JP5595191B2 - Laminate for transfer printing - Google Patents

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, it relates to a laminate for transfer printing used in decorative molded products for applications such as mobile phone parts, housings for home appliances such as air conditioners, and containers. The present invention relates to a laminate for transfer printing excellent in sharpness and image clarity.

  Conventionally, there is a transfer method 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 uses a transfer material in which a transfer layer consisting of a release layer (which serves as a protective layer on the surface of the molded product), a design printing layer, an adhesive layer, etc. is formed on a base sheet, and the transfer material is molded by heating and pressing. In this method, the base sheet is peeled off after being adhered to the surface, and only the transfer layer is transferred to the surface of the molded product.

And generally as a base sheet (base film) in this transfer material, a polyethylene terephthalate film is generally used (for example, refer to patent documents 1 and 2).
Moreover, as a base material sheet (base film), a polyvinyl alcohol film, a polyvinyl butyral film, an ethylene vinyl alcohol copolymer film, etc. are mentioned as a film which consists of resin which has the characteristic of melt | dissolution elution or swelling peeling (for example, , See Patent Document 3).

Japanese Patent Laid-Open No. 2005-96156 JP 2002-293094 A JP 2001-270293 A

  However, the polyethylene terephthalate film used as the base sheet in Patent Documents 1 and 2 has poor release properties from the release layer (protective layer), and usually the polyethylene terephthalate film is subjected to a release treatment or separately released. Layers need to be provided and further improvements are desired.

  Moreover, using the base material sheet disclosed in Patent Document 3, for example, a normal polyvinyl alcohol film or an ethylene vinyl alcohol copolymer film, that is, an unstretched polyvinyl alcohol film or an ethylene vinyl alcohol copolymer film. When transfer printing is performed, transfer characteristics such as glossiness, sharpness and image clarity are still insufficient.

  Therefore, in the present invention, under such a background, the base film and the release layer (protective layer: a layer in which the curable resin layer is cured) are excellent in peelability, and further, glossiness, sharpness, image clarity, etc. An object of the present invention is to provide a laminate for transfer printing excellent in transfer characteristics.

  However, as a result of intensive studies in view of such circumstances, the present inventor has used a stretched film of an ethylene-vinyl ester copolymer saponified product as a base sheet (base film), thereby providing a coating property of a curable resin. Can be formed, and a uniform coating film can be formed. Furthermore, it has excellent releasability from the protective layer after transfer (a layer in which the curable resin layer is cured), and in addition, transfer characteristics such as gloss, clarity and image clarity. The present invention was completed.

  That is, the gist of the present invention is a laminate for transfer printing in which a base film [I], a curable resin layer [II], and a printing layer [III] are laminated, and the base film [I] is an ethylene-vinyl ester type. The present invention relates to a laminate for transfer printing, which is a stretched film (A) comprising a saponified copolymer (a).

  The curable resin layer [II] is obtained after the transfer printing laminate of the present invention is adhered to the transfer target, the printing layer [III] is transferred to the transfer target, and the base film [I] is peeled off. , Which serves as a protective layer for protecting the surface, and thermosetting resins and active energy ray curable resins are usually used.

  The laminate for transfer printing of the present invention is excellent in peelability between the base film and the protective layer (layer in which the curable resin layer is cured), and further excellent in transfer characteristics such as glossiness, sharpness, and image clarity. It has an effect, interior materials or exterior materials of vehicles such as automobiles, construction members such as baseboards, wrapping edges, window frames, door frames, etc., interior materials of buildings such as walls, floors, ceilings, It is very useful for producing decorative molded products for uses such as housings and containers of household electric appliances such as television receivers, mobile phone parts, and air conditioners.

The present invention is described in detail below.
The laminate for transfer printing of the present invention comprises a base film [I], a curable resin layer [II], and a printing layer [III] that are laminated.
The base film [I] used in the present invention is a stretched film (A) composed of an ethylene-vinyl ester copolymer saponified product (hereinafter sometimes abbreviated as EVOH) (a).
First, EVOH (a) used in the present invention will be described.

  EVOH (a) used in the present invention is a known resin and is a water-insoluble thermoplastic resin. EVOH (a) is usually obtained by copolymerizing a vinyl ester monomer (for example, fatty acid vinyl ester) and ethylene to obtain an ethylene-vinyl ester copolymer and saponifying it. That is, it mainly contains ethylene structural units and vinyl alcohol structural units, and contains some amount of vinyl ester structural units generated by saponification. In the copolymerization, a known polymerization method such as a solution polymerization method can be employed.

  As the vinyl ester monomer, vinyl acetate is usually used from an economical point of view. Other examples include aliphatic vinyl esters such as vinyl formate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl versatate, and benzoic acid. Examples thereof include aromatic vinyl esters such as vinyl acid, and are usually aliphatic vinyl esters having 3 to 20 carbon atoms, preferably 4 to 10 carbon atoms, and particularly preferably 4 to 7 carbon atoms. These are usually used alone, but a plurality of them may be used simultaneously as necessary.

  Further, the ethylene content of EVOH (a) is determined at the time of polymerization of ethylene and a vinyl ester monomer, and does not change before and after saponification. The content of the ethylene structural unit measured based on ISO 14663 is usually 20 to 60 mol%, preferably 20 to 55 mol%, particularly preferably 25 to 50 mol%. If the ethylene content is too low, impact resistance and workability tend to be reduced and stretching tends to be difficult, and if it is too high, solvent resistance tends to be low.

  Furthermore, the saponification degree of EVOH (a) is a value measured by a titration method (JIS K6726) (however, EVOH is a solution uniformly dissolved in water / methanol solvent), and is usually 90 to 100 mol%, preferably Is 95 to 100 mol%, particularly preferably 98 to 100%. If the degree of saponification is too low, the solvent resistance tends to decrease.

  The melt flow rate of EVOH (a) (hereinafter sometimes referred to as MFR) is a value measured at 210 ° C. and a load of 2160 g, and is usually 0.1 to 100 g / 10 minutes, preferably 1 to 50 g / 10 minutes. Most preferably, it is 2-40 g / 10min. If this value is too high or too low, the extrudability tends to decrease.

  In the present invention, in addition to ethylene and a fatty acid vinyl ester, an ethylenically unsaturated monomer that can be copolymerized within a range that does not impair the properties required for EVOH (a) may be copolymerized. Examples of the monomer include the following. For example, olefins such as propylene, 1-butene, isobutene, 2-propen-1-ol, 3-buten-1-ol, 4-penten-1-ol, 5-hexen-1-ol, 3,4 -Hydroxy group-containing α-olefins such as dihydroxy-1-butene and 5-hexene-1,2-diol, and esterified products thereof, 3,4-diacyloxy-1-butene, in particular, 3,4-diacetoxy- 1-butene and the like. In addition, unsaturated acids or salts thereof such as acrylic acid, methacrylic acid, crotonic acid, (anhydrous) phthalic acid, (anhydrous) maleic acid, (anhydrous) itaconic acid, and mono- or dialkyl esters having 1 to 18 carbon atoms Is given. Further, acrylamide such as acrylamide, C1-C18 N-alkylacrylamide, N, N-dimethylacrylamide, 2-acrylamidepropanesulfonic acid or a salt thereof, and acrylamidepropyldimethylamine or an acid salt thereof or a quaternary salt thereof. Methacrylamide, N-alkylmethacrylamide having 1 to 18 carbon atoms, N, N-dimethylmethacrylamide, 2-methacrylamideamidopropanesulfonic acid or its salt, methacrylamidepropyldimethylamine or its acid salt and its quaternary And methacrylamides such as salts. Also, N-vinylamides such as N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, vinyl cyanides such as acrylonitrile and methacrylonitrile, alkyl vinyl ethers having 1 to 18 carbon atoms, hydroxyalkyl vinyl ethers, alkoxy Vinyl ethers such as alkyl vinyl ethers, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, vinyl halides such as vinyl bromide, vinyl silanes such as trimethoxyvinyl silane, and allyl acetate, allyl chloride, trimethyl- ( 3-acrylamido-3-dimethylpropyl) -ammonium chloride, acrylamido-2-methylpropanesulfonic acid, vinyl ethylene carbonate, glycerin monoallyl ether and the like. Further, it may be post-modified such as urethanization, acetalization, cyanoethylation, oxyalkylene formation, or the like. In particular, EVOH copolymerized with hydroxy group-containing α-olefins is preferable in that secondary moldability such as stretching and vacuum / pressure forming is improved. Among them, EVOH having 1,2-diol in the side chain is preferable. preferable.

  In the EVOH (a) used in the present invention, a compounding agent generally blended with EVOH within a range not inhibiting the effects of the present invention, such as a heat stabilizer, an antioxidant, an antistatic agent, a colorant, and an ultraviolet absorber. , Lubricant, plasticizer, light stabilizer, surfactant, antibacterial agent, drying agent, antiblocking agent, flame retardant, crosslinking agent, curing agent, foaming agent, crystal nucleating agent, antifogging agent, biodegradation additive, A silane coupling agent, an oxygen absorbent and the like may be contained.

  As the above heat stabilizer, organic acids such as acetic acid, propionic acid, butyric acid, lauric acid, stearic acid, oleic acid, behenic acid or their alkali metals are used for the purpose of improving various physical properties such as heat stability during melt molding. Salts (sodium, potassium, etc.), alkaline earth metal salts (calcium, magnesium, etc.); or inorganic acids such as sulfuric acid, sulfurous acid, carbonic acid, phosphoric acid, boric acid, or their alkali metal salts ( Sodium, potassium, etc.), alkaline earth metal salts (calcium, magnesium, etc.), zinc salts and other additives may be added. Among these, it is particularly preferable to blend boron compounds including acetic acid, boric acid and salts thereof, acetates and phosphates.

  When acetic acid is blended, the blending amount is usually 0.001 to 1 part by weight, preferably 0.005 to 0.2 part by weight, particularly preferably 0.010 to 0 part per 100 parts by weight of EVOH (a). .1 part by weight. If the blending amount of acetic acid is too small, there is a tendency that the effect of containing acetic acid is not sufficiently obtained. Conversely, if the blending amount is too large, it tends to be difficult to obtain a uniform film.

  Moreover, when mix | blending a boron compound, the compounding quantity is 0.001-1 weight part normally in boron conversion (after ashing and analyzed by ICP emission spectrometry) with respect to EVOH (a) 100 weight part. Yes, preferably 0.002 to 0.2 parts by weight, particularly preferably 0.005 to 0.1 parts by weight. If the compounding amount of the boron compound is too small, the compounding effect of the boron compound may not be sufficiently obtained. Conversely, if the compounding amount is too large, it tends to be difficult to obtain a uniform film.

  Moreover, as a compounding quantity of acetate and phosphate (including hydrogen phosphate), it is usually in metal conversion (analyzed by ICP emission spectrometry after ashing) with respect to 100 parts by weight of EVOH (a). 0.0005 to 0.1 part by weight, preferably 0.001 to 0.05 part by weight, particularly preferably 0.002 to 0.03 part by weight. If the amount is too small, the content effect may not be sufficiently obtained. Conversely, if the amount is too large, it tends to be difficult to obtain a uniform film. In addition, when mix | blending 2 or more types of salts with EVOH, it is preferable that the total amount exists in the range of said compounding quantity.

  In the present invention, two or more types of EVOH may be blended and used. In this case, the ethylene composition and the saponification degree are represented by the average value of the blend ratio. Furthermore, resins other than EVOH (a) can be blended within a range that does not impair the effects of the present invention.

Next, the stretched film (A) made of EVOH (a) obtained above will be described.
The stretched film (A) made of EVOH (a) is produced by the steps of (1) forming an unstretched film of EVOH (a) and (2) stretching the unstretched film.

First, the shaping | molding of the unstretched film of EVOH (a) is demonstrated.
The unstretched film of EVOH (a) is obtained by melting and extruding EVOH pellets as a raw material from a die using an extruder and cooling with a cooling roll or water or air. When using a cast type extruder, a T die is used, and when using a tubular type extruder, a tubular die is used. As the extruder, a general screw type extruder is used. As a kind of screw type extruder, any of a single screw extruder, a twin screw extruder (same direction, different direction rotation), etc. may be sufficient. The melting temperature is selected at a temperature setting 10 to 80 ° C., preferably 20 to 60 ° C. higher than the melting point of EVOH (a). If it is too low, the extrusion load tends to be high due to poor melting, or poor stretching tends to occur. If it is too high, a non-stretched film with good quality tends to be difficult to obtain due to the generation of cross-linked gel, burn, and kogation due to thermal degradation.

  It is important that the unstretched film to be a raw fabric has a uniform thickness. Therefore, it is preferable to use a technique useful for forming the thickness uniformly. Installing a mixer such as a gear pump at the outlet of the extruder is effective for stabilizing the discharge of the molten resin. In addition, when cross-linked gels, burns, and kogation are generated, it is necessary to remove them. For this purpose, it is also effective to use various filters including a screen pack.

  In the stretching step, since reheating of the unstretched film is necessary, it is effective to keep the crystallinity of the unstretched film as low as possible. For this reason, in cast film formation, it is preferable to set the temperature of the cooling roll low and quench the molten resin film. If the roll surface is too low, the roll surface may condense and the film-forming state may change, so it is important to set it low enough to prevent condensation. Generally, it is preferable to set at 30 to 90 ° C. It is important that the contact between the cooling roll and the molten resin film is uniform. For this reason, it is a common practice to use ancillary equipment for promoting uniform contact with the cooling roll. For example, an air knife, an air chamber, a vacuum chamber, electrostatic pinning, a touch roll, or the like is applied.

  In tubular film formation, downward water cooling or air cooling can be applied, but in general, water cooling is used. The water temperature is preferably lower, usually 5 to 40 ° C, particularly 10 to 30 ° C.

  Although the thickness of an unstretched film is decided by the thickness of the target stretched film, generally it is 20-600 micrometers, Especially 40-600 micrometers is preferable. If it is too thin, there is a tendency that the stretching ratio cannot be increased due to breakage, and if it is too thick, the stretching load tends to be high and impractical.

Next, stretching of an unstretched film of EVOH (a) will be described.
Although a well-known method can be applied as the stretching method, for example, (1) chuck-type stretching, (2) roll-type stretching, (3) tenter-type stretching, (4) tubular-type stretching, etc. Can be mentioned. (1) is suitable for producing a batch-type stretched film, and (2) is suitable for uniaxial stretching. Further, although the apparatus becomes large, (3) is effective for producing a stretched film on an industrial scale. Sequential biaxial stretching can also be performed by combining (2) and (3). (4) is stretched by putting air into a water-cooled tubular film and sandwiching the top and bottom with a pinch roll. Although it is difficult to obtain the thickness accuracy after stretching, it is not general-purpose, but it is called “double bubble method” and is one of the biaxial stretching methods used industrially. As the stretching method, any one of uniaxial stretching, sequential biaxial stretching, and simultaneous biaxial stretching may be adopted.

  The unstretched film is preheated before stretching, but the heat source and method used for heating are not particularly limited. General heating methods such as a method of blowing warm air preheated, a method of passing through a temperature-controlled space, a method of using a general-purpose heater such as infrared rays or hot water, and a method of heating through a temperature-controlled roll can be applied.

(1) In the chuck fixing type stretching method, a commercially available batch type stretching machine can be used. After the unstretched film is fixed to the chuck, preheating is performed by a predetermined method, and uniaxial stretching or biaxial stretching is performed.
(2) In the roll-type stretching method, a uniaxially stretched film is obtained by passing an unstretched film through a plurality of rolls driven at different speeds and stretching the unstretched film in the longitudinal direction with a difference in peripheral speed. Preheating may be performed in advance, or by preheating by heating the drawing roll.
(3) Tenter-type stretching is a method in which a clamp attached to a sliding belt or chain sandwiches an ear end of a film and the clamp stretches while changing the width. The width of the stretched film is determined by a machine called a tenter frame. It can be stretched in the transverse and longitudinal directions.
(4) In the tubular stretching method, an unstretched film is formed in a tube shape, and is passed through a preheating unit after being sandwiched between nip rolls. A necessary amount of air is blown into the tube and is further sandwiched between nip rolls. A stretched film can be continuously produced by being expanded by air pressure when passing through the preheating zone.

  Thus, a stretched film can be obtained. The stretched film (A) used in the present invention preferably has a total stretch ratio of 1.5 to 16 times, particularly 2 to 2 in terms of the surface uniformity of the film. It is preferably 12 times, more preferably 3 to 10 times. Alternatively, the draw ratio is 1.5 to 10 times in the longitudinal direction, particularly 2 to 8 times, more preferably 3 to 5 times, and 1.5 to 10 times, particularly 2 to 8 times, further 3 to 3 times in the transverse direction. A film stretched 5 times is preferably applied in terms of the surface uniformity of the film. In the case of biaxial stretching, it is preferable that the film is stretched 1.5 to 4 times, particularly 2 to 3.5 times in both length and width, from the viewpoint of the surface uniformity of the film. When the draw ratio is too low, stretch unevenness tends to remain, and when the draw ratio is too high, the film tends to be easily broken.

  The stretching temperature depends on the thickness of the unstretched film, but is about 60 to 160 ° C. If the stretching temperature is too low, the stretching load tends to increase, and if it is too high, stretching tends to be impossible due to insufficient tension. Moreover, you may heat-fix as needed in order to show dimensional stability. Although the heat setting temperature is determined while observing the state of the stretched film (A), it is generally 110 to 160 ° C., preferably 120 to 150 ° C., 5 to 60 seconds, preferably 10 to 30 seconds. Good to do.

  The thickness of the stretched film (A) thus obtained is preferably 5 to 120 μm, particularly 5 to 110 μm, more preferably 10 to 10 μm from the viewpoint of coating properties of the paint and followability with the adherend during transfer. 80 μm is preferable. If the thickness is too thin, there is a tendency that coating spots of the paint and breakage at the time of transfer tend to occur. If the thickness is too thick, wrinkles or the like are likely to occur at the time of transfer, and the surface of the transferred product tends to be uneven.

  In addition, the elongation at break of the stretched film (A) is preferably 150% or more, more preferably 180% or more under the conditions 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 at the time of printing or to reduce the throwing power at the time of transfer. The upper limit of elongation at break is usually 400%. Here, the breaking elongation of the stretched film is measured according to JIS K 7127 (1999).

  The stretched film (A) obtained in this way is very useful as a base film [I] for transfer printing, and when considering such applications, its thickness is particularly in the range of 5 to 120 μm. It is preferable to set, and more preferably 10 to 100 μm.

  And it is preferable to preserve | save the stretched film (A) obtained by forming a film in a suspended state in the atmosphere of 10-25 degreeC, for example by processing a conventionally well-known moisture-proof packaging.

Next, the curable resin layer [II] of the laminate for transfer printing of the present invention will be described.
The curable resin layer [II] is a layer that becomes the outermost surface of the transfer object when the base film [I] is peeled off, and the cured resin layer until the base film [I] is peeled off. Is cured to become a protective layer for protecting the surface of the transfer object. As the material, for example, polyacrylic resin, polyester resin, polyvinyl chloride resin, cellulose resin, rubber resin, polyurethane resin, polyvinyl acetate resin, etc. are used, as well as UV curable resin composition and electron beam curable resin. Active energy ray-curable resin compositions such as 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 preferably one containing, for example, an acrylic resin and a urethane (meth) acrylate compound.

  Examples of such acrylic resins include homopolymers or copolymers of acrylic ester monomers, and acrylic copolymers having other ethylenically unsaturated monomers as copolymerization components.

  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.

As other ethylenically unsaturated monomer (a2), 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 the other ethylenically unsaturated monomer, 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, such as radical copolymerization of the polymerization component in an organic solvent.

  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, particularly preferably 30 to 120 ° C, and more preferably 40. ~ 110 ° C. If the glass transition point (Tg) is too low, the curable resin layer such as the active energy ray curable resin composition is sticky and causes problems (such as winding and printing defects during the process) when post-processing is performed. If it is too high, it tends to become brittle when a curable resin layer such as an active energy ray-curable resin composition is cured to form a protective layer.

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 before curing becomes soft and sticky, so that a problem (process) If it is too large, it will be difficult to obtain film thickness uniformity during coating of the curable resin layer, and the coating film hardness after drying will be more than necessary. It becomes high and tends to cause defects (cracking of the coating film, delamination, etc.) when performing post-processing.

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

  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 such polyols 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, Polyether polyol having at least one structure of block copolymer or random copolymerization of tylene oxide / propylene oxide; the polyhydric alcohol or polyether polyol and maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, adipine Examples include polyester polyols that are condensates with polybasic acids such as acids and isophthalic acids; caprolactone-modified polyols such as caprolactone-modified polytetramethylene polyol; polyolefin-based polyols; polybutadiene-based polyols such as hydrogenated polybutadiene polyols, and the like.

  Furthermore, as such polyols, 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 Also included are carboxyl group-containing polyols such as homogentisic acid, sulfonic acid group or sulfonate group-containing polyols such as sodium 1,4-butanediol sulfonate, and the like.

  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.

  As a method for producing the urethane (meth) acrylate compound, for example, a hydroxyl group-containing (meth) acrylic compound and a polyvalent isocyanate compound are mixed in an inert gas atmosphere, and usually reacted at 30 to 80 ° C. for 2 to 10 hours. The method of making it include. 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 important 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.

  Thus, an active energy ray-curable resin composition containing an acrylic resin and a urethane (meth) acrylate compound is obtained. When the active energy ray-curable resin composition is an ultraviolet curable resin composition, It is preferable to contain a photopolymerization initiator. In the case of an electron beam curable resin composition, a photopolymerization initiator is unnecessary.

  Examples of such photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy- 2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) Acetophenones such as butanone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomers; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. Benzoin 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 chloride, etc. Benzophenones: 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy)- 3,4- Thioxanthones such as methyl-9H-thioxanthone-9-one mesochloride; 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphos And acylphosphine oxides such as fin 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.

  These auxiliary agents include triethanolamine, triisopropanolamine, 4,4′-dimethylaminobenzophenone (Michler ketone), 4,4′-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, 4-dimethylaminobenzoic acid. Ethyl, 4-dimethylaminobenzoic acid (n-butoxy) ethyl, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone Etc. can be used in combination.

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.

  In the present invention, the thickness of the curable resin layer [II] is preferably 1 to 150 μm, particularly 2 to 120 μm, more preferably 2 to 100 μm, in terms of wear resistance and chemical resistance. preferable. 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 deteriorated, which tends to cause burrs and the like.

  In forming the curable resin layer [II], the raw material resin or the raw material resin composition is coated with a gravure coating method, a roll coating method, a bar coating method, a comma coating method, a lip coating method, a gravure printing method, What is necessary is just to laminate | stack by printing methods, such as a screen printing method.

  When the above active energy ray-curable resin composition is used, after laminating a layer made of the active energy ray-curable resin composition (curable resin layer [II]) on the base film [I], When the printing layer [III] is transferred to the transfer target and the base film [I] is peeled off, the active energy ray is irradiated and cured at an arbitrary stage to form a protective layer (hard coat layer). Good. For example, (1) an active energy ray-curable resin composition layer is laminated on the base film [I] and then cured by irradiation with active energy rays, or (2) the active energy ray is cured on the base film [I]. After laminating the functional resin composition layer, a printed layer [III] described later is formed and then cured by irradiating active energy rays from the base film [I] side, or (3) an adhesive layer [described later] IV] is laminated after irradiation with active energy rays from the base film [I] side, or (4) the base film [I] side after the transfer printing laminate of the present invention is adhered to the transfer target. The method of irradiating more active energy rays and making it harden etc. is mentioned.

  In addition, when curing the curable resin layer by irradiating active energy rays, the active energy rays include, 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 beams, neutron beams, and the like can be used, but curing by ultraviolet irradiation is advantageous from the viewpoint of curing speed, availability of an irradiation device, price, and the like.

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.

  In the present invention, the printing layer [III] is a layer for forming a design, and the materials of the printing layer include polyvinyl resins, polyamide resins, polyester resins, acrylic resins, polyurethane resins, polyvinyl acetals. It is preferable to use a colored ink containing a resin such as a polyester resin, a polyester urethane resin, a cellulose ester resin, or an alkyd resin as a binder and an appropriate color pigment or dye as a colorant.

  As a method for forming the printing layer, a normal printing method such as an offset printing method, a gravure printing method, a screen printing method, or the like can be used. In particular, the offset printing method and the gravure printing method are suitable for performing multicolor printing and gradation expression.

  The laminate for transfer printing of the present invention is one in which the base film [I], the curable resin layer [II], and the printing layer [III] are laminated, preferably the upper layer of the printing layer [III]. In addition, the adhesive layer [IV] is laminated.

  The adhesive layer [IV] is for adhering the above laminate to the surface of the transfer target. It may be formed when the adhesive force between the printed layer and the molded product is weak. As the material of the adhesive layer [IV], a heat-sensitive or pressure-sensitive resin suitable for the material of the transfer object may be used as appropriate. For example, a polyester resin, an acrylic resin, a polystyrene resin, a polyamide resin, Examples include chlorinated polyolefin resins, chlorinated ethylene-vinyl acetate copolymer resins, cyclized rubbers, and coumarone indene resins.

  Examples of the method for forming the adhesive layer [IV] include a coating method such as a gravure coating method, a roll coating method, a bar coating method and a comma coating method, a printing method such as a gravure printing method and a screen printing method. In addition, an adhesive sheet [IV] can be formed by laminating adhesive sheets made of the above-described materials by a laminating method or the like. The adhesive layer [IV] may also serve as the printing layer [III].

  The thickness of the adhesive layer [IV]] is preferably 0.5 to 50 μm, particularly 1 to 40 μm, more preferably 2 to 30 μm, from the viewpoint of followability to the adherend. If the thickness is too thin, the followability to the adherend during transfer tends to decrease, and if it is too thick, the cost tends to increase, which is uneconomical.

  A method for decorating the surface of the transfer object using the transfer method using the transfer printing laminate of the present invention will be described.

  First, the adhesive layer [IV] side of the laminate for transfer printing is brought into close contact with the surface of the transfer target. 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 Heat and pressure are applied from the base film [I] side of the laminate for transfer printing via an elastic body. By doing so, the adhesive layer [IV] adheres to the surface of the transfer target.

  After cooling, the curable resin layer [II] is cured by irradiation with active energy rays to form a protective layer, and finally the base film [I] is peeled off to remove the base film [I] and the protective layer (cured cured Peeling occurs at the interface with the conductive resin layer [II]), and the transfer is completed.

  Next, a method for decorating the surface of a resin molded product, which is a transfer target, using the transfer printing laminate of the present invention and utilizing the simultaneous molding method by injection molding will be described.

  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 advisable to use a feeding device having a positioning mechanism so that the registration of the printing layer [III] of the laminate for transfer printing and the mold for molding coincide. . 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 positional deviation of the printing layer [III] does not occur.

  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. And after hardening curable resin layer [II] by active energy ray irradiation etc. to make a protective layer, when base film [I] is finally peeled off, base film [I] and protective layer (cured curable property) Separation occurs at the interface with the resin layer [II]), and the transfer is completed.

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.

Example 1
[Manufacture of base film [I]]
A 40 mmφ single screw extruder (L / D = 28) using a full flight type screw with a compression ratio of 3.4 and a 450 mm width coated hanger die (L / D = 28), ethylene content 32 mol%, saponification degree 99.6 mol%, melt A monolayer film having a thickness of 100 μm was produced by a take-up device having EVOH extruded with a flow rate value (MFR) of 3.2 g / 10 min and having a cooling roll controlled at 30 ° C. in the first roll. In addition, the screen pack used two 120 mesh metal nets. The obtained single-layer film was cut into a square size of 92 mm × 92 mm and set on a fixing jig of a stretching apparatus KARO IV manufactured by Bruekner. Next, the film is moved to the first oven, the temperature is raised to 120 ° C. with a preheating time of 20 seconds, the film is stretched three times in the longitudinal direction and the transverse direction by simultaneous biaxial stretching, and the film thickness is 11 μm. A biaxially stretched film was obtained.

[Manufacture of curable resin]
An active energy ray-curable resin composition was prepared as follows.
Kaneka Co., Ltd., polymethylmethacrylate "MN" solid content 50 parts, Nippon Synthetic Chemical Industry Co., Ltd., urethane acrylate "UV-3520" solid content 40 parts, Osaka Organic Chemical Industry Co., Ltd., photopolymerizable monomer In a solution obtained by diluting and mixing 10 parts of “Biscoat # 300” with 2-butanone so that the total solid content concentration becomes 50%, “Irgacure 819” manufactured by Nagase Sangyo Co., Ltd. as a photopolymerization initiator is 3 It mixed so that it might become a part.

[Manufacture of design printing inks]
A gravure printing ink comprising 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.

[Manufacture of coating solution for thermocompression bonding layer]
Made by Nippon Synthetic Chemical Industry Co., Ltd., Polyester “SP-185” (polyester resin) is stirred under heated reflux conditions so as to be 20% with respect to a mixed solvent of toluene and 2-butanone in a ratio of 4: 1 (weight ratio). Dissolved.

<Manufacture of laminate for transfer printing>
On the above base film [I], the above active energy ray-curable resin composition is applied with a bar coater so as to have a thickness of 160 μm, and dried at 80 ° C. for 15 minutes, whereby a base film is obtained. A laminate (α) in which a curable resin layer [II] having a thickness of 80 μm was laminated on [I] was produced.
On the surface of the curable resin layer [II] of the laminate (α), a pattern on the lattice is formed by the gravure printing method using the above printing ink, and the bale film [I] / curable resin layer [II] ] / Laminate (β) consisting of printing layer [III] was obtained.
Further, the above-mentioned coating solution for thermocompression bonding adhesive layer is applied on the printed layer [III] surface of the laminate (β) with a bar coater so as to have a thickness of 100 μm and dried at 80 ° C. for 15 minutes. Then, a thermocompression bonding layer [IV] having a thickness of 20 μm is formed, and a laminate (γ) composed of the bale film [I] / curable resin layer [II] / printing layer [III] / bonding layer [IV] is formed. Obtained.
Using the obtained laminate (γ), a sample for evaluation was prepared as follows, and the following evaluation was performed.

[Preparation of sample for evaluation]
The obtained laminate (γ) and soda glass substrate (thickness 2.8 mm) are preheated in a dryer heated to 130 ° C. for 3 minutes to melt the thermocompression adhesive of the laminate (γ), and this adhesion The layer [IV] surface was pressed against a blue plate glass substrate with a hand roller to prepare a bonded sample.
The obtained pasted sample is irradiated with 1000 mJ of ultraviolet rays through the base film [I], and the curable resin layer [II] is cured to form a protective layer (cured curable resin layer: hard coat layer). A sample for evaluation was used.

[Evaluation of sample for evaluation]
(1) Peelability of base film from protective layer In the sample for evaluation, the peelability of the base film [I] was observed by peeling the base film and the protective layer (cured curable resin layer). It was evaluated according to the criteria.
○: Easily peelable ×: Not peelable

(2) Surface gloss of protective layer In the sample for evaluation, after peeling the base film [I], the fluorescent lamp is reflected on the surface of the protective layer (cured curable resin layer), and the fluorescent lamp is visually observed. The sharpness was evaluated according to the following criteria.
○: The outline of the fluorescent lamp is clearly visible.
Δ: The outline of the fluorescent lamp appears blurred.
X: The outline of the fluorescent lamp cannot be confirmed.

(3) Image clarity of protective layer In the sample for evaluation, after peeling off the base film [I], the image clarity measuring device ICM- of the Suga Test Machine was applied to the surface of the protective layer (cured curable resin layer). Using 1DP, measurement was performed under the following conditions, and evaluation was performed 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)
S: Rank 90% or more A: Rank 70 to less than 90% B: Rank 30 to less than 70% C: Rank less than 30%

Example 2
In Example 1, EVOH was changed to EVOH having an ethylene content of 38 mol% and a saponification degree of 99.6 mol%, and a biaxially stretched film obtained in the same manner was used as in Example 1. Was evaluated.

Example 3
In Example 1, EVOH was obtained in the same manner except that EVOH was changed to EVOH having an ethylene content of 44 mol%, a saponification degree of 99.6 mol%, and a melt flow rate value (MFR) of 3.5 g / 10 min. Evaluation similar to Example 1 was performed using the biaxially stretched film.

Example 4
In Example 1, EVOH has an ethylene content of 38 mol%, a saponification degree of 99.6 mol%, a side chain 1,2-diol bond content of 1.5 mol%, a melt flow rate value (MFR) of 4. Evaluation similar to Example 1 was performed using a biaxially stretched film obtained in the same manner except that the EVOH was changed to 0 g / 10 min.

Example 5
In Example 1, it carried out similarly except having changed base film [I] into the following biaxially stretched films, and the same evaluation as Example 1 was performed.
[Manufacture of base film [I]]
In a 40 mmφ single screw extruder (L / D = 28) using a full flight type screw with a compression ratio of 3.4 and a 450 mm width coated hanger die, the ethylene content was 38 mol%, the saponification degree was 99.6 mol%, the melt A monolayer film having a thickness of 60 μm was produced by a take-up device having EVOH extruded with a flow rate value (MFR) of 3.2 g / 10 min and having a cooling roll controlled at 30 ° C. in the first roll. In addition, the screen pack used two 120 mesh metal nets. The obtained single-layer film was cut into a square size of 92 mm × 92 mm and set on a fixing jig of a stretching apparatus KARO IV manufactured by Bruekner. Next, the film is moved to the first oven, the temperature is raised to 70 ° C. with a preheating time of 20 seconds, the film is stretched twice in the longitudinal direction and the transverse direction by simultaneous biaxial stretching, and the film thickness is 15 μm. A biaxially stretched film was obtained.

Example 6
In Example 1, it carried out similarly except having changed base film [I] into the following biaxially stretched films, and the same evaluation as Example 1 was performed.
[Manufacture of base film [I]]
In a 40 mmφ single screw extruder (L / D = 28) using a full flight type screw with a compression ratio of 3.4 and a 450 mm width coated hanger die, the ethylene content was 38 mol%, the saponification degree was 99.6 mol%, the melt A monolayer film having a thickness of 500 μm was produced by a take-up device having EVOH extruded with a flow rate value (MFR) of 3.2 g / 10 min and having a cooling roll controlled at 30 ° C. in the first roll. In addition, the screen pack used two 120 mesh metal nets. The obtained single-layer film was cut into a square size of 92 mm × 92 mm and set on a fixing jig of a stretching apparatus KARO IV manufactured by Bruekner. Next, the film is moved to the first oven, the temperature is raised to 120 ° C. with a preheating time of 20 seconds, and the film is stretched three times in the longitudinal direction and the transverse direction by simultaneous biaxial stretching, and the film thickness is 55 μm. A biaxially stretched film was obtained.

Example 7
In Example 1, it carried out similarly except having changed base film [I] into the following biaxially stretched films, and the same evaluation as Example 1 was performed.
[Manufacture of base film [I]]
In Example 1, a biaxially stretched film having a thickness of 11 μm was obtained by performing the same operation except that the stretching operation was sequentially biaxial.

Example 8
In Example 1, it carried out similarly except having changed base film [I] into the following uniaxially stretched film, and evaluated similarly to Example 1. FIG.
[Manufacture of base film [I]]
A 40 mmφ single screw extruder (L / D = 28) using a full flight type screw with a compression ratio of 3.4 and a 450 mm width coated hanger die (L / D = 28), ethylene content 32 mol%, saponification degree 99.6 mol%, melt A monolayer film having a thickness of 60 μm was produced by a take-up device having EVOH extruded with a flow rate value (MFR) of 3.2 g / 10 min and having a cooling roll controlled at 30 ° C. in the first roll. In addition, the screen pack used two 120 mesh metal nets. The obtained single-layer film was cut into a square size of 92 mm × 92 mm and set on a fixing jig of a stretching apparatus KARO IV manufactured by Bruekner. Next, the film was moved to the first oven, the temperature was raised to 80 ° C. with a preheating time of 20 seconds, and the film was stretched four times in the longitudinal direction by uniaxial stretching to obtain a uniaxially stretched film having a thickness of 15 μm. .

Comparative Example 1
In Example 1, it carried out similarly except having changed base film [I] into the following unstretched films, and the same evaluation as Example 1 was performed.
[Manufacture of base film]
A 40 mmφ single screw extruder (L / D = 28) using a full flight type screw with a compression ratio of 3.4 and a 450 mm width coated hanger die (L / D = 28), ethylene content 32 mol%, saponification degree 99.6 mol%, melt A monolayer film having a thickness of 60 μm was produced by a take-up device having EVOH extruded with a flow rate value (MFR) of 3.2 g / 10 min and having a cooling roll controlled at 30 ° C. in the first roll. Such a single layer film was used as a base film without being stretched.

Comparative Example 2
A sample for evaluation was obtained by performing the same operation as in Example 1 except that a biaxially stretched polyethylene terephthalate film (“Cosmo Shine E5000” manufactured by Toyobo Co., Ltd.) having a film thickness of 38 μm was used as the base film. However, when the base film and the protective layer were to be peeled off, they were not peelable.
The evaluation results of Examples and Comparative Examples are shown in Table 1.

  From the results of the above Examples and Comparative Examples, since the EVOH uniaxially stretched or biaxially stretched film is used as the base film, it has excellent effects in all of peelability, glossiness and image clarity. You can see that On the other hand, in Comparative Example 1, since an unstretched film of EVOH is used, the gloss and image clarity are clearly inferior, and the conventional polyethylene terephthalate film is not subjected to a release treatment. In Comparative Example 2 used in the above, the base film could not be peeled off and could not be put to practical use.

  The laminate for transfer printing of the present invention is excellent in peelability between the base film and the protective layer (cured curable resin layer), and further has excellent transfer characteristics such as glossiness, sharpness and image clarity. Interior materials or exterior materials for vehicles such as automobiles, construction materials such as skirting boards and fringes, furniture such as window frames and door frames, interior materials for buildings such as walls, floors, and ceilings, television receivers It is very useful for manufacturing decorative molded products for uses such as housings and containers of home appliances such as machines, mobile phone parts, and air conditioners.

Claims (5)

A laminate for transfer printing in which a base film [I], a curable resin layer [II], and a printing layer [III] are laminated, and the base film [I] is a saponified ethylene-vinyl ester copolymer (a) A laminate for transfer printing, which is a stretched film (A) comprising: The ethylene content of the saponified ethylene-vinyl ester copolymer (a) is 20 to 60 mol%, the saponification degree is 90 to 100 mol%, 210 ° C, and the melt flow rate value at a load of 2160 g is 0.1 to 100 g. The laminate for transfer printing according to claim 1, wherein the laminate is / 10 minutes. The laminate for transfer printing according to claim 1 or 2, wherein the stretched film (A) is a stretched film having a total stretch ratio of 1.5 to 16 times. The stretched film (A) is a biaxially stretched film having a stretch ratio of 1.5 to 4 times in the longitudinal direction and a stretch ratio of 1.5 to 4 times in the transverse direction. A laminate for transfer printing. The laminate for transfer printing according to any one of claims 1 to 4, wherein the stretched film (A) has a thickness of 5 to 120 µm.