CN102731946A - Polyvinyl alcohol series film and producing method thereof and lamination body for thermal transfer using the same - Google Patents

Abstract

The invention aims to provide a polyvinyl alcohol series film and a producing method thereof and a lamination body for thermal transfer using the same. The polyvinyl alcohol series film has good demould property as a base film suitable for thermal transfer. The polyvinyl alcohol series film contains 1-20 parts by weight of non-ionic series surfactant (B) relative to 100 parts by weight of polyvinyl alcohol series resin (A), and the non-ionic series surfactant (B) contains oxygen ethylidene and oxygen propylidene.

Description

The method of manufacture of polyvinyl alcohol film and polyvinyl alcohol film and used its hot transfer printing to use duplexer

Technical field

The present invention relates to the excellent polyvinyl alcohol film of release property; If further detail; Then relate to the method for manufacture of polyvinyl alcohol film and this polyvinyl alcohol film and used the hot transfer printing of this polyvinyl alcohol film to use duplexer, said polyvinyl alcohol film has applicable to basement membrane (base film) the such release property of hot transfer printing with duplexer.

Background technology

As the trailing of moulding article, there be the method for transfer film of using with the transfer printing layer transfer printing of transfer film.Transfer film is the transfer film at basement membrane laminated transfer printing layer, and said transfer printing layer is to comprise resin layer and the patterned layer on this resin layer that will become protection after the transfer printing and be transferred the resist of material surface, adhesive linkage etc.

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

The hydraulic-transfer method is meant: through with the mode that the face of the transfer printing layer side of film is positioned at the top it being bubbled through the water column with hydraulic-transfer; From film top moulding article etc. are transferred thing and are pushed on transfer printing layer; Transfer printing layer is needed on is transferred thing; Take out and be transferred thing, wash and dissolve the removal basement membrane, thereby pattern etc. is needed on the method that is transferred thing thereafter.In such hydraulic-transfer method, the polyvinyl alcohol film of the water-soluble excellence of known use is as basement membrane (for example patent documentation 1,2).

On the other hand, the hot transfer film that uses in the thermal transfer can use the hot transfer film that on the basement membrane that is formed by thermoplastic resin membrane etc., obtains with the range upon range of transfer printing layer of strippable state; Resin layer as resist generally is made up of the excellent resin combination of surface physical properties such as hardness, solvent resistance.The heat-transferring method that use has the transfer film of this formation is meant: after the face of the transfer printing layer side of transfer film is crimped on the surface that is transferred thing, basement membrane is peeled off removal from transfer printing layer, thereby transfer printing layer is needed on the method that is transferred the thing surface.

Basement membrane as so hot transfer film; Use polyester based resin films such as pet film all the time; But the polyester based resin film is common and the affinity of transfer printing layer is high, thereby is to guarantee release property between transfer printing layer and the basement membrane through releasing agent layers such as melamine resin or silicon-type, fluorine system are situated between.But, from the environment aspect and the cost aspect consider that it is disadvantageous that such releasing agent is handled, therefore seek the basement membrane that does not need releasing agent to handle.

Under such situation, in recent years, carried out polyvinyl alcohol film is also compatibly used in hot transfer printing with the basement membrane of duplexer research.For example, in patent documentation 3, disclose decoration that one side at transparent film (being equivalent to basement membrane) is provided with ornament layer (being equivalent to transfer printing layer) with film (hot transfer film) in, use the polyvinyl alcohol resin film as transparent film.In addition, in patent documentation 4, proposed single face stacked above one another peel ply, patterned layer, bond layer and in the transfer foil that obtains, used with polyvinyl alcohol resin to the resin film of staple as this basement membrane at basement membrane.

The prior art document

Patent documentation

Patent documentation 1: TOHKEMY 2007-152622 communique

Patent documentation 2: TOHKEMY 2011-11540 communique

Patent documentation 3: japanese kokai publication hei 7-40515 communique

Patent documentation 4: japanese kokai publication hei 9-277458 communique

Summary of the invention

The problem that invention will solve

Polyvinyl alcohol film is as the excellent film of release property and known, but as not using under the situation of hot transfer printing with the basement membrane of laminate film of releasing agent, requires to have more than the release property of excellence in the past.Practical situation are release properties that commercially available polyvinyl alcohol film does not possess this height usually, are the basement membrane of hot transfer film, also can't satisfy release property even use the basement membrane of film to migrate hydraulic-transfer.

And then; There is the requirement of the productivity of mould release film purposes that is applicable in recent years and the ornamental that improves thermal transfer printing; In addition; Consider also to require excellent release property from the viewpoint of the meticulous appearance design formation property of height, but the concrete polyvinyl alcohol film that uses is not exclusively to satisfy in the above-mentioned patent documentation.

Under such background, the object of the present invention is to provide: have the polyvinyl alcohol film of very excellent release property, particularly applicable to employed hot transfer printing in the trailing of having used thermal transfer with the method for manufacture of the polyvinyl alcohol film of the basement membrane of duplexer release property such, that have excellence and this polyvinyl alcohol film and used the transfer printing of this polyvinyl alcohol film to use duplexer.

The scheme that is used to deal with problems

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

All the time, contain tensio-active agent usually in the known polyvinyl alcohol film.In the manufacturing scene of polyvinyl alcohol film; From guarantee with system become during film substrate, cylinder or the viewpoint consideration that sticks together during with the peeling off easness and prevent pulling out when the film winding roller is pulled out film of substrate when going up the polyvinyl alcohol film that obtains through the system film and batch, add tensio-active agent in order to alleviate connecting airtight property.For example, in above-mentioned patent documentation 1,2, use polyoxyethylene 20 sorbitan monolaurate, polyoxyethylene alkyl amine (polyoxyethylene alkylamine) etc. as tensio-active agent.

But; As the desired release property of basement membrane the object of the invention, hot transfer film is to make to constitute the temporary transient release property that forms layer degree that under the situation that does not have releasing agent, can easily peel off of duplexer, and is higher than the on-the-spot desired release property of manufacturing of polyvinyl alcohol film far away.Thus, normally used tensio-active agent (only containing polyoxyethylene is tensio-active agent as the nonionic of polyoxy alkylidene) and content thereof are inadequate.

The invention is characterized in, than to contain nonionic obsolete usually in the actual manufacturing of polyvinyl alcohol film, that have the oxygen propylidene more be tensio-active agent in order to improve system film property and the general content of normally used tensio-active agent.

The present invention also provides the method for manufacture of polyvinyl alcohol film; It makes the nonionic that contains 1～20 weight part with respect to polyvinyl alcohol resin (A) 100 weight parts is that the polyvinyl alcohol resin aqueous solution that tensio-active agent (B) forms carries out curtain coating and makes film, and this nonionic is that tensio-active agent (B) contains aerobic ethylidene and oxygen propylidene.

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

The effect of invention

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

Embodiment

[polyvinyl alcohol film]

At first, polyvinyl alcohol film of the present invention is described.

Polyvinyl alcohol film of the present invention is that in polyvinyl alcohol resin (A), to contain nonionic be the polyvinyl alcohol film that tensio-active agent (B) forms, and this nonionic is that tensio-active agent (B) contains aerobic ethylidene and oxygen propylidene.

(1) polyvinyl alcohol resin (A)

The polyvinyl alcohol resin that uses among the present invention (A) be according to ordinary method with the polymerization of vinyl ester based compound, then its saponification is obtained.In the present invention, polyvinyl alcohol resin (A) not only can use separately, also can mix as required more than 2 kinds and uses.

As above-mentioned vinyl ester based compound, can enumerate out vinyl formate, vinyl-acetic ester, vinyl trifluoroacetate, propionate, vinyl butyrate, capric acid vinyl acetate, vinyl laurate, tertiary ethylene carbonate, palmitinic acid vinyl acetate, stearic acid vinyl ester etc.They can use separately or also with more than 2 kinds, in practicality, be fit to use vinyl-acetic ester.

In addition, as the polyvinyl alcohol resin that uses among the present invention (A), the unmodified polyvinyl alcohol resin of preferred usually use is a resin but also can use partially modified modified polyvinyl alcohol.As modified polyvinyl alcohol is resin; Can enumerate the resin that other monomer minor amounts of copolymerized of sening as an envoy to obtains in the vinyl ester based compound; Monomeric ratio in the case is not for hindering the scope of effect of the present invention, for example is 10 moles below the %, is preferably 7 moles below the %.

As above-mentioned other monomer; For example can enumerate out: olefines such as ethene, propylene, iso-butylene, α-octene, α-dodecylene, α-vaccenic acid; Unsaturated acids such as vinylformic acid, methylacrylic acid, Ba Dousuan, toxilic acid, maleic anhydride, methylene-succinic acid or its salt or its mono alkyl ester or dialkyl etc.; Nitrile such as vinyl cyanide, methacrylonitrile; Amides such as acrylic amide, USAF RH-1; Alkene sulfonic acid or its salt such as ethylene-sulfonic acid, allyl sulphonic acid, methallylsulfonic acid; The alkyl vinyl ethers; Polyoxyalkylene (methyl) allyl etherss such as T 46155 (methyl) allyl ethers, polyoxypropylene (methyl) allyl ethers; Polyoxyalkylene (methyl) propenoate such as T 46155 (methyl) propenoate, polyoxypropylene (methyl) propenoate; Polyoxyalkylene (methyl) acrylic amides such as T 46155 (methyl) acrylic amide, polyoxypropylene (methyl) acrylic amide, T 46155 [1-(methyl) acrylamido-1,1-dimethyl propyl] ether, T 46155 vinyl ether, polyoxypropylene vinyl ether, T 46155 allyl amine, polyoxypropylene allyl amine, T 46155 vinyl amine, polyoxypropylene vinyl amine, two acryl pyroracemamides (diacryl acetone amide), (N acrylamide ylmethyl) trimethyl ammonium chloride, allyl group trimethyl ammonium chloride, dimethyl diallyl ammonium chloride, dimethyl-allyl vinyl ketone, N-vinyl pyrrolidone, vinylchlorid, vinylidene chloride etc.These other monomers can use separately or and with more than 2 kinds.

Explain that in the present invention, (methyl) allyl group is represented allyl group or methylallyl, (methyl) acryl is represented acryl or methacryloyl, and (methyl) propenoate is represented propenoate or methacrylic ester.

And, when using above-mentioned vinyl ester based compound to carry out polymerization (perhaps copolymerization), can not receive especially restrictedly to use known polymerization method, be that solvent carries out solution polymerization with alcohol such as methyl alcohol, ethanol or Virahols usually.In addition, except solution polymerization, also can carry out letex polymerization, suspension polymerization.

In addition; Polyreaction is used known catalysts for radical polymerization such as Diisopropyl azodicarboxylate, acetylperoxide, Lucidol, lauroyl peroxide and is carried out; Temperature of reaction is selected from the scope of 35 ℃～boiling point usually, more preferably is selected from the scope about 50～80 ℃.

Then, with resulting vinyl ester based polymer saponification the time, above-mentioned vinyl ester based polymer is dissolved in alcohol and in the presence of alkaline catalysts, carries out.As above-mentioned alcohol, can enumerate out methyl alcohol, ethanol, butanols etc., the concentration of the vinyl ester based copolymer in the above-mentioned alcohol can suitably be selected in the scope of 20～50 weight %.

Alkaline catalysts during as above-mentioned saponification can use alkali-metal oxyhydroxide, the such alkaline catalystss of alkoxide such as sodium hydroxide, Pottasium Hydroxide, sodium methylate, sodium ethylate, potassium methylate.The consumption of above-mentioned alkaline catalysts can be suitably to select in the normal scope of 1～100 mmole with respect to the vinyl ester based polymer.Explain, also can according to circumstances utilize acid catalyst to carry out saponification.

Can obtain polyvinyl alcohol resin (A) through such operation.

In addition, as polyvinyl alcohol resin (A), also preferably use side chain to have 1, the polyvinyl alcohol resin of 2-diol bond; Above-mentioned side chain has 1; The polyvinyl alcohol resin of 2-diol bond can obtain through following method: for example; (i) with vinyl-acetic ester and 3, the multipolymer saponified method of 4-diacetoxy-1-butylene is (ii) with the multipolymer saponification of vinyl-acetic ester and vinylethylene carbonate and the method for decarbonate; (iii) with vinyl-acetic ester and 2; 2-dialkyl group-4-vinyl-1, the multipolymer saponification of 3-dioxolane is also taken off the method for ketalization, (iv) with multipolymer saponified method of vinyl-acetic ester and allylin etc.

In the present invention; The average saponification deg of above-mentioned polyvinyl alcohol resin (A) is generally 70 moles more than the %; For example; The preferred average saponification deg of purposes of paying attention to the high temperature processing appropriateness down more than 100 ℃ is 70～90 moles of %, on the other hand, pay attention to stable on heating purposes preferably on average saponification deg be 90 moles more than the %.Wherein, can be suitably to select in 70 moles of scopes more than the % from average saponification deg according to processing conditions, purpose.Explain that the average saponification deg of polyvinyl alcohol resin (A) is crossed when low, not only film strength reduces, and exists when making and be difficult to from the tendency of curtain coating face stripping film.

Explain that above-mentioned average saponification deg is measured according to JIS K 6726.

And then 20 ℃ of following 4 weight % solution viscosities of polyvinyl alcohol resin (A) are preferably the scope of 5～70mPas, the more preferably scope of 15～60mPas.4 weight % solution viscosities are crossed the tendency of the intensity reduction that has film when hanging down.There is the tendency that viscosity is high, be difficult to make film when on the other hand, 4 weight % solution viscosities are too high.Explain that above-mentioned 20 ℃ of following 4 weight % solution viscosities are measured according to JIS K 6726.

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

The nonionic that uses among the present invention be tensio-active agent (B) contain aerobic ethylidene and oxygen propylidene structural unit as oxyalkylene.Generally speaking, for become from will make film the time base material, cylinder or be with and peel off, improve batching property of roller, how in polyvinyl alcohol film, to be added with tensio-active agent.The tensio-active agent of compounding uses the excellent oxygen ethylidene of wetting ability as the oxyalkylene structural unit with such purpose.The nonionic that uses among the present invention is that tensio-active agent (B) is characterised in that hydrophilic parts comprises the oxygen ethylidene, and hydrophobic parts comprises the oxygen propylidene.Usually comprise chain alkyl as hydrophobic parts, and hydrophobic adjusting waits by the length of alkyl chain and regulate, but in the present invention, employed nonionic is proportional adjusting that contain of tensio-active agent (B) through oxygen ethylidene and oxygen propylidene.

As the nonionogenic tenside (B) that contains aerobic ethylidene and these two kinds of structural units of oxygen propylidene; For example can enumerate out the polyol ester etc. of alkyl phenyl ether, addition aerobic ethylidene and oxygen propylidene of polyol ethers (B3), addition aerobic ethylidene and oxygen propylidene of fatty ester (B2), addition aerobic ethylidene and oxygen propylidene of alkyl oxide (B1), addition aerobic ethylidene and the oxygen propylidene of addition aerobic ethylidene and oxygen propylidene, use to be selected from least a kind in them.Among them; Consider from the viewpoint of release property effect and the easy degree obtained; The polyol ethers (B3) of fatty ester (B2), addition aerobic ethylidene and the oxygen propylidene of alkyl oxide (B1), addition aerobic ethylidene and the oxygen propylidene of preferred addition aerobic ethylidene and oxygen propylidene, the more preferably polyol ethers (B3) of alkyl oxide (B1), addition aerobic ethylidene and the oxygen propylidene of addition aerobic ethylidene and oxygen propylidene.

Alkyl oxide (B1) as above-mentioned addition aerobic ethylidene and oxygen propylidene; For example can enumerate out the polyoxyethylene polyoxy-propylene class; As object lesson, can enumerate out 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.

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

Polyol ethers (B3) as above-mentioned addition aerobic ethylidene and oxygen propylidene; For example can enumerate out polyoxyethylene polyoxypropylene polyvalent alcohol ethers; As object lesson, can enumerate out polyoxyethylene polyoxypropylene glyceryl ether, polyoxyethylene polyoxypropylene Glycerol dimer base ether, polyoxyethylene polyoxypropylene sorb alcohol ether etc.

Alkyl phenyl ether as above-mentioned addition aerobic ethylidene and oxygen propylidene; For example can enumerate out polyoxyethylene polyoxypropylene alkyl phenyl ethers; As object lesson, can enumerate out polyoxyethylene polyoxypropylene hexyl phenyl ether, polyoxyethylene polyoxypropylene heptyl phenyl ether, polyoxyethylene polyoxypropylene octyl phenyl ether etc.

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

In the present invention, nonionic is that the structural unit number of the oxygen ethylidene in the tensio-active agent (B) is preferably 1～70, more preferably 2～60, further be preferably 4～50.The tendency that said structural unit number exists the polyvinyl alcohol resin viscosity in aqueous solution to uprise when too much, the tendency that exists the plane smoothness of resulting film to reduce.In addition, nonionic is that the structural unit number of the oxygen propylidene in the tensio-active agent (B) is preferably 1～70, more preferably 2～60, further be preferably 4～50.The tendency that said structural unit number exists the polyvinyl alcohol resin viscosity in aqueous solution to uprise when too much, the tendency that exists the plane smoothness of resulting film to reduce.And then the total of the structural unit number of oxygen ethylidene and the structural unit number of oxygen propylidene is preferably 2～100, more preferably 4～85, further be preferably 6～80, and especially be preferably 20～80.When said structural unit number is too much, the tendency that exists the polyvinyl alcohol resin viscosity in aqueous solution to uprise, the tendency that exists the plane smoothness of resulting film to reduce.

Tensio-active agent (B) comprises under the situation of a plurality of oxygen ethylidene and oxygen propylidene; Be that oxygen ethylidene unit and oxygen propylidene unit carry out block copolymerization and material that the material that obtains obtains with carrying out random copolymerization all can; As tensio-active agent; In order to make the oxygen ethylidene work, make the oxygen propylidene to give full play to the effect as hydrophobic portion as hydrophilic portion, preferably the mode with T 46155 portion and polyoxypropylene portion exists, and therefore is preferably segmented copolymer.

In addition; In the present invention; The viewpoint that increases from release property considers that nonionic is that oxygen ethylidene and contain proportional (the oxygen ethylidene/oxygen propylidene) of oxygen propylidene the tensio-active agent (B) is preferably 90/10～10/90 with molar ratio computing; More preferably 80/20～20/80, further be preferably 70/30～30/70.Containing of oxygen ethylidene and oxygen propylidene is proportional too small or excessive, all has the tendency with respect to the release property reduction of curable resin layer.

And then, in the present invention, consider that from the viewpoint of the increase of release property, suitableization of viscosity nonionic is that the weight-average molecular weight of tensio-active agent (B) is preferably 100～10000, more preferably 200～8000.Said weight-average molecular weight exists release property to reduce when too small tendency exists the polyvinyl alcohol resin viscosity in aqueous solution to uprise and when making film, causes the tendency of obstruction when excessive.

In the present invention, consider that from the viewpoint of release property nonionic is that the HLB of tensio-active agent (B) is preferably 2～18, more preferably 2～15, further be preferably 3～12.HLB value described in the present invention is meant the value of calculating through lattice Lifei method (Griffin method), can be calculated by following formula.

HLB=20 * (molecular weight of the molecular weight/integral body of hydrophilic portion)

Here, hydrophilic portion mainly is meant the total molecular weight of oxygen ethylidene structural unit.Therefore, the HLB value of the ratio of expression oxygen ethylidene structural unit in the molecule integral body of tensio-active agent (B) is preferably above-mentioned scope.The HLB value is meant for the tensio-active agent (B) of above-mentioned scope: in the scope of not damaging dispersiveness in water, have the hydrophobic balance that possesses appropriateness.Can think,, can guarantee its good dispersion in polyvinyl alcohol resin, and under the state that hydrophobicity improves, become the state that easily oozes out from polyvinyl alcohol film through having such balance.Supposition is to work owing to the tensio-active agent (B) that oozes out into the polyvinyl alcohol film surface can be used as a kind of releasing agent, so as under the situation of hot transfer printing with the basement membrane of duplexer, after transfer printing, help to improve peeling off of curable resin layer and basement membrane.

In the present invention; Consider from the viewpoint of release property and film appearance; Above-mentioned nonionic is that the content of tensio-active agent (B) is preferably 1～20 weight part with respect to polyvinyl alcohol resin (A) 100 weight parts; More preferably 2～15 weight parts further are preferably 3～10 weight parts, are preferably 5～8 weight parts especially.Usually for the cylinder that improves the substrate with as the system film time or the release property between being with and add tensio-active agent; Its content is lower than 1 weight part with respect to polyvinyl alcohol resin 100 weight parts, and therefore polyvinyl alcohol film of the present invention is characterised in that more than common amount.This be because, be tensio-active agent (B) for the nonionic that uses among the present invention, in order to be the increase effect that oozing out of tensio-active agent (B) obtains release property through nonionic, the amount that in the past contained as additive is inadequate.On the other hand, when content became too much, the nonionic that oozes out to the surface was that tensio-active agent (B) quantitative change is many, and it is glutinous greasy that film surface is easy to become.Its result under other the situation of resin of film laminated, repels other resin sometimes.This situation for example as hot transfer printing during with the basement membrane of duplexer since be easy to repel range upon range of reasons such as curable resin, and become the reason of the surface luster generation reduction of reason that the superficiality of transfer printing layer reduces and then the resist that becomes resulting moulding article.

(3) other composition

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

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

Tensio-active agent except above-mentioned nonionic is tensio-active agent (B) (below be called " other tensio-active agent (B ') ") is purpose and compounding to improve as the metallic surface of the cylinder of the film forming apparatus of polyvinyl alcohol film or band etc. with making release property between the film that film goes out.

As other tensio-active agent (B '); For example; As nonionic is tensio-active agent; Can enumerate out except the aforesaid nonionic that contains aerobic ethylidene and oxygen propylidene be the tensio-active agent the tensio-active agent; For example, only contain a kind of polyoxyalkylenes alkyl ether in aerobic ethylidene or the oxygen propylidene, polyoxyalkylenes alkyl phenyl ethers, polyoxyalkylenes alkyl esters, sorbitan fatty acid ester class, polyoxyalkylenes alkyl amine, polyoxyalkylenes alkylamide, W 166 ethers, ethanetetrayl glycol (acetylene glycol) class, allyl phenyl ethers etc.

In addition, as other tensio-active agent (B '), being not limited to nonionic is tensio-active agent, and also can use negatively charged ion is that tensio-active agent, positively charged ion are tensio-active agent, amphoterics.As negatively charged ion is tensio-active agent, and for example, the negatively charged ion of sulfonic acid types such as sulfuric acid ester types such as carboxylic acid types such as potassium laurate, octyl group sulfuric ester, DBS is that tensio-active agent is fit to.As positively charged ion is tensio-active agent, for example can enumerate out pyridinium salts such as quaternary ammonium salts such as amine, lauryl trimethyl ammonium chloride, lauryl chloride pyridine such as laurylamine hydrochloride etc.As amphoterics, for example can enumerate out N-alkyl-N, N-Dimethyl Ammonium trimethyl-glycine etc.

Other tensio-active agent (B ') can use a kind perhaps to make up use more than 2 kinds.

The content of other tensio-active agent (B ') is not as long as for damaging the degree of the object of the invention; In addition; The degree that is exuded to reduction such as the superficiality that do not have for example surperficial albefaction gets final product, and is below 1 weight part with respect to polyvinyl alcohol resin 100 weight parts usually.

(3-2) softening agent

As above-mentioned softening agent, for example can enumerate out glycerols such as glycerine, Glycerol dimer, triglycerin, aklylene glycol classes such as triethylene glycol, polyoxyethylene glycol, W 166, dipropylene glycol, TriMethylolPropane(TMP) etc.They can use separately or and with more than 2 kinds the use.

Compounding is preferably below 30 weight parts with respect to polyvinyl alcohol resin (A) 100 weight parts in the compounding amount of the softening agent of above-mentioned polyvinyl alcohol resin (A), more preferably below 20 weight parts.When the compounding amount of above-mentioned softening agent is too much, exist the hardness of film to disappear and the reluctant tendency that becomes.Explain that the lower value of softening agent is generally 0.5 weight part.

(3-3) filler

As above-mentioned filler, for example can enumerate out the organic dust of starch (being not only various roughs, also can be etherificate article, oxidation article, modification article), polymethylmethacrylate etc., the inorganic powder of talcum, mica, silicon-dioxide etc. etc.They can use separately or and with more than 2 kinds the use.Wherein can compatibly use starch.

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

(3-4) other additive

And then; Can be at the scope that does not hinder effect of the present invention suitably compounding inhibitor (phenol system, amine system etc.), stablizer (phosphoric acid ester etc.), colouring matter, spices, extender, skimmer, rust-preventive agent, UV light absorber, also suitably other water-soluble high-molecular compound (ZX-I, T 46155, PVP K120, dextrin, chitosan, chitin, methylcellulose gum, Natvosol etc.) of compounding waits other additive.

The polyvinyl alcohol film of the present invention of technical scheme with above that kind is because release property is excellent; Processing under the situation of hot transfer film; Even between curable resin layer and polyvinyl alcohol film, be not situated between, also can after hot transfer printing, easily will be transferred to the surperficial curable resin layer (resist) of moulding article and peel off as the polyvinyl alcohol film of basement membrane at releasing agent layer.

Explain; Polyvinyl alcohol film of the present invention not only is endowed release property excellent as above-mentioned, has also kept the characteristic that existing polyvinyl alcohol film had, promptly; Excellent specific properties such as wetting ability, water-soluble, organic solvent resistance, barrier properties for gases have been kept; Therefore be not defined for the basement membrane of hot transfer printing with duplexer, also can be used for the basement membrane of hydraulic-transfer with duplexer, the purposes that also can be used as other polyvinyl alcohol film is used for present known purposes.

[method of manufacture of polyvinyl alcohol film]

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

At first; The above-mentioned polyvinyl alcohol resin of compounding amount compounding (A) according to the rules, nonionic are tensio-active agent (B); And other tensio-active agent (B '), softening agent, other additive etc. of compounding as required, it is dissolved in the water, thus the preparation polyvinyl alcohol resin aqueous solution.

As the concentration of the polyvinyl alcohol resin aqueous solution, be preferably 10～30 weight % usually, more preferably 15～25 weight %.Said concentration is crossed the tendency that the stability that has thickness when low reduces, and exists viscosity to uprise when too high and is difficult to make the tendency of film.

Then, the polyvinyl alcohol resin aqueous solution is cast on the system film band or makes on the membrane cylinder from the T type die, make its drying and film likeization, thereby further heat-treat manufacturing as required.

Here, above-mentioned system film band is meant to have endless belt between the pair of rolls of being set up in, that divide a word with a hyphen at the end of a line, will be from the effusive polyvinyl alcohol resin aqueous solution of T type die curtain coating on the endless belt and make its exsiccant system film band.Above-mentioned endless belt preference is as being processed by stainless steel, and its outer surface has been implemented the band of mirror finish.

In addition, above-mentioned system membrane cylinder is meant, the system membrane cylinder of the cylinder forming roll of rotation, and it will be extended down on the swing roller forming roll more than 1 and make its exsiccant system membrane cylinder from the effusive polyvinyl alcohol resin water solution flow of T type die.

Under the situation of using system film band, drying temperature is preferably 80～160 ℃ usually, more preferably 90～150 ℃.Drying temperature is crossed and is had the dry not enough and tendency of peeling off dull from being with when hanging down, and has the tendency that moisture rate became low, film becomes fragile when too high.

In addition, under the situation of using the system membrane cylinder, system film first cylinder is preferably 80～100 ℃, more preferably 82～99 ℃ usually.Drying temperature cross exist when low dry not enough, from the tendency of peeling off dull of cylinder, have the tendency that moisture rate became low, film becomes fragile when too high.Here, above-mentioned system film first cylinder is meant, is positioned at the cylinder of the cylinder forming roll of curtain coating to carrying out from the effusive polyvinyl alcohol resin aqueous solution of T type die, upstream side.

After above-mentioned drying, heat-treat as required, as said heat-treating methods, for example can enumerate out methods such as hot-rolling (comprising stack), hot blast, far infrared rays, induction heating.In addition, be preferably and make the face that the film band is perhaps made contacted opposition side of membrane cylinder by heat treated face.In addition, the water cut of implementing heat treated film is preferably about 4～8 weight % usually.And then the water cut of the film after the thermal treatment is preferably 2～6 weight % usually.

Explain that the moisture rate of polyvinyl alcohol film for example can use Ka Er Fischer moisture content tester (capital of a country Electronics Industry Company system, " MKS-210 ") and measure.

Thermal treatment based on above-mentioned heat-treating machine is preferably carried out under 50～130 ℃ usually, more preferably under 60～120 ℃, carries out.That is, above-mentioned heat treated temperature is crossed when low, becomes and is difficult for handling thereby exist with system film band or make contacted tendency that takes place to curl of film first cylinder; When heat treated temperature is too high,, when stretching, observe the orientation grow on the long side direction (longitudinal direction), the tendency of reduced width in order to batch because film becomes soft with not producing fold.And then the needed time of above-mentioned thermal treatment is relevant with its surface temperature under the situation of Heat treating roll, is made as usually 0.2～15 second, preferably is made as 0.5～12 second.Above-mentioned thermal treatment normally after the dryer roll that is used for dry film is handled, then waits usually and carries out through other Heat treating roll, floating type moisture eliminator (floating dryer).

So can obtain polyvinyl alcohol film.

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

As the moisture rate of the polyvinyl alcohol film of above-mentioned gained, be preferably the scope of 0.5～8 weight %, more preferably 1～6 weight %.Moisture rate is crossed and is had the tendency that becomes fragile when hanging down, and has the tendency of adhesion when moisture rate is too high.

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

(i) through adjusting the drying machine temperature when the polyvinyl alcohol resin aqueous solution carried out drying system film up and down, carry out polyvinyl alcohol film humidification/dehumidifying method and moisture rate is adjusted.About the temperature of resin aqueous solution, its temperature exerts an influence to drying efficiency, therefore is adjusted into 70～98 ℃ scope.In addition; Preferably; When dry, preferably between 150～50 ℃, more preferably between 145～60 ℃, have in the hot air dryer more than at least 2 of thermograde and carry out drying, and then; Consider preferably to carry out 1～12 minute drying from the viewpoint of moisture adjustment, more preferably carry out 1～11 minute drying.

When the gradient scope of above-mentioned drying temperature excessive or time of drying is long, there is dry excessive tendency, when the gradient scope of drying temperature too small or time of drying is too short on the contrary, has dry insufficient tendency.

The said temperature gradient is the thermograde that between 150～50 ℃, changes drying temperature interimly; Usually; Slow raising temperature when drying begins; Reach till the water ratio of regulation and the highest drying temperature in the temporary transient drying temperature scope of setting, it is effective then slowly reducing drying temperature and finally obtain the target water ratio.This carries out for crystallization control property, release property, productivity etc., for example can enumerate out 120 ℃-130 ℃-115 ℃-100 ℃, 130 ℃-120 ℃-110 ℃, 115 ℃-120 ℃ of-110 ℃ of-90 ℃ of isothermal gradients and set, and can suitably select and implement.

(ii) through make polyvinyl alcohol film before batching through the damping groove, carry out the humidification/dehumidifying of polyvinyl alcohol film, carry out the adjustment of moisture rate.

(iii) through batch preceding to polyvinyl alcohol film or batch after heat-treat, and carry out the dehumidifying of polyvinyl alcohol film, thereby carry out the adjustment of moisture rate.

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

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

As under the situation of stretched film, the applicable known method of drawing process, for example can be enumerated out the fixed stretching of (1) chuck, the stretching of (2) roll-type, the stretching of (3) tentering formula etc. as general method.(1) be suitable for the making of batch-wise stretched film, (2) are suitable for uniaxial stretching.Device can become on a large scale in addition, but (3) are being effective aspect technical scale making stretched film.(2) also capable of being combined and (3) and carry out biaxial stretch-formed one by one.Drawing process can adopt uniaxial extension, biaxial stretch-formed (Sequential Biaxial Stretching), in simultaneously biaxial stretch-formed any one by one, wherein considers the biaxial stretch-formed of preferably combination (2) and (3) from the inhomogeneity viewpoint of thickness.

Consider that from the viewpoint of the surface uniformity of film total stretching ratio of said stretched film is preferably 1.5～16 times, more preferably 2～12 times, further is preferably 3～10 times.Perhaps; Consider to be suitable for from the viewpoint of the surface uniformity of film: for to be preferably 1.5～10 times, more preferably 2～8 times, further to be preferably 3～5 times, be preferably 1.5～10 times, more preferably 2～8 times at transverse direction, further be preferably 3～5 times mode and stretch at longitudinal direction with stretching ratio.Under biaxial stretch-formed situation; Consider to be preferably 1.5～4 times, more preferably 2～3.5 times at longitudinal direction from the viewpoint of the surface uniformity of film; Be preferably 1.5～4 times at transverse direction, more preferably 2～3.5 times mode stretches, and then more preferably is identical multiplying power in length and breadth.Under the low excessively situation of stretching ratio, easy residual stretching is irregular, under the too high situation of stretching ratio, and the tendency that exists film to become to be easy to rupture.

About the preservation of polyvinyl alcohol film, preferably for example carry out the processing of known water vapor proof barrier packaging in the past, under 10～25 ℃ atmosphere, preserve with vacant state.

[duplexer is used in hot transfer printing]

It is range upon range ofly to have the hot transfer printing of basement membrane [I], curable resin layer [II], printed layers [III] to use duplexer that duplexer is used in hot transfer printing of the present invention.

(1) basement membrane [I]

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

In the present invention, the thickness of basement membrane [I] is preferably set in the scope of 5～120 μ m especially, more preferably 10～100 μ m.

In addition, in the present invention, the surfaceness (Ra) of curable resin layer [II] side of basement membrane [I] is considered to be preferably below the 1 μ m from the viewpoint of surface luster property, and more preferably 0.001～0.7 μ m further is preferably 0.01～0.5 μ m.There is the tendency of surface luster property reduction in said surfaceness (Ra) when excessive.Explain almost do not observe the tendency that surperficial glossiness is improved even said surfaceness (Ra) less than 0.001 μ m, also exists.In said basement membrane [I]; Be adjusted into the method for above-mentioned scope as the surfaceness (Ra) with curable resin layer [II] side, can enumerate out: the surfaceness of the casting belt (casting belt) during with the system film of basement membrane [I] is made as below the 1S, the stretching ratio during with basement membrane [I] system film is made as method more than at least 1.5 times, or with the method for both combinations etc.

Explaining that surfaceness (Ra) is used KEYENCE CORPORATION system " colored 3D laser microscope VK-9700 ", is that benchmark instrumentation profile arithmetic average error (Ra) obtains according to JIS B 0601-2001.

(2) curable resin layer [II]

Said curable resin layer [II] is through peeling off basement membrane [I] and become the layer on the top layer of decorated molded article, time till peeling off to basement membrane [I] or peel off after fixing, becomes the resist on the surface that is used to protect transfer printing body.

As the material that constitutes curable resin layer [II]; For example can enumerate out: ROHM resinoid, vibrin, PVC RESINS, celluosic resin, rubber resin, urethane resin, these thermoplastic resins of vinylite; Ultra-violet solidified resin composition, electron(beam)curing property resin combination isoreactivity energy ray-curable resin combination, compositions of thermosetting resin etc.As resist, consider from the viewpoint of giving chemical-resistant, wear resistant, preferably use actinic energy ray curable resion composition.

Said actinic energy ray curable resion composition for example is preferably the actinic energy ray curable resion composition that contains acrylic resin and ammonia ester (methyl) propenoate based compound.

As said acrylic resin, for example can enumerate out: with the monomeric homopolymer of acrylic ester or multipolymer, other ethylenically unsaturated monomer is acrylic copolymer of copolymer composition etc.

As the acrylic ester monomer; For example can enumerate out (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) Bing Xisuandingzhi, (methyl) NSC 11786, (methyl) 2-EHA, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, (methyl) benzyl acrylate, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid dimethylamino ethyl ester, (methyl) Isooctyl acrylate monomer, (methyl) vinylformic acid n-octyl, (methyl) lauryl acrylate, (methyl) vinylformic acid 2-methoxyl group ethyl ester, (methyl) vinylformic acid butoxy ethyl ester, (methyl) vinylformic acid methoxyl group triglycol ester etc.; Wherein the carbonatoms of preferred alkyl is 1～12 alkyl acrylate, more preferably (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) Bing Xisuandingzhi, (methyl) 2-EHA.

As other ethylenically unsaturated monomer; For example can enumerate out: the unsaturated monomer of hydroxyls such as (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 ester, (methyl) vinylformic acid binaryglycol ester, (methyl) polyalkylene glycol acrylate ester, N-methylol (methyl) acrylic amide; SY-Monomer G, methylacrylic acid allyl glycidyl etc. contain the unsaturated monomer of glycidyl; 2-acryloxy ethyl isocyanate, 2-methacryloxyethyl isocyanic ester etc. contain the unsaturated monomer of NCO; The unsaturated monomer of amide-containings such as acrylic amide, USAF RH-1, N-(n-butoxy alkyl) acrylic amide, N-(n-butoxy alkyl) USAF RH-1; Acrylamido-3-methylbutyl methylamine, dimethylamino alkyl acrylamide, dimethylamino alkyl methyl acrylic amide etc. contain amino unsaturated monomer; Alkene sulfonic acids such as ethylene-sulfonic acid, allyl sulphonic acid, methallylsulfonic acid; 2-acrylamido-2-methyl propane sulfonic acid, styrene sulfonic acid or its salt etc. contain sulfonic unsaturated monomer, vinylbenzene, vinyl-acetic ester; Vinyl cyanide, acrylic amide etc.

Contain proportional (copolymerization ratio) of said acrylic ester monomer and other ethylenically unsaturated monomer do not limit especially; For example; Preferred acrylate is that monomer is that 20～100 weight %, other ethylenically unsaturated monomer are 0～80 weight %; More preferably the acrylic ester monomer is that 40～100 weight %, other ethylenically unsaturated monomer are 0～60 weight %, and further preferred acrylate is that monomer is that 80～100 weight %, other ethylenically unsaturated monomer are 0～20 weight %.Acrylic ester is monomeric contain proportional when very few, the tendency that exists the weather resistance such as water tolerance/humidity resistance of the cured article (resist) of curable resin layer to reduce.

Above-mentioned acrylic resin can as make aforementioned polymerization composition carry out in the organic solvent free-radical polymerized, by one of skill in the art known method and easily making.

As the acrylic resin that uses in the actinic energy ray curable resion composition, its second-order transition temperature (Tg) is preferably 20～130 ℃, more preferably 30～120 ℃, further is preferably 40～110 ℃.Second-order transition temperature (Tg) is crossed when low, and the curable resin layer that has an actinic energy ray curable resion composition etc. has tackiness and causes when implementing post-treatment, taking place the tendency of bad phenomenon (in the operation for coiling/printing bad etc.); When too high, exist the curable resin layer make actinic energy ray curable resion composition etc. to solidify and the tendency that becomes fragile when becoming resist.

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

When the weight-average molecular weight of said acrylic resin (Mw) was too small, curable resin layer softnessization before solidifying also had tackiness, therefore existed in the upward tendency of generation bad phenomenon during the enforcement post-treatment (coiling/printing in the operation is bad etc.) of this layer; When excessive, have tendency as follows: the hardness that is difficult to when coating curable resin layer, to obtain film uniformity and dried coating is higher than aequum, and bad phenomenon (be full of cracks/splitting of filming etc.) takes place when causing implementing post-treatment.

Ammonia ester (methyl) propenoate based compound is for having (methyl) propenoate based compound of ammonia ester bond at intramolecularly, can make through making (methyl) the acrylic acid series compound that contains hydroxyl and polyisocyanate compound and polyol reaction as required.

As above-mentioned (methyl) acrylic acid series compound that contains hydroxyl; For example can enumerate 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) acryloxy ethyl-2-hydroxypropyl phthalic ester, 2-hydroxyl-3-(methyl) acryloxy (methyl) propyl acrylate, caprolactone modification 2-hydroxyethyl (methyl) propenoate, tetramethylolmethane three (methyl) propenoate, Dipentaerythritol five (methyl) propenoate, caprolactone modification Dipentaerythritol five (methyl) propenoate, caprolactone modification tetramethylolmethane three (methyl) propenoate, ethylene oxide modification Dipentaerythritol five (methyl) propenoate, ethylene oxide modification tetramethylolmethane three (methyl) propenoate etc., wherein preferred (methyl) acrylic acid series compound that uses hydroxyl with the acryl more than 3.In addition, they can use a kind or make up more than 2 kinds and to use.

As above-mentioned polyisocyanate compound; For example can enumerate out POLYMETHYLENE POLYPHENYLISOCYANATE such as fragrant family, fatty family, ester ring type system; Wherein enumerate out: tolylene diisocyanate, diphenylmethanediisocyanate, hydrogenated diphenyl methane diisocyanate, many phenylmethanes POLYMETHYLENE POLYPHENYLISOCYANATE, modified diphenylmethane diisocyanate, the inferior dimethyl-vulcabond of hydrogenation of benzene, XDI, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, tetramethylxylene diisocyanate, isophorone diisocyanate, norbornylene vulcabond, 1; POLYMETHYLENE POLYPHENYLISOCYANATE such as two (isocyanato-methyl) hexanaphthenes of 3-, phenylene vulcabond, LDI, Lysine triisocyanate, naphthalene diisocyanate are the trimer compound or the polymer compound of these POLYMETHYLENE POLYPHENYLISOCYANATE perhaps; Biuret type POLYMETHYLENE POLYPHENYLISOCYANATE, water dispersive polyisocyanate are (for example; Nippon Polyurethane Industry Co., " Aquanate 100 " of Ltd. system, " Aquanate 110 ", " Aquanate 200 ", " Aquanate210 " etc.) or the reaction product of these POLYMETHYLENE POLYPHENYLISOCYANATE and polyvalent alcohol etc.

As said polyvalent alcohol; For example can enumerate out: terepthaloyl moietie, Diethylene Glycol, triethylene glycol, TEG, polyoxyethylene glycol, Ucar 35, dipropylene glycol, W 166, butyleneglycol, polytetramethylene glycol, 1; Polyvalent alcohols such as 6-pinakon, NSC 6366, cyclohexanedimethanol, Hydrogenated Bisphenol A 99, polycaprolactone, trimethylolethane, TriMethylolPropane(TMP), many TriMethylolPropane(TMP)s, tetramethylolmethane, many tetramethylolmethanes, sorbyl alcohol, N.F,USP MANNITOL, glycerine, poly-glycerine, polytetramethylene glycol; Have the block of T 46155, polyoxypropylene, ethylene oxide/propylene oxide or the polyether glycol of at least a kind of structure in the random copolymerization; The polyester polyol of the condenses of polyprotonic acids such as this polyvalent alcohol or polyether glycol and maleic anhydride, toxilic acid, fumaric acid, itaconic anhydride, methylene-succinic acid, hexanodioic acid, m-phthalic acid; Caprolactone modification polyvalent alcohols such as caprolactone modification polytetramethylene polyvalent alcohol; The polyolefin polyvalent alcohol, polyhutadiene such as hydrogenation polybutadiene polyol are polyvalent alcohol etc.

And then, as said polyvalent alcohol, for example also can enumerate out: 2; Two (methylol) butyric acid of 2-, tartrate, 2,4-resorcylic acid, 3,5-resorcylic acid, 2; Two (methylol) propionic acid, 2 of 2-, two (hydroxyethyl) propionic acid, 2 of 2-, two (hydroxypropyl) propionic acid of 2-, dihydroxymethyl acetate, two (4-hydroxy phenyl) acetate, 4; Carboxylic polyvalent alcohols such as two (4-hydroxy phenyl) valeric acids of 4-, homogentisic acid, 1,4-butyleneglycol sodium sulfonate etc. contains the polyvalent alcohol of sulfonic group or azochlorosulfonate acid alkali etc.

Under the situation of the reaction product of using POLYMETHYLENE POLYPHENYLISOCYANATE and polyvalent alcohol, for example, above-mentioned polyvalent alcohol and above-mentioned POLYMETHYLENE POLYPHENYLISOCYANATE are reacted and the end that obtains contains the POLYMETHYLENE POLYPHENYLISOCYANATE of NCO and gets final product.In the reaction of said POLYMETHYLENE POLYPHENYLISOCYANATE and polyvalent alcohol, to promote that reaction is that purpose is also preferably used the such metal catalyst of dibutyl tin laurate, 1, the amine series catalysts that 8-diazabicyclo [5.4.0] 11 carbon-7-alkene is such etc.

Method of manufacture as above-mentioned ammonia ester (methyl) propenoate based compound; For example can enumerate out: (methyl) acrylic acid series compound and polyisocyanate compound with hydroxyl under non-active gas atmosphere mix, usually with 2～10 hours method of 30～80 ℃ of reactions.In this reaction, preferably use 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) propenoate based compound is preferably 300～4000, and more preferably 1000～3500, further be preferably 1200～3000.Exist when said weight-average molecular weight is too small the curable resin layer is solidified the insufficient tendency of back cohesive force, the tendency that exists viscosity to become too high, be difficult to make when excessive.

Explain; Above-mentioned weight-average molecular weight is meant the weight-average molecular weight that converts and obtain according to the polystyrene standard molecular weight; In high performance liquid chromatograph (clear and electrician's corporate system, " Shodex GPC system-11 type "), use 3 placed in-line chromatographic columns: Shodex GPC KF-806L (exclusion limit molecular weight: 2 * 10 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 μ m) measure.

Thus; Can obtain to contain the actinic energy ray curable resion composition of acrylic resin and ammonia ester (methyl) propenoate based compound; But at actinic energy ray curable resion composition is under the situation of ultra-violet solidified resin composition, preferably further contains Photoepolymerizationinitiater initiater.At the next Photoepolymerizationinitiater initiater that do not need of the situation of electron(beam)curing property resin combination.

As said Photoepolymerizationinitiater initiater; For example can enumerate out: acetophenones such as 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-morpholino phenyl) butanone, 2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] acetone oligopolymer, bitter almond oil camphor classes such as bitter almond oil camphor, benzoin methylether, ethoxybenzoin, benzoin iso-propylether, bitter almond oil camphor ethyl isobutyl ether, UVNUL MS-40, 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) UVNUL MS-40,2,4; 6-tri-methyl benzophenone, 4-benzoyl-N; Benzophenones such as N-dimethyl--N-[2-(1-oxo-2-propenyl oxygen base) ethyl] xylylene benzyl brometo de amonio, (4-benzoyl-benzyl) trimethyl ammonium chloride, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2; 4-two clopenthixal ketones, 1-chloro-4-propoxy-thioxanthone, 2-(3-dimethylamino-2-hydroxyl)-3; 4-dimethyl--9H-thioxanthone-thioxanthene ketones such as 9-ketone methochloride, 2,4; 6-trimethylbenzoyl-diphenyl phosphine oxide, two (2; 6-dimethoxy benzoyl-)-2,4,4-trimethylammonium-amyl group phosphine oxide, two (2; 4, the 6-trimethylbenzoyl)-acylphosphine oxide classes such as phenyl phosphine oxide etc.Explain that these Photoepolymerizationinitiater initiaters can only use a kind separately, also can be also with more than 2 kinds.

In addition; As their auxiliary agent; Also can and use: trolamine, tri-isopropanolamine, 4,4 '-dimethylamino UVNUL MS-40 (michaelis ketone), 4,4 '-diethylamino UVNUL MS-40,2-dimethyl aminoethyl phenylformic acid, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid (n-butoxy) ethyl ester, 4-dimethylaminobenzoic acid isopentyl ester, 4-dimethylaminobenzoic acid 2-ethylhexyl, 2; 4-diethyl thioxanthone, 2,4-di-isopropyl thioxanthone 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 considered to be preferably 1～150 μ m from the viewpoint of wear resistant, chemical-resistant, and more preferably 2～120 μ m further are preferably 2～100 μ m.Said thickness is crossed and is had the tendency that wear resistant reduces, chemical-resistant reduces when thin, then tends to become film fracture variation after the transfer printing when blocked up, causes the reason of burr etc.

When forming curable resin layer [II]; Above-mentioned material resin or material resin compsn are coated with coating methods such as method, scraper coating method, lip coating method through photogravure coating method, rolling method, rod, print processes such as gravure processes, silk screen print method are carried out range upon range of getting final product.

Under the situation of having used above-mentioned actinic energy ray curable resion composition; Behind the layer (curable resin layer [II]) that basement membrane [I] laminated is formed by actinic energy ray curable resion composition; [III] is needed on the transfer printing body with printed layers; Can the time till being stripped to basement membrane [I], any stage irradiation active energy beam and make its curing, also can peel off basement membrane [I] back irradiation active energy beam and make its curing, thereby process resist (hard coat).

For example can carry out as follows: (a) behind basement membrane laminated actinic energy ray curable resion composition layer, irradiation active energy beam and solidifying; (b) behind basement membrane laminated actinic energy ray curable resion composition layer, the printed layers of stating after the formation is solidified from basement membrane side irradiation active energy beam thereafter; (c) behind the adhesive linkage of stating after further being laminated to from basement membrane side irradiation active energy beam and solidify; (d) make transfer printing of the present invention be adhered to behind the transfer printing body from basement membrane side irradiation active energy beam and solidify with duplexer; (e) make transfer printing of the present invention be adhered to transfer printing body with duplexer after, peel off basement membrane and shine active energy beam and solidify.The viewpoint of the following property of the transfer printing body to hot transfer printing the time considers, preferably makes it in (d) of transfer printing the after fixing perhaps method of (e), the more preferably method of (e).Explain; Transfer printing of the present invention with duplexer can be as above-mentioned (a)～(c) the mode of the duplexer of ground after solidifying with the curable resin layer supply with, preferably like above-mentioned (d) with (e) supply with the mode of the duplexer that contains the preceding curable resin layer of curing.

Explain, when the curable resin layer being solidified, as active energy beam at the irradiation active energy beam; For example; Light such as far ultraviolet rays yue capable of using, ultraviolet ray, near-ultraviolet ray, infrared rays, hertzian wave such as X ray, gamma-rays, electron rays capable of using in addition, proton ray, neutron ray etc.; That considers curing speed, irradiating unit obtains easness, price etc., is favourable based on the curing of uviolizing.

As make its solidified method through uviolizing, need only use and send the high pressure mercury vapour lamp of the light of 150～450nm wavelength region may, extra-high-pressure mercury vapour lamp, carbon arc lamp, metal halide lamp, xenon lamp, chemical lamp etc., with 0.01～10J/cm ²Degree shine and get final product.After uviolizing, also can heat as required and seek completely solidified.

(3) printed layers [III]

Printed layers [III] is for being printed with the layer of pattern etc.; Material as printed layers; Can use: contain Vilaterm base system resin, polyamide-based resin, polyester based resin, acrylic resin, polyurethane series resin, polyvinyl acetal and be resin, polyester-polyurethane and be resin, cellulose ester and be resins such as resin, Synolac as sticker, contain pigment or the dyestuff of appropriate color painted China ink as tinting material.

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

(4) adhesive linkage [IV]

It is range upon range ofly to have the transfer printing of above-mentioned basement membrane [I], curable resin layer [II], printed layers [III] to use duplexer that duplexer is used in transfer printing of the present invention, preferably at the range upon range of adhesive linkage in the upper strata of printed layers [III] [IV].

Adhesive linkage [IV] is adhered to above-mentioned duplexer and is transferred dignity.Can under the situation a little less than the bonding force of printed layers and moulding article, form.Material as adhesive linkage [IV]; Be suitable for the raw-material thermo-sensitivity of transfer printing body or the resin of pressure-sensitive as long as suitably use, for example can enumerate out polyester based resin, acrylic resin, polystyrene resin, polyamide-based resin, chlorinated polyolefin resin, ethylene chloride-vinyl acetate copolymer resin, thermoprene, coumarone indeneresin (coumarone-indene resin) etc.

As the formation method of adhesive linkage [IV], can enumerate out photogravure coating method, rolling method, rod and be coated with coating methods such as method, scraper coating method, print processes such as gravure processes, silk screen print method.In addition, can process adhesive linkage [IV] through the sheet material that applyings such as laminating are formed by above-mentioned material with cementability.In addition, adhesive linkage [IV] but also double as printed layers [III].

The thickness of adhesive linkage [IV] is from considering to be preferably 0.5～50 μ m to the viewpoint of the following property of adherend, and more preferably 1～40 μ m further is preferably 2～30 μ m.Said thickness is crossed when thin, when having transfer printing to the tendency of the following property reduction of adherend, the tendency that exists cost to uprise when blocked up, and uneconomical.

[hot transfer printing of the present invention with the method for use of duplexer: thermal transfer]

To having used hot transfer printing of the present invention to describe with the heat-transferring method of duplexer.

(1) to being transferred the method that dignity is decorated

At first, transfer printing is closely attached on the transfer printing layer of duplexer (transfer printing layer has under the situation of adhesive linkage [IV] and is adhesive linkage [IV], does not have under the situation of adhesive linkage [IV] to be printed layers [III]) is transferred dignity.Then; Use possesses the elastomeric roller transfer machines of heat resistant rubber shape such as Zylox, transfer machine such as transfer machine up and down; Jie is by the heat resistant rubber shape elastomerics that temperature is set at about 80～270 ℃, pressure is set at the condition about 490～1960Pa, applies heat and pressure from transfer printing with basement membrane [I] side of duplexer.Through such operation, make adhesive linkage [IV] or printed layers [III] be adhered to the transfer printing body surface.

After cooling; After curable resin layer [II] being solidified process resist (hard coat) through active energy beam irradiation etc.; When peeling off basement membrane [I] at last, (the curable resin layer [II] after the curing: interface hard coat) causes to be peeled off, and transfer printing finishes at basement membrane [I] and resist.

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

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

At first, use duplexer to send in the mold for forming as the mode of fixed mould (being generally former) side transfer printing with basement membrane.Transfer printing can be that the transfer printing of monolithic is sent into more than of duplexers with sending into of duplexer, also can be the necessary of duplexer of long size partly intermittently sent into.Under the situation of transfer printing of using long size with duplexer, can use transporter with orientation mechanism, carry out transfer printing with the printed layers [III] of duplexer and the alignment of orientation (register) of mold for forming.In addition; When transfer printing is sent into duplexer off and on; As long as with sensor detecting go out transfer printing with the position of duplexer after with moveable die (former) and fixed mould (formpiston) stationary transfer with duplexer; Owing to often can use duplexer in the same position stationary transfer, the dislocation of printed layers [III] does not take place, thereby convenient.

Closed moulding with mould after, from cast gate fused moulding resin injection is filled in the mould, thereby makes the transfer printing body moulding.Side by side send into transfer printing with the moulding of transfer printing body and use duplexer, it is adhered to the transfer printing body surface.

As the moulding resin of the material that becomes transfer printing body, can enumerate out resins for universal use such as polystyrene resin, polyolefin-based resins, ABS resin, AS resin, AN resin.In addition; Also can use ppe-polystyrene resin, polycarbonate-based resin, polyacetal is general engineering resins such as resin, acrylic resin, polycarbonate modified polyphenylene oxide resin, polybutylene terephthalate resin, polyvinyl resin with super-high molecular weight, and polysulfone resin, polyphenylene sulfide are that resin, ppe are that resin, polyarylate resin, polyetherimide resin, polyimide resin, liquid-crystal polyester resin, polyene propyl group are special engineered resins such as heat stable resin.Also can use the compound resin that has added strongtheners such as spun glass, mineral filler.By the transfer printing body of these resin formation can be in transparent, translucent, opaque any.In addition, transfer printing body can be painted, also can be not painted.

After will cooling off as the synthetic resin of transfer printing body, open mold for forming and take out synthetic resin.Transfer printing of the present invention is very little than the stripping strength between transfer printing body and the transfer printing layer with the stripping strength of the basement membrane of duplexer and curable resin layer; Thereby in the method that hot transfer printing is sent into duplexer continuously, when the demoulding of moulding article, cause peeling off of curable resin layer and basement membrane.Even under the situation that hot transfer film is sent into single chip mode, also can from the moulding article that taken out, only peel off basement membrane simply.

Through such operation, can obtain the moulding article of curable resin layer for top layer.Curing at the moment of the demoulding, taking-up curable resin layer does not have under the situation of end, it is solidified accomplish.Curable resin layer [II] after the curing becomes the resist of moulding article.

The decorated molded article of operating like this and obtaining is also excellent aspect surface luster.Reason is not clear and definite as yet; But in view of glossiness can obtain through fine concavo-convex (particularly be 1 μ m following concavo-convex) of film coated surface; Can think this be because: between basement membrane and curable resin layer, can be situated between at the tensio-active agent that is oozed out; Not have the curable resin of end to be pullled thereby when basement membrane is peeled off, prevented to solidify, perhaps in moulding, suppressed basement membrane related fold during the curing of being cured property resin to basement membrane.

Embodiment

Below enumerate embodiment the present invention further is described particularly, but the present invention only otherwise exceeding its purport just is not subject to following embodiment.

Explain that " part ", " % " represent weight basis in the example.

[evaluation of measuring method]

(1) evaluation method of polyvinyl alcohol film

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

With PVA (PVOH) FILM at 23 ℃, 50%RH environment held after 24 hours; Under this environment with glass ribbon (the Nichiban Co. of width 24mm; Ltd. make Cellotape (registered trademark) LP-24) be cut to length 10cm, utilize the roller of 2kg to carry out 1 air surface that is attached at PVA (PVOH) FILM back and forth and with said glass ribbon.Then use tensile testing machine, glass ribbon is peelled off from face with the speed of 300mm/ second to the direction of 90 degree, the average load when peelling off 30mm with this moment is measured as stripping strength.

(1-2) resistance to blocking

Cut out the sample strip of 100mm * 100mm from PVA (PVOH) FILM.For 2 sample strip, the face of the air surface side when making film and the face of curtain coating face side are overlapping, after carrying out damping in 24 hours under the 23 ℃ * 60%RH, former state ground under the environment of 23 ℃ * 60%RH from top the hammer of carrying 500g, further placed 24 hours.Thereafter, the situation when peeling off 2 sample strip of institute's eclipsed with hand is estimated resistance to blocking according to following benchmark.

Zero: the degree of overall separation only takes place, sample strip not adhesion each other basically when attempting stripping film.

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

*: the degree of peeling off the needs effort of sample, sample strip is adhered each other.

(2) transfer printing is with the evaluation of duplexer

< transfer printing is with the making of duplexer >

With PVA (PVOH) FILM as basement membrane [I]; Utilizing rod to be coated with machine is that the mode of 160 μ m is coated on this basement membrane [I] with actinic energy ray curable resion composition with thickness; And with it 80 ℃ of dryings 15 minutes, thereby produce the duplexer (α) that the curable resin layer [II] of thickness 80 μ m is arranged in basement membrane [I] laminated.

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

And then; Being coated with machine with rod is coated on above-mentioned thermo-compressed adhesive linkage on printed layers [III] face of duplexer (β) with the mode of coating fluid with thickness 100 μ m; And with it 80 ℃ of dryings 15 minutes; Form the thermo-compressed adhesive linkage [IV] of thickness 20 μ m, obtained the duplexer (γ) that forms by basement membrane [I]/curable resin layer [II]/printed layers [III]/adhesive linkage [IV].

In being heated to 130 ℃ drying machine, duplexer (γ) and blue or green sheet glass substrate (thickness 2.8mm) are carried out preheating in 3 minutes; Make the thermo-compressed caking agent fusion of duplexer (γ); With hand roller (hand roller) this adhesive linkage [IV] face is pressed signature on blue or green sheet glass substrate, thereby produce the applying sample.

For resulting applying sample, the ultraviolet ray across basement membrane [I] irradiation 1000mJ makes curable resin layer [II] be solidified to form resist (the curable resin layer after the curing: hard coat).After forming resist, as following, the resist of peeling off behind the basement membrane is estimated.

< evaluation of resist >

(2-1) the surface luster property of resist

Make the face reflector fluorescent light of resist (the curable resin layer after the curing), according to following benchmark the clarity of luminescent lamp is estimated through visual observation.

Zero: the profile that can clearly see luminescent lamp.

△: the soft edge of luminescent lamp.

*: the profile that can't confirm luminescent lamp.

(2-2) image definition of resist (image clarity)

For the face of resist (the curable resin layer after the curing), use Suga Test Instruments Co., the image definition determinator ICM-1DP of Ltd. measures under following condition, estimates by following benchmark.

(condition determination)

Measuring method: reflection

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

Slit (slit): 0.03mm

Measure hole: 20mm

Light comb width (optical comb width): 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: the minimum light quantity during light comb width (mm)

(metewand)

The above rank of S:90%

A:70～be lower than 90% rank

B:30～be lower than 70% rank

C: be lower than 30% rank

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

In 100 parts of the Z 150PH (A) of the average viscosity (20 ℃) that has shown in the table 1 the such saponification deg and 4% aqueous solution; The polyoxyalkylene alkyl that has the characteristic shown in the table 1 (containing of oxygen ethylidene and oxygen propylidene is proportional, weight-average molecular weight, HLB) according to the amount compounding shown in the table 1; Further add as nonionic be 0.3 part in the polyoxy alkylamino ether (B '-1) of tensio-active agent (B '), as 1 part of the glycerine of softening agent, prepared the polyvinyl alcohol resin aqueous solution (doping) of solid constituent concentration 18%.

This polyvinyl alcohol resin solution spued from the T type die is adjusted into the stainless steel endless belt of 90 ℃ rotation to surface temperature, carry out casting film, has obtained the PVA (PVOH) FILM of thickness shown in the table 1.For resulting PVA (PVOH) FILM, stripping strength and resistance to blocking are estimated based on above-mentioned evaluation method.The result is shown in table 1.

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

The PVA (PVOH) FILM No.1-7 of above-mentioned making is used as basement membrane [I], makes transfer printing based on above-mentioned transfer printing with the making method of duplexer and use duplexer, surperficial glossiness, image definition are estimated based on above-mentioned evaluation method.Result's merging is shown in table 1.

Explain, constitute curable resin layer [II] the active energy beam resin combination, be used for printed layers [III] the appearance design printing with China ink, be used for adhesive linkage [IV] adhesive linkage with coating fluid as following prepare.

(1) actinic energy ray curable resion composition

To become 50% mode 10 parts of solution that carry out diluted mixture and obtain of photopolymerization monomer " Biscoat # 300 " with whole admittedly constituent concentrations with 2-butanone in, being that 3 parts mode is mixed as the rapids industry corporate system of the length of Photoepolymerizationinitiater initiater " IRGACURE 819 " with respect to 100 parts of solid compositions to 40 parts of the solid compositions of the urethane acrylate " UV-3520 " of 50 parts of the solid compositions of the polymethylmethacrylate " MN " of KANEKA CORPORATION system, Japanese synthetic chemical industry corporate system and Osaka organic chemistry industrial system.

(2) the appearance design printing is with China ink

Prepare the intaglio printing that comprises 10 parts of black pigments, 5 parts of Nitrocelluloses, 15 parts of Synolac, 30 parts of toluene, 30 parts in ETHYLE ACETATE, 10 parts of Virahols and used China ink.

(3) adhesive linkage is used coating fluid

The POLY ESTER " SP-185 " (vibrin) of Japanese synthetic chemical industry corporate system is become mode stirring and dissolving under heating circulation condition of 20% with the mixed solvent with respect to 4: 1 (weight ratio) of toluene and 2-butanone.

Table 1

With respect to Z 150PH 100 mass parts; By containing nonionic more than 1 mass parts, that have oxygen ethylidene and oxygen propylidene is tensio-active agent (B) and the stripping strength of the polyvinyl alcohol film No.1-4 that the compsn that obtains forms; With by compounding more than 1 mass parts, only to have any nonionic in oxygen ethylidene or the oxygen propylidene be that tensio-active agent and the polyvinyl alcohol film No.5 that the compsn that obtains forms, the stripping strength of No.6 are in a ratio of below 1/10, can know that its release property is excellent.In addition, be under the situation of tensio-active agent (B) even used nonionic with oxygen ethylidene and oxygen propylidene, the No.7 that contains quantity not sufficient 1 mass parts does not find the reduction of stripping strength yet.Therefore can know that to contain nonionic more than 1 mass parts, that have oxygen ethylidene and oxygen propylidene be tensio-active agent as far as the attenuating of stripping strength with respect to Z 150PH 100 mass parts is effective.In addition, contain 1 mass parts above, have oxygen ethylidene unit and the unitary nonionic of oxygen propylidene is that tensio-active agent does not influence for the resistance to blocking relevant with polyvinyl alcohol film connecting airtight property each other basically.

Can know that in addition about the transfer printing duplexer, under the situation of using the little hot transfer film No.1-4 of stripping strength, the situation of the hot transfer film No.5-7 big with using stripping strength is compared, its surface luster, image definition excellence.

Utilizability on the industry

Polyvinyl alcohol film of the present invention is because release property is excellent, thereby can be used as the basement membrane at a distance from film, transfer film.

Claims (15)

1. a polyvinyl alcohol film is characterized in that, the nonionic that contains 1～20 weight part with respect to polyvinyl alcohol resin (A) 100 weight parts is that tensio-active agent (B) forms, and this nonionic is that tensio-active agent (B) contains aerobic ethylidene and oxygen propylidene.

2. polyvinyl alcohol film according to claim 1; It is characterized in that nonionic is a tensio-active agent (B) for being selected from least a kind in the group of being made up of the polyol ethers (B3) of the fatty ester (B2) of alkyl oxide (B1), addition aerobic ethylidene and the oxygen propylidene of addition aerobic ethylidene and oxygen propylidene and addition aerobic ethylidene and oxygen propylidene.

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

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

5. polyvinyl alcohol film according to claim 1 is characterized in that, nonionic is that the weight-average molecular weight of tensio-active agent (B) is 100～10000.

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

7. according to each described polyvinyl alcohol film in the claim 1～6, it is hydrophilic portion with the polyoxyethylene blocks, is hydrophobic portion with the polyoxypropylene block.

8. according to each described polyvinyl alcohol film in the claim 1～6, it is characterized in that the saponification deg of polyvinyl alcohol resin (A) is 70 moles more than the %.

9. according to each described polyvinyl alcohol film in the claim 1～6, it is characterized in that 20 ℃ of following 4 weight % solution viscosities of polyvinyl alcohol resin (A) are 5～70mPas.

10. a polyvinyl alcohol film is characterized in that, it is that tensio-active agent (B) forms with respect to the nonionic that polyvinyl alcohol resin (A) 100 weight parts contain 1～20 weight part, and this nonionic is that tensio-active agent (B) contains aerobic ethylidene and oxygen propylidene,

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

11. polyvinyl alcohol film according to claim 10, wherein, said nonionic is that the hydrophilic portion of tensio-active agent (B) is a polyoxyethylene blocks, and hydrophobic portion is the polyoxypropylene block, and HLB is 2～18.

12. the method for manufacture of a polyvinyl alcohol film; It is characterized in that; Making the nonionic that contains 1～20 weight part with respect to polyvinyl alcohol resin (A) 100 weight parts is that the polyvinyl alcohol resin aqueous solution that tensio-active agent (B) forms carries out curtain coating and makes film, and this nonionic is that tensio-active agent (B) contains aerobic ethylidene and oxygen propylidene.

13. the method for manufacture of polyvinyl alcohol film according to claim 12 is characterized in that, the concentration of the polyvinyl alcohol resin aqueous solution is 10～30 weight %.

14. duplexer is used in a transfer printing, it is characterized in that, range upon range of in regular turn have basement membrane [I], curable resin layer [II], a printed layers [III] that is formed by each described polyvinyl alcohol film in the claim 1～11.

15. duplexer is used in transfer printing according to claim 14, it is characterized in that, the surfaceness (Ra) of curable resin layer [II] side of basement membrane [I] is below the 1 μ m.