.For obtained PVA (PVOH) FILM, based on above-mentioned evaluation method, stripping strength and resistance to blocking are evaluated.Show the result in table 1.

[the transfer printing making of duplexer No.1-7 and evaluation]

The PVA (PVOH) FILM No.1-7 of above-mentioned making is used as basement membrane [I], and the making method based on above-mentioned transfer printing duplexer makes transfer printing duplexer, evaluates based on above-mentioned evaluation method effects on surface glossiness, image definition.Result is merged and is shown in table 1.

Be explained, form the active energy beam resin combination of curable resin layer [II], black for the appearance design printing of printed layers [III], prepare as in the following manner for the adhesive linkage coating fluid of adhesive linkage [IV].

(1) actinic energy ray curable resion composition

To with 2-butanone with in the solution that all admittedly the constituent concentration mode that becomes 50% is carried out dilution mixture and obtained the solid composition 50 parts of the polymethylmethacrylate " MN " of KANEKACORPORATION, the solid composition 40 parts of the urethane acrylate " UV-3520 " of Japanese synthetic chemical industry Inc. and the photopolymerization monomer " Biscoat#300 " 10 parts of Osaka Organic Chemical Industry Inc., mix Chang Lai industry companies system " IRGACURE819 " as Photoepolymerizationinitiater initiater in the mode that is 3 parts relative to solid composition 100 parts.

(2) appearance design printing ink

Prepare the intaglio printing ink comprising black pigment 10 parts, Nitrocellulose 5 parts, Synolac 15 parts, toluene 30 parts, ethyl acetate 30 parts, Virahol 10 parts.

(3) adhesive linkage coating fluid

POLYESTER " SP-185 " (vibrin) of Japanese synthetic chemical industry Inc. is become mode stirring and dissolving under heating flooding disaster of 20% with the mixed solvent of 4: 1 (weight ratios) relative to toluene and 2-butanone.

Table 1

Relative to polyvinyl alcohol 100 mass parts, by containing more than 1 mass parts, the stripping strength of nonionic system tensio-active agent (B) with oxygen ethylidene and oxygen propylidene and polyvinyl alcohol film No.1-4 that the composition that obtains is formed, with by more than compounding 1 mass parts, only there is the nonionic system tensio-active agent of any one in oxygen ethylidene or oxygen propylidene and the stripping strength of polyvinyl alcohol film No.5, No.6 that the composition that obtains is formed is in a ratio of less than 1/10, its release property known is excellent.In addition, even when employing nonionic system tensio-active agent (B) with oxygen ethylidene and oxygen propylidene, the No.7 containing quantity not sufficient 1 mass parts does not find the reduction of stripping strength yet.Therefore known, the attenuating of nonionic system tensio-active agent that contain more than 1 mass parts relative to polyvinyl alcohol 100 mass parts, that have oxygen ethylidene and oxygen propylidene for stripping strength is effective.In addition, containing more than 1 mass parts, the nonionic system tensio-active agent with oxygen ethylene units and oxygen propylene unit there is no impact for the resistance to blocking relevant to polyvinyl alcohol film adhesion each other.

In addition we know, about transfer printing duplexer, when the hot transfer film No.1-4 using stripping strength little, compared with the situation of the hot transfer film No.5-7 large with using stripping strength, its surface luster, image definition excellence.

utilizability in industry

Polyvinyl alcohol film of the present invention, due to release property excellence, thus can be used as the basement membrane every film, transfer film.

Claims (13)

1. a polyvinyl alcohol film, is characterized in that, nonionic system tensio-active agent (B) containing 1 ~ 20 weight part relative to unmodified polyethylene alcohol system resin (A) 100 weight part forms,

This nonionic system tensio-active agent (B) containing aerobic ethylidene and oxygen propylidene,

Described nonionic system tensio-active agent (B) is for being selected from least a kind in the group that is made up of the alkyl oxide (B1) of addition aerobic ethylidene and oxygen propylidene, addition aerobic ethylidene and the fatty acid ester (B2) of oxygen propylidene and the polyol ethers (B3) of addition aerobic ethylidene and oxygen propylidene

And the structural unit number of the structural unit number of oxygen ethylidene and oxygen propylidene add up to 20 ~ 100.

2. polyvinyl alcohol film according to claim 1, is characterized in that, the structural unit number of the oxygen ethylidene in nonionic system tensio-active agent (B) is 1 ~ 70, and the structural unit number of oxygen propylidene is 1 ~ 70.

3. polyvinyl alcohol film according to claim 1, is characterized in that, the oxygen ethylidene in nonionic system tensio-active agent (B) and oxygen propylidene containing proportional with molar ratio computing oxygen ethylidene/oxygen propylidene for 10/90 ~ 90/10.

4. polyvinyl alcohol film according to claim 1, is characterized in that, the HLB of nonionic system tensio-active agent (B) is 2 ~ 18.

5. the polyvinyl alcohol film according to any one of Claims 1 to 4, it is hydrophilic portion with polyoxyethylene blocks, take oxypropylene block as hydrophobic portion.

6. the polyvinyl alcohol film according to any one of Claims 1 to 4, is characterized in that, the saponification deg of described unmodified polyethylene alcohol system resin (A) is more than 70 % by mole.

7. the polyvinyl alcohol film according to any one of Claims 1 to 4, is characterized in that, at 20 DEG C of described unmodified polyethylene alcohol system resin (A), 4 % by weight solution viscosities are 5 ~ 70mPas.

8. a polyvinyl alcohol film, is characterized in that, its nonionic system tensio-active agent (B) containing 1 ~ 20 weight part relative to unmodified polyethylene alcohol system resin (A) 100 weight part forms,

This nonionic system tensio-active agent (B) containing aerobic ethylidene and oxygen propylidene,

Described nonionic system tensio-active agent (B) is for being selected from least a kind in the group that is made up of the alkyl oxide (B1) of addition aerobic ethylidene and oxygen propylidene, addition aerobic ethylidene and the fatty acid ester (B2) of oxygen propylidene and the polyol ethers (B3) of addition aerobic ethylidene and oxygen propylidene

And the structural unit number of the structural unit number of oxygen ethylidene and oxygen propylidene add up to 20 ~ 100,

The structural unit number of the oxygen ethylidene in described nonionic system tensio-active agent (B) is 1 ~ 70, the structural unit number of oxygen propylidene is 1 ~ 70, this oxygen ethylidene and oxygen propylidene containing proportional with molar ratio computing oxygen ethylidene/oxygen propylidene for 10/90 ~ 90/10.

9. polyvinyl alcohol film according to claim 8, wherein, the hydrophilic portion of described nonionic system tensio-active agent (B) is polyoxyethylene blocks, and hydrophobic portion is oxypropylene block, and HLB is 2 ~ 18.

10. the manufacture method of a polyvinyl alcohol film, it is characterized in that, the polyvinyl alcohol resin aqueous solution containing nonionic system tensio-active agent (B) of 1 ~ 20 weight part relative to unmodified polyethylene alcohol system resin (A) 100 weight part is made to carry out curtain coating and masking, this nonionic system tensio-active agent (B) is containing aerobic ethylidene and oxygen propylidene

Described nonionic system tensio-active agent (B) is for being selected from least a kind in the group that is made up of the alkyl oxide (B1) of addition aerobic ethylidene and oxygen propylidene, addition aerobic ethylidene and the fatty acid ester (B2) of oxygen propylidene and the polyol ethers (B3) of addition aerobic ethylidene and oxygen propylidene

And the structural unit number of the structural unit number of oxygen ethylidene and oxygen propylidene add up to 20 ~ 100.

The manufacture method of 11. polyvinyl alcohol films according to claim 10, is characterized in that, the concentration of the polyvinyl alcohol resin aqueous solution is 10 ~ 30 % by weight.

12. 1 kinds of transfer printing duplexers, is characterized in that, are sequentially laminated with basement membrane [I], curable resin layer [II], printed layers [III] that the polyvinyl alcohol film according to any one of claim 1 ~ 9 is formed.

13. transfer printing duplexers according to claim 12, is characterized in that, the surface roughness Ra of curable resin layer [II] side of basement membrane [I] is less than 1 μm.