JP2005246960A - Film for hydraulic transfer, and hydraulic transfer body using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a film for hydraulic transfer, which has an excellent appearance, abrasion resistance, chemical agent resistance, boiling water resistance, and plastic workability. <P>SOLUTION: This film for hydraulic transfer has a transfer layer which comprises a substrate film and a curable resin layer; the curable resin layer contains a polyester resin composition which is composed of a polyester resin having 5,000-300,000 Mw and whose aromatic ring ratio Q (mass%) is in the range of 38-65 mass%, a polyester acrylate, and an epoxy acrylate; the polyester resin composition of the curable resin layer is in the range of 20-80 mass%; and the mass ratio P between the polyester acrylate and the epoxy acrylate is in the range of 1/5-3/2. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a hydraulic transfer film having a curable resin layer and a hydraulic transfer body obtained by hydraulic transfer of the film.

  The hydraulic transfer method is a method that can apply a decorative layer rich in design to a molded article having a complicated three-dimensional shape. However, after the hydraulic transfer, it is necessary to spray-apply a curable resin as a protective layer to the decorative layer that has been hydraulically transferred. . For this reason, the manufacture of molded products by the hydraulic transfer method is costly because the manufacturing process is complicated and painting equipment is required in addition to the hydraulic transfer equipment, and the molded products manufactured by the hydraulic transfer method are expensive. It was limited to goods.

  As a means for solving this complexity and high cost, a technique for transferring a thermoplastic resin layer and a decoration layer to a transfer object using a hydraulic transfer film provided with a thermoplastic resin layer and a decoration layer as a transfer layer is disclosed. (For example, refer to Patent Document 1). However, in this technique, the protective layer is made of a thermoplastic resin, specifically, a copolymer of butyl acrylate and ethyl acrylate, and the surface properties such as solvent resistance and surface hardness cannot be sufficiently imparted to the transfer target. .

  On the other hand, it is composed of a compound having a radically polymerizable unsaturated group in a polymer having a glass transition temperature of 0 to 250 ° C. and / or a compound having a melting point of 20 to 250 ° C. and having a radically polymerizable unsaturated group, in an uncured state. A hydraulic transfer sheet that is solid at normal temperature and has a non-adhesive coating layer, and the coating layer is transferred to a transfer medium using the hydraulic transfer sheet, and then the coating layer is irradiated with ionizing radiation or heat. The manufacturing method of the molded article which has the cured resin layer which hardens a layer is disclosed (for example, refer patent document 2).

However, the cured transfer layer obtained by the method disclosed in the claims and specification of the publication simultaneously solves the drying property during printing coating and the stability during storage. A compound having a radically polymerizable unsaturated group in a polymer having a transition temperature of 0 to 250 ° C. alone is difficult to activate the coating film during hydraulic transfer, and has a melting point of 20 to 250 ° C. and is not radically polymerizable. With a compound having a saturated group, it is impossible to form a flexible coating film that can be wound up alone. Even in a combination of this and a compound having a radically polymerizable unsaturated group in a polymer having a glass transition temperature of 0 to 250 ° C., it is extremely difficult to achieve both flexible film formation and activatable film formation. It was.
Therefore, it solves simultaneously the flexibility of the rollable coating film, the storage stability after winding, and the solubility during transfer suitable for activation, which are required as a hydraulic transfer sheet having a curable resin layer. It was difficult.
Recently, the molded product after hydraulic transfer is required to have a calm appearance, a sense of depth, a sense of depth, etc., and this is usually dealt with by increasing the thickness of the protective layer. However, the hydraulic transfer sheet disclosed in the publication has a tendency to be inferior in plastic workability when a non-adhesive coating layer serving as a protective layer is a thick film.

  As a countermeasure against these problems, the specification of the publication describes a method of adding a thermoplastic resin, wax or the like to the curable coating film. There is no disclosure of specific examples related to this in this publication, but when these are carried out according to a known method, the curable resin layer has a property of being solid and non-adhesive at room temperature in an uncured state. In addition to lowering, even in a cured coating film, these thermoplastic components bleed into the cured coating film after a certain time or cure shrinkage under a high temperature condition of about 40 ° C. to 100 ° C. which is considered as a use condition. As a result, the coating film was swollen or peeled off, which caused the appearance of a remarkable defect on the surface of the cured coating film.

Curing shrinkage of reaction curable resin composition is a phenomenon that has been known for a long time, and in the case of unsaturated polyester resin, a method of adding a thermoplastic resin such as polystyrene or polyvinyl acetate as a low shrinkage agent is often used. However, there have been few reports on such attempts for epoxy acrylates and urethane acrylates. The reason for this is that even if a thermoplastic resin such as polystyrene or polyvinyl acetate, which is used as a low shrinkage agent in the case of an unsaturated polyester resin, is added, the cohesive strength within the molecule when epoxy acrylate or urethane acrylate is cured. Is extremely incompatible, so even if it is temporarily compatible, there is a problem that phase separation occurs immediately with the change in polarity of the matrix during the curing process, or conversely, compatibility with epoxy acrylate or urethane acrylate It is considered that if the value is too good, it becomes difficult to separate the microphase at the time of curing, and the low shrinkage is not exhibited. Therefore, the resulting molded product has cracks and two-phase separation, and the appearance is poor, or when the compatibility is good, the appearance is relatively transparent, but the low shrinkage effect does not appear and distortion and cracks occur. A problem occurs. This phenomenon is particularly noticeable when the film thickness is 30 μm or more. Therefore, plastic processing of a thick cured resin layer using a reaction curable resin composition, in particular, has been very difficult.
Japanese Patent Laid-Open No. 4-197699 Japanese Patent Laid-Open No. 64-22378 (Japanese Patent Publication No. 7-29084)

  The problem of the present invention is that the curable resin layer has sufficient adhesion and film-forming ability to the water-soluble support film in an uncured state, and the curable resin layer has a sufficient shape even after forming the hydraulic transfer film. It shows maintainability and can be activated by an organic solvent at the time of hydraulic transfer, and the cured resin layer obtained by curing by irradiation or heating of the active energy ray after transfer has high gloss, high definition, It has excellent appearance such as sufficient depth, surface protection performance such as scratch resistance, impact resistance, chemical resistance, and boiling water resistance that is practically acceptable, and a coating thickness of 30 μm or more. However, an object of the present invention is to provide a hydraulic transfer film having plastic workability.

As a result of intensive studies to solve the above problems, the present inventors have found that the curable resin layer is
It consists of a polyester resin having a weight average molecular weight of 5,000 to 300,000 obtained by copolymerizing an aromatic or aliphatic dicarboxylic acid and an aromatic or aliphatic diol, and has an aromatic ring ratio Q (mass%) of 38 mass% or more. 65% by mass or less of the polyester resin composition (component A), the weight average molecular weight of 400 to 10,000, the polyester acrylate (component B), the polyester resin composition (component A) and the polyester acrylate (component B) ) Compatible with epoxy acrylate (component C) at a specific ratio, coating printability to water-soluble support film, adhesion, drying after coating printing, storage stability, Furthermore, it can be activated with organic solvents, and at the same time, it can be cured by irradiation with active energy rays after transfer. Rukoto becomes possible, it found that to solve the above problems, and have completed the present invention.

That is, the present invention has a support film made of a water-soluble or water-swellable resin and a transfer layer that can be dissolved in an organic solvent provided on the support film, and the transfer layer is irradiated with active energy rays and heated. A hydraulic transfer film having a curable resin layer curable with at least one of the curable resin layer,
It consists of a polyester resin having a weight average molecular weight of 5,000 to 300,000 obtained by copolymerizing an aromatic or aliphatic dicarboxylic acid and an aromatic or aliphatic diol, and has an aromatic ring ratio Q (mass%) of 38 mass% or more. The polyester resin composition (component A) which is 65% by mass or less (however, the aromatic ring ratio Q (mass%) is obtained from the aromatic ring ratio q (mass%) of the polyester contained in the polyester resin composition below. Value.

2) A polyester acrylate (component B) having a weight average molecular weight of 400 to 10,000, and 3) an epoxy acrylate (component C) compatible with the polyester (component A) and the polyester acrylate (component B). The polyester resin composition (component A) in the curable resin layer is 20% by mass or more and 80% by mass or less, and the mass ratio P of the polyester acrylate (component B) to the epoxy acrylate (component C) : {The total mass of the polyester acrylate (component B)} / {The total mass of the epoxy acrylate (component C)} is 1/5 or more and 3/2 or less.

  The curable resin layer referred to in the present invention means an uncured layer at the transfer stage, and a layer that forms a cured resin layer after curing. The cured resin layer means a layer produced by a curing reaction after transfer.

  Further, the present invention uses the hydraulic transfer film of the present invention to hydraulically transfer the curable resin layer onto the surface of the transfer object, and then cure the curable resin layer with at least one of active energy ray irradiation and heating. There is provided a hydraulic transfer body having a cured resin layer.

The hydraulic transfer film of the present invention is
(1) Flexibility that can be wound even in an uncured state, and good storage stability such as no blocking after winding and stable shape maintenance,
(2) Uniform activation in the hydraulic transfer process is possible,
(3) Cured with active energy rays after transfer, excellent appearance such as high gloss, high definition, sufficient depth, scratch resistance, impact resistance, chemical resistance, etc. It has surface protection performance such as boiling water resistance and plastic workability.

[Support film for hydraulic transfer film]
The support film made of a water-soluble or water-swellable resin used for the hydraulic transfer film of the present invention is a film made of a resin that can be dissolved or swollen with water.
Examples of the support film made of a water-soluble or water-swellable resin (hereinafter abbreviated as support film) include, for example, PVA (polyvinyl alcohol), polyvinylpyrrolidone, acetylcellulose, polyacrylamide, acetylbutylcellulose, gelatin, Films such as sodium alginate, hydroxyethyl cellulose, carboxymethyl cellulose and the like can be used.

  Among them, a PVA film generally used as a hydraulic transfer film is particularly preferable because it is easily dissolved in water, easily available, and suitable for printing a curable resin layer. The thickness of the support film used is preferably about 10 to 200 μm.

[Transfer layer of hydraulic transfer film]
The transfer layer provided on the support film of the hydraulic transfer film of the present invention is a curable resin layer (hereinafter abbreviated as a curable resin layer, which can be cured by at least one of active energy ray irradiation and heating). The resin layer composition is abbreviated as curable resin composition D.). The transfer layer may have a curable resin layer and a decorative layer (hereinafter abbreviated as a decorative layer) made of a printing ink film or a paint film provided thereon. The curable resin layer in the present invention forms a non-adhesive film at room temperature even before curing, and does not cure at room temperature and can be cured by at least one of active energy ray irradiation and heating.

  When the decorative layer is provided, the curable resin layer is preferably transparent because the design of the decorative layer of the hydraulic transfer body can be expressed well. However, depending on the required characteristics of the hydraulic transfer body, it is sufficient that the color and pattern of the decorative layer of the obtained hydraulic transfer body can be seen basically, and the curable resin layer does not need to be completely transparent and is transparent. To translucent materials.

(Active energy rays)
The active energy ray means visible light, ultraviolet ray, electron beam, and gamma ray, and any of them can be used, but ultraviolet ray is particularly preferable. As the ultraviolet light source, sunlight, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like is used.

[Curable resin layer of transfer layer]
The curable resin layer of the hydraulic transfer film of the present invention is
(1) Flexibility that can be wound even in an uncured state, and good storage stability that does not cause blocking even after winding and the shape is stably maintained,
(2) Uniform activation in the hydraulic transfer process is possible,
(3) Cured by at least one of active energy ray irradiation and heating after transfer, excellent appearance such as high gloss, high sharpness, sufficient depth, scratch resistance and chemical resistance at a level that is practically acceptable It is necessary to have surface protection performance such as water resistance and boiling water resistance.
For this purpose, the curable resin composition D is an essential component (Component A) having a weight average molecular weight of 5,000 to 300,000 obtained by copolymerizing an aromatic or aliphatic dicarboxylic acid and an aromatic or aliphatic diol. A polyester acrylate (component C) comprising a certain polyester resin and having an aromatic ring ratio Q (mass%) of 40 mass% or more and 65 mass% or less (component B) having a weight average molecular weight of 400 or more and 10,000 or less. It is necessary to contain an epoxy acrylate that is compatible with the polyester resin composition (component A) and the polyester acrylate (component B).

(Polyester resin composition (component A))
The polyester resin composition used in the present invention comprises a polyester resin obtained by copolymerizing an aromatic or aliphatic dicarboxylic acid and an aromatic or aliphatic diol. (Hereinafter, the polyester resin constituting the polyester resin composition used in the present invention is abbreviated as “polyester resin P1”.)
The weight average molecular weight of the polyester resin P1 is preferably 5,000 or more and 300,000 or less, more preferably 7,000 or more and 80,000 or less, and even more preferably 8,000 or more and 50,000 or less.
If the weight average molecular weight of the polyester resin P1 exceeds 300,000, activation of the curable resin layer before curing with an organic solvent tends to be difficult. On the other hand, when the molecular weight is less than 5,000, it is difficult to suppress the fluidity and tackiness of the uncured curable resin layer, and the cured resin film moves to the coating film surface at a high temperature. Reduces coating performance.

  The polyester resin composition used in the present invention is not particularly limited to a combination of an aromatic or aliphatic dicarboxylic acid or an aromatic or aliphatic diol as a raw material of the polyester resin P1, and one or several kinds of polyester resins P1 are used. When blended into a composition, the aromatic ring ratio Q (mass%) of the composition may be in the range of 40 mass% to 65 mass%. The aromatic ring ratio Q (mass%) is a value obtained from the aromatic ring ratio q (mass%) of the polyester contained in the polyester resin composition.

In said formula, q (mass%) represents the gross mass of the aromatic ring which this polyester resin has with respect to the gross mass of the polyester resin P1 which comprises a polyester resin composition. The total mass of the aromatic rings of the polyester resin P1 can be calculated by the ratio of polyester raw materials or NMR. For example, q (mass%) of the polyester resin whose NMR analysis results are terephthalic acid skeleton 50 mol%, ethylene glycol 12 mol%, propylene glycol 35 mol%, the mass per mol of terephthalic acid skeleton is 132 g, and the ethylene glycol skeleton is 1 mol. Is 60 g, and the mass per propylene glycol skeleton is 102 g.
q = (132 × 50%) / (132 × 50% + 60 g × 12% + 102 g × 35%)
= 66.6%
And q is 66.6% by mass.

Moreover, in said formula, Ci represents the composition rate of the polyester resin P1 which comprises a polyester resin composition. For example, 1 is used when one kind of polyester resin P1 is used, and 0.5 when two kinds are used at a ratio of 1: 1.
The product obtained by multiplying Ci by the sum of the aromatic ring ratios of the polyester resin P1 constituting the polyester resin composition to give a percentage is the aromatic ring ratio Q (% by mass) of the composition.

  The aromatic ring ratio Q of the polyester resin composition (component A) is such that the aromatic ring ratio Q (mass%) is 38 mass% or more and 65 mass% or less from the viewpoint that it is easy to balance plastic workability and surface hardness. More preferably, it is 40 mass% or more and 62 mass% or less, More preferably, it is 43 mass% or more and 58 mass% or less. When the aromatic ring ratio Q is less than 38% by mass, the surface hardness and storage stability decrease, and when the aromatic ring ratio Q exceeds 65% by mass, the plastic workability, particularly when the coating film thickness is 20 μm or more, greatly decreases. .

  The polyester resin composition (component A) contained in the curable resin composition D is preferably 20% by mass or more and 80% by mass or less in order to further secure the film forming ability, drying property, and storage stability. More preferably, they are 30 to 75 mass%, More preferably, they are 35 to 70 mass%.

  Further, the glass transition temperature (Tg) of each polyester resin constituting the polyester resin composition (component A) is preferably 5 ° C. or higher and 100 ° C. or lower, more preferably 10 ° C. or higher and 95 ° C. or lower, and further preferably 20 ° C. It is 90 degrees C or less. When the Tg of the polyester is less than 5 ° C., the storage stability of the curable resin composition D is poor, and the heat resistance of the cured coating film is adversely affected. On the other hand, when the Tg of the polyester resin exceeds 100 ° C., it becomes difficult to be compatible with the curable resin composition D and to be activated by an organic solvent during hydraulic transfer.

  The polyester resin composition (component A) used in the present invention may be a mixture of one or two or more polyester resins obtained by copolymerizing an aromatic or aliphatic dicarboxylic acid and an aliphatic diol. preferable. Among them, a polyester resin synthesized from an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid and an aliphatic diol (component A1), or a polyester resin synthesized from the component A1, an aromatic dicarboxylic acid and an aliphatic diol (component) A mixture with A2) is preferred.

  Specific examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, and 2,2 ′. -Diphenyl dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid and the like.

  Examples of the aliphatic dicarboxylic acid include adipic acid, suberic acid, sebacic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, and the like.

  Aliphatic diols include ethylene glycol, propylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1, 5-pentanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 2,2,4-trimethyl-1,3-pentanediol, neo Pentylhydroxypivalate ester, 1,4-cyclohexanedimethanol, 1.3-cyclohexanedimethanol, 1,2 cyclohexanedimethanol, tricyclodecane dimethanol, hydrogenated bisphenol A, hydrogenated bisphenol S, hydrogenated bisphenol Ethylene oxide adduct of A and propylene oxide Adduct, ethylene oxide adduct and propylene oxide adduct of bisphenol S, ethylene oxide adduct and propylene oxide adduct of hydrogenated bisphenol S, 1,9-nonanediol, 2-methyloctanediol, 1 , 10-decanediol, 2-butyl-2-ethyl-1,3-propanediol, tricyclodecane dimethanol and the like. Examples of the polyether polyol include polyethers such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

  From the viewpoint of easy availability of raw materials and compatibility with other components, terephthalic acid and isophthalic acid are preferable as aromatic dicarboxylic acids, and aliphatic dicarboxylic acids having 4 to 12 carbon atoms are preferable as aliphatic dicarboxylic acids, and adipic acid is particularly preferable. , Suberic acid and sebacic acid are preferably used, and aliphatic diols having 2 to 12 carbon atoms are preferred, especially ethylene glycol, propylene glycol, 1,3-propanediol, neopentyl glycol. Is preferred.

  In addition, polycarboxylic acids such as trimellitic anhydride and pyromellitic anhydride, hydroxycarboxylic acids such as 2,2-dimethyl 3-hydroxypropionic acid, trimethylol ethane, and trimethylol, as long as the content of the invention is not impaired. Polyvalent polyols such as propane, glycerin and pentaerythritol, metal salts such as 5-sulfoisophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, 5 [4-sulfophenoxy] isophthalic acid, or 2-sulfo-1, A dicarboxylic acid or glycol containing a sulfonate metal base such as a metal salt such as 4-butanediol, 2,5-dimethyl-3-sulfo-2,5-hexanediol may be used in combination.

  The polyester resin is post-added with trimellitic anhydride, phthalic anhydride, pyromellitic anhydride, succinic anhydride, 1,8-naphthalic anhydride, 1,2-cyclohexanedicarboxylic anhydride, etc. to give an acid value. Also good.

  Polyester resin composition (component A1) synthesized from an aromatic dicarboxylic acid or an aliphatic dicarboxylic acid and an aliphatic diol constituting the polyester resin composition (component A), and a polyester synthesized from an aromatic dicarboxylic acid and an aliphatic diol As the resin (component A2), a commercially available product may be used. Specific examples include, for example, Byron 103, Byron 200, Byron 220, Byron 240, Byron 245, Byron 270, Byron 290, Byron 296, Byron 300, Byron 530. Byron 560, Byron 600, Byron 630, Byron 650, Byron GK110, Byron GK130, Byron GK140, Byron GK150, Byron GK190, Byron GK250, Byron GK330, Byron GK360, Byron GK590, Byron GK640, Byron GK680, Byron GK780, Byron GK810, Byron GK880, Byron GK890 (trade name; all manufactured by Toyobo Co., Ltd.), Eritel UE3200, Eritel UE3201, Eritel UE3203, Eritel UE3216, Eritel UE3215, Eritel UE3215 Elitel UE3220, Elitel UE3620, Elitel UE3240, Elitel UE3250, Elitel UE3320, Elitel UE3370, Elitel UE3380, Elitel UE3350, Elitel UE3300, Elitel UE3500, Elitel UE9200, Elitel UE9200, all made by Elitel XA-0611 ) Among these, from the viewpoint of desirable film properties are easily obtained, Byron 650, Byron GK880, Elitel XA-0611 is preferably used. These polyesters may be dissolved products that are already dissolved in an organic solvent containing toluene or methyl ethyl ketone. The polyester resin (component A1) and the polyester resin (component A2) may be used alone or in combination of two or more.

  The polyester resin composition (component A) preferably has solvent solubility. Solvent-soluble as used herein means 3% or more soluble at 25 ° C. in any one or more of toluene, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, ethyl acetate alone or a mixed solvent having any mixing ratio composed of any of these plural types. (No gelation or precipitation after storage at 25 ° C. for 24 hours after dissolution at a concentration of 3%). In practice, it is desired that 5% or more, more preferably 10% or more, still more preferably 15% or more, particularly preferably 20% or more, and most preferably 22%, be dissolved in any one or more of the above solvents.

(Polyester acrylate (component B))
The polyester acrylate (component B) used in the present invention is a saturated or unsaturated polyester having a weight average molecular weight of 400 or more and 10,000 or less and containing at least one (meth) acryloyl group in one molecule. The weight average molecular weight is preferably 600 or more and 8,000 or less, more preferably 800 or more and 6,500 or less. Most preferably, it is 400 or more and 10,000 or less. When the weight average molecular weight exceeds 10,000, compatibility with other components tends to be poor and handling as a composition tends to be difficult.

  The average number of functional groups of the polyester acrylate (component B) used in the present invention is preferably 3 or more. When the average number of functional groups is less than 3, the crosslinking density when cured is too small, and the desired properties such as bleed suppression of the polyester (component A) are difficult to be expressed.

  The polyester which is a constituent component of the polyester acrylate (component B) used in the present invention is obtained by an ester reaction of a glycol component, if necessary, a triol component and a dibasic acid, and if necessary, a tribasic acid component. At that time, if necessary, a monoepoxy compound or a polyepoxy compound may be used in combination. The content of the polyester acrylate (component B) in the curable resin layer is preferably 20% by mass or more and 80% by mass or less in total with the epoxy acrylate (component C) described later, and the polyester acrylate (component B). Ratio P: {mass sum of polyester acrylate (component B)} / {mass sum of epoxy acrylate (component C)} is preferably 1/5 or more and 3/2 or less. 3/10 or more and 11/8 or less are more preferable, and 2/5 or more and 5/4 or less are still more preferable. When the mass ratio P is less than 1/5, durability of the cured coating film, in particular, boiling water resistance cannot be ensured. Conversely, when the mass ratio P exceeds 3/2, the plastic workability of the cured coating film is lowered.

  Examples of the glycol that is a raw material for the polyester include ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, hexylene glycol, dimethylolcyclohexane, 2,4,4-trimethyl-1,3-pentanediol, and the like. Alkylene glycols; polyalkylene glycols typified by diethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, polybutylene glycol, etc .; divalent typified by bisphenol A, bisphenol F, bisphenol S, tetrabromobisphenol A, etc. There are addition reaction products of phenol and alkylene oxides typified by ethylene oxide and propylene oxide. Examples of the triol include glycerin, trimethylolpropane, trimethylolethane, and 1,2,6-hexanetriol. Examples of the tetraol unit include pentaerythritol, diglycerol, and 1,2,3,4-butanetetraol.

  Dibasic acids (anhydrides) include o-phthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic acid, tetrabromophthalic acid, malonic acid, succinic acid, adipic acid, azelaic acid, 1,1 , 2-dodecanoic acid, maleic acid, fumaric acid, itaconic acid, himitic acid, het acid, etc., and tribasic acid units include trimellitic acid, aconitic acid, butanetricarboxylic acid, 6-carboxy-3-methyl- There are 1,2,3,6-hexahydrophthalic acid and the like, and examples of the 4-basic acid unit include pyromellitic acid and butanetetracarboxylic acid.

  Examples of the monoepoxy compound include ethylene oxide, propylene oxide, epichlorohydrin, styrene oxide, and phenyldaricidyl ether. Moreover, as a polyepoxy compound, what is called a diepoxy compound can be used conveniently, for example, the Nikkan Kogyo Shimbun plastic material course 1 "epoxy resin" (issued May 10, 1946, written by Kuniyuki Stripe) Mention may be made of the epoxy resins described on pages 19 to 48.

  As a method for producing the polyester acrylate, for example, a method by an esterification reaction of glycol, if necessary, a trihydric alcohol with (meth) acrylic acid and a dibasic acid, and if necessary a tribasic or higher polybasic acid is generally used. A production method by esterification of a compound having a (meth) acryloyl group and a hydroxyl group with a dibasic acid and, if necessary, a tribasic or higher polybasic acid may be used.

  The unsaturated polyester as a constituent component of the polyester acrylate is produced by polycondensation of α, β-unsaturated dibasic acid or its acid anhydride, aromatic saturated dibasic acid or its acid anhydride, and glycols. In some cases, those produced by using an aliphatic or aliphatic saturated dibasic acid as the acid component may be mentioned.

  Examples of the α, β-unsaturated dibasic acid or acid anhydrides thereof include maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chloromaleic acid, and esters thereof. As aromatic saturated dibasic acid or acid anhydride thereof, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, halogenated phthalic anhydride and these Examples of the aliphatic or alicyclic saturated dibasic acid include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, hexahydrophthalic anhydride, and esters thereof. These are used alone or in combination.

  As glycols, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 2-methylpropane-1,3-diol, neopentyl glycol, triethylene glycol, Examples include tetraethylene glycol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, ethylene glycol carbonate, 2,2-di- (4-hydroxypropoxydiphenyl) propane, and the like. Alternatively, they are used in combination, but in addition, adducts such as ethylene oxide and propylene oxide can be used in the same manner. In addition, polycondensates such as polyethylene terephthalate having a hydroxyl group or a carboxyl group as a part of glycols and an acid component can also be used.

  Examples of unsaturated glycidyl compounds include glycidyl esters of unsaturated monobasic acids such as acrylic acid and methacrylic acid, such as glycidyl acrylate and glycidyl methacrylate, with glycidyl acrylate being preferred.

  The polyester acrylate (component B) may be a commercially available product. Specific examples thereof include M-7100, M-8030, M-8060, M-8100, M-8530, M-8560, M-9050 (trade names: above) All manufactured by Toagosei Co., Ltd.), and M-7100 or M-8530, which has a slightly high molecular weight between crosslinks, is preferably used because it is easy to balance the physical properties of the coating film.

(Epoxy acrylate (component C))
The epoxy (meth) acrylate (component C) that is compatible with the polyester resin (component A) and the polyester acrylate (component B) is obtained by reacting polyepoxide with (meth) acrylic acid or its anhydride (meth). Acrylate.

  The epoxy acrylate (component C) used in the present invention preferably has an average number of functional groups of 1.5 or more on average. If the average number of functional groups is less than 1.5 on average, the crosslinking density when cured is small, and the surface protection performance of the resulting coating film may be poor.

  The content of the epoxy acrylate (component C) in the curable resin layer is preferably 20% by mass or more and 80% by mass or less in total with the polyester acrylate (component B) described above, and the polyester acrylate (component B). Ratio P: {mass sum of polyester acrylate (component B)} / {mass sum of epoxy acrylate (component C)} is preferably 1/5 or more and 3/2 or less. 3/10 or more and 11/8 or less are more preferable, and 2/5 or more and 5/4 or less are still more preferable. When the mass ratio P is less than 1/5, durability of the cured coating film, in particular, boiling water resistance cannot be ensured. Conversely, when the mass ratio P exceeds 3/2, the plastic workability of the cured coating film is lowered.

  The polyepoxide is preferably an epoxy resin having an average of 1.5 or more, and preferably an average of 2 to 5 epoxy groups in one molecule. Among the epoxy resins, a bisphenol type epoxy resin is preferable because it can form a cured coating film having an excellent balance between hardness and elongation. Polyepoxides can be used alone or in combination of two or more. Specific examples of polyepoxides include, for example, bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, and the like, and hydrogenated aromatic rings of bisphenol type epoxy resins. .

  The reaction of the polyepoxide with (meth) acrylic acid or its anhydride is usually performed at a temperature in the range of 50 ° C. to 150 ° C. for about 1 to 8 hours. In the reaction, a catalyst is preferably used. Specific examples of the catalyst include amines such as triethylamine, dimethylbutylamine and tri-n-butylamine, quaternary ammonium salts such as tetramethylammonium salt, tetraethylammonium salt, tetrabutylammonium salt and benzyltriethylammonium salt, Alternatively, quaternary phosphonium salts, phosphines such as triphenylphosphine, and imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole can be used.

  In the reaction, alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve and ethyl cellosolve, esters such as methyl cellosolve acetate and ethyl celloacetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone Solvents, aromatic compounds such as benzene, toluene, chlorobenzene, and dichlorobenzene can be used as the reaction solvent. During the reaction, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, 4-methylquinoline, phenothiazine, or the like may be allowed to coexist in the reaction system as a polymerization inhibitor.

  In the reaction, in order to suppress the polymerization reaction of acrylic acid or methacrylic acid, in some cases, the reaction may be performed under an air stream such as air. At that time, an antioxidant such as 2,6-di-t-butyl-4-methylphenol may be used in combination in order to prevent an oxidation reaction by air.

  As the epoxy acrylate (component C), bisphenol A type epoxy acrylate is preferable. Moreover, you may use a commercial item. As specific examples, NK oligo EA-1020, NK ester A-B1206PE, NK ester ABE-300, NK ester A-BPE-4, NK ester A-BPE-6, NK ester A-BPE-10, NK ester A -BPE-20, NK ester A-BPE-30, NK ester BPE-80N, NK ester BPE-100N, NK ester BPE-500, NK ester BPE-900, NK ester BPE-1000N, NK ester A-9300, NK Oligo EA-5220, NK Oligo EMA-5220, NK Oligo EA-5221, NK Oligo EA-5222, NK Oligo EA-5223, NK Ester A-BPFL-4E (trade name: all manufactured by Shin-Nakamura Chemical Co., Ltd.) Listed and obtained hard EA-1020 is preferably used from the viewpoint of the physical properties of the coated coating film and economic reasons.

(Photopolymerization initiator)
The curable resin composition D may contain a conventional photopolymerization initiator or photosensitizer as necessary. Typical photopolymerization initiators include acetophenone compounds such as diethoxyacetophenone and 1-hydroxycyclohexyl-phenyl ketone; benzoin compounds such as benzoin and benzoin isopropyl ether; 2,4,6-trimethylbenzoin diphenylphosphine. Acylphosphine oxide compounds such as oxides; Benzophenone, benzophenone compounds such as methyl-4-phenylbenzophenone o-benzoylbenzoate; Thioxanthone compounds such as 2,4-dimethylthioxanthone; Amino compounds such as 4,4'-diethylaminobenzophenone Examples include benzophenone compounds.

  A photoinitiator is 0.5-15 mass% normally with respect to the acrylate total amount to be used, Preferably it is 1-8 mass%. Examples of the photosensitizer include amines such as triethanolamine and ethyl 4-dimethylaminobenzoate. Furthermore, onium salts such as benzylsulfonium salt, benzylpyridinium salt, and arylsulfonium salt are known as photocation initiators, and these initiators can also be used, and are used in combination with the above-mentioned photo radical generator. You can also.

  As a coating method of the curable resin composition D, a gravure coater, a gravure reverse coater, a flexo coater, a blanket coater, a roll coater, a knife coater, an air knife coater, a kiss touch coater, and a comma coater can be used.

  The thicker the curable resin layer, the greater the protective effect of the resulting molded product, and the greater the effect of absorbing the irregularities of the decorative layer, so that the molded product can have excellent gloss. Therefore, the film thickness of the curable resin layer is specifically 3 μm or more, preferably 15 μm or more. When the thickness of the curable resin layer exceeds 200 μm, it is difficult to sufficiently activate the curable resin layer with an organic solvent. From the viewpoints of sufficient activation of the curable resin layer by the organic solvent, function as a protective layer for the decoration layer, absorption of unevenness of the decoration layer, and the like, the dry film thickness of the curable resin layer should be 3 to 200 μm. More preferably, it is 10-100 micrometers, More preferably, it is 15-50 micrometers.

(Decoration layer)
The printing ink film or paint film used as a decorative layer provided on the curable resin layer is preferably activated by an organic solvent to obtain sufficient flexibility for transfer, and after drying the curable resin layer, The decorative layer is preferably formed by a method such as printing.

  Varnish resins used for printing ink or paint are acrylic resin, polyurethane resin, polyamide resin, urea resin, epoxy resin, polyester resin, vinyl resin (vinyl chloride, vinyl acetate copolymer resin), vinylidene resin (vinylidene chloride, vinylidene fluoride) ), Thermoplastic resins such as ethylene-vinyl acetate resin, polyolefin resin, chlorinated olefin resin, ethylene-acrylic resin, petroleum resin, and cellulose derivative resin are preferably used.

  The colorant used in the printing ink or paint is preferably a pigment, and any of inorganic pigments and organic pigments can be used. It is also possible to use a metallic gloss ink containing a metal fine particle obtained from a paste of metal cutting particles or a deposited metal film as a pigment. These metals include aluminum (Al), gold (Au), silver (Ag), brass (Cu—Zn), titanium (Ti), chromium (Cr), nickel (Ni), nickel chrome (Ni—Cr). Stainless steel (SUS) or the like is preferably used. These metal strips may be surface-treated with a cellulose derivative such as epoxy resin, polyurethane, acrylic resin, nitrocellulose, etc. in order to improve dispersibility, oxidation prevention and strength of the ink layer.

  The decoration layer uses a gravure coater, gravure reverse coater, flexo coater, blanket coater, roll coater, knife coater, air knife coater, kiss touch coater, comma coater, etc. on the curable resin layer formed on the support film. And print. Among these, gravure printing, flexographic printing, offset printing, screen printing, inkjet printing, thermal transfer printing, and the like are preferable, and gravure printing is particularly preferable. It is preferable that the dry film thickness of a decoration layer is 0.5-15 micrometers, More preferably, it is 1-7 micrometers. A colored layer having no pattern and a colorless varnish resin layer can also be formed by coating.

  When a decorative layer is applied on the curable resin layer provided on the support film, the curable resin layer needs to be in a tack-free state without stickiness. Depending on the resin composition, a tack-free state may not be obtained only by a normal drying process. In that case, by irradiating the curable resin layer with an active energy dose lower than the irradiation amount of the active energy ray necessary for complete curing of the curable resin layer, the curable resin layer is pre-cured or semi-cured. The tack-free state is preferable.

  In addition, when there is a bleed-out of the resin component from the curable resin layer to the decorative layer, the decorative layer is not sufficiently dried, so the interface between the transfer layer and the transfer layer composed of the curable resin layer and the decorative layer. A peelable film that can be peeled off may be provided. Specifically, a film made of a material such as polypropylene, polyethylene, polyester, nylon, or polyvinyl chloride can be used as the peelable film, and the thickness is preferably 20 μm to 250 μm.

  In addition, in the curable resin layer and the decorative layer, as long as the designability and spreadability are not impaired, an antifoaming agent, an anti-settling agent, a leveling agent, a pigment dispersant, a fluidity modifier, an antiblocking agent, a lubricant, Various conventional additives such as antistatic agents, antioxidants, light stabilizers and ultraviolet absorbers can be added.

  The obtained film for hydraulic transfer of the present invention has a low blocking property, is covered with light-shielding paper, and does not unnecessarily proceed with the curing reaction if stored in a dark place such as a warehouse. Thus, the curable resin layer, or the curable resin layer and the decorative layer can be activated and transferred, and has sufficient market distribution unless actively exposed to ultraviolet rays or sunlight.

In addition, low blocking property means that the curable resin layer dried at 120 ° C. for 1 minute and the coating layer on which the decorative layer is overprinted or coated are overlapped with the support film, and 1 kg / cm with a blocking tester. ^When the load of ² is applied and left at 20 ° C. for 1 week, when the support film and the coating film surface are peeled off, the coating film surface does not adhere to the support film and is easily peeled off.

(Method for producing hydraulic transfer body)
The method for producing a hydraulic transfer body according to the present invention comprises the step of floating the support film of the hydraulic transfer film according to the present invention in water, and forming a transfer layer having a curable resin layer or a decorative layer and a curable resin layer with an organic solvent. After activation, the transfer layer is hydraulically transferred to the transfer target, the support film is removed, and then the transfer layer is cured by at least one of active energy ray irradiation and heating. Water pressure transfer can be performed in a similar manner. The outline of the manufacturing method of the decorative molded product using the hydraulic transfer film is as follows.

(1) The support film of the hydraulic transfer film is faced down, the transfer layer is faced up and floated on water in a water tank, and the support film is dissolved or swollen with water.
(2) An organic solvent is applied or sprayed onto the transfer layer of the hydraulic transfer film to activate the transfer layer comprising the cured resin layer or the curable resin layer and the decoration layer.
The activation of the transfer layer with an organic solvent may be performed before the film is floated on water.
(3) While the transfer target is pressed against the transfer layer of the hydraulic transfer film, the transfer target and the hydraulic transfer film are submerged in water, and the transfer layer is brought into close contact with the transfer target by water pressure and transferred.
(4) The support film is removed from the transfer medium that has been removed from the water, and the curable resin layer of the transfer layer transferred to the transfer medium is cured by at least one of irradiation with active energy rays and heating to form a cured resin formation layer Alternatively, a molded product having a curable resin layer and a decorative layer is obtained.

  The transfer layer of the hydraulic transfer film of the present invention comprising a curable resin layer or a curable resin layer and a decorative layer is activated by applying or spraying an organic solvent, and is sufficiently solubilized or softened. The activation mentioned here means that the transfer layer is solubilized without being completely dissolved by applying or spraying an organic solvent to the transfer layer, and the transfer layer is transferred to the transfer layer by providing flexibility. It means improving the followability and adhesion to the body. This activation may be performed to such an extent that when the transfer layer is transferred from the hydraulic transfer film to the transfer body, these transfer layers are softened and can sufficiently follow the three-dimensional curved surface of the transfer body. Hereinafter, the organic solvent used here is abbreviated as “activator”.

  The water in the water tank in the hydraulic transfer functions as a hydraulic medium that swells or dissolves the support film and also causes the hydraulic transfer film to adhere to the three-dimensional curved surface of the transfer target when transferring the transfer layer. Specifically, water such as tap water, distilled water and ion exchange water may be used, and depending on the support film used, inorganic salts such as boric acid and alcohols may be dissolved in water within 10%. But you can.

(Activator)
The activator used in the present invention preferably does not evaporate until the hydraulic transfer process is completed. As the activator used in the present invention, an activator used for general hydraulic transfer can be used. Specifically, toluene, xylene, ethylbenzene, hexane, cyclohexane, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, propyl acetate, isobutyl acetate, 1-propanol, 2-propanol, 1-butanol, 2-butanol, ethyl Examples include cellosolve, cellosolve acetate, butyl cellosolve, carbitol, carbitol acetate, butyl carbitol acetate, solfit acetate, mineral spirit, diacetone alcohol and mixtures thereof.

  In order to improve the adhesion between the printing ink or paint and the molded product, this activator may contain some resin components. For example, adhesion may be increased by including 1 to 10% of an ink binder having a similar structure such as polyurethane, acrylic resin, or epoxy resin.

  For the same purpose, the above-mentioned radical polymerizable compound and photopolymerization initiator may be dissolved in the activator and used.

  After the transfer layer is hydraulically transferred to the transfer target, the support film is removed by dissolving or peeling with water and drying. The support film is removed from the transfer target by dissolving or peeling the support film with a water flow in the same manner as in the conventional hydraulic transfer method.

  The curable resin layer is cured by irradiation with active energy rays and / or heating after drying water and the activator. Although the curing time depends on the composition and the type of curing agent, it is preferable in the process that curing proceeds within a few minutes to 1 hour.

(Molded product to be transferred)
It is preferable that the molded product to be transferred is sufficiently adhered to the surface of the curable resin layer or the decorative layer. For this reason, a primer layer is provided on the surface of the molded product as necessary. As the resin forming the primer layer, a conventional resin can be used as the primer layer without particular limitation, and examples thereof include a urethane resin, an epoxy resin, and an acrylic resin. Further, the primer treatment is not necessary for a molded product made of a resin component having a high solvent absorbability such as an ABS resin or SBS rubber having good adhesion. If the material of the molded product is even primed and has a level of waterproofness that will not cause a quality problem even if submerged in water, metal, plastic, wood, pulp mold, glass, etc. There is no particular limitation.

  Specific examples of molded products to which the present invention can be applied include household appliances such as televisions, videos, air conditioners, radio cassettes, mobile phones, refrigerators, OA equipment such as personal computers and printers, and other households such as petroleum fan heaters and cameras. Applicable to the housing part of the product. Also, furniture components such as tables, chests, and pillars, building components such as bathtubs, system kitchens, doors, window frames, surrounding edges, writing utensils, calculators, electronic notebooks, cases and other miscellaneous goods, stationery, automobile interior panels, automobiles, etc. And motorcycle outer panels, wheel caps, ski carriers, car carrier bags, golf clubs, yachts and other ship parts, skis, snowboards, helmets, goggles, monuments, etc. and require design It is particularly useful for molded articles and can be used in a very wide range of fields.

  Hereinafter, the present invention will be described with reference to examples. Unless otherwise specified, “part” and “%” are based on mass.

(Production Example 1) <Production of lattice pattern film P1>
Printed ink G1 of the following composition is printed on a 50 μm thick unstretched polypropylene film (hereinafter abbreviated as PP film) manufactured by Toyobo Co., Ltd., 3 prints of pattern and solid with a thickness of 4 g (solid content) / m 2 To produce a lattice print film P1.
<Composition of printing ink G1, black, red, yellow, white>
Polyurethane (Dainippon Ink, Vernock EZL676): 20 parts Pigment (black, red, yellow, white): 10 parts Ethyl acetate / toluene (1/1): 60 parts Additives such as wax: 10 parts

(Production Example 2) <Manufacture of abstract pattern film P2>
On an unstretched polypropylene film (hereinafter abbreviated as PP film) having a thickness of 50 μm manufactured by Toyobo Co., Ltd., 4 g (solid content) / m 2 of an abstract pattern and solid are printed with the printing ink G1 having the above composition by gravure printing. An abstract pattern printing film P2 was produced by printing on a plate.

<Method for testing molded product after hydraulic transfer>
The hydraulically transferred samples obtained in Examples and Comparative Examples were evaluated by the following tests.

(Pattern reproducibility)
About the pattern reproducibility in a three-dimensional solid molded product, it evaluated visually as follows by the pattern reproduction area ratio.
○: Pattern reproduction area ratio 95% or more (Good pattern reproducibility)
Δ: Pattern reproduction area ratio 80% to less than 95% (slightly poor pattern reproducibility)
×: Pattern reproduction area ratio less than 80% (pattern reproducibility is poor)

(Adhesion)
For samples subjected to hydraulic transfer to the following primer-treated galvanized steel plate (flat plate: 100 mm × 100 mm × 0.5 mm) or ABS resin plate (flat plate: 100 mm × 100 mm × 3 mm), according to the cross-cut tape method (JIS K5400) Ink adhesion was evaluated (full score of 10).

<Primer-treated galvanized steel sheet>
Dai Nippon Ink Chemical Co., Ltd. Beckolite 57-206-40 (linear polyester resin having a hydroxyl group at its terminal, number average molecular weight 10,000) 45 parts in terms of solid content, titanium white 50 parts, cyclohexanone / isophorone / xylol = Mixing 20 parts of 30/50/20 mixed solvent, bead milling, and after finishing, 5 parts xylene diisocyanate (XDI) and 0.5 parts dibutyltin dilaurate (TK-1) as curing agents In addition, the top coating obtained was applied to a chromate-treated hot-dip galvanized steel sheet (plating coverage 60 g / m ² ) with a barco overnight so that the dry film thickness was 40 μm, and baked at a maximum plate temperature of 235 ° C. A primer-treated galvanized steel sheet was obtained.

(Curing shrinkage)
The curable resin composition was coated on a 10 cm square PET film having a thickness of 50 μm with a bar coater so as to have a dry film thickness of 25 μm. The obtained coated sample was dried at 60 ° C. for 30 minutes, and then passed through the UV irradiation apparatus once (corresponding to a UV irradiation amount of 2400 mJ / cm ² ) to completely cure the curable resin. After allowing to cool, the coated sample was placed on a flat plate, the rolling distance (mm) of the four corners of the coated sample was measured, and the sum of these was used as an index of curing shrinkage.

(Pencil hardness)
The coating film hardness was measured by using JIS-K5401 “Pencil scratch tester for coating film”. The length of the core was 45 degrees with a 3 mm coated cotton, the load was 1 kg, the scratching speed was 0.5 mm / min, the scratching length was 3 mm, and the pencil used was Mitsubishi Uni.

(Surface gloss)
20 degree and 60 degree specular glossiness (JIS K5400) was measured.

(Vividness)
The sharpness of the water-transferred sample was measured with a portable sharpness gloss meter PGD-4 manufactured by Nippon Color Research Laboratory. The sharpness as used in the present invention means the sharpness of image reflection, that is, the sharpness of a specular image captured on a hydraulically transferred sample, and high sharpness means that the sharpness is 0.6 or more. Sure.

(Surface smoothness)
The surface roughness Ra was measured with a laser microscope.

(Deep feeling)
The calmness, depth, and depth of the coating film were visually judged according to the following criteria.
A: The feeling of calmness, depth and depth is very good.
○: Excellent calmness, depth, and depth.
X: There is no feeling of calm, depth, and depth.

(Abrasion resistance)
A rubbing tester (load 800 g) is used for a sample that has been hydraulically transferred to a primer-treated galvanized steel plate (flat plate: 100 mm × 100 mm × 0.5 mm) or ABS resin plate (flat plate: 100 mm × 100 mm × 3 mm) used in the adhesion test. The surface gloss retention after 100 times of dry wiping was evaluated.

(Chemical resistance 1: Alcohol resistance)
1-butanol was included in the sample that was hydraulically transferred to the primer-treated galvanized steel plate (flat plate: 100 mm × 100 mm × 0.5 mm) or ABS resin plate (flat plate: 100 mm × 100 mm × 3 mm) used in the adhesion test. A rubbing test (load 800 g, 100 reciprocations) was performed using absorbent cotton, and the surface gloss retention after the test was measured.

(Chemical resistance 2: acid resistance / alkali resistance)
Protective films (made by Nitto Denko Corporation) on the end face (from the end to 3 mm inside) and back face of the sample that was hydraulically transferred to the primer-treated galvanized steel sheet (flat plate: 100 mm x 100 mm x 0.5 mm) used in the adhesion test The surface gloss retention rate after immersion in a 5% aqueous acetic acid solution or a 5% aqueous sodium hydroxide solution for 72 hours was measured with a Nitoflon adhesive tape No. 903UL).

(Adhesion after hot water treatment)
The hydraulically transferred sample was heat treated in hot water (water temperature 98 ° C.) for 2 hours, and then 100 100 × 1 × 1 mm grids were made on the coating film. Was peeled off rapidly, and the peeled state of the coating film was visually observed and evaluated in the following three stages.

○: No peeling was observed.
(Triangle | delta): 1-30% of the whole peeled.
X: 31-100% of the whole peeled off.

(Gloss retention after hot water treatment)
The hydrostatically transferred sample was heat-treated in hot water (water temperature 98 ° C.) for 2 hours, and then the gloss retention before and after the hydrothermal treatment was calculated by measuring 60 ° gloss with a gloss meter.

(Plastic workability)
The Erichsen value (constant distance method, JIS-K5400) of the hydraulically transferred sample was carried out, and the surface state after extrusion of a steel ball 5 mm was observed and evaluated.
○: No cracking or peeling.
X: There are cracks and peeling.

(Impact resistance)
A sample that was hydraulically transferred to an ABS resin plate (flat plate: 100 mm x 100 mm x 3 mm) used in the adhesion test was subjected to a DuPont impact test (25 ° C, 100 g, 100 mm, 1/2 inch diameter), and the surface of the hitting part The state was observed and evaluated.
○: No cracking or peeling.
X: There are cracks and peeling.

(Example 1)
A curable resin composition D1 having the following composition was applied to a PVA film having a thickness of 30 μm, which was a support film, with a lip coater to a dry film thickness of 40 μm, and then dried at 60 ° C. for 3 minutes. The curable resin layer of the film coated with the obtained curable resin composition D1 and the printed layer of the lattice pattern film P1 are laminated to face each other at 60 ° C., and the temperature is 30 ° C. and the humidity is 50% for 96 hours. An aged hydraulic transfer film F1 with release paper was prepared.

<Composition of curable resin composition D1>
Epoxy acrylate "NK Oligo EA-1020" manufactured by Shin-Nakamura Chemical Co., Ltd.
: 50 parts polyester acrylate "M-8530" manufactured by Toagosei Co., Ltd.
(Weight average molecular weight 1,200): 50 parts Polyester “Byron GK880” manufactured by Toyobo Co., Ltd.
(Weight average molecular weight 54,000, Tg = 84 ° C., qi = 67%): 50 parts Polyester “Byron 650” manufactured by Toyobo Co., Ltd.
(Weight average molecular weight 51,000, Tg = 10 ° C., qi = 35%): 50 parts Toluene: 130 parts Methyl ethyl ketone: 130 parts Photopolymerization initiator “Irgacure 184” manufactured by Ciba Specialty Chemicals
: 4 parts (coating composition: polyester acrylate / epoxy acrylate = 1/1,
{Polyester resin / curable resin layer} × 100 = 50 mass%,
Aromatic ring ratio Q = 51 mass%)
However, the coating film composition refers to the coating film composition after drying excluding additives such as a photopolymerization initiator.

The PP film is peeled off from the obtained hydraulic transfer film F1 and allowed to stand for 1 minute in a 30 ° C. water bath with the coated surface facing up, and then an activator (xylene / methyl isobutyl ketone / 3-methyl 3-methoxybutyl). Acetate / butyl acetate = 50/25/15/10) 50 g / m ² was sprayed on the film. Further, after standing for 20 seconds, a primer-treated galvanized steel sheet molded product (petroleum fan heater housing) was pressed from the vertical direction, and the transfer layer was hydraulically transferred. After the transfer, the molded product was washed with water and dried at 120 ° C. for 30 minutes. Next, by passing the sample once through a UV irradiation device (corresponding to a UV irradiation amount of 2400 mJ / cm ² ), the curable resin layer is completely cured, and a hydraulic transfer body Z1 having an excellent surface gloss and a clear pattern is obtained. Obtained.

(Example 2)
A hydraulic transfer body Z2 having an excellent surface gloss and a sharp pattern is processed in the same manner as in Example 1 except that the curable resin composition D1 in Example 1 is changed to the curable resin composition D2 having the following composition. Got.
<Composition of curable resin composition D2>
Epoxy acrylate "NK Oligo EA-1020" manufactured by Shin-Nakamura Chemical Co., Ltd.
: 50 parts polyester acrylate "M-8530" manufactured by Toagosei Co., Ltd.
(Weight average molecular weight 1,200): 50 parts Polyester “Byron GK880” manufactured by Toyobo Co., Ltd.
(Weight average molecular weight 54,000, Tg = 84 ° C., qi = 67%): 10 parts Polyester “Byron 650” manufactured by Toyobo Co., Ltd.
(Weight average molecular weight 51,000, Tg = 10 ° C., qi = 35%): 100 parts Toluene: 140 parts Methyl ethyl ketone: 140 parts Photopolymerization initiator “Irgacure 184” manufactured by Ciba Specialty Chemicals
: 4 parts (coating composition: polyester acrylate / epoxy acrylate = 1/1
{Polyester resin / curable resin layer} × 100 = 52 mass%
Aromatic ring ratio Q = 38% by mass)

(Example 3)
Except for changing the curable resin composition D1 in Example 1 to the curable resin composition D3 having the following composition, and further changing the lattice pattern film P1 to the abstract pattern film P2, the same treatment as in Example 1 was performed. A hydraulic transfer member Z3 having a surface gloss and a clear pattern was obtained.
<Composition of curable resin composition D3>
Epoxy acrylate "NK Oligo EA-1020" manufactured by Shin-Nakamura Chemical Co., Ltd.
: 50 parts polyester acrylate "M-8530" manufactured by Toagosei Co., Ltd.
(Weight average molecular weight 1,200): 50 parts Polyester “Byron GK880” manufactured by Toyobo Co., Ltd.
(Weight average molecular weight 54,000, Tg = 84 ° C., qi = 67%): 90 parts Polyester “Byron 650” manufactured by Toyobo Co., Ltd.
(Weight average molecular weight 51,000, Tg = 10 ° C., qi = 35%): 30 parts Toluene: 150 parts Methyl ethyl ketone: 150 parts Photopolymerization initiator “Irgacure 184” manufactured by Ciba Specialty Chemicals
: 4 parts (coating composition: polyester acrylate / epoxy acrylate = 1/1
{Polyester resin / curable resin layer} × 100 = 55 mass%
Aromatic ring ratio Q = 59% by mass)

Example 4
A hydraulic transfer member Z4 having an excellent surface gloss and a clear pattern is processed in the same manner as in Example 1 except that the curable resin composition D1 in Example 1 is changed to the curable resin composition D4 having the following composition. Got.
<Composition of curable resin composition D4>
Epoxy acrylate "NK Oligo EA-1020" manufactured by Shin-Nakamura Chemical Co., Ltd.
: 50 parts polyester acrylate "M-8530" manufactured by Toagosei Co., Ltd.
(Weight average molecular weight 1,200): 60 parts Polyester “Byron GK640” manufactured by Toyobo Co., Ltd.
(Weight average molecular weight 58,000, Tg = 79 ° C., qi = 66%): 60 parts Polyester “Byron 650” manufactured by Toyobo Co., Ltd.
(Weight average molecular weight 51,000, Tg = 10 ° C., qi = 35%): 68 parts Toluene: 150 parts Methyl ethyl ketone: 150 parts Photopolymerization initiator “Irgacure 184” manufactured by Ciba Specialty Chemicals
: 4 parts (coating composition: polyester acrylate / epoxy acrylate = 6/5,
{Polyester resin / curable resin layer} × 100 = 54% by mass,
Aromatic ring ratio Q = 50 mass%)

(Example 5)
A hydraulic transfer member Z5 having an excellent surface gloss and a sharp pattern is processed in the same manner as in Example 3 except that the curable resin composition D3 in Example 3 is changed to the curable resin composition D5 having the following composition. Got.
<Composition of curable resin composition D5>
Epoxy acrylate “NK Oligo EA-1020” manufactured by Shin-Nakamura Chemical Co., Ltd .: 55 parts Polyester acrylate “M-8530” manufactured by Toagosei Co., Ltd.
(Weight average molecular weight 1,200): 15 parts Polyester “Byron GK880” manufactured by Toyobo Co., Ltd.
(Weight average molecular weight 54,000, Tg = 84 ° C., qi = 67%): 42 parts Polyester “Byron 650” manufactured by Toyobo Co., Ltd.
(Weight average molecular weight 51,000, Tg = 10 ° C., qi = 35%): 50 parts Toluene: 110 parts Methyl ethyl ketone: 110 parts Photopolymerization initiator “Irgacure 184” manufactured by Ciba Specialty Chemicals: 3 parts (Coating composition) : Polyester acrylate / epoxy acrylate = 3/11
{Polyester resin / curable resin layer} × 100 = 57 mass%,
Aromatic ring ratio Q = 50 mass%)

(Example 6)
A hydraulic transfer body Z6 having an excellent surface gloss and a clear pattern is processed in the same manner as in Example 3 except that the curable resin composition D3 in Example 3 is changed to the curable resin composition D6 having the following composition. Got.
<Composition of curable resin composition D6>
Epoxy acrylate “NK Oligo EA-1020” manufactured by Shin-Nakamura Chemical Co., Ltd .: 50 parts Polyester acrylate “M-7100” manufactured by Toagosei Co., Ltd.
(Weight average molecular weight 1,200): 50 parts Polyester “Byron GK880” manufactured by Toyobo Co., Ltd.
(Weight average molecular weight 54,000, Tg = 84 ° C., qi = 67%): 60 parts Polyester “Byron 650” manufactured by Toyobo Co., Ltd.
(Weight average molecular weight 51,000, Tg = 10 ° C., qi = 35%): 40 parts Toluene: 140 parts Methyl ethyl ketone: 130 parts Photopolymerization initiator “Irgacure 184” manufactured by Ciba Specialty Chemicals Co., Ltd .: 4 parts (Coating composition) : Polyester acrylate / epoxy acrylate = 1/1
{Polyester resin / curable resin layer} × 100 = 50 mass%,
Aromatic ring ratio Q = 54% by mass)

(Example 7)
A hydraulic transfer body Z7 having an excellent surface gloss and a clear pattern, except that the curable resin composition D3 in Example 3 was changed to the curable resin composition D7 having the following composition. Got.
<Composition of curable resin composition D7>
Epoxy acrylate “NK Oligo EA-1020” manufactured by Shin-Nakamura Chemical Co., Ltd .: 35 parts Polyester acrylate “M-8530” manufactured by Toagosei Co., Ltd.
(Weight average molecular weight 1,200): 35 parts Polyester “Byron GK880” manufactured by Toyobo Co., Ltd.
(Weight average molecular weight 54,000, Tg = 84 ° C., qi = 67%): 69 parts Polyester “Byron 650” manufactured by Toyobo Co., Ltd.
(Weight average molecular weight 51,000, Tg = 10 ° C., qi = 35%): 79 parts Toluene: 150 parts Methyl ethyl ketone: 140 parts Photopolymerization initiator “Irgacure 184” manufactured by Ciba Specialty Chemicals: 3 parts (Coating composition) : Polyester acrylate / epoxy acrylate = 1/1
{Polyester resin / curable resin layer} × 100 = 68% by mass,
Aromatic ring ratio Q = 50 mass%)

(Example 8)
A hydraulic transfer member Z8 having an excellent surface gloss and a clear pattern is processed in the same manner as in Example 3 except that the curable resin composition D3 in Example 3 is changed to the curable resin composition D8 having the following composition. Got.
<Composition of curable resin composition D8>
Epoxy acrylate "NK Oligo EA-1026" manufactured by Shin-Nakamura Chemical Co., Ltd .: 65 parts Polyester acrylate "M-8530" manufactured by Toagosei Co., Ltd.
(Weight average molecular weight 1,200): 25 parts Polyester “Byron GK880” manufactured by Toyobo Co., Ltd.
(Weight average molecular weight 54,000, Tg = 84 ° C., qi = 67%): 35 parts Polyester “Byron 650” manufactured by Toyobo Co., Ltd.
(Weight average molecular weight 51,000, Tg = 10 ° C., qi = 35%): 45 parts Polyester “Byron 240” manufactured by Toyobo Co., Ltd.
(Weight average molecular weight 41,000, Tg = 60 ° C., qi = 41%): 10 parts Toluene: 120 parts Methyl ethyl ketone: 120 parts Photopolymerization initiator “Irgacure 184” manufactured by Ciba Specialty Chemicals: 4 parts (coating composition) : Polyester acrylate / epoxy acrylate = 5/13
{Polyester resin / curable resin layer} × 100 = 44 mass%,
Aromatic ring ratio Q = 48% by mass)

Example 9
A hydraulic transfer member Z9 having an excellent surface gloss and a clear pattern is processed in the same manner as in Example 3 except that the curable resin composition D3 in Example 3 is changed to the curable resin composition D9 having the following composition. Got.
<Composition of curable resin composition D9>
Epoxy acrylate “NK Oligo EA-1020” manufactured by Shin-Nakamura Chemical Co., Ltd .: 75 parts Polyester acrylate “M-8530” manufactured by Toagosei Co., Ltd.
(Weight average molecular weight 1,200): 75 parts Polyester “Byron GK880” manufactured by Toyobo Co., Ltd.
(Weight average molecular weight 54,000, Tg = 84 ° C., qi = 67%): 24 parts Polyester “Byron 650” manufactured by Toyobo Co., Ltd.
(Weight average molecular weight 51,000, Tg = 10 ° C., qi = 35%): 40 parts Toluene: 140 parts Methyl ethyl ketone: 140 parts Photopolymerization initiator “Irgacure 184” manufactured by Ciba Specialty Chemicals: 6 parts (coating composition) : Polyester acrylate / epoxy acrylate = 1/1
{Polyester resin / curable resin layer} × 100 = 30% by mass,
Aromatic ring ratio Q = 47% by mass)

(Example 10)
A hydraulic transfer member Z10 having an excellent surface gloss and a clear pattern is processed in the same manner as in Example 3 except that the curable resin composition D3 in Example 3 is changed to the curable resin composition D10 having the following composition. Got.
<Composition of curable resin composition D10>
Epoxy acrylate "NK Oligo EA-1020" manufactured by Shin-Nakamura Chemical Co., Ltd.
: 50 parts polyester acrylate "M-8530" manufactured by Toagosei Co., Ltd.
(Weight average molecular weight 1,200): 50 parts polyester manufactured by Unitika Ltd. “Eritel XA-0611”
(Weight average molecular weight 54,000, Tg = 67 ° C., qi = 61%): 50 parts Polyester “Byron 650” manufactured by Toyobo Co., Ltd.
(Weight average molecular weight 51,000, Tg = 10 ° C., qi = 35%): 50 parts Toluene: 130 parts Methyl ethyl ketone: 130 parts Photopolymerization initiator “Irgacure 184” manufactured by Ciba Specialty Chemicals
: 4 parts (coating composition: polyester acrylate / epoxy acrylate = 1/1,
{Polyester resin / curable resin layer} × 100 = 50 mass%,
Aromatic ring ratio Q = 48% by mass)

(Example 11)
A hydraulic transfer body Z11 having an excellent surface gloss and a clear pattern is processed in the same manner as in Example 3 except that the curable resin composition D3 in Example 3 is changed to the curable resin composition D11 having the following composition. Got.
<Composition of curable resin composition D11>
Epoxy acrylate "NK Oligo EA-1020" manufactured by Shin-Nakamura Chemical Co., Ltd.
: 50 parts polyester acrylate "M-8530" manufactured by Toagosei Co., Ltd.
(Weight average molecular weight 1,200): 50 parts Polyester “Byron 240” manufactured by Toyobo Co., Ltd.
(Weight average molecular weight 41,000, Tg = 60 ° C., qi = 41%): 50 parts Polyester “Byron 650” manufactured by Toyobo Co., Ltd.
(Weight average molecular weight 51,000, Tg = 10 ° C., qi = 35%): 50 parts Toluene: 130 parts Methyl ethyl ketone: 130 parts Photopolymerization initiator “Irgacure 184” manufactured by Ciba Specialty Chemicals
: 4 parts (coating composition: polyester acrylate / epoxy acrylate = 1/1,
{Polyester resin / curable resin layer} × 100 = 50 mass%,
Aromatic ring ratio Q = 38% by mass)

(Example 12)
A 30 g (solid content) / m 2 curable resin layer of the following composition was applied to the surface of a PVA film having a thickness of 30 μm as a support film with a comma coater, and then dried at 60 ° C. for 5 minutes. did. Next, the printing ink G1 was printed by gravure printing at a thickness of 4 g (solid content) / m2 to print a pattern and a solid with three plates to form a decorative layer, thereby producing a hydraulic transfer film F6.
<Composition of curable resin composition D12>
Epoxy acrylate "NK Oligo EA-1020" manufactured by Shin-Nakamura Chemical Co., Ltd.
: 65 parts Polyester acrylate "M-8530" manufactured by Toagosei Co., Ltd.
(Weight average molecular weight 1,200): 15 parts Polyester “Byron GK880” manufactured by Toyobo Co., Ltd.
(Weight average molecular weight 54,000, Tg = 84 ° C., qi = 67%): 60 parts Polyester “Byron 650” manufactured by Toyobo Co., Ltd.
(Weight average molecular weight 51,000, Tg = 10 ° C., qi = 35%): 35 parts Toluene: 120 parts Methyl ethyl ketone: 110 parts Photopolymerization initiator “Irgacure 184” manufactured by Ciba Specialty Chemicals
: 3 parts (coating composition: polyester acrylate / epoxy acrylate = 3/13,
{Polyester resin / curable resin layer} × 100 = 54% by mass,
Aromatic ring ratio Q = 55% by mass)

The resulting hydraulic transfer film F10 was left in a 30 ° C. water bath for 1 minute with the coated surface facing up, and then the activator (xylene / methyl isobutyl ketone / 3-methyl 3-methoxybutyl acetate / butyl acetate = 50). / 25/15/10) 50 g / m ² was sprayed onto the film. Further, after standing for 10 seconds, a primer-treated galvanized steel sheet molded product (petroleum fan heater housing) was pressed from the vertical direction to transfer the curable resin layer. After the transfer, the molded product was washed with water and dried at 110 ° C. for 15 minutes. Next, the curable resin layer is completely cured and cured by irradiating the molded product with ultraviolet rays (ultraviolet irradiation device: UV-0308 manufactured by Nippon Battery Co., Ltd., irradiation condition: irradiation with ultraviolet rays of 2400 mJ / cm2 once). The water-based transfer layer Z10 having an excellent surface gloss and a clear pattern was obtained by completely curing the conductive resin layer.

(Comparative Example 1)
A hydraulic transfer body Z51 was obtained in the same manner as in Example 1 except that the curable resin composition D1 in Example 1 was changed to the curable resin composition D51 having the following composition.

<Composition of curable resin composition D51>
Epoxy acrylate "NK Oligo EA-1020" manufactured by Shin-Nakamura Chemical Co., Ltd .: 60 parts Polyester acrylate "M-8530" manufactured by Toagosei Co., Ltd.
(Weight average molecular weight 1,200): 60 parts Polyester “Byron GK880” manufactured by Toyobo Co., Ltd.
(Weight average molecular weight 54,000, Tg = 84 ° C., qi = 67%): 57 parts Toluene: 120 parts Methyl ethyl ketone: 120 parts Photopolymerization initiator “Irgacure 184” manufactured by Ciba Specialty Chemicals: 5 parts (coating composition) : Polyester acrylate / epoxy acrylate = 1/1
{Polyester resin / curable resin layer} × 100 = 32% by mass,
Aromatic ring ratio Q = 67% by mass)

(Comparative Example 2)
Example except that the curable resin composition D1 in Example 1 was changed to the curable resin composition D51 used in Comparative Example 1, and the coating film thickness by the lip coater was changed to 20 μm. In the same manner as in No. 1, a hydraulic transfer member Z52 was obtained.

(Comparative Example 3)
A hydraulic transfer member Z53 was obtained in the same manner as in Example 1 except that the curable resin composition D1 in Example 1 was changed to the curable resin composition D53 having the following composition.
<Composition of curable resin composition D53>
Shin Nakamura Chemical Co., Ltd. epoxy acrylate “NK Oligo EA-1020”: 70 parts Polyester acrylate “M-8530” manufactured by Toagosei Co., Ltd.
(Weight average molecular weight 1,200): 20 parts Toluene: 60 parts Methyl ethyl ketone: 60 parts Photopolymerization initiator “Irgacure 184” manufactured by Ciba Specialty Chemicals Co., Ltd .: 4 parts (Coating composition: polyester acrylate / epoxy acrylate = 2/7) ,
(Polyester resin is not included)

(Comparative Example 4)
A hydraulic transfer member Z54 was obtained in the same manner as in Example 1 except that the curable resin composition D1 in Example 1 was changed to the curable resin composition D54 having the following composition.

<Composition of curable resin composition D54>
Epoxy acrylate "NK Oligo EA-1020" manufactured by Shin-Nakamura Chemical Co., Ltd .: 10 parts Polyester acrylate "M-8530" manufactured by Toagosei Co., Ltd.
(Weight average molecular weight 1,200): 10 parts Polyester “Byron GK880” manufactured by Toyobo Co., Ltd.
(Weight average molecular weight 54,000, Tg = 84 ° C., qi = 67%): 90 parts polyester “Byron 650” manufactured by Toyobo Co., Ltd.
(Weight average molecular weight 51,000, Tg = 10 ° C., qi = 35%): 90 parts Toluene: 135 parts Methyl ethyl ketone: 135 parts Photopolymerization initiator “Irgacure 184” manufactured by Ciba Specialty Chemicals Co., Ltd .: 0.8 parts Film configuration: polyester acrylate / epoxy acrylate = 1/1
{Polyester resin / curable resin layer} × 100 = 90% by mass,
Aromatic ring ratio Q = 51 mass%)

(Comparative Example 5)
Although it tried to process similarly to Example 1 except having changed the curable resin composition D1 in Example 1 into the curable resin composition D55 of the following composition, when the hydraulic transfer film which had been roll-stored was drawn out, Since the unevenness of the film cutting part affected the inside of the roll winding, the subsequent work was stopped.

<Composition of curable resin composition D55>
Shin-Nakamura Chemical Co., Ltd. epoxy acrylate “NK Oligo EA-1020”: 75 parts Polyester acrylate “M-8530” manufactured by Toagosei Co., Ltd.
(Weight average molecular weight 1,200): 19 parts “Byron 500” manufactured by Toyobo Co., Ltd.
(Weight average molecular weight 41,000, Tg = 4 ° C., qi = 27%): 95 parts toluene: 125 parts methyl ethyl ketone: 125 parts “Irgacure 184” manufactured by Ciba Specialty Chemicals Co., Ltd .: 4 parts (coating composition: polyester acrylate / Epoxy acrylate = 19/75,
{Polyester resin / curable resin layer} × 100 = 50 mass%,
Aromatic ring ratio Q = 27% by mass)

Tables 1 to 4 show the evaluation results of the transfer product of the hydraulic transfer body obtained by hydraulic transfer of the hydraulic transfer film of the present invention together with comparative examples.

  It can be seen that the transfer bodies obtained by hydraulic transfer of the hydraulic transfer films of Examples 1 to 12 have a surface smoothness Ra of 11 μm or less, and have excellent low curing shrinkage and gloss. On the other hand, in Comparative Examples 1-5, the balance of a resin composition collapse | crumbles and it turns out that the desired performance is no longer obtained. The features of the embodiment will be briefly described below.

Example 1: Polyester resin composition aromatic ring ratio Q is 51 mass%.
Example 2: Polyester resin composition aromatic ring ratio Q is 38 mass%.
Example 3: Polyester resin composition aromatic ring ratio Q is 59 mass%.
Example 4: Mass ratio P of polyester acrylate / epoxy acrylate is 6/5.
Example 5: Mass ratio P of polyester acrylate / epoxy acrylate is 3/11.
Example 6: The type of polyester acrylate was changed.
Example 7: 68% of the polyester resin composition was used.
Example 8: Tg of polyester resin is changed.
Example 9: 30% of the polyester resin composition was used.
Example 10: Polyester resin composition aromatic ring ratio Q is 48 mass%.
Example 11: Polyester resin composition aromatic ring ratio Q is 38% by mass.
(A combination of polyesters different from Example 2)
Example 12: Manufactured by applying a curable resin layer to PVA and printing on it.

In the above examples, after hydraulic transfer and curing, excellent appearance such as high gloss, high definition, sufficient depth, and scratch resistance, impact resistance, chemical resistance, The hydraulic transfer film which can manufacture the hydraulic transfer body which has surface protection performances, such as boiling water, was able to be provided. On the other hand, since the aromatic ring rate Q of the polyester resin composition to be used was too large, Comparative Examples 1 and 2 could not satisfy both physical properties of depth, impact resistance, and plastic workability. Moreover, since the polyester resin was not mix | blended with the comparative example 3, cure shrinkage was large, adhesiveness was bad, and the feeling of depth was not acquired. In Comparative Example 4, the amount of the polyester resin was too large, the surface hardness was low, and the surface protection performance such as scratch resistance was greatly reduced. In Comparative Example 5, since the aromatic ring ratio Q of the polyester resin composition used was too small, the surface hardness was low, and the surface protection performance such as scratch resistance was greatly reduced.

Claims (7)

It has a support film made of a water-soluble or water-swellable resin and a transfer layer that can be dissolved in an organic solvent provided on the support film, and the transfer layer can be cured by at least one of active energy ray irradiation and heating. A hydraulic transfer film having a curable resin layer, wherein the curable resin layer is
1) A polyester resin having a weight average molecular weight of 5,000 to 300,000 obtained by copolymerizing an aromatic or aliphatic dicarboxylic acid and an aromatic or aliphatic diol, and having an aromatic ring ratio Q (mass%) of 38 mass. % Or more and 65% by mass or less of a polyester resin composition (component A);
(However, the aromatic ring ratio Q (mass%) is a value obtained below from the aromatic ring ratio q (mass%) of the polyester contained in the polyester resin composition.)

2) a polyester acrylate (component B) having a weight average molecular weight of 400 or more and 10,000 or less;
3) containing an epoxy acrylate (component C) compatible with the polyester resin composition (component A) and polyester acrylate (component B);
The said polyester resin composition (component A) in the said curable resin layer is 20 mass% or more and 80 mass% or less, and mass ratio P of the said polyester acrylate (component B) and epoxy acrylate (component C): {The total mass of the polyester acrylate (component B)} / {the total mass of the epoxy acrylate (component C)} is 1/5 or more and 3/2 or less. The hydraulic transfer film according to claim 1, wherein the epoxy acrylate (component C) is a bisphenol A type epoxy acrylate. The hydraulic transfer film according to claim 1 or 2, wherein a glass transition temperature (Tg) of each polyester of the polyester resin composition (component A) is 5 ° C or higher and 100 ° C or lower. The polyester resin composition (component A) is
The hydraulic transfer according to any one of claims 1 to 3, which is a mixture of one or more polyester resins obtained by copolymerizing an aromatic or aliphatic dicarboxylic acid and an aliphatic diol. the film. The aromatic dicarboxylic acid is terephthalic acid and / or isophthalic acid, the aliphatic dicarboxylic acid is an aliphatic dicarboxylic acid having 4 to 12 carbon atoms, and the aliphatic diol is an aliphatic having 2 to 12 carbon atoms. The hydraulic transfer film according to claim 4, which is a diol. The film for hydraulic transfer according to any one of claims 1 to 5, further comprising a decorative layer made of a printing ink film or a paint film on the curable resin layer. Using the hydraulic transfer film according to any one of claims 1 to 6, after the hydraulic transfer of the curable resin layer onto the surface of the transfer target, the curable resin layer is irradiated with active energy rays. A hydraulic transfer body having a cured resin layer cured by at least one kind of heating.