JP2012144040A - Laminate for transfer-printing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate for transfer-printing having superior productivity, which provides superior matte effect of a matte decorative molded article.SOLUTION: The laminate for transfer-printing as one embodiment is a laminate laminated with a base film formed of a polyvinyl alcohol-based film containing a filler, a curable resin layer and a design layer, in this order. Other embodiment is a laminate which is formed by further laminating an adhesive layer on that design layer.

Description

  The present invention relates to interior materials or exterior materials for vehicles such as automobiles, construction members such as skirting boards and circular edges, furniture such as window frames and door frames, interior materials for buildings such as walls, floors, and ceilings, and television receivers. In addition, the present invention relates to a laminate for transfer printing used in the manufacture of matte decorative molded products used in housings and containers of home appliances such as mobile phone parts and air conditioners. The present invention relates to a laminate for transfer printing which is excellent in matting effect of a product and excellent in productivity.

  A transfer method is known as a method for printing a design on the surface of a molded product such as a home appliance, a cosmetic container, or a miscellaneous product. The transfer method is a method in which a transfer layer in a transfer printing laminate is transferred to the surface of a molded product using the transfer printing laminate.

  As shown in FIG. 4, the transfer printing laminate is usually a laminate in which a release layer 12, a hard coat layer 13, a design layer 14, and an adhesive layer 15 are laminated in order on a base sheet 11. The hard coat layer 13, the design layer 14, and the adhesive layer 15 serve as a transfer layer C that is transferred to the surface of the molded product 20. That is, when the laminate for transfer printing as shown in FIG. 4 is adhered to the surface of the molded product via the adhesive layer 15 and then peeled off by the release layer 12, only the transfer layer C is formed on the surface of the molded product 20. Can be transferred.

In recent years, there has been a demand for matte decorative molded products that are matte (matte) by roughening the surface of the molded product in order to prevent glare on the surface of the molded product and to improve the design. Is increasing.
As a laminate for transfer printing used in a transfer method for making the surface matte, for example, a water base in which a base sheet, a release layer, and a matting agent are dispersed in JP-A-2001-260596 (Patent Document 1). A laminated body for transfer printing in which a partial mat layer having fine irregularities, a hard coat layer, a design layer, and an adhesive layer made of a conductive resin is disclosed (claim 1, paragraph numbers 0016, 0021). In such a laminate for transfer printing, the partial mat layer, the hard coat layer, the design layer, and the adhesive layer serve as a transfer layer transferred to the surface of the molded product.

  In the laminate for transfer printing disclosed in Patent Document 1, as the base sheet, a polypropylene resin, a plastic film such as a polyester film, and as the release layer, an aminoalkyd resin is used (paragraph numbers 0016, 0039). As the partial mat layer, a material obtained by dispersing a matting agent with an inorganic pigment such as silica particles or an organic pigment such as phthalocyanine in a water-soluble resin such as sodium polyacrylate or polyvinyl alcohol (paragraph number 0017, 0040). As the hard coat layer, an active energy ray-curable resin that is cured by ultraviolet rays or the like is used (paragraph number 0019).

  After transferring such a laminate for transfer printing to a molded article that is a transfer target, the hard coat layer is crosslinked and cured by irradiation with active energy rays, and then the water-soluble resin of the partial mat layer is removed by washing with water. Thus, a partially matte decorative molded product is manufactured (paragraph numbers 0020 and 0045). By removing the portion that was the partial mat layer, the surface of the remaining portion has irregularities and is matte.

  Japanese Unexamined Patent Application Publication No. 2008-173858 (Patent Document 2) discloses a decorative molded product with a mat hard coat layer. The mat-like decorative molded product disclosed here is a mat hard coat layer containing fine particles having a particle size of 0.1 to 2 μm formed on the hard coat layer. By transferring as a transfer layer of a laminate for transfer printing, or by molding a resin containing fine particles as a matting agent into a mold (paragraph number 0021) or containing fine particles in a molded product The mat hard coat layer is formed by coating the hard coat resin solution (paragraph number 0022).

JP 2001-260596 A JP 2008-173858 A

  In the method of Patent Document 1 described above, a dispersion liquid for forming a partial mat layer is applied to a base sheet having a release layer that has been conventionally used, and exhibits a matte effect. The uneven surface to be formed is formed by washing and removing the partial mat layer after curing the curable resin by irradiation with active energy rays. A commonly used base sheet having a release layer is expensive, but is necessary for the production method of applying a dispersion. Moreover, the said washing-and-removal process is an alternative process from the viewpoint of water-saving, a wastewater treatment viewpoint, and the complexity of manufacturing management by an increase in an operation | work process. Furthermore, when the mat surface is formed not on the partial mat but on the whole, it is not yet a satisfactory level in terms of mattness.

  In the method of Patent Document 2 described above, the water washing removal step is unnecessary, but the matte effect is based on irregular reflection of fine particles contained in the mat hard coat layer constituting the surface layer portion. Therefore, in order to obtain a sufficient matting effect, it is necessary to increase the proportion of the fine particles present on the surface portion, and consequently to increase the fine particle content of the mat hard coat layer. However, as the fine particle content increases, the fluidity of the resin decreases, and troubles are likely to occur in the injection process into the mold, which impairs continuous moldability. According to the method of coating the mat hard coat resin solution, such troubles can be prevented, but after the hard coat is formed, the mat hard coat resin solution coating operation and further a drying step are required. Therefore, the number of work steps required to obtain the matte effect of the mat-like decorative molded product is increased, and the production management is complicated and troublesome.

  The present invention has been made in view of the situation as described above, and after transfer, a transfer layer surface having an excellent matting effect can be obtained by a simple process, resulting in productivity of matte decorative molded products. An object of the present invention is to provide an excellent laminate for transfer printing.

  In order to increase the productivity of a decorative molded product, particularly a mat-like decorative molded product, by a simple method, the active energy ray-curable resin is cured with an active energy ray and then washed with water. It should be possible to avoid unnecessary steps such as a removal step, a coating step, and a drying step, and a simple step such as peeling was considered to be the most efficient. Transfer printing laminates that only need to be peeled off after transfer include transfer printing lamination using a polyvinyl alcohol film as a base film. However, this transfer printed laminate is not used for the production of a mat-like decorative molded product, and the matte effect is not imparted to the surface of the transfer layer. Therefore, the present inventors have intensively researched and completed the present invention in order to create a laminate for transfer printing that can impart a matte effect to the surface of the transfer layer simply by peeling after transfer.

That is, the laminate for transfer printing of the present invention is a laminate for transfer printing in which a curable resin layer and a design layer are laminated in order on a base film made of a polyvinyl alcohol film containing a filler. It is the laminated body for transfer printing characterized by these.
In the laminate for transfer printing of the present invention, the curable resin layer and the design layer serve as a transfer layer. The transfer printing laminate of the present invention may be one in which an adhesive layer is further laminated on the design layer. In this case, the curable resin layer, the design layer, and the adhesive layer serve as the transfer layer.

  The curable resin layer is transferred to the surface of the molded product and then cured to form a protective layer for the resulting decorative molded product. After the curable resin is cured, the base film can be easily peeled off, thereby forming a protective layer surface having a matte effect. Therefore, the laminate for transfer printing of the present invention having the above-described configuration is suitably used for the production of a matte decorative molded product.

  According to the laminate for transfer printing of the present invention, since the surface layer portion of the decorative molded product is transferred so as to be an uneven surface, it is possible to decorate only by curing the curable resin layer and peeling off the base film. A protective layer having a matte tone can be formed on the surface of the molded product. Therefore, by using the laminate for transfer printing of the present invention, an excellent matting effect can be obtained without requiring extra equipment such as a water washing removal process, a coating process, and a drying process, and wastewater treatment. A mat-like decorative molded product having the above can be manufactured, which is economical.

It is a schematic cross section which shows the structure of one Embodiment of the laminated body for transfer printing of this invention. It is a schematic cross section which shows the structure of other embodiment of the laminated body for transfer printing of this invention. It is a schematic diagram for demonstrating the structure of the matte decoration molded product manufactured using the laminated body for transfer printing of FIG. It is a schematic cross section which shows the structure of the conventional laminated body for transfer printing.

  As shown in FIG. 1, the laminate for transfer printing of the present invention comprises a base film 1, a curable resin layer 2, and a design layer 3 made of a polyvinyl alcohol film containing a filler, which are laminated in order. Further, as shown in FIG. 2, the adhesive layer 4 may be laminated on the design layer 3. Hereinafter, each layer will be described in detail.

<Base film>
The base film 1 is a polyvinyl alcohol film containing a filler. That is, a polyvinyl alcohol film containing a filler is used as the base film 1.

  The polyvinyl alcohol film used in the present invention is a film-forming belt formed of a polyvinyl alcohol resin composition in which a polyvinyl alcohol resin and a filler, and other plasticizers, surfactants, and the like, if necessary, are blended in a predetermined blending amount. It is obtained by casting on an upper or film-forming drum, drying, and peeling off from the film-forming belt or film-forming drum. After casting and drying the polyvinyl alcohol-based resin composition, it is continuously peeled off from the film-forming belt or from the film-forming drum, and continuously wound around a core material, etc. A wound body can be manufactured. The polyvinyl alcohol film produced in this manner usually has a concavo-convex surface due to the filler on the surface not in contact with the film-forming belt or film-forming drum.

  The polyvinyl alcohol-based resin may be either polyvinyl alcohol or modified polyvinyl alcohol. Among them, polyvinyl alcohol is preferably used in the present invention.

  Polyvinyl alcohol is produced by homopolymerizing vinyl acetate and further saponifying it. The modified polyvinyl alcohol is produced by saponifying a polymer of vinyl acetate and another unsaturated monomer, or is produced by post-modifying polyvinyl alcohol. The amount of modification is preferably 10 mol% or less, particularly 7 mol% or less, and more preferably 5 mol% or less.

  Examples of the other unsaturated monomers include olefins such as ethylene, propylene, isobutylene, α-octene, α-dodecene, α-octadecene, acrylic acid, methacrylic acid, crotonic acid, maleic acid, and maleic anhydride. Acids, unsaturated acids such as itaconic acid or salts thereof, mono- or dialkyl esters, nitriles such as acrylonitrile and methacrylonitrile, amides such as acrylamide and methacrylamide, ethylene sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, etc. Olefin sulfonic acids or salts thereof, alkyl vinyl ethers, N-acrylamidomethyltrimethylammonium chloride, allyltrimethylammonium chloride, dimethylallyl vinyl ketone, N-vinylpyrrolidone, vinyl chloride, chloride Polyoxyalkylenes such as Nilidene, Polyoxyethylene (meth) allyl ether, Polyoxyalkylene (meth) allyl ether such as polyoxypropylene (meth) allyl ether, Polyoxyethylene (meth) acrylate, Polyoxypropylene (meth) acrylate, etc. (Meth) acrylate, polyoxyethylene (meth) acrylamide, polyoxyalkylene (meth) acrylamide such as polyoxypropylene (meth) acrylamide, polyoxyethylene (1- (meth) acrylamide-1,1-dimethylpropyl) ester, Polyoxyethylene vinyl ether, polyoxypropylene vinyl ether, polyoxyethylene allylamine, polyoxypropylene allylamine, polyoxyethylene vinylamine, polyoxypropylene Pyrene vinyl amine.

  Examples of post-modification methods include acetoacetate esterification, acetalization, urethanization, etherification, grafting, phosphate esterification, and oxyalkyleneation.

  Moreover, it is also preferable to use a polyvinyl alcohol resin having a 1,2-diol bond in the side chain as the polyvinyl alcohol resin, and the polyvinyl alcohol resin having a 1,2-diol bond in the side chain is, for example, ( a) a method of saponifying a copolymer of vinyl acetate and 3,4-diacetoxy-1-butene; (b) a method of saponifying and decarboxylating a copolymer of vinyl acetate and vinyl ethylene carbonate; c) A method of saponifying and deketalizing a copolymer of vinyl acetate and 2,2-dialkyl-4-vinyl-1,3-dioxolane; (d) a copolymer of vinyl acetate and glycerol monoallyl ether; Can be obtained by a method of saponification of

  Among these polyvinyl alcohol resins, those having a saponification degree of 75 mol% or more are preferable, more preferably 78 to 99.7 mol%, and particularly preferably 85 to 95 mol%. If the degree of saponification is too low, the releasability of the hard coat layer made of a cured product of the curable resin layer 2 tends to decrease.

The viscosity of a 4% by weight aqueous solution of the polyvinyl alcohol resin at 20 ° C. is preferably 10 to 70 mPa · s (20 ° C.), more preferably 15 to 60 mPa · s (20 ° C.), particularly 20 to 50 mPa · s ( 20 ° C.) is preferred. If the viscosity is too low, mechanical properties such as film strength tend to decrease, and if it is too high, film forming property tends to decrease.
The viscosity is measured according to JIS K6726.

  Further, in the polyvinyl alcohol resin, the amount of sodium acetate contained in the resin is adjusted to 0.8% by weight or less, preferably 0.5% by weight or less in order to prevent coloring of the film and strength reduction. Is advantageous. For adjusting the content of sodium acetate, a method of washing with an alcohol such as methanol or water is generally used.

  Examples of the filler contained in the polyvinyl alcohol film include polysaccharides and / or inorganics. Among the polysaccharides, starch is preferable. Physically modified starch (α-starch, fractionated amylose, wet heat-treated starch, etc.); Enzyme-modified starch (hydrolyzed dextrin, enzyme-degraded dextrin, amylose, etc.); Chemically-modified modified starch (acid-treated starch) , Hypochlorite oxidized starch, dialdehyde starch, etc.); chemically modified starch derivatives (esterified starch, etherified starch, cationized starch, crosslinked starch, etc.) and the like are used. Among the chemically modified starch derivatives, esterified starch includes acetate esterified starch, succinate esterified starch, nitrate esterified starch, phosphate esterified starch, urea phosphate esterified starch, xanthate esterified starch, acetate Examples of etherified starch such as acetate esterified starch include allyl etherified starch, methyl etherified starch, carboxymethyl etherified starch, hydroxyethyl etherified starch, hydroxypropyl etherified starch, and the like. -Crosslinked starch, such as a reaction product of diethylaminoethyl chloride, a reaction product of starch and 2,3-epoxypropyltrimethylammonium chloride, formaldehyde cross-linked starch, epichlorohydrin cross-linked starch, phosphate cross-linked starch, acrolein cross-linked starch, etc. That. Among them, raw starch is preferably used from the viewpoint of easy availability and economical efficiency.

  Examples of the inorganics include talc, clay, silica, diatomaceous earth, kaolin, mica, asbestos, gypsum, graphite, glass balloon, glass beads, calcium sulfate, barium sulfate, ammonium sulfate, calcium sulfite, calcium carbonate, whisker-like Examples thereof include calcium carbonate, magnesium carbonate, dosonite, dolomite, potassium titanate, carbon black, glass fiber, alumina fiber, boron fiber, processed mineral fiber, carbon fiber, carbon hollow sphere, bentonite, montmorillonite, and copper powder.

  These fillers may be used alone or in combination of two or more, but are preferably starch. The polyvinyl alcohol-based resin composition containing starch as a filler, compared with the polyvinyl alcohol-based resin composition containing inorganics as a filler, in the production of a polyville alcohol-based film, from a film-forming belt or film-forming drum. Excellent peelability. Therefore, using starch as a filler is excellent in the productivity of the polyvinyl alcohol film used as the base film, and is easy to peel off, so even a thin film extends to the surface opposite to the peeling surface. Since the influence of peeling is small, there is an advantage that an uneven surface proportional to the filler content is easily obtained.

  The content of the filler is preferably 3 to 30 parts by weight, more preferably 5 to 25 parts by weight, particularly preferably 8 to 20 parts by weight, with respect to 100 parts by weight of the polyvinyl alcohol resin. Preferably it is 10-20 weight part. If the filler content is too low, the matte effect of the decorative molded product tends to be low, and if it is too high, the strength and flexibility of the polyvinyl alcohol film will be reduced, so that the transferred object having a curved surface will appear. Moreover, when it is necessary to transfer along the three-dimensional shape of the transfer object, the followability to the transfer object as a transfer printing laminate tends to be reduced.

  In addition, the polyvinyl alcohol-type film containing a filler is also known also as the polyvinyl alcohol-type film generally used as a water-soluble film normally. However, in the present invention, the polyvinyl alcohol film used as the base film of the laminate for transfer printing contains a larger amount of filler than the filler content contained in a commonly used water-soluble film. There is a feature. That is, the polyvinyl alcohol film used in the present invention has a role of forming a matte surface by forming a surface having sufficient unevenness in addition to the role as a base film of a laminate for transfer printing. This is because it is preferable to contain a sufficient amount of filler within a range that does not impair the flexibility and strength of the film.

  The average particle size of the filler is preferably 0.1 to 30 μm, particularly 0.3 to 25 μm, and more preferably 0.5 to 20 μm. If the average particle size is too small, the matting effect of the decorative molded product tends to be reduced. On the other hand, when the average particle diameter is too large, it becomes easy to bite bubbles when the curable resin composition that is the material of the curable resin layer is applied on the base film 1, and the curable resin layer having bubbles is formed. It becomes easy to form. In addition, about the particle diameter of the filler to contain, it is important to adjust suitably also in relation to the thickness of a polyvinyl alcohol-type film, and to carry out so that the unevenness | corrugation resulting from a filler may be formed in the polyvinyl alcohol-type film surface.

  In producing a polyvinyl alcohol film, it is also preferable to appropriately add a plasticizer and a surfactant as necessary, in addition to the polyvinyl alcohol resin and the filler.

  Examples of the plasticizer include glycerins such as glycerin, diglycerin, and triglycerin, alkylene glycols such as triethylene glycol, polyethylene glycol, polypropylene glycol, and dipropylin glycol, and trimethylolpropane. These may be used alone or in combination of two or more.

  It is preferable that content of the plasticizer mix | blended with the said polyvinyl alcohol-type resin is 20 weight part or less with respect to 100 weight part of polyvinyl alcohol-type resin, Most preferably, it is 1-15 weight part. If the content of the plasticizer is too small, the plasticizing effect is low, which tends to cause breakage of the obtained base film. If the content is too large, the standing stability tends to be lowered.

  By containing the surfactant, the releasability between the metal surface such as a drum or belt, which is a film forming apparatus for a polyvinyl alcohol film, and the formed film is further improved, and therefore, it is preferably blended. Specific examples of the surfactant include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl nonyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene Polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyalkylene alkyl ether phosphate monoethanolamine salt, polyoxyethylene laurylamine, polyoxyethylene stearylamine, etc. Examples thereof include oxyethylene alkylamine. These may be used alone or in combination of two or more. Among these, it is preferable to use polyoxyalkylene alkyl ether phosphate monoethanolamine salt, polyoxyethylene alkylamine, and polyoxyethylene sorbitan monolaurate from the viewpoint of peelability.

  About content of the said surfactant, it is preferable that it is 0.01-20 weight part with respect to 100 weight part of polyvinyl alcohol-type resin, and it is more preferable that it is 0.03-15 weight part. If the content of the surfactant is too small, the peelability between the metal surface such as a drum or belt of the film forming apparatus and the film formed tends to decrease, and the productivity of the polyvinyl alcohol film tends to decrease, On the other hand, if the amount is too large, bleeding tends to occur when the curable resin layer is coated by bleeding on the film surface.

  The polyvinyl alcohol film further has a crosslinking agent, an antioxidant (phenolic, amine, etc.), a stabilizer (phosphate ester, etc.), a colorant, a fragrance, and an extender as long as the effects of the present invention are not hindered. Other anti-foaming agents, rust inhibitors, UV absorbers, and other water-soluble polymer compounds (sodium polyacrylate, polyethylene oxide, polyvinylpyrrolidone, dextrin, chitosan, chitin, methylcellulose, hydroxyethylcellulose, etc.) Additives may be blended.

  Using a polyvinyl alcohol-based film as a film-forming material, a resin composition obtained by blending the above-mentioned polyvinyl alcohol-based resin and filler, and other necessary plasticizers, surfactants, and the like at a predetermined blending amount. Is made.

  The polyvinyl alcohol-based film can be produced, for example, by casting a polyvinyl alcohol-based resin composition, which is a film-forming material, from a T die onto a film-forming belt or a film-forming drum and drying it. After drying, if necessary, heat treatment may be performed.

Here, the film-forming belt has an endless belt that runs across a pair of rolls, and the film-forming material flowing out from the T-die is cast on the endless belt and dried. The endless belt is preferably made of, for example, stainless steel, and its outer peripheral surface is mirror-finished.
The film-forming drum is a rotating drum-type roll, and the film-forming material flowing out from the T-die is cast onto one or more rotary drum-type rolls and dried.

About a drying temperature, when using a film forming belt, it is preferable that it is 80-160 degreeC normally, and 90-150 degreeC is especially preferable. If the drying temperature is too low, drying tends to be insufficient and the appearance of the product tends to be lowered. If too high, the heat treatment tends to be high and the moisture content tends to be too low.
Regarding the drying temperature in the case of using a film-forming drum, the film-forming first drum is usually preferably 80 to 100 ° C, and particularly preferably 82 to 99 ° C. If the drying temperature is too low, drying tends to be insufficient and the appearance of the product tends to be lowered. If too high, the heat treatment tends to be high and the moisture content tends to be too low. Here, the film-forming first drum is a drum-type roll located on the most upstream side where the film forming material flowing out from the T die is cast.

  As described above, when the film is dried by heating the film-forming drum or the film-forming belt, the temperature and the amount of moisture differ between the film belt or the drum-contacting surface and the non-contacting surface. As a result, the obtained film may curl or the like. The curl of the film can cause problems in the formation of the curable resin layer and the transfer process. Therefore, it is preferable to perform a heat treatment in order to prevent curling of the film and further to improve the film strength.

The heat treatment can be performed by using, for example, a hot roll (including a calender roll), hot air, far infrared rays, dielectric heating, or the like. The heat treatment may be performed in a state where the film is placed on the film forming belt or the film forming drum after drying, or may be performed in a state of the film alone taken out from the film forming belt or the film forming drum. The heat treatment is usually performed using a separate heat treatment roll following the drying roll treatment for drying the film.
The water content of the film subjected to the heat treatment is usually preferably about 4 to 8% by weight, and the water content of the film can be usually set to 2 to 6% by weight by the heat treatment.

  It is preferable to perform heat processing at 50-180 degreeC, More preferably, it is 60-160 degreeC, Most preferably, it is 70-150 degreeC. If the temperature of the heat treatment is too low, curling of the surface in contact with the film forming belt or the film forming first drum may occur. On the other hand, if the temperature of the heat treatment is too high, the film becomes soft, so that wrinkles are easily formed and the quality tends to be lowered. In the case of a heat treatment roll, the heat treatment time is usually 1 to 180 seconds, preferably 10 to 120 seconds, although it depends on the surface temperature. Moreover, in this invention, it is preferable that the said heat processing is performed with respect to the surface at the side of the curable resin layer of a base film.

Furthermore, as a moisture content of the polyvinyl alcohol-type film used for a base film, it is preferable that it is the range of 0.5-10 weight%, More preferably, it is 1-6 weight%. If the moisture content is too low, the film becomes brittle and tends to break in the slitting process and the curable resin layer forming process. Conversely, if the moisture content is too high, the film tends to stretch and the standing stability decreases. In the process of forming the curable resin layer, the thickness of the curable resin layer tends to be uneven.
The moisture content of the polyvinyl alcohol film can be measured using, for example, a Karl Fischer moisture meter (“MKS-210” manufactured by Kyoto Electronics Industry Co., Ltd.).

  Examples of the method for adjusting the moisture content of the polyvinyl alcohol film include the methods shown in the following (a) to (c).

(A) The drier temperature in which the polyvinyl alcohol-based resin is dissolved is dried to increase or decrease the dryer temperature to humidify / dehumidify the polyvinyl alcohol-based film and adjust the moisture content.
The temperature of the dope is adjusted within the range of 70 to 98 ° C. because it affects the drying efficiency. Further, the drying is preferably performed in at least two or more hot air dryers having a temperature gradient between 150 and 50 ° C., more preferably between 145 and 60 ° C. It is preferable from the viewpoint of moisture adjustment to dry for 1 minute, more preferably for 1 to 10 minutes.

  If the gradient range of the drying temperature is too large or the drying time is too long, there is a tendency to overdry, and conversely if the gradient range of the drying temperature is too small or the drying time is too short, the drying is insufficient. Tend to be.

  The above temperature gradient gradually changes the drying temperature between 150 and 50 ° C. Usually, the temperature is gradually increased from the start of drying and once set until a predetermined moisture content is reached. It is effective to reach the highest moisture temperature in the drying temperature range, and then gradually lower the drying temperature to finally achieve the desired moisture content. This is performed to control crystallinity, releasability, productivity, and the like. For example, 120 ° C-130 ° C-115 ° C-100 ° C, 130 ° C-120 ° C-110 ° C, 115 ° C-120 ° C. The temperature gradient is set such as −110 ° C. to 90 ° C., and is appropriately selected and executed.

(B) The polyvinyl alcohol film is humidified and dehumidified by passing it through a humidity control tank before winding the polyvinyl alcohol film, and the moisture content is adjusted.
(C) Before or after winding the polyvinyl alcohol film, the polyvinyl alcohol film is dehumidified by performing the aforementioned heat treatment to adjust the moisture content.

The polyvinyl alcohol film obtained as described above is used as a base film.
The thickness of the polyvinyl alcohol-based film used as the base film is preferably 5 to 120 μm, particularly 10 to 80 μm, more preferably 15 from the viewpoint of coating properties of the paint and followability with the transfer target during transfer. ˜70 μm is preferred. If the thickness is too thin, there is a tendency that the coating spots of the paint and breakage at the time of transfer tend to occur, and if it is too thick, the uneven shape due to the filler tends to be difficult to occur. The surface of the object tends to be non-uniform.

  The breaking elongation of the polyvinyl alcohol film used as the base film is preferably 150% or more, and more preferably 180% or more under the condition of 23 ° C. and 50% RH humidity control. If the elongation at break is too low, there is a tendency for paper breakage to occur in the slit process and the process of continuously forming the curable resin layer. The upper limit of the elongation at break is usually 350%. Here, the breaking elongation of the base film is measured according to JIS K 7127 (1999).

  Further, the surface roughness (Ra) of the base film 1 on the side where the curable resin layer 2 is laminated is preferably 0.3 to 5 μm in terms of the matte effect, more preferably 1 to 4.5 μm. More preferably, the thickness is 1.5 to 4 μm. If the surface roughness (Ra) is too small, the matting effect tends not to be obtained remarkably, and if it is too large, the film strength tends to decrease.

  Examples of the method for adjusting the surface roughness (Ra) of the polyvinyl alcohol film to the above range include a method of adjusting by the amount of filler, a method of adjusting by the type and particle size of the filler, a method of combining both, and the like. It is done. In addition, surface roughness (Ra) measured the arithmetic mean roughness (Ra) based on JISB0601-2001 using "Color 3D laser microscope VK-9700" by Keyence Corporation.

  When the polyvinyl alcohol film as described above is used as a base film after a predetermined period of time, for example, a conventionally known moisture-proof packaging is performed and stored in a suspended state in an atmosphere of 10 to 25 ° C. It is preferable to keep it.

<Curable resin layer>
The curable resin layer 2 is a layer that, after being transferred to the transfer target, is cured before the base film 1 is peeled off, and becomes the outermost surface of the transfer target (decorative molded product). The cured product of the curable resin layer is not only a role as a protective layer for protecting the design layer transferred to the transfer target, but also a layer that exhibits the matte effect of the matte decorative molded product.

(1) Curable resin composition Examples of the curable resin composition constituting the curable resin layer include, for example, polyacrylic resins, polyester resins, polyvinyl chloride resins, cellulose resins, rubber resins, polyurethane resins, and polyvinyl acetate resins. In addition, active energy ray-curable resin compositions such as ultraviolet curable resin compositions and electron beam curable resin compositions, and thermosetting resin compositions are also preferably used. In the present invention, it is preferable to use an active energy ray-curable resin composition in terms of chemical resistance and abrasion resistance of the molded product.

  Such an active energy ray-curable resin composition is, for example, a composition comprising (i) an acrylic resin and (ii) a urethane (meth) acrylate compound, preferably (iii) a photopolymerizable monomer. It is the composition formed. In addition, when the active energy ray curable resin composition is an ultraviolet curable resin composition, it is preferable to further contain (iv) a photopolymerization initiator. In the case of an electron beam curable resin composition, a photopolymerization initiator is unnecessary.

(I) Acrylic resin Examples of the acrylic resin include homopolymers or copolymers of acrylic ester monomers, and acrylic copolymers having other ethylenically unsaturated monomers as copolymerization components. It is done.

  Examples of acrylic ester monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl ( (Meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, 2-methoxyethyl (meth) ) Acrylate, butoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, etc., among them, alkyl acrylates having 1 to 12 carbon atoms in the alkyl group. Le are preferred, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate is particularly preferably used.

Other ethylenically unsaturated monomers include, for example,
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-chloro 2-hydroxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, Hydroxyl group-containing unsaturated monomers such as diethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, N-methylol (meth) acrylamide;
Glycidyl group-containing unsaturated monomers such as glycidyl methacrylate and allyl glycidyl methacrylate;
Isocyanate group-containing unsaturated monomers such as 2-acryloyloxyethyl isocyanate and 2-methacryloyloxyethyl isocyanate;
Amide group-containing unsaturated monomers such as acrylamide, methacrylamide, N- (n-butoxyalkyl) acrylamide, N- (n-butoxyalkyl) methacrylamide;
Amino group-containing unsaturated monomers such as acrylamide-3-methylbutylmethylamine, dimethylaminoalkylacrylamide, dimethylaminoalkylmethacrylamide;
Olefin sulfonic acids such as ethylene sulfonic acid, allyl sulfonic acid and methallyl sulfonic acid, sulfonic acid group-containing unsaturated monomers such as 2-acrylamido-2-methylpropane sulfonic acid, styrene sulfonic acid or salts thereof;
Examples include styrene, vinyl acetate, acrylonitrile, acrylamide and the like.

  The content ratio (copolymerization ratio) of the acrylate ester monomer and other ethylenically unsaturated monomers is not particularly limited. For example, 20 to 100% by weight of the acrylate ester monomer and other ethylenically unsaturated monomers are added. It is preferably 0 to 80% by weight, particularly 40 to 100% by weight of the acrylate ester monomer, 0 to 60% by weight of other ethylenically unsaturated monomers, and further 80 to 100% of the acrylate ester monomer. It is preferable to make 0% to 20% by weight of other ethylenically unsaturated monomers. If the content of the acrylate monomer is too small, the cured coating film tends to have lower durability such as water resistance and moist heat resistance.

  The acrylic resin is easily produced by a method known to those skilled in the art, specifically, by polymerizing the polymerization component in an organic solvent by radical copolymerization or the like.

  Thus, the acrylic resin used in the present invention is obtained. The glass transition temperature (Tg) of the acrylic resin is preferably 20 to 130 ° C, more preferably 30 to 120 ° C, and still more preferably 40. ~ 110 ° C. If the glass transition point (Tg) is too low, the curable resin layer made of the active energy ray-curable resin composition is sticky and causes problems when it is post-processed (winding, printing defects, etc. even during the process) If it is too high, the cured product of the curable resin layer composed of the active energy ray-curable resin composition or the like tends to be brittle.

  The weight average molecular weight (Mw) of the acrylic resin is preferably 10,000 to 500,000, more preferably 20,000 to 100,000, and particularly 30,000 to 80,000. preferable.

  If the weight average molecular weight (Mw) of the acrylic resin is too small, the curable resin layer becomes soft and sticky.・ When printing is too large, it is difficult to obtain film thickness uniformity when the curable resin composition is applied, and the hardness of the coating film after drying becomes higher than necessary. There is a tendency to cause defects (cracking of the coating film, delamination, etc.) during processing.

(Ii) Urethane (meth) acrylate compound The urethane (meth) acrylate compound is a (meth) acrylate compound having a urethane bond in the molecule, and a (meth) acrylic compound containing a hydroxyl group and a polyvalent isocyanate compound. Can be further produced by reacting a polyol as necessary.

  Examples of the (meth) acrylic compound containing a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth). Acrylate, 6-hydroxyhexyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, caprolactone modified 2-hydroxy Ethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, caprolactone modified pen Examples include erythritol tri (meth) acrylate, ethylene oxide-modified dipentaerythritol penta (meth) acrylate, ethylene oxide-modified pentaerythritol tri (meth) acrylate, etc. Among them, a hydroxyl group-containing (meth) acrylic group having three or more acryloyl groups A compound is preferably used. Moreover, these can be used 1 type or in combination of 2 or more types.

  Examples of the polyvalent isocyanate compound include aromatic, aliphatic and alicyclic polyisocyanates, among which tolylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, Modified diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, phenylene diisocyanate , Lysine diisocyanate, lysine triisocyanate, naphthalenedi Polyisocyanates such as cyanate or trimer compounds or multimer compounds of these polyisocyanates, burette type polyisocyanates, water-dispersed polyisocyanates (for example, “Aquanate 100” and “Aquanate 110 manufactured by Nippon Polyurethane Industry Co., Ltd.) ”,“ Aquanate 200 ”,“ Aquanate 210 ”, etc.), or reaction products of these polyisocyanates and polyols.

Examples of the polyol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, polybutylene glycol, 1,6-hexanediol, and neopentyl glycol. , Cyclohexanedimethanol, hydrogenated bisphenol A, polycaprolactone, trimethylolethane, trimethylolpropane, polytrimethylolpropane, pentaerythritol, polypentaerythritol, sorbitol, mannitol, glycerin, polyglycerin, polytetramethylene glycol, etc. Alcohol: Polyethylene oxide, Polypropylene oxide, D Polyether polyol having at least one structure of block or random copolymerization of lenoxide / propylene oxide; the polyhydric alcohol or polyether polyol and maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, adipine Examples thereof include polyester polyols that are condensates with polybasic acids such as acids and isophthalic acid; caprolactone-modified polyols such as caprolactone-modified polytetramethylene polyol; polyolefin-based polyols; polybutadiene-based polyols such as hydrogenated polybutadiene polyol.
In addition, for example, 2,2-bis (hydroxymethyl) butyric acid, tartaric acid, 2,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2,2-bis (hydroxymethyl) propionic acid, 2,2- Bis (hydroxyethyl) propionic acid, 2,2-bis (hydroxypropyl) propionic acid, dihydroxymethylacetic acid, bis (4-hydroxyphenyl) acetic acid, 4,4-bis (4-hydroxyphenyl) pentanoic acid, homogentisic acid, etc. Carboxyl group-containing polyols, sulfonic acid groups such as sodium 1,4-butanediol sulfonate, or sulfonate group-containing polyols can also be used.

  When using the reaction product of polyisocyanate and polyol, for example, it may be used as a terminal isocyanate group-containing polyisocyanate obtained by reacting the polyol with the polyisocyanate. In the reaction between the polyisocyanate and the polyol, a metal catalyst such as dibutyltin dilaurate or an amine catalyst such as 1,8-diazabicyclo [5.4.0] undecene-7 is used for the purpose of promoting the reaction. Is also preferable.

  The urethane (meth) acrylate compound is a mixture of the above hydroxyl group-containing (meth) acrylic compound and a polyvalent isocyanate compound in an inert gas atmosphere, and is usually reacted at 30 to 80 ° C. for 2 to 10 hours. Can be manufactured. In this reaction, it is preferable to use a urethanization catalyst such as tin octenoate, di-n-butyltin dilaurate, lead octylate, potassium octylate, potassium acetate, stannous octoate, or triethylenediamine.

  The weight average molecular weight of the urethane (meth) acrylate compound is preferably 300 to 4000, more preferably 1000 to 3500, and particularly preferably 1200 to 3000. If the weight average molecular weight is too small, the cohesive force tends to be insufficient after the curable resin layer is cured, and if it is too large, the viscosity becomes too high and the production tends to be difficult.

In addition, said weight average molecular weight is a weight average molecular weight by standard polystyrene molecular weight conversion, a column: Shodex GPC KF-806L (in Showa Denko Co., Ltd. make, "Shodex GPC system-11 type | mold"). Exclusion limit molecular weight: 2 × 10 ⁷ , separation range: 100 to 2 × 10 ⁷ , theoretical plate number: 10,000 plate / book, filler material: styrene-divinylbenzene copolymer, filler particle size: 10 μm) 3 Measured by using this series.

(Iii) Photopolymerizable monomer A photopolymerizable monomer is a polymer that itself forms a polymer when irradiated with light such as ultraviolet rays, and generally has a single functional group. And a polyfunctional monomer having two or more functional groups. Examples of such photopolymerizable monomers include the following.

  Examples of the monofunctional monomer include styrene, vinyl toluene, chlorostyrene, α-methyl styrene, methyl (meth) acrylate, ethyl (meth) acrylate, acrylonitrile, vinyl acetate, 2-hydroxyethyl (meth) acrylate, 2- Hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 3 -Chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, glycidyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, isovo Nyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, n-butyl (meth) acrylate , Hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, n-stearyl (meth) acrylate , Benzyl (meth) acrylate, phenol ethylene oxide modified (n = 2) (meth) acrylate, nonylphenol propylene oxide modified (n = 2.5) (meth) acrylate, 2- (meth) acrylo Half (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, carbitol (meth) of phthalic acid derivatives such as yloxyethyl acid phosphate and 2- (meth) acryloyloxy-2-hydroxypropyl phthalate Acrylate, benzyl (meth) acrylate, butoxyethyl (meth) acrylate, allyl (meth) acrylate, acryloylmorpholine, 2-hydroxyethylacrylamide, N-methylol (meth) acrylamide, N-vinylpyrrolidone, 2-vinylpyridine, poly Examples thereof include oxyethylene secondary alkyl ether acrylate.

  Among the polyfunctional monomers, examples of the bifunctional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and propylene glycol. Di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide modified bisphenol A type di (meth) Acrylate, propylene oxide modified bisphenol A type di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, ethoxylated cyclohexane Sandimethanol di (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, penta Erythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, hydroxypivalic acid modified neopentyl glycol di (meth) Examples thereof include acrylate and isocyanuric acid ethylene oxide-modified diacrylate.

  Examples of the trifunctional or higher monomer among the polyfunctional monomers include, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth). Acrylate, dipentaerythritol hexa (meth) acrylate, tri (meth) acryloyloxyethoxytrimethylolpropane, glycerin polyglycidyl ether poly (meth) acrylate, isocyanuric acid ethylene oxide modified triacrylate, caprolactone modified dipentaerythritol penta (meth) acrylate , Caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified pentaerythritol tri ( ) Acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, ethylene oxide modified dipentaerythritol penta (meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, ethylene oxide modified pentaerythritol tri (meth) acrylate, ethylene Examples thereof include oxide-modified pentaerythritol tetra (meth) acrylate and ethoxylated glycerin triacrylate.

  In addition, Michael adduct of acrylic acid or 2-acryloyloxyethyl dicarboxylic acid monoester is also mentioned. Examples of acrylic acid Michael adduct include acrylic acid dimer, methacrylic acid dimer, acrylic acid trimer, methacrylic acid trimer, acrylic acid. Examples include tetramers and tetramers of methacrylic acid. The 2-acryloyloxyethyl dicarboxylic acid monoester is a carboxylic acid having a specific substituent, for example, 2-acryloyloxyethyl succinic acid monoester, 2-methacryloyloxyethyl succinic acid monoester, 2-acryloyloxy Examples thereof include ethylphthalic acid monoester, 2-methacryloyloxyethylphthalic acid monoester, 2-acryloyloxyethyl hexahydrophthalic acid monoester, and 2-methacryloyloxyethyl hexahydrophthalic acid monoester. Furthermore, other oligoester acrylates can be mentioned.

  In the present invention, the content ratio of the acrylic resin, urethane (meth) acrylate compound, and photopolymerizable monomer is 20 to 300 parts by weight of urethane (meth) acrylate compound with respect to 100 parts by weight of acrylic resin. 40 to 250 parts by weight, more preferably 60 to 200 parts by weight, and more preferably 5 to 80 parts by weight of the photopolymerizable monomer, particularly preferably 10 to 60 parts by weight, and more preferably 15 to 50 parts by weight.

(Iv) Photopolymerization initiator Examples of the photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, and 4- (2-hydroxyethoxy) phenyl. -(2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- Acetophenones such as (4-morpholinophenyl) butanone and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomer; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether , Benzoin isobutyl ether, etc. Benzoins; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethananium bromide, (4-benzoylbenzyl) trimethylammonium Benzophenones such as chloride; 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy ) − Thioxanthones such as 2,4-dimethyl-9H-thioxanthone-9-one mesochloride; 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl -Acyl phosphine oxides such as pentylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; In addition, these photoinitiators may be used individually by 1 type, and 2 or more types may be used together.

  The content of the photopolymerization initiator is 0.5 to 15 parts by weight with respect to 100 parts by weight of the urethane (meth) acrylate-based compound to be used (the total amount when the photopolymerizable monomer is blended). It is particularly preferably 0.5 to 10 parts by weight, more preferably 1 to 8 parts by weight.

(V) Auxiliary agents Further, as these auxiliary agents, triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (Michler ketone), 4,4'-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, 4 -Ethyl dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate (n-butoxy), isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4 -It is also possible to use diisopropylthioxanthone or the like together.

  Among these, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoyl isopropyl ether, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 2-hydroxy-2-methyl-1- It is preferable to use phenylpropan-1-one.

(2) Curable resin layer The curable resin layer 2 is formed by coating the curable resin composition as described above with a gravure coating method, a roll coating method, a bar coating method, a comma coating method, a lip coating method, or the like. It is formed by laminating on a base film by a printing method such as a printing method or a screen printing method.

  In addition, when a curable resin layer is comprised with an active energy ray resin composition, hardening of an active energy ray curable resin composition is, for example, (a) active energy ray curable resin composition layer on a base film. After the lamination, the active energy ray is irradiated and cured; (b) after laminating the active energy ray-curable resin composition layer on the base film, a design layer described later is formed, and then the active energy ray is applied from the base film side. Irradiation and curing; (c) Further, after laminating up to the adhesive layer described later, irradiation with active energy rays from the base film side and curing; (d) After adhering the transfer printing laminate of the present invention to the transfer target Curing by irradiating active energy rays from the base film side; (e) After adhering the transfer printing laminate of the present invention to the transfer target, the base film is peeled off and the active energy rays are irradiated It can be carried out by curing Te. From the viewpoint of followability to the transfer target during thermal transfer, the method (d) or (e) in which curing is performed after transfer is preferable, and the method (e) is particularly preferable. In addition, although the laminated body for transfer printing of this invention can also be used as a laminated body by which the curable resin layer was hardened | cured like said (a)-(c), said (d) and (e It is preferable to provide as a laminate containing a curable resin layer before curing.

  The thickness of the curable resin layer 2 is preferably 1 to 150 μm, particularly 2 to 120 μm, and more preferably 2 to 100 μm in terms of wear resistance and chemical resistance. If the thickness is too thin, there is a tendency that the wear resistance and chemical resistance are lowered. If the thickness is too thick, film breakage after transfer tends to be insufficient, which tends to cause burrs and the like.

<Design layer>
The design layer 3 is a layer that forms a design such as a design on the surface of the matte decorative molded product.
The design layer 3 is made of a resin such as polyvinyl resin, polyamide resin, polyester resin, acrylic resin, polyurethane resin, polyvinyl acetal resin, polyester urethane resin, cellulose ester resin, alkyd resin, and the like. It is composed of colored inks containing various color pigments or dyes as colorants.

The design layer 3 is formed by printing a design such as a pattern on the curable resin layer 2 by using a color ink by a normal printing method such as an offset printing method, a gravure printing method, or a screen printing method. The In order to perform multicolor printing and gradation expression, an offset printing method and a gravure printing method are suitable.
Moreover, the design layer formed by using the above printing method on the film having releasability, the laminate in which the curable resin layer is laminated on the base film, and the design surface and the surface of the curable resin layer are in contact with each other. Moreover, you may form a design layer on a curable resin layer by bonding together by the dry lamination method.

  The laminate for transfer printing of the present invention is a laminate having a three-layer structure in which the base film 1, the curable resin layer 2, and the design layer 3 formed as described above are laminated in this order. Alternatively, as shown in FIG. 2, the adhesive layer 4 may be further laminated on the design layer 3. When the affinity between the molded product and the design layer is low and the adhesive force is weak, a laminate for transfer printing provided with an adhesive layer is preferably used.

<Adhesive layer>
In the case of the laminate for transfer printing having the adhesive layer 4, the transfer layer is the adhesive layer 4, the design layer 3, and the curable resin layer 2. Therefore, when the affinity between the transferred object and the design layer is low and the adhesive force is weak, the adhesive force of the transfer layer to the transferred object can be improved by interposing the adhesive layer.

  As the constituent material of the adhesive layer 4, a heat-sensitive or pressure-sensitive resin suitable for the material of the molded product that is the transfer target may be used as appropriate, depending on the material of the molded product, the type of resin that constitutes the design layer, and the like. For example, polyester resin, acrylic resin, polystyrene resin, polyamide resin, chlorinated polyolefin resin, chlorinated ethylene-vinyl acetate copolymer resin, cyclized rubber, coumarone indene resin, etc. Is mentioned.

  The adhesive layer 4 is formed by printing on the design layer 3 by a printing method such as a gravure coating method, a roll coating method, a bar coating method or a comma coating method, a gravure printing method, or a screen printing method. Alternatively, the adhesive layer 4 may be formed on the design layer 3 by bonding a sheet made of the adhesive layer constituting material to the design layer 3 by a laminating method or the like.

  The thickness of the adhesive layer 4 is preferably 0.5 to 50 μm, more preferably 1 to 40 μm, and still more preferably 2 to 30 μm, from the viewpoint of followability to the transfer target. If the thickness is too thin, the followability to the transfer medium at the time of transfer tends to decrease, and if it is too thick, the cost tends to be high, which is uneconomical.

  The laminate for transfer printing having the above-described configuration is particularly suitable for the production of a matte decorative molded product. Hereinafter, a method for producing a mat-like decorative molded product using the laminate for transfer printing of the present invention will be described.

[Method of manufacturing matte decorative molded product]
Matte decorative molded products are manufactured by transferring the transfer layer of the laminate for transfer printing of the present invention onto the surface of a molded product that has been molded in advance (post transfer method), manufacturing of molded products by injection molding, It can be produced by any of the methods for simultaneously transferring (molding simultaneous transfer method).
As shown in FIG. 1, a transfer printing laminate in which the transfer layer A is a curable resin layer and a design layer, and as shown in FIG. 2, the transfer layer B is a curable resin layer, a design layer, and an adhesive layer. Regardless of which printing laminate is used, both the post-transfer method and the simultaneous molding transfer method can be applied.

  In addition, the kind of the molded product on which the matte decoration is performed using the laminate for transfer printing of the present invention is not particularly limited, and it can be applied to various molded products such as a resin molded product, a metal molded product, and a composite material molded product. On the other hand, it is applicable.

<Post-transfer method>
Since it is a method of decorating a pre-molded molded product, it can be applied not only to resin molded products but also to various materials such as metal molded products and composite material molded products.
First, the laminated body for transfer printing is adhered to the surface of the transfer target. When using the type of transfer printing laminate of FIG. 1, a design layer is applied, and when using the type of transfer printing laminate of FIG. 2, an adhesive layer is applied.
Next, using a transfer machine such as a roll transfer machine or an up-down transfer machine provided with a heat-resistant rubber-like elastic body such as silicon rubber, a heat-resistant rubber-like condition set at a temperature of about 80 to 270 ° C. and a pressure of about 490 to 1960 Pa. It heats and pressurizes from the base film side of the laminate for transfer printing via an elastic body. As a result, the design layer (in the case of a laminate for transfer printing having an adhesive layer) adheres to the surface of the transfer target.

  After cooling in a state where the laminate for transfer printing is in close contact, the curable resin layer is cured. When the curable resin layer is composed of an active energy ray-curable resin composition, it is cured by irradiation with active energy rays.

  As active energy rays, for example, rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, electromagnetic waves such as X rays and γ rays, electron beams, proton rays, neutron rays, etc. can be used. Curing by ultraviolet irradiation is advantageous from the standpoint of availability of the device and price.

As a method of curing by ultraviolet irradiation, 0.01 to 10 J / cm using a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, or the like that emits light in a wavelength range of 150 to 450 nm. ^It is sufficient to irradiate about ² times. After the ultraviolet irradiation, heating can be performed as necessary to complete the curing.

  When the base film 1 is peeled off after the curable resin layer 2 is cured, a cured product of the design layer and the curable resin layer covering the design layer (hereinafter, curable resin formed on the molded product surface). The cured product of the layer is simply referred to as a “protective layer”. Since the surface of the protective layer is a rough surface having irregularities based on the interface with the base film, it is in a matte state. In this way, a matte decorative molded product is obtained.

<Simultaneous molding transfer method>
When decorating a plastic molded product molded by injection molding, the surface can be decorated in a matte style simultaneously with the production of the molded product, so that the productivity of matte decorated plastic molded product can be improved Convenient as.
First, the transfer printing laminate is fed into a molding die composed of a movable die and a fixed die. In that case, the sheet | seat laminated body for transfer printing may be sent one by one, and the required part of a long laminated body may be sent intermittently. When using a long laminate for transfer printing, it is preferable to use a feeding device having a positioning mechanism so that the register of the design layer of the laminate for transfer printing matches the molding die. In addition, when the transfer printing laminate is intermittently fed, if the transfer printing laminate is fixed between the movable mold and the fixed mold after the position of the transfer printing laminate is detected by the sensor, it is always the same. This is convenient because the laminate for transfer printing can be fixed at the position, and the design layer is not displaced.

  After closing the molding die, the molding resin melted from the gate is injected and filled into the die, and at the same time as the transfer body is formed, the transfer printing laminate is adhered to the surface. Examples of the molding resin include general-purpose resins such as polystyrene resin, polyolefin resin, ABS resin, AS resin, and AN resin. Also, general engineering resins such as polyphenylene oxide / polystyrene resins, polycarbonate resins, polyacetal resins, acrylic resins, polycarbonate modified polyphenylene ether resins, polybutylene terephthalate resins, ultrahigh molecular weight polyethylene resins, polysulfone resins, polyphenylene sulfide resins Super engineering resins such as polyphenylene oxide resins, polyarylate resins, polyetherimide resins, polyimide resins, liquid crystal polyester resins, and polyallyl heat-resistant resins can also be used. Furthermore, composite resins to which reinforcing materials such as glass fibers and inorganic fillers are added can also be used. These resin molded products may be transparent, translucent, or opaque. Further, the molded product may be colored or may not be colored.

  After the resin molded product that is the transfer target is cooled, the molding die is opened and the resin molded product is taken out. After taking out the molded product, the curable resin layer is cured. When the curable resin layer is composed of an active energy ray curable resin composition, the curable resin is irradiated with active energy rays on the laminate for transfer printing adhered to the molded product. Harden the layer. When the base film is peeled off after curing, peeling occurs at the boundary surface between the base film and the protective layer, and a protective layer having an uneven surface corresponding to the uneven surface of the base film is formed on the surface of the molded product. Become.

  As described above, since the laminate for transfer printing of the present invention uses a polyvinyl alcohol-based film having excellent releasability as a base film, the curable resin layer can be used without providing a separate release layer. Can be peeled off. In addition, a polyvinyl alcohol film roughened by blending the filler is used as the base film, and a curable resin layer is laminated on the rough surface, so a matting agent or the like is added to the curable resin layer. Even if it does not do, the boundary surface of the protective layer and base film which are formed becomes an uneven surface. Therefore, when the base film is peeled and removed, the surface of the protective layer having irregularities appears and becomes a matte surface.

  FIG. 3 is a schematic cross-sectional view showing the configuration of a matte decorative molded product manufactured using the laminate for transfer printing having the configuration shown in FIG. The transfer layer (curable resin layer, design layer, adhesive layer) of the laminate for transfer printing is transferred to the transfer target 10, and the cured product of the design layer 3 'and the curable resin layer via the adhesive layer 4'. (That is, a protective layer) 2 'is laminated. The surface of the protective layer 4 ′ that is the outermost surface, that is, the peeled surface from the base film 1 is an uneven surface having a matte effect.

  In this way, by applying the transfer method using the laminate for transfer printing of the present invention, it is possible to achieve excellent matte by simply peeling off the base film without performing extra work steps such as washing and drying after transfer. A protective layer having a surface can be formed, which is economical. Moreover, since processes such as transfer, curing of the curable resin layer, and peeling of the base film can be continuously performed, the productivity of the decorative molded product is increased.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to a following example, unless the summary is exceeded.
In the examples, “parts” and “%” mean weight basis.
[Measurement evaluation method]
First, the measurement evaluation method performed in the following examples will be described.
(1) Surface Roughness of Polyvinyl Alcohol Film Arithmetic average roughness (Ra) was measured according to JIS B0601-2001 using “Color 3D Laser Microscope VK-9700” manufactured by Keyence Corporation.

(2) Preparation of sample for evaluation The produced laminate for transfer printing and the blue glass substrate (thickness 2.8 mm) are preheated for 3 minutes in a dryer heated to 130 ° C., and the thermocompression adhesive of the laminate is melted. The melted surface was pressed against a blue plate glass substrate with a hand roller and bonded. Then, 1000 mJ of ultraviolet rays were irradiated through the base film, the curable resin layer was cured, and a sample for evaluation was obtained.

(3) Peelability of base film In the sample for evaluation, the base film is peeled and removed from the cured curable resin layer, that is, the hard coat layer (which is a protective layer in the decorative molded product), according to the following criteria: The peelability of the base film was evaluated.
○: Easily peelable ×: Unpeelable

(4) Matte property In the sample for evaluation, after the base film was peeled and removed, the surface of the cured curable resin layer (hard coat layer: protective layer of the decorative molded product) (the side on which the base film was laminated) The surface of the fluorescent lamp was reflected, and the degree of scattering of the fluorescent lamp was visually observed and evaluated according to the following criteria.
A: The fluorescent lamp outline cannot be confirmed.
○: The outline of the fluorescent lamp appears blurred.
X: The outline of the fluorescent lamp is clearly visible.

(5) Image clarity In the sample for evaluation, after peeling and removing the base film, the surface of the cured curable resin layer (hard coat layer: protective layer of the decorative molded product) (on the side on which the base film was laminated) Surface) using a Suga test machine image clarity measuring device ICM-1DP under the following conditions, and evaluated according to the following criteria.

(Measurement condition)
Measurement method: Reflection Measurement angle: 45 ° incidence, 45 ° light reception Slit: 0.03 mm
Measurement hole: 20 mm
Optical comb width: 2.0mm
Image clarity: C = [(M−m) / (M + m)] × 100 (%)
C: Image definition (%) when the optical comb width is (mm)
M: Maximum light intensity when optical comb width (mm) m: Minimum light intensity when optical comb width (mm) (Evaluation criteria)
◎ ・ ・ ・ C value less than 30% (with sufficient matting effect)
○ ... C value 30 to less than 70% (with matte effect)
Δ: C value less than 70-90% (Slightly matte effect)
× ・ ・ ・ C value 90% or more (no matting effect)

[Production and evaluation of laminate for transfer printing]
(1) Production of base film 100 parts of polyvinyl alcohol resin having a saponification degree of 88 mol% and a 4% aqueous solution viscosity of 23 mPa · s at 20 ° C., the amount of starch (average particle diameter of 15 μm) as a filler shown in Table 1, surfactant (Polyoxyethylene sorbitan monolaurate) 0.5 parts, 20% aqueous solution consisting of 5 parts of glycerin as a plasticizer is discharged from a T-die onto a rotating stainless steel endless belt whose surface temperature is adjusted to 90 ° C. The film was formed, and subsequently heat treatment was performed using an anti-curl treatment with a hot roll adjusted to 95 ° C. As described above, a polyvinyl alcohol film having a thickness of 40 μm with different filler contents was obtained, and this was used as a base film of a laminate for transfer printing. The surface roughness of each polyvinyl alcohol film is as shown in Table 1.

(2) Preparation of curable resin composition 40 parts of solid content of urethane acrylate "UV-3520" manufactured by Nippon Synthetic Chemical Industry Co., Ltd. and 50 parts of solid content of polymethyl methacrylate "MN" manufactured by Kaneka Corporation and Osaka “Irgacure” manufactured by Nagase Sangyo Co., Ltd. was used as a photopolymerization initiator in a solution obtained by diluting and mixing 10 parts of a photopolymerizable monomer “Biscoat # 300” manufactured by Organic Chemical Industry Co., Ltd. with 2-butanone so that the total solid concentration was 50%. 819 "was mixed so as to be 3 parts with respect to 100 parts of the solid content to obtain an active energy ray-curable resin composition constituting the curable resin layer.

(3) Preparation of design printing ink A gravure printing ink consisting of 10 parts of black pigment, 5 parts of nitrocellulose, 15 parts of alkyd resin, 30 parts of toluene, 30 parts of ethyl acetate and 10 parts of isopropyl alcohol was prepared.

(4) Preparation of coating solution for thermocompression bonding adhesive layer Polyester “SP-185” (polyester resin) manufactured by Nippon Synthetic Chemical Industry Co., Ltd. with respect to a mixed solvent of 4: 1 (weight ratio) of toluene and 2-butanone The mixture was dissolved with stirring under heated reflux conditions so as to be 20%.

(5) Manufacture of laminate for transfer printing On the heat-treated surface of the above base film, the active energy ray-curable resin composition prepared above is applied with a bar coater so as to have a thickness of 160 μm. A curable resin layer having a thickness of 80 μm was laminated on the base film by drying at a temperature of 15 ° C. for 15 minutes. On the surface of the curable resin layer, using the above printing ink, a lattice-like pattern is formed by a gravure printing method to form a design layer, and on the design layer, the above thermocompression bonding layer is used. The coating solution was applied with a bar coater to a thickness of 100 μm, and dried at 80 ° C. for 15 minutes to form a thermocompression bonding layer having a thickness of 20 μm. As described above, a laminate for transfer printing composed of a bale film / curable resin layer / design layer / adhesive layer was obtained. About the obtained laminated body, peelability, matteness, and image clarity were evaluated based on the said measurement evaluation method. The results are shown in Table 1.
For comparison, a polyvinyl alcohol film produced in the same manner except that no filler was added was used as a base film, and a curable resin layer, a design layer, and an adhesive layer were laminated thereon in the same manner as described above. Thus, the produced laminate for transfer printing was similarly evaluated as a comparative example. The results of this comparative example are also shown in Table 1.

  From Table 1, about the laminated body for transfer printing of an Example, since the polyvinyl-alcohol-type film formed by using a filler is used as a base film, it was excellent not only in peelability but also in matteness. Recognize. In contrast, Comparative Example 1 uses a polyvinyl alcohol-based film that does not contain a filler. Therefore, although the image clarity evaluation shows a slight matte effect, the fluorescent lamp has a clear outline in the matte evaluation. The matteness was not satisfactory.

  The transfer printing laminate of the present invention can remove the base film after transfer, and the surface of the cured product (hard coat layer) of the curable resin layer that is exposed after the peeling can exhibit a matte effect. Since it is a surface, it is convenient for the production of matte decorative molded products. Therefore, interior materials or exterior materials for vehicles such as automobiles, construction materials such as baseboards and rims, furniture such as window frames and door frames, interior materials for buildings such as walls, floors and ceilings, television receivers, mobile phones It is very useful for improving the productivity of matte decorative molded products for applications such as telephone parts, housings and containers for home appliances such as air conditioners.

DESCRIPTION OF SYMBOLS 1 Base film 2 Curable resin layer 3 Design layer 4 Adhesive layer 10 Transfer object

Claims (12)

  A laminate for transfer printing, wherein a base film made of a polyvinyl alcohol film containing a filler, a curable resin layer, and a design layer are laminated in this order.   The laminate for transfer printing according to claim 1, wherein the content of the filler is 3 to 30 parts by weight with respect to 100 parts by weight of the polyvinyl alcohol resin.   The laminate for transfer printing according to claim 1 or 2, wherein the filler is starch.   The laminate for transfer printing according to any one of claims 1 to 3, wherein the surface roughness (Ra) of the base film on the side of the curable resin layer is 0.3 to 5 µm.   The laminate for transfer printing according to any one of claims 1 to 4, wherein the surface of the base film on the side of the curable resin layer is heat-treated at a temperature of 50 to 180 ° C.   The saponification degree of the polyvinyl alcohol-based resin constituting the polyvinyl alcohol-based film is 75 mol% or more, and the viscosity of a 4 wt% aqueous solution at 20 ° C is 10 to 70 mPa · s. The laminate for transfer printing described.   The thickness of a base film is 5-120 micrometers, The laminated body for transfer printing in any one of Claims 1-6 characterized by the above-mentioned.   The laminate for transfer printing according to any one of claims 1 to 7, wherein the polyvinyl alcohol film contains a surfactant.   The filler is starch, contained in an amount of 3 to 30 parts by weight with respect to 100 parts by weight of the polyvinyl alcohol resin, and the surface roughness (Ra) on the side of the curable resin layer of the base film is 0.3 to 5 μm. The laminate for transfer printing according to any one of claims 1 to 8.   The polyvinyl alcohol resin constituting the polyvinyl alcohol film has a saponification degree of 75 mol% or more, a 4 wt% aqueous solution viscosity at 20 ° C of 10 to 70 mPa · s, and a filler having an average particle size of 0.1 to 30 µm. It is starch, content of a filler is 3-30 weight part with respect to 100 weight part of polyvinyl alcohol-type resin, and the thickness of a base film is 5-120 micrometers, The any one of Claims 1-9 characterized by the above-mentioned. A laminate for transfer printing.   The laminate for transfer printing according to any one of claims 1 to 10, wherein an adhesive layer is further laminated on the design layer.   The laminate for transfer printing according to any one of claims 1 to 11, which is used for producing a mat-like decorative molded product.

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