JP2014162089A - Transfer material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide, by targeting a final product obtained by heat-pressing a transfer material onto a molding, a transfer material yielding a recyclable final product by easily releasing the transfer material from the final product.SOLUTION: The provided recyclable transfer material is a recyclable transfer material obtained by laminating a release layer (A), a printing ink layer (B), a molten layer (C), and an adhesive layer (D) atop a film substrate in proper order wherein the molten layer (C) has either a monolayer constitution of a polyvinyl alcohol resin layer (c1) formed from a polyvinyl alcohol resin composition or a bilayer constitution consisting of the resin layer (c1) and a polyurethane resin layer (c2) formed from a polyurethane resin composition.

Description

  The present invention relates to a transfer material in the field of so-called transfer, which is used to decorate molded articles such as plastic automobile interior / exterior products, home appliances, and mobile phones.

  Conventionally, the transfer method is a kind of printing technique that has been widely used as a method for forming a pattern on the surface of various molding substrates. Generally, a transfer material is configured by providing a release layer, a pattern ink layer, and an adhesive layer. When this transfer material is transferred to a molded product such as polycarbonate and the film substrate is peeled off, the release layer is designed to be the uppermost layer of the molded product, and is used as a method for easily painting.

JP-A-5-139093 JP 2002-273830 A

The pattern ink layer constituting the transfer material is a pattern ink layer using a resin composition that has adhesion to the release layer and the adhesive layer, and does not generate cracks on the surface of the transferred material with respect to the uneven shape when molding. To design. Molded products made by thermocompression bonding of this decorative sheet and molded substrate are difficult to remove the ink layer. So far, the molded products have been crushed or dissolved as pellets in the soil and disposed of by combustion. Yes.
In order to recycle the molding substrate, it is necessary to separate the thermocompression-bonded ink layer and the molding substrate, but the technology has not been established at present.

As a result of extensive studies, the present invention has been completed.
That is, the present invention is a recycling transfer material in which a release layer (A), a printing ink layer (B), a dissolution layer (C), and an adhesive layer (D) are sequentially laminated on a film substrate,
The present invention relates to a transfer material for recycling, wherein the dissolved layer (C) is a layer formed by laminating at least a polyvinyl alcohol resin layer (c1).

Furthermore, the present invention relates to the cycle transfer material, wherein the dissolved layer (C) is a layer formed by laminating at least a polyvinyl alcohol resin layer (c1) and a polyurethane resin layer (c2).

Furthermore, the present invention is characterized in that the dissolved layer (C) is a layer formed by sequentially laminating a polyurethane resin layer (c2), a polyvinyl alcohol resin layer (c1), and a polyurethane resin layer (c2). It relates to the above-mentioned transfer material for recycling.

Furthermore, the present invention relates to the above-mentioned transfer material for recycling, wherein a hard coat layer (E) is further laminated between the release layer (A) and the printing ink layer (B).

Furthermore, the present invention relates to the above-mentioned transfer material for recycling, wherein the polyvinyl alcohol resin in the polyvinyl alcohol resin layer has a saponification degree of 80% to 90%.

Furthermore, the present invention relates to a molded product obtained by transferring the above-mentioned recycling transfer material onto a molding substrate.

Furthermore, the present invention relates to a method of immersing a molded product in an aqueous solution and detaching a printing ink layer and a dissolved layer from the molded product.

Completion of the present invention makes it possible to easily separate the ink layer and the molding substrate from the molded product and to suitably recover the molding substrate.

Examples of the film substrate include polyethylene terephthalate, polypropylene, polyethylene, polyvinyl alcohol, and triacetyl acetate film. Polyethylene terephthalate is preferable.

  Examples of the release layer (A) include acrylic resin, polyester resin, and chlorinated rubber resin. Preferred is an acrylic resin alone or a mixture of an acrylic resin and a chlorinated rubber resin.

  The printing ink layer (B) is a layer containing a pigment or a dye in order to impart design properties, concealment properties, and the like. Although a specific method will be described later, it is necessary to remove the pigment and dye in the ink layer when recovering the molded substrate from the molded product. The printing kinky layer (B) is obtained by coating and printing printing ink. Examples of the binder resin for printing ink include polyurethane resin, chlorinated rubber resin, and vinyl chloride / vinyl acetate copolymer resin. A chlorinated rubber resin alone or a mixture of a polyurethane resin and a vinyl chloride / vinyl acetate copolymer resin is preferred.

The polyurethane resin used for printing ink is produced by reacting with a polymer diol, diisocyanate, and chain extender. As a synthesis method, a polymer diol and a diisocyanate are reacted with a solvent inert to an isocyanate group, if necessary, and further with a urethanization catalyst, if necessary, at a temperature of 10 ° C. to 150 ° C. Manufacturing a prepolymer having an isocyanate group, and then reacting the prepolymer with a chain extender and a terminal terminator to obtain a polyurethane resin, or reacting a polymer diol, diisocyanate and chain extender in one step The polyurethane resin can be produced by a known method such as a one-shot method.

The polyurethane resin preferably has a weight average molecular weight of 10,000 to 80,000. If it is less than 10,000, it is difficult to ensure wear resistance, and if it is greater than 80000, it is difficult to ensure the printing effect because the solubility of the ink in the solvent is poor. Preferably it is 30000-70000.
Examples of the polymer diol include polyester diol and polyether diol. The polyester diol is obtained from glycol and dibasic acid by a known method. Examples of the glycol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, pentanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 3-methyl- 1,5-pentanediol, hexanediol, octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4 One or more selected from butynediol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-cyclohexanedimethanol, diethylene glycol, polypropylene glycol, dipropylene glycol and the like can be used. Among these, since the branched monomer gives the polyester an alkyl side chain, the steric hindrance effect lowers the crystallinity of the polyester. Therefore, the flexibility of the film can be improved, and the processing suitability associated with the transfer can be improved.

As other diols, dimer diols and polymerized fatty acid polyester diols can be used. Dimer diol is obtained by reducing the carboxyl group of dimer acid which is a dimerization reaction product of unsaturated fatty acid. The polymerized fatty acid polyester diol is obtained by a reaction product of a dimer diol and a dicarboxylic acid or an anhydride thereof, or a reaction of a dimer acid and a diol compound.

Dibasic acids include adipic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, speric acid, azelaic acid, sebacic acid, Examples thereof include polyvalent carboxylic acids such as trimellitic acid and pyromellitic acid, and anhydrides thereof. Among these, it is preferable to use adipic acid from the viewpoint of solubility in a non-toluene solvent.

The number average molecular weight of the polyester diol is appropriately determined in consideration of the solubility, drying property, blocking resistance and the like of the resulting polyurethane resin, and is usually 700 to 10,000, preferably 1000 to 6,000. . If the number average molecular weight is less than 700, the printability tends to be inferior due to a decrease in solubility due to an increase in the amount of hard segments. On the other hand, if the number average molecular weight exceeds 10,000, the proportion of hard segments decreases, and drying and blocking resistance are reduced. Tend to decrease.

In addition, the weight average molecular weight mentioned above used GPC (gel permeation chromatography) "ShodexGPC System-21" by Showa Denko KK. GPC is liquid chromatography that separates and quantifies substances dissolved in a solvent based on the difference in molecular size. Tetrohydrofuran is used as a solvent, and the weight average molecular weight is determined in terms of polystyrene.

Further, the number average molecular weight was calculated from the hydroxyl value.

The hydroxyl value is a value obtained by converting the amount of hydroxyl group in 1 g of resin calculated by esterifying or acetylating the hydroxyl group in the resin with an excess of anhydrous acid and back titrating the remaining acid with alkali to the number of mg of potassium hydroxide. Thus, it is a value performed according to JISK0070.
The amine value is the number of mg of potassium hydroxide equivalent to the equivalent amount of hydrochloric acid required to neutralize the amino group contained in 1 g of resin.

Examples of the polyether polyol include polymer diols such as ethylene oxide, propylene oxide, and tetrahydrofuran, or copolymers.

Other than the polymer diol, triethylene glycol, glycerin having two or more hydroxyl groups, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, sorbitol, pentaes It is also possible to use a trivalent or higher molecular polyol such as lithol as a urethane monomer, and further to use it as a raw material for various polymer polyols.

Examples of the diisocyanate used in the polyurethane resin include various known aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates that are generally used in the production of polyurethane resins. For example, 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1 , 3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, Cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate Nate, dimethylene diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, m-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, tri Examples thereof include diisocyanate, dimerisocyanate obtained by converting a diisocyanate carboxyl group into diisocyanate, bis-chloromethyl-diphenylmethane-diisocyanate, 2,6-diisocyanate-benzyl chloride, and a dimer acid carboxyl group. These diisocyanate compounds can be used alone or in admixture of two or more.

,
Examples of chain extenders include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, dicyclohexylmethane-4,4′-diamine, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropyldiamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypyrroleethylenediamine, di-2-hydroxypyrroleethylenediamine, di-2 -Amines having a hydroxyl group in the molecule such as hydroxypropylethylenediamine can also be used. These chain extenders can be used alone or in admixture of two or more.

In the present invention, the polyurethane resin used for the printing ink layer (B) is a resin synthesized with polyester diol, diisocyanate, and amine chain extender, so that the film followability during transfer, the adhesion between the layers of the transfer material, This is particularly preferable in terms of balance such as peeling during use.

A monovalent active hydrogen compound can also be used as a terminal terminator for the purpose of terminating the reaction. Examples of such compounds include compounds having primary and secondary amino groups, dialkylamines such as di-n-butylamine, amino alcohols having a hydroxyl group, and alcohols such as ethanol and isopropyl alcohol. Furthermore, amino acids such as glycine and L-alanine can be used as a reaction terminator, particularly when it is desired to introduce a carboxyl group into the polyurethane resin. Among these, amino alcohols having primary and secondary amino groups need to be controlled so as to react only with amino groups while avoiding reaction at high temperature when used as a terminal terminator. These end terminators can be used alone or in admixture of two or more. Here, when an amino group is used as a chain extender, it reacts with an isocyanate group to form a urea bond, so that the resulting resin is a polyurethane / urea resin. In the present invention, these resins are also polyurethane resins. To do.

When using an end-stopper, the end-stopper and chain extender may be used together to carry out a chain extension reaction. Thus, an end termination reaction may be performed. On the other hand, the molecular weight can be controlled without using a terminal terminator, but in this case, a method of adding a prepolymer to a solution containing a chain extender is preferable in terms of reaction control.

The amine value of the polyurethane resin used in the present invention is preferably 0.5 to 20 mgKOH / g. When the amine value is lower than 0.5 mgKOH / g, it is difficult to ensure adhesion, and when it is greater than 20 mgKOH / g, it may be difficult to ensure ink stability when an isocyanate curing agent is added.

A catalyst can also be used in the urethanization reaction. Examples of catalysts that can be used include tertiary amine catalysts such as triethylamine and dimethylaniline; metal catalysts such as tin and zinc. These catalysts are usually used in the range of 0.001 to 1 mol% with respect to the polyol.

Solvents used to synthesize polyurethane resins include ketones such as acetone, methyl ethyl ketone, and cyclohexanone, ethers such as dioxane and tetrahydrofuran, aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate and butyl acetate, and chlorobenzene. And halogen-based hydrocarbons such as parkren. These may be used alone or in combination as a mixed solvent.

The printing ink layer (B) constituting the structure of the present invention is preferably a vinyl chloride / vinyl acetate copolymer resin, particularly a hydroxyl group-containing one in addition to the polyurethane resin. A vinyl chloride / vinyl acetate copolymer resin having a hydroxyl group is a partially saponified copolymer of a vinyl chloride monomer and a vinyl acetate monomer, or a monomer having a hydroxyl group that can be copolymerized with a vinyl chloride monomer and a vinyl acetate monomer, for example, It can be obtained by copolymerizing 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate or the like. The copolymer may also contain acrylamide, acrylonitrile, glycidyl methacrylate, dimethylaminoethyl (meth) acrylate, and the like.

The hydroxyl value of the vinyl chloride / vinyl acetate copolymer resin is preferably 70 to 180 mgKOH / g. When it is less than 70 mgKOH / g, the color developability of the pigment is poor, and when it is more than 180 mgKOH / g, the water resistance of the coating film is poor. Moreover, it is preferable to use the usage-amount of vinyl chloride / vinyl acetate copolymer resin in the range of polyurethane resin / vinyl chloride-vinyl acetate copolymer = 50: 50-90: 10 (solid content ratio). If the amount of the polyurethane resin used is less than 50, the heat and pressure resistance at the time of molding becomes poor, and if it is more than 90, the color developability of the organic pigment is inferior.

In the printing ink layer, a chlorinated rubber resin may be used alone. Known chlorinated rubber resins can be used. Other resins include chlorinated polypropylene resin, vinyl acetate resin, polyamide resin, nitrocellulose, acrylic resin, polyester resin, alkyd resin, polyvinyl chloride resin, rosin resin, rosin modified, depending on the application and molding substrate. Mention may be made of maleic acid resins, terpene resins, phenol-modified terpene resins, ketone resins, cyclized rubbers, butyral resins, petroleum resins, and modified resins thereof. These resins can be used alone or in admixture of two or more.

The printing ink used for the printing ink layer (B) is composed of pigment, silica, solvent and the like in addition to the above resin.
Commonly used pigments can be used as the pigment, and among them, pigments with high light resistance and weather resistance are desirable. Examples of pigments having high light resistance and high weather resistance include quinacridone, anthraquinone, perylene, perinone, diketopyrrolopyrrole, isoindolinone, condensed azo, benzimidazolone, monoazo, insoluble azo , Naphthol, flavanthrone, anthrapyrimidine, quinophthalone, pyranthrone, pyrazolone, thioindigo, anthanthrone, dioxazine, phthalocyanine, indanthrone, and other organic pigments, nickel dioxin yellow, copper Examples thereof include metal complexes such as azomethine yellow, metal oxides such as titanium oxide, iron oxide and zinc oxide, metal salts such as barium sulfate and calcium carbonate, and inorganic pigments such as carbon black, aluminum and mica.
Examples of the dye include azo series, quinoline series, stilbene series, thiazole series, indigoid series, anthraquinone series, and oxazine series.

Silica includes naturally collected and synthetic silica. In synthetic silica, there are wet method silica (precipitation method, gel method) and dry method silica (combustion method, arc method) from the production method, and further, the particle surface is made of organic substances such as silane coupling agent, microcrystalline, and alumina, Some are surface-treated with an inorganic substance. Silica is not limited to those that have not been subjected to surface treatment, those that have been subjected to surface treatment, and in particular differences in the production method.
Furthermore, the particle diameter of silica is preferably 1 to 20 μm, more preferably 1 to 10 μm. The shape can be either spherical or irregular, but more preferably spherical.

When 0.1 to 5% by weight of silica is used in the printing ink, the overprinting property is improved.
As fillers other than silica, inorganic fillers such as alumina, talc, magnesium carbonate, calcium carbonate, natural mica, synthetic mica, aluminum hydroxide, precipitated barium sulfate, precipitated barium carbonate, barium titanate, and barium sulfate are used in combination. be able to. You may use the said filler 1 type or in mixture of 2 or more types.

For printing inks, if necessary, add additives such as antifoaming agents and leveling agents, UV absorbers, light stabilizers, antioxidants, fungicides, fungicides, pigments or dyes to the final physical properties of the cured film. Can be used within the range that does not affect.

Solvents used in printing inks include aromatic organic solvents such as toluene and xylene, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate, n-propyl acetate, isopropyl acetate, isobutyl acetate, propylene glycol monoethyl ether acetate, Known solvents such as ester solvents such as propylene glycol monomethyl ether acetate, alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, propylene glycol monoethyl ether and propylene glycol monomethyl ether can be used.

The printing ink layer (B) is formed by coating and printing of printing ink.
As coating methods, gravure coating method, gravure offset method, reverse coating method, die coating method, lip coating method, comma coating method, blade coating method, roll coating method, knife coating method, curtain coating method, slot orifice method, spray Examples include a coating method. In this case, it may be applied in several times, may be applied once, or a plurality of different methods may be combined.

The printing ink layer (B) in the present invention may be a single layer of printing ink or a layer of printing ink layers, for example, a single layer of white ink, a single layer of color ink, or a color ink layer / white. A layered ink layer can be used.

The dissolved layer (C) needs to be dissolved in an aqueous solution at the time of recovery of the molding substrate. When the dissolved layer (C) is dissolved in the aqueous solution, the ink layer can be separated from the molded substrate, and the molded substrate can be recovered and reused.
The polyvinyl alcohol resin layer (c1) formed from the polyvinyl alcohol resin composition used in the dissolved layer (C) contains a polyvinyl alcohol resin, and the resin completely or partially saponifies the vinyl ester polymer. It can obtain using the well-known method.
Examples of the vinyl ester include vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl versatate, etc. Among them, vinyl acetate is industrially most preferable.

  Other vinyl compounds can be copolymerized with the vinyl ester. Other vinyl monomers include unsaturated monocarboxylic acids such as crotonic acid, acrylic acid, and methacrylic acid and their esters, salts, anhydrides, amides, nitriles, and unsaturated acids such as maleic acid, itaconic acid, and fumaric acid. Examples thereof include dicarboxylic acids and salts thereof, α-olefins having 2 to 30 carbon atoms, alkyl vinyl ethers, vinyl pyrrolidones and the like. As the saponification method, a known alkali saponification method or acid saponification method can be used, and among them, a method of alcoholysis using an alkali hydroxide in methanol is preferable. If the degree of saponification is too low, the film-forming property is lowered and the barrier performance is lowered. From the viewpoint of the release property of the ink layer, the saponification degree of the polyvinyl alcohol resin is preferably 80% or more, and the polymerization degree is preferably 300 or more and 2500 or less. More preferably, the saponification degree is 80% or more and 90% or less, and the polymerization degree is 1000 or more and 2000 or less.

As the polyurethane resin used for the polyurethane resin layer (c2) constituting the dissolved layer (C), the polyurethane resin described in the above-described printing ink layer (B) can be used. In this case, the polyurethane resin of the polyurethane resin layer (c2) may be the same as or different from the polyurethane resin used for the printing ink layer (B).
Moreover, it is preferable that the polyurethane resin composition used for a polyurethane resin layer (c2) contains the vinyl chloride / vinyl acetate copolymer mentioned above other than a polyurethane resin. By containing a vinyl chloride / vinyl acetate copolymer, heat resistance is improved and excellent transfer performance is obtained.

Examples of the adhesive layer (D) include acrylic resin, polyester resin, vinyl chloride / vinyl acetate copolymer resin, vinyl acetate resin, xylene resin, polyester polyol, and acrylic polyol. An acrylic resin alone or a mixture of an acrylic resin and a xylene resin is preferable.

 Addition of xylene resin further improves the adhesion to the molded product. Xylene resin is a multimer composition with a basic structure in which xylene is cross-linked by a methylene group or an ether bond, and the terminal part is an OH group, so it has excellent compatibility with many synthetic resins. It is possible to improve transfer performance such as improvement of adhesiveness. A xylene resin having a viscosity of 100 to 1000 (mPa · S) and a hydroxyl value of 10 to 30 (mgKOH / g) can be used. The viscosity is preferably 200 to 400 (mPa · S), and the hydroxyl value is 15 to 25 (mgKOH / g).

As a molding substrate to which the transfer material for recycling of the present invention can be applied, PS (polystyrene), ABS (acrylic butadiene styrene), PC (polycarbonate), PVC (vinyl chloride), PP (polypropylene) which are known molding substrates. ), PE (polyethylene), PET (polyester), and the like. As applications, for example, it can be used for toys, food containers, cosmetic containers, stationery, light electrical appliances, miscellaneous goods, dashboards, PVC blow bottles, PVC cards, washbasins, household goods, play equipment, bottles and the like.

Transfer of the transfer material for recycling onto the molding substrate is performed by a known method. For example, there is a simultaneous molding transfer method in which a transfer material is placed in a cavity and a pattern is transferred to a molded product simultaneously with injection molding.

The specific constitution of the transfer material in the present invention is constitution 1: film base material / peeling layer (A) / printing ink layer (B) / polyvinyl alcohol resin layer (c1) / adhesive layer (D).
Configuration 2: film base material / peeling layer (A) / printing ink layer (B) / polyvinyl alcohol resin layer (c1) / polyurethane resin layer (c2) / adhesive layer (D).
Configuration 3: film substrate / release layer (A) / printing ink layer (B) / polyurethane resin layer (c2) / polyvinyl alcohol resin layer (c1) / adhesive layer (D).
Configuration 4: film base material / release layer (A) / printing ink layer (B) / polyurethane resin layer (c2) / polyvinyl alcohol resin layer (c1) / polyurethane resin layer (c2) / adhesive layer (D).
Etc. are raised. In any configuration, the final molded product onto which the transfer material has been transferred is excellent in recyclability. In particular, the dissolved layer (C) is polyurethane resin layer (c2) / polyvinyl alcohol resin layer (c1) / polyurethane resin layer (c2). By doing so, a transfer material excellent in adhesion and recyclability between the transfer material and the molded product can be obtained.

A hard coat layer (E) may be provided between the release layer (A) and the printing ink layer (B). The hard coat layer (E) can be obtained by curing the active energy ray-curable composition with active energy rays. The composition comprises an active energy ray-curable monomer, an active energy ray-curable oligomer, a resin, a photopolymerization initiator, and the like.
The active energy ray-curable monomer is added for the purpose of improving the physical properties of the surface protective layer and adjusting the viscosity of the active energy ray-curable composition, and includes monofunctional and polyfunctional monomers having a (meth) acrylate group. Can be mentioned.

 Monofunctional monomers include 2- (2-ethoxyethoxy) ethyl acrylate, stearyl acrylate, tetrahydrofurfuryl acrylate, lauryl acrylate, 2-phenoxyethyl acrylate, indecyl acrylate, isooctyl acrylate, tridecyl acrylate, caprolactone acrylate, 4 -Hydroxybutyl acrylate, ethoxylated noniphenol acrylate, propoxylated nonylphenol acrylate, phenoxyethyl acrylate, phenoxydiethylene acrylate, ethylene oxide modified nonylphenyl acrylate, methoxytriethylene glycol acrylate, ethylene oxide 2-ethylhexyl acrylate, isobornyl acrylate, di Propylene glycol acrylate DOO, or the like, or methacrylate monomers.

Examples of polyfunctional monomers include tris (2-hydroxyethyl) isocyanurate triacrylate, ethylene oxide modified trimethylolpropane triacrylate, propylene oxide modified trimethylolpropane triacrylate, propylene oxide modified glyceryl triacrylate, pentaerythritol triacrylate, trimethylol. Propane acrylate, ethylene oxide modified trimethylolpropane acrylate, propylene oxide modified trimethylolpropane acrylate, tris (acryloxyethyl) isocyanurate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hydroxypentaacrylate, ethoxylated pentaerythris Lito Le tetraacrylate, pentaacrylate ester, and dipentaerythritol hexaacrylate, or the like, or methacrylate monomers.

The active energy ray-curable oligomer imparts resistance and flexibility to the surface protective layer, and those having a molecular weight of 1000 or more are preferably used. Examples thereof include urethane acrylate having a (meth) acrylate group, polyester acrylate, acrylic acrylate, epoxy acrylate and the like. Of these, urethane acrylate is preferable in terms of both surface hardness and moldability.

  For the hard coat layer (E), a resin such as a thermoplastic acrylic resin, a polyester resin, or a vinyl chloride-vinyl acetate copolymer is used in order to suppress surface tackiness and impart flexibility. Acrylic resin is preferable.

 Examples of the curing method of the active energy ray-curable composition include electron beam curing and ultraviolet curing. Any method may be used, but when UV curing is performed, a photoinitiator is required for curing. Commonly used photoinitiators include acetophenones such as diacetoxyacetophenone and 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzoin ethers such as isobutyl benzoin ether and isopropyl benzoin ether, benzyldimethyl ketal, Examples include benzyl ketals such as hydroxycyclohexyl phenyl ketone, and ketones such as benzophenone and 2-chlorothioxanthone. In the case of the electron beam curable type, a photoinitiator is not necessarily required.

In the case of curing with an electron beam, a conventionally known curing apparatus can be used, and the irradiation dose is preferably 10 kGy to 200 kGy, and more preferably 30 kGy to 100 kGy. If it is less than 10 kGy, complete curing cannot be achieved, and if it exceeds 200 kGy, the life of the electron beam irradiation tube is remarkably shortened, which is not economical.

When a hard coat layer (E) is provided between the release layer (A) and the printing ink layer (B), a known two-component curing obtained by reacting an acrylic polyol and an isocyanate in addition to the active energy ray-curable composition. Mold resin can also be used.

Examples of the transfer material of the present invention including the hard coat layer (E) include the following.
Configuration 5: film base material / release layer (A) / hard coat layer (E) / printing ink layer (B) / polyvinyl alcohol resin layer (c1) / adhesive layer (D).
Configuration 6: film base material / release layer (A) / hard coat layer (E) / printing ink layer (B) / polyurethane resin layer (c2) / polyvinyl alcohol resin layer (c1) / adhesive layer (D).
Configuration 7: film substrate / release layer (A) / hard coat layer (E) / printing ink layer (B) / polyurethane resin layer (c2) / polyvinyl alcohol resin layer (c1) / polyurethane resin layer (c2) / adhesion Layer (D).

The ink detachment solution used in the present invention needs to be a solution containing water. When water is contained, the polyvinyl alcohol resin layer of the dissolving layer is dissolved, and the ink layer containing the colored pigment can be suitably detached. By separating the ink layer, the molded substrate can be reused suitably.
In addition, it is preferable not to use organic solvents other than methanol, ethanol, isopropyl alcohol, and N propyl alcohol together because the organic solvent tends to attack the molding substrate.
Furthermore, from the viewpoint of solubility of the polyvinyl alcohol resin, the aqueous solution is preferably weakly acidic to alkaline (pH is 5 or more), more preferably neutral to alkaline (pH 7 or more).

Next, an Example is given and this invention is demonstrated concretely. In the examples, “parts” represents parts by weight.
Film base material, release layer (A), printing ink layer (B), dissolved layer (C), adhesive layer (D) and hardware constituting the transfer material in Examples 1 to 9 and Comparative Examples 1 and 2 The coat layer (E) is shown below. In addition, it is the same in each Example except the polyvinyl alcohol resin layer (c1) of a melt | dissolution layer (C).

(1) Film base: Polyethylene terephthalate (Toyobo polyester film mirror thickness 25 μm) (hereinafter referred to as PET film)
(2) Release layer (A): 20 parts of acrylic resin (Dianar BR101, manufactured by Mitsubishi Rayon Co., Ltd.), 5 parts of chlorinated rubber (Pergut S-20, manufactured by Bayer), solvent (toluene / methyl ethyl ketone = 5/2) 75 A release varnish formed by mixing the parts was formed by coating by a gravure coating method.

(3) Printing ink layer (B): 20 parts of indigo pigment, 15 parts of polyurethane resin solution, and 10 parts of n-propyl acetate / isopropyl alcohol mixed solution (weight ratio 75/25) were stirred and mixed and kneaded with a sand mill. Indigo ink was obtained by stirring and mixing 45 parts of a polyurethane resin solution and 10 parts of a mixed solution of n-propyl acetate / isopropyl alcohol (weight ratio 75/25). Furthermore, 100 parts of indigo ink was diluted with 50 parts of the mixed solution and printed by gravure to form a printing ink layer.
The polyurethane resin solution was adjusted as follows.

<Preparation of polyurethane resin solution>
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 18.6 parts of PMPA (poly-3-methyl-1,5-pentaneadipate, number average molecular weight 2000), polypropylene glycol (number Average molecular weight 2000) 3.2 parts and 2.4 parts of isophorone diisocyanate were charged, reacted at 120 ° C. for 6 hours under a nitrogen stream, cooled by adding 10 parts of n-propyl acetate, and 34.1 terminal isocyanate prepolymer solution 34.1. Got a part. Next, a solvent solution of the obtained terminal isocyanate prepolymer was added to a solution obtained by mixing 0.91 part of isophoronediamine, 0.014 part of di-n-butylamine, 46.3 parts of n-propyl acetate and 18.8 parts of isopropyl alcohol. 1 part was gradually added at room temperature, and then reacted at 50 ° C. for 1 hour to obtain a polyurethane resin solution having a solid content of 25%, a weight average molecular weight of 76000, and an amine value of 1.5 mgKOH / resin 1 g.

(4) Polyvinyl alcohol resin layer (c1): A polyvinyl alcohol resin was dissolved in water to obtain a polyvinyl alcohol resin solution having a solid content of 10%. A polyvinyl alcohol resin layer (c1) was formed by printing this solution by a gravure method. In addition, polyvinyl alcohol resin layer (c1) produced polyvinyl alcohol resin layers (c1-1) to (c1-6), a total of six types, depending on the type of polyvinyl alcohol.

Polyvinyl alcohol having various saponification degrees and polymerization degrees was obtained from Kuraray Co., Ltd.
The breakdown of the polyvinyl alcohol used in (c1-1) to (c1-6) is as follows.
(C1-1): PVA-105 (saponification degree 98%, polymerization degree 500, manufactured by Kuraray Co., Ltd.)
(C1-2): PVA-117 (saponification degree 98%, polymerization degree 1700, manufactured by Kuraray Co., Ltd.)
(C1-3): PVA-124 (degree of saponification 98%, degree of polymerization 2400, manufactured by Kuraray Co., Ltd.)
(C1-4): PVA-205 (saponification degree 89%, polymerization degree 500, manufactured by Kuraray Co., Ltd.)
(C1-5): PVA-217 (degree of saponification 89%, degree of polymerization 1700, manufactured by Kuraray Co., Ltd.)
(C1-6): PVA-224 (degree of saponification 89%, degree of polymerization 2400, manufactured by Kuraray Co., Ltd.)

(5) Polyurethane resin layer (c2): applying a resin coating agent for gravure coating (solid content 20%) obtained by mixing the polyurethane resin solution and a mixed solvent (ethyl acetate / isopropyl alcohol = 75/25). Formed with.

(6) Adhesive layer (D): 40 parts of acrylic resin (Dianar BR101, manufactured by Mitsubishi Rayon Co., Ltd.), 10 parts of xylene resin (Nikanol Y-50, manufactured by Mitsubishi Gas Chemical Co., Ltd.), mixed solvent (toluene / methyl ethyl ketone = 1 / 1) It was formed by applying an adhesive formed by mixing 50 parts.

(7) Hard coat layer (E): An active energy ray-curable resin composition (Harima Kasei Co., Ltd. curable resin HFC-MR02 / H-240F) was applied and cured.

[Example 1]
The transfer product 1 was obtained by the following lamination procedure (1) to (5).
(1) A release agent (A) was applied to a PET film substrate by a gravure coating method to form a release layer having a thickness of 1 μm.
(2) The printing ink (B) was printed on the release layer by a gravure printing method with a screen gravure plate having a plate depth of 35 μm at a printing speed of 60 (m / min).
(3) The polyurethane resin layer (c2) was printed on the printing ink at a printing speed of 60 (m / min) by a gravure printing method with a screen gravure plate having a plate depth of 35 μm.
(4) The polyvinyl alcohol resin layer (c1-1) was printed on the polyurethane resin layer (c2) by a gravure printing method with a screen gravure plate having a plate depth of 35 μm at a printing speed of 60 (m / min).
(5) The adhesive layer (D) is printed on the polyvinyl alcohol resin layer (c1-1) at a printing speed of 60 (m / min) by a gravure printing method and a gravure printing plate having a plate depth of 35 μm. The recycle transfer material 1 shown was obtained.
Transfer material 1: PET film / peeling layer (A) / printing ink layer (B) / polyurethane resin layer (c2) / polyvinyl alcohol resin layer (c1-1) / adhesive layer (D)

[Examples 2 to 7]
Also in Examples 2 to 7, transfer materials 2 to 7 were obtained by the same method and conditions as in Example 1. Furthermore, each transfer material was transcribe | transferred to the shaping | molding base material (polycarbonate), and the transcription | transfer materials 2-7 were obtained. A specific configuration of the transfer material is described below.

Example 2 (transfer material 2): PET film / peeling layer (A) / printing ink layer (B) / polyurethane resin layer (c2) / polyvinyl alcohol resin layer (c1-2) / adhesive layer (D)
Example 3 (transfer material 3): PET film / peeling layer (A) / printing ink layer (B) / polyurethane resin layer (c2) / polyvinyl alcohol resin layer (c1-3) / adhesive layer (D)
Example 4 (transfer material 4): PET film / peeling layer (A) / printing ink layer (B) / polyurethane resin layer (c2) / polyvinyl alcohol resin layer (c1-4) / adhesive layer (D)
Example 5 (transfer material 5): PET film / peeling layer (A) / printing ink layer (B) / polyurethane resin layer (c2) / polyvinyl alcohol resin layer (c1-5) / adhesive layer (D)
Example 6 (transfer material 6): PET film / peeling layer (A) / printing ink layer (B) / polyurethane resin layer (c2) / polyvinyl alcohol resin layer (c1-6) / adhesive layer (D)
Example 7 (transfer material 7): PET film / peeling layer (A) / printing ink layer (B) / polyurethane resin layer (c2) / polyvinyl alcohol resin layer (c1-5) / polyurethane resin layer (c2) / adhesion Layer (D)

[Example 8]
A release agent was applied to a PET film substrate by a gravure coating method to obtain a release layer having a thickness of 1 μm. Next, an active energy ray-curable resin was printed on a gravure printing method (a screen gravure plate with a plate depth of 35 μm). 60 (m / min)), printing was performed on the release layer, and the printed matter including the release layer was dried with hot air at 90 ° C. to form an uncured hard coat layer. Then, a hard coat layer was obtained by curing under two metal halide pumps with an output of 80 (W / CM).
Next, printing ink was printed on the hard coat layer by a gravure printing method with a screen gravure plate having a plate depth of 35 μm at a printing speed of 60 (m / min).
Next, the polyurethane resin layer (c2) was printed on the printing ink by a gravure printing method with a screen gravure plate having a plate depth of 35 μm at a printing speed of 60 (m / min).
Furthermore, the polyvinyl alcohol resin layer (c1-1) was printed on the polyurethane resin layer (c2) by a gravure printing method with a screen gravure plate having a plate depth of 35 μm at a printing speed of 60 (m / min).
Next, an adhesive layer is formed on the polyvinyl alcohol resin layer (c1-1) at a printing speed of 60 (m / min) by a gravure printing method with a screen gravure plate having a plate depth of 35 μm. 8 was obtained.
Example 8 (transfer material 8): PET film / peeling layer (A) / hard coat layer (E) / printing ink layer (B) / polyurethane resin layer (c2) / polyvinyl alcohol resin layer (c1-1) / adhesion Layer (D).
The transfer material 8 obtained by the above method was transferred to a molding substrate (polycarbonate) at 230 ° C. to obtain a molded product. After cooling to room temperature, the transfer product 8 was obtained by peeling the PET film from the transfer product by hand.

[Example 9]
A release agent was applied to the PET film substrate by gravure coating to obtain a release layer with a thickness of 1 μm. Next, an active energy ray-curable resin was printed with a gravure printing method on a screen gravure plate with a plate depth of 35 μm. Printing was performed on the release layer at a speed of 60 (m / min), and the printed matter including the release layer was dried with hot air at 90 ° C. to form an uncured hard coat layer. Then, a hard coat layer was obtained by curing under two metal halide pumps with an output of 80 (W / CM).
Next, printing ink was printed on the hard coat layer by a gravure printing method with a screen gravure plate having a plate depth of 35 μm at a printing speed of 60 (m / min).
Next, the polyurethane resin layer (c2) was printed on the printing ink layer by a gravure printing method with a screen gravure plate having a plate depth of 35 μm at a printing speed of 60 (m / min).
Next, a polyvinyl alcohol resin layer (c1-5) was formed on the polyurethane resin layer (c2) at a printing speed of 60 (m / min) by a gravure printing method and a gravure printing plate having a plate depth of 35 μm.
Next, the polyurethane resin layer (c2) was printed on the polyvinyl alcohol resin layer (c1-5) by a gravure printing method with a screen gravure plate having a plate depth of 35 μm at a printing speed of 60 (m / min).
Further, the adhesive layer was printed on the polyurethane resin layer (c2) by a gravure printing method with a screen gravure plate having a plate depth of 35 μm at a printing speed of 60 (m / min) to obtain a recycle transfer material 9 shown below.
Transfer material 9: PET film / peeling layer (A) / hard coat layer (E) / printing ink layer (B) / polyurethane resin layer (c2) / polyvinyl alcohol resin layer (c1-5) / polyurethane resin layer (c2) ) / Adhesive layer (D).
The transfer material 9 obtained by the above method was transferred to a molding substrate (polycarbonate) at 230 ° C. to obtain a molded product. After cooling to room temperature, the transfer product 9 was obtained by peeling the PET film from the transfer product by hand.

In addition, the polyvinyl alcohol resin used for the melt | dissolution layer (C) of Examples 1-6 was used as aqueous solution melt | dissolved in resin 5% and water 95%. When the polyvinyl alcohol resin had a saponification degree of 98% and a molecular weight exceeding 500, the solubility in water was poor, and products having a saponification degree of 98% and a molecular weight exceeding 500 were excluded from the test.

[Comparative Example 1]
A release agent was applied to a PET film substrate by a gravure coating method to obtain a release layer having a film thickness of 1 μm. Next, a printing ink was applied by a gravure printing method with a screen gravure plate having a plate depth of 35 μm and a printing speed of 60 ( m / min) on the release layer. Next, the adhesive layer was printed on a printing ink at a printing speed of 60 (m / min) with a gravure printing method and a screen gravure plate having a plate depth of 35 μm to obtain a recycle transfer material 10 shown below.
Transfer material 10: PET film / peeling layer (A) / printing ink layer (B) / adhesive layer (D).
The transfer material 10 obtained by the above method was transferred to a molding substrate (polycarbonate) at 230 ° C. to obtain a molded product. After cooling to room temperature, the transfer product 10 was obtained by peeling the PET film from the transfer product by hand.

[Comparative Example 2]
A release agent was applied to a PET film substrate by a gravure coating method to obtain a release layer having a film thickness of 1 μm. Next, a printing ink was applied by a gravure printing method with a screen gravure plate having a plate depth of 35 μm and a printing speed of 60 ( m / min) on the release layer. Next, the polyurethane resin layer (c2) was printed on the printing ink by a gravure printing method with a screen gravure plate having a plate depth of 35 μm at a printing speed of 60 (m / min). Next, the adhesive layer was printed on a printing ink by a gravure printing method with a screen gravure plate having a plate depth of 35 μm at a printing speed of 60 (m / min) to obtain a recycle transfer material 11 shown below.
Transfer material 11: PET film / peeling layer (A) / printing ink layer (B) / polyurethane resin layer (c2) / adhesive layer (D).
The transfer material 11 obtained by the above method was transferred to a molding substrate (polycarbonate) at 230 ° C. to obtain a molded product. After cooling to room temperature, the transfer material 11 was obtained by peeling the PET film from the transfer material by hand.

  The recycle transfer materials and transfer products obtained in Examples 1 to 9 and Comparative Examples 1 and 2 were evaluated for followability during molding and ink detachability (distilled water, aqueous caustic soda, hydrochloric acid). The evaluation method and evaluation criteria are shown below.

1. Followability at the time of molding Using the created transfer material, the surface and side surfaces of the molded base material (polycarbonate) molded product were simultaneously transferred by the simultaneous molding method, and the occurrence of cracks on the side surface (R processed portion) was evaluated.
Judgment criteria: ○ Cracks do not occur on the side surface (R processed part).
Δ: A small crack occurs in a part of the side surface (R processed portion).
×: Cracks occur on the entire side surface (R processed part).
The practical level is Δ or more.

2. Ink layer release (distilled water)
Using the created transfer material, the molded base material (polycarbonate) molded product is immersed in water (distilled water) for 24 hours by the simultaneous molding method, and then the water is stirred to form a printing ink layer (polycarbonate) from the molded base material (polycarbonate). The release property of B) was evaluated. The pH of distilled water was 7.
Judgment criteria: ◎ Peeling area is 99% or more
○ Stripping area is 97% or more and less than 99%
○ △ Peeling area is 93% or more and less than 97%
△ Peeling area is 90% or more and less than 93%
× Peeling area is less than 90%
The practical level is Δ or more.

3. Ink layer detachability (caustic soda solution)
Using the created transfer material, the molded base material (polycarbonate) molded product is immersed in an aqueous caustic soda solution for 24 hours by the simultaneous molding method, and the aqueous caustic soda solution is stirred to print the ink layer (B) from the molded base material (polycarbonate). The release property of was evaluated. Judgment criteria are the same as the evaluation of detachability using distilled water. The pH of the aqueous caustic soda solution was 12.5.

4). Ink layer release (hydrochloric acid solution)
Using the created transfer material, the molded substrate (polycarbonate) molded product is immersed in a hydrochloric acid solution for 24 hours by the simultaneous molding transfer method, and then the hydrochloric acid solution is stirred and the printing ink layer (B) from the molded substrate (polycarbonate) The release property of was evaluated. Judgment criteria are the same as the evaluation of detachability using distilled water. The pH of the hydrochloric acid solution was 2.5.

The evaluation results are shown in Table 1.
From the results of Examples 1 to 9, the transfer material for recycling of the present invention has excellent followability at the time of molding, and further, the printing ink layer (B) can be separated from the molding substrate (distilled water, aqueous caustic soda, hydrochloric acid). I found it excellent.
In addition, the results of Comparative Examples 1 and 2 indicate that the ink releasability is poor when the dissolved layer (C) does not exist and when the dissolved layer (C) does not have the polyvinyl alcohol resin layer (c1). It was done.
The releasability was better when a neutral to alkaline aqueous solution was used.

Claims (7)

A transfer material for recycling in which a release layer (A), a printing ink layer (B), a dissolved layer (C), and an adhesive layer (D) are sequentially laminated on a film substrate,
A transfer material for recycling, wherein the dissolved layer (C) is a layer formed by laminating at least a polyvinyl alcohol resin layer (c1). The cycle transfer material according to claim 1, wherein the dissolved layer (C) is a layer formed by laminating at least a polyvinyl alcohol resin layer (c1) and a polyurethane resin layer (c2). The dissolved layer (C) is a layer formed by laminating a polyurethane resin layer (c2), a polyvinyl alcohol resin layer (c1), and a polyurethane resin layer (c2) in this order. The transfer material for recycling described. The transfer material for recycling according to any one of claims 1 to 3, wherein a hard coat layer (E) is further laminated between the release layer (A) and the printing ink layer (B). The transfer material for recycling according to any one of claims 1 to 4, wherein the saponification degree of the polyvinyl alcohol resin in the polyvinyl alcohol resin layer is 80% to 90%. A molded product, wherein the recycling transfer material according to claim 1 is transferred to a molding substrate. A method of immersing the molded product according to claim 6 in an aqueous solution and detaching the printing ink layer and the dissolved layer from the molded product.