JP2003191695A - Method of manufacturing decorative molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a decorative molded article having good adhesion of a decorative layer and excellent heat resistance even on a transfer receiving body having poor adhesion to a decorative layer such as a metal. SOLUTION: From a hydraulic transfer film comprising a support film (F) made of a hydrophilic resin and a hydrophobic transfer layer (T) provided on the support film and soluble in an organic solvent, the transfer layer is formed. A decorative molded product wherein the transfer layer comprises a decorative layer (T1) composed of a printing ink film or a paint film, wherein the primer layer comprises: (P)
Comprises a resin composition obtained by subjecting a diglycidyl ether of a (poly) alkylene glycol (P1) to a phosphoric esterification reaction with a phosphorus compound (P2) having at least one P-OH bond. Method for producing decorative molded articles.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a decorative layer comprising a printing ink film or a paint film, or a printing ink film or a paint film, from a film for hydraulic transfer using a three-dimensional molded product having a primer layer having excellent adhesiveness as a transfer object. And a transparent curable resin layer curable by at least one of irradiation with active energy rays and heating. INDUSTRIAL APPLICABILITY The manufacturing method of the present invention is particularly useful for decorating a transfer target made of metal.

[0002]

2. Description of the Related Art In recent years, due to the diversification of demand, not only design requirements for various molded products but also color and pattern have been emphasized. For example, for household appliances such as refrigerators and washing machines, BACKGROUND ART A method of forming a metal plate and then applying various colors by spray painting or the like, or a method of forming a coated steel plate called a pre-coated metal (PCM) is used. However, it is difficult to decorate a metal molded product with a pattern by these methods, and it is almost impossible to give a pattern by painting.

A method of pasting a printed film on the surface of these molded products is also practiced. However, in the case of a product whose pattern can be changed in a short period of time, a film is a simple and advantageous method, but it is said that it has sufficient durability for products with a long period of use such as home appliances. It is difficult to say, and depending on the three-dimensional shape of the molded product, there are problems that it is difficult to bring the film into close contact with the molded product, and that trimming such as screw holes of the molded product is required later.

On the other hand, in the hydraulic transfer method, a support film made of a hydrophilic resin having a decorative layer with a pattern is floated on water to dissolve or swell the support film.
A method of transferring a decorative layer having a pattern to a transfer target by activating the decoration layer with a solvent, pressing the transfer target from above the support film and immersing it in water It is an excellent decoration method that has a wide range of moldings and a high degree of freedom in design, but its application is limited to the production of some high-end products that require particularly designability because the process is complicated. It was

Further, in the decoration-formed product produced by the hydraulic transfer method, the adhesion between the hydraulically transferred decorative layer and the transferred material is important. For example, if the transferred material is made of resin,
Adhesion between the decorative layer that has been hydraulically transferred and the transfer target is relatively good, but if the transfer target is a metal molded product such as a galvanized steel sheet, it does not adhere to the transferred coating film or printing ink film. Since the adhesion is low, hydraulic transfer itself is possible,
There are problems that the transferred pattern collapses and that the coating film or printing ink film peels off during washing with water or after drying. Therefore, a method has been carried out in which a primer layer is previously applied to those transfer targets to improve the adhesion to a coating film or a printing ink film to be transferred.

In Japanese Patent Publication No. 7-37196, a curable resin layer which has been dried but not yet completely cured (curable resin layer in a semi-cured state or an uncured state) is formed on the surface of a transfer-receiving member. And transfer the printed pattern layer from the film for hydraulic transfer by hydraulic transfer, spray-coat the curable resin that covers the printed pattern layer, and then completely cure the curable resin layers above and below the printed pattern layer. A method for producing a decorative molded article is disclosed, and it is described that a decorative molded article with improved water resistance and wet heat resistance of the printed pattern layer can be obtained.

However, in the method of the above publication, a complicated process of the conventional hydraulic transfer method, in which a curable resin is applied to a transfer target and dried, and then a curable resin is applied and dried after hydraulic transfer, It remained unimproved. Further, what has been described as the curable resin on the surface of the transferred material as the primer resin layer is a conventionally known thermosetting resin or an ionizing radiation curable composition, and when the transferred material is a metal, its adhesion The sex was not always sufficient.

[0008]

The problem to be solved by the present invention is to provide a decorative molded article which has a good adhesiveness to the decorative layer and is excellent in heat resistance even on a transferred material having a poor adhesiveness to the decorative layer such as a metal. It is to provide a manufacturing method of.

[0009]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, by using a non-curable resin having a specific composition as a primer layer of a transfer body for hydraulic transfer, A decorative layer with a high design property such as a pattern can be easily transferred to the transferred material, and when the curable resin layer and the decorative layer are simultaneously transferred and laminated, the decorative layer is sufficiently protected. The inventors have found that a molded product can be produced and completed the present invention.

That is, the present invention is a hydraulic transfer film comprising a support film (F) made of a hydrophilic resin and a hydrophobic transfer layer (T) which is provided on the support film and is soluble in an organic solvent. From the decorative layer (T1) comprising a printing ink film or a paint film, wherein the transfer layer is hydraulically transferred onto a transfer target coated with a primer layer (P). And a resin obtained by subjecting the primer layer (P) to a phosphoric esterification reaction between a diglycidyl ether of (poly) alkylene glycol (P1) and a phosphorus compound (P2) having at least one P—OH bond. Provided is a method for producing a decorative molded article, which comprises a composition.

The present invention also relates to a hydraulic transfer film comprising a support film (F) made of a hydrophilic resin and a hydrophobic transfer layer (T) which is provided on the support film and is soluble in an organic solvent. From the above, a method for producing a decorative molded article, wherein the transfer layer (T) is hydraulically transferred to a transfer target covered with a primer layer (P), wherein the transfer layer (T) is provided on the support film. A transparent curable resin layer (T2) that can be cured by at least one of radiation and heating
And a decorative layer (T
1) and the primer layer (P) is a diglycidyl ether of (poly) alkylene glycol (P1)
And a phosphorus-based compound (P2) having at least one P-OH bond, which is a resin composition obtained by a phosphoric acid esterification reaction.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION First, constituent elements of a hydraulic transfer film used in the present invention will be described in detail in order. The support film (F) made of a hydrophilic resin is a support film made of a hydrophilic resin that is swellable or soluble in water. Examples of the support film (F) made of a hydrophilic resin include:
Polyvinyl alcohol, polyvinyl pyrrolidone, acetyl cellulose, polyacrylamide, acetyl butyl cellulose, gelatin, glue, sodium alginate,
Films of hydroxyethyl cellulose, carboxymethyl cellulose, etc. can be used.

Among them, a polyvinyl alcohol film which is generally used as a water pressure transfer film is easily dissolved in water and easily available, and is suitable for printing a curable resin layer, and is particularly preferable. The thickness of the support film (F) used is preferably about 10 to 200 μm.

Support film (F) made of hydrophilic resin
Is required to have enough flexibility to follow the curved surface of the transfer body having a three-dimensional structure when the transfer target to be transferred is placed on the hydraulic transfer film and submerged in water. Is. The support film (F) may be one that swells in water without being completely dissolved. Further, the time for bringing the support film (F) made of a hydrophilic resin into contact with water in order to impart the swelling property or the solubility necessary for the hydraulic transfer is, for example, a polyvinyl alcohol film is used and the water temperature is 4
When the temperature is about 0 ° C., it is generally 30 seconds or more and 5 minutes or less, preferably 1 minute or more and 3 minutes or less.

Next, the transfer layer (B) will be described. The transfer layer (B) of the hydraulic transfer film used in the production method of the first aspect of the present invention is formed of a hydrophobic printing ink film or paint film which is provided on the support film (F) and is soluble in an organic solvent. The decorative layer (T1).

The transfer layer (B) of the hydraulic transfer film used in the production method of the second embodiment of the present invention can be cured by at least one of irradiation with active energy rays and heating provided on the support film (F). Transparent curable resin layer (T2)
And a decorative layer (T1) made of a hydrophobic printing ink film or paint film that can be dissolved in an organic solvent.

The total film thickness of the transfer layer (B) is not particularly limited, but is preferably 1 to 300 μm. More preferably, it is 10 to 150 μm. 1μ
If it is less than m, it is difficult to form / apply a coating film that realizes a sufficient surface protection function or decoration that satisfies the required design property. If it exceeds 300 μm, the film thickness is too large and the transfer layer during hydraulic transfer ( It becomes difficult to uniformly activate B).

The term "activation" means that the transfer layer is solubilized without completely dissolving the resin constituting the transfer layer including the decorative layer and the cured resin layer by applying or spraying an organic solvent to the transfer layer. In addition to facilitating the separation of the hydrophobic transfer layer from the hydrophilic support film at the time of hydraulic transfer, by imparting flexibility to the transfer layer, the transfer layer can follow the three-dimensional curved surface of the transfer target. It means to improve the adhesion.

Next, the decorative layer (T1) will be described.
The printing ink or paint used for the decorative layer (T1) needs to be activated by an organic solvent, but the property that flexibility can be maintained to the extent that the pattern does not flow is important, and gravure printing ink is particularly preferable.

Resins for varnish used in these printing inks or paints include acrylic resin, polyurethane resin, polyamide resin, urea resin, epoxy resin, polyester resin, vinyl resin (vinyl chloride, vinyl acetate copolymer resin), vinylidene resin (vinylidene resin). A thermoplastic resin such as chloride, vinylidene fluoride), ethylene-vinyl acetate resin, polyolefin resin, chlorinated olefin resin, ethylene-acrylic resin, petroleum resin, or cellulose derivative resin is preferably used. Among these, alkyd resin, acrylic resin, polyurethane resin, cellulose derivative resin and ethylene vinyl acetate resin are particularly preferable.

The colorant of the printing ink or paint in the decorative layer (T1) is preferably a pigment, and either an inorganic pigment or an organic pigment can be used. Furthermore, it is also possible to use a metallic luster ink containing a paste of metal cutting particles or a metal strip obtained from a vapor-deposited metal film as a pigment. Examples of these metals include aluminum (Al), gold (Au), silver (Ag), brass (Cu-Zn), titanium (Ti), chromium (Cr), nickel (Ni), nickel chrome (N).
i-Cr) and stainless steel (SUS) are preferably used. These metal strips may be surface-treated with an epoxy resin, polyurethane, an acrylic resin, a cellulose derivative such as nitrocellulose, or the like in order to improve dispersibility, oxidation resistance, and strength of the ink layer.

As long as design and spreadability are not impaired,
Defoamer, anti-settling agent, pigment dispersant, fluidity modifier, anti-blocking agent, antistatic agent, antioxidant, light stabilizer, UV absorber, internal curing agent in curable resin layer and decorative layer Agents, various additives for the purpose of improving scratch resistance, etc. may be added.

In order to impart a high degree of designability such as surface protection and glossiness and depth to the decorated metal molded article by hydraulically transferring the decorative layer (T1), the decorative layer formed on the metal molded article ( It is desirable to further provide a curable resin layer as a protective layer on T1).

As a method of providing a curable resin layer on the decorative layer (T1) formed on a metal molded product having a three-dimensional shape, it can be cured by at least one of irradiation with active energy rays and heating, and curing The material may be spray-coated with a transparent curable resin composition, and a known conventional method such as a method of curing with at least one of irradiation with active energy rays and heating may be used, or only the curable resin layer may be hydraulically transferred again. A method of transferring onto the decorative layer (T1) formed on the metal molded product may be used, and any method can be used.

The physical properties required for the resin composition for forming the curable resin layer are, in addition to having sufficient scratch resistance and weather resistance as a protective layer, coating on the decorative layer (T1) so that the decorative layer ( The adhesiveness to T1) is excellent, and the cured product of the resin composition is transparent. The transparency of the curable resin layer depends on the required characteristics of the decorative molded product, but basically it is a good level as long as it does not impair the design of the final product, and it does not need to be completely transparent. , Transparent to translucent.

In the method for producing a metal molded article according to the second embodiment of the present invention, the transfer layer (B) is a decorative layer (a printing ink film or a paint film provided on the support film (F) ( T1) and a hydraulic transfer having a transparent curable resin layer (T2) curable by at least one of irradiation with active energy rays and heating between the support film (F) and the decorative layer (T1). Use film. According to this manufacturing method, the decorative layer (T1) and the curable resin layer (T2) which is the protective layer thereof can be simultaneously transferred onto the coating surface of the metal molded product by one hydraulic transfer.

Next, the curable resin layer (T2) of the present invention will be described. The curable resin layer (T2) is made of at least one of a transparent active energy ray curable resin and a thermosetting resin, and is preferably non-sticky.
For this reason, it is preferable that 1 to 70 parts by mass of the non-adhesive thermoplastic resin is contained with respect to 100 parts by mass of these curable resin layers (T2).

The transparency of the curable resin layer (T2) depends on the required characteristics of the decorative transferred material, but basically it is sufficient if the color and pattern of the decorative layer (T1) can be seen through and is completely transparent. It includes everything from transparent to semi-transparent without needing anything. Further, the curable resin layer (T2), like the decorative layer (T1), easily separates from the hydrophilic support film (F) at the time of hydraulic transfer and is transferred to a three-dimensional molded body that is a transfer target. Must be done. Therefore, the resin forming the curable resin layer (T2) needs to be hydrophobic as a whole.

The non-adhesive thermoplastic resin is extremely effective in improving the drying property of the curable resin layer. However, since it may hinder the curing reaction of the curable resin, the non-adhesive thermoplastic resin should be added in an amount not exceeding 70 parts by mass with respect to 100 parts by mass of the curable resin layer (T2). Is preferred.

Another necessary characteristic of the curable resin layer (T2) is that it is activated by an organic solvent to be sprayed and is sufficiently solubilized or softened before being hydraulically transferred.
In this solubilization, the organic solvent penetrates into the curable resin layer (T2) and the decorative layer (T1), and the curable resin layer (T2) and the decorative layer (T1) are used as an integrated transfer layer from the hydraulic transfer film. It is sufficient that the transfer layer composed of the curable resin layer (T2) and the decorative layer (T1) is made flexible enough to follow the three-dimensional curved surface of the transfer target when transferring the transfer target. If the resin components of the decorative layer (T1) and the curable resin layer (T2) are excessively solubilized and dissolved due to solubilization, the pattern of the decorative layer is disturbed and gloss is lowered, which is not preferable.

The curable resin forming the curable resin layer (T2) is roughly classified into an active energy ray curable resin which is cured by irradiation with an active energy ray and a thermosetting resin which is cured by heating. In the present invention, the active energy ray is
Visible light, ultraviolet rays, electron beams, gamma rays and the like can be mentioned.
The active energy ray curable resin is one having two or more curable groups which can be cured in one molecule directly by the active energy ray or by reaction with an initiating species generated by the active energy ray, and is a radical curable resin. Alternatively, a cation-curable resin is preferable.

These are resins having a curable group which initiates polymerization by a radical source or a cation source in the main chain, side chain or terminal group. Such a curable group, an acryloyl group, an allyl group, a styryl group, a vinyl ester group, a vinyl ether group, a vinyl group such as an allenyl group, an acetylene group, a maleimide group, an epoxy group, a cyclic carbonate group, an oxetane group, Ring-opening curable groups such as oxazoline groups are available, but are not limited to.

The active energy ray-curable resin used for the curable resin layer (T2) is preferably an acrylic resin,
Of these, an acrylate in which the acrylic resin has two or more (meth) acryloyl groups is preferable. The acrylate having a (meth) acryloyl group in the present invention means a resin having a methacryloyl group or an acryloyl group.

The resin having a (meth) acryloyl group used in the present invention can be used without any problem as long as it is an acrylic resin generally used as a resin for paints. Specific examples thereof include (a) urethane. (Meth) acrylate, (b) polyester (meth) acrylate,
As (c) polyacrylic (meth) acrylate, (d) epoxy (meth) acrylate, (e) polyether (meth) acrylate, and other (meth) acrylate, silicon (meth) acrylate, polybutadiene (meth) acrylate, Examples thereof include silicon (meth) acrylate, amino resin (meth) acrylate, and maleimide (meth) acrylate.

These (meth) acrylate oligomers and polymers may be used singly or may be blended in a mixture range. Furthermore, it may be used by blending it with a thermosetting polymer or oligomer described later in a range in which it can be mixed.

Among them, (a) urethane (meth) acrylate is preferable, and urethane (meth) acrylate is obtained by addition reaction of polyisocyanate obtained by reaction of polyol such as triol and tetraol with diisocyanate and hydroxyl group-containing acrylate. be able to.

Examples of the hydroxyl group-containing (meth) acrylate include acrylic acid or methacrylic acid such as (meth) acrylic acid 2-hydroxyethyl ester, (meth) acrylic acid 2-hydroxypropyl ester and (meth) acrylic acid 3-hydroxypropyl ester. Mention may be made of hydroxyalkyl esters of acids having 2 to 8 carbon atoms.

The curable resin layer (T2) containing these active energy curable resins may optionally contain known and commonly used photopolymerization initiators and photosensitizers. Typical examples of such photopolymerization initiators include acetophenone compounds such as diethoxyacetophenone and 1-hydroxycyclohexyl-phenylketone; benzoin;
Benzoin-based compounds such as benzoin isopropyl ether; Acylphosphine oxide-based compounds such as 2,4,6-trimethylbenzoindiphenylphosphine oxide;

A variety of benzophenone compounds such as benzophenone and methyl-4-phenylbenzophenone o-benzoylbenzoate; thioxanthone compounds such as 2,4-dimethylthioxanthone; aminobenzophenone compounds such as 4,4'-diethylaminobenzophenone. Compounds of Examples of such photosensitizers include amines such as triethanolamine and ethyl 4-dimethylaminobenzoate.

The photopolymerization initiator is generally necessary when ultraviolet rays are used and is not necessary when active energy rays such as other electron rays are used. The photopolymerization initiator is not particularly limited, and various known ones can be used, and the amount thereof is usually 0.5 to 15 mass% with respect to the active energy ray-curable resin used, preferably 1 to 8% by weight is used.

Next, the thermosetting resin used for the curable resin layer (T2) will be described. Since the thermosetting resin also needs printability or coatability as in the case of the active energy ray-curable resin, the molecular weight of the resin is preferably high, and specifically, the mass average molecular weight of 1000 to 100,00.
0 is preferable, and more preferably 3,000 to 30,0.
00. In this region, if the resin has a high molecular cohesive property, sufficient drying property during printing or coating can be obtained.

The thermosetting resin is a compound having two or more functional groups capable of reacting with heat in one molecule,
Alternatively, a thermosetting compound serving as a main agent is mixed with a thermosetting compound serving as a crosslinking agent. As the functional group capable of reacting with heat, for example, an N-methylol group, an N-alkoxymethyl group, an amino group, a hydroxyl group, an isocyanate group,
Examples thereof include a carboxyl group, an epoxy group, and a methylol group. In addition, an acid anhydride and a carbon-carbon double bond are also thermally reactive.

Those having a carbon-carbon double bond in the molecule and capable of undergoing a crosslinking reaction by chain polymerization are curable resins of the same kind as the energy ray curable resin, and these curable resins and radical sources are heated by heating. A thermosetting resin can be obtained by combining with an initiator that generates
As the initiator at this time, a usual radical initiator such as benzoyl peroxide or azobisisobutyronitrile is used.

Examples of the combination of the main agent and the curing agent include, for example, a main agent having a hydroxyl group or an amino group and a curing agent blocked isocyanate, an N-methylol- or N-alkoxymethylated melamine or a benzoguanamine as a main agent having a hydroxyl group or a carboxyl group and a curing agent. Amino resin such as, a base compound having an epoxy group or a hydroxyl group and an acid anhydride such as phthalic anhydride as a curing agent, a carboxyl group or a carbon-carbon double bond,
A phenol resin as a main agent having a nitrile group or an epoxy group and a curing agent, and an epoxy group-containing compound as a main agent having a carboxyl group or an amino group and a curing agent can be used.

However, many of these thermosetting resins gradually undergo a curing reaction during storage without heating, and if the curing reaction proceeds during the storage period, the activation of the transfer layer by the activator is sufficient. If not performed, it may cause transfer failure. Therefore, a room temperature curable thermosetting resin is not preferable, and among thermosetting resins, a system using a polyol as a main component and a blocked isocyanate as a curing agent is preferable.

Examples of the polyol include acrylic polyol, poly-p-hydroxystyrene, polyether polyol, polyester polyol, polyvinyl alcohol and polyethylene vinyl alcohol copolymer, and acrylic polyol is particularly preferable.

As the blocked isocyanate, those in which an isocyanate group is protected by a blocking group such as alcohol can be used. Examples of the blocking group include phenol, cresol, aromatic secondary amine, tertiary alcohol, lactam and oxime. And so on. Blocking groups such as alcohols of these blocked isocyanates are liberated by heating, and therefore, the crosslinking reaction is initiated only by heating above the liberation temperature of these blocking groups.

The thermosetting resin used in the curable resin layer (T2) of the present invention is particularly preferably one using acrylic polyol as the main agent and blocked isocyanate as the curing agent. The mass average molecular weight of the acrylic polyol preferably used in the present invention is preferably 3,000 to 100,000, and more preferably 10,000 to 70,000.
Is.

The transparent curable resin layer (T2) of the present invention contains as a main component a resin containing at least one of the active energy ray curable resin and the thermosetting resin as described above. Generally, a curable resin has a low molecular weight in order to improve the curing density, and in many cases, it remains tacky before curing. For this reason, when the printing ink is overprinted after applying the curable resin, the pattern collapses and the concealment failure of the solid portion occurs due to coating film cracking on the coating surface, printing ink transfer failure, and the like.
Further, the curable resin may become cloudy or bleed even in the decorative layer, resulting in blocking with the non-printed or non-coated surface. Therefore, for the purpose of improving the drying property and the printability, the curable resin layer (T2) has a resin content of 70 parts by mass per 100 parts by mass.
It is preferable to add a non-adhesive thermoplastic resin within a range not exceeding the mass part.

The non-adhesive thermoplastic resin used in the curable resin layer (T2) of the present invention is used in combination with a resin containing at least one active energy ray curable resin or thermosetting resin. It is necessary to be able to sufficiently mix with these curable resins, and it is not preferable that they become cloudy or undergo two-phase separation during mixing. Further, it is preferable that the non-adhesive thermoplastic resin has a high Tg because the tackiness tends to decrease.

Specific examples of the non-adhesive thermoplastic resin include poly (meth) acrylate, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate and polyester. The vinyl polymer may be a copolymer of different types of vinyl monomers. Among these, poly (meth) acrylate, polystyrene, and polyvinyl chloride-vinyl acetate copolymer have high Tg and are suitable for improving the drying property during printing.
Among them, poly (meth) acrylate mainly composed of polymethylmethacrylate, which is excellent in transparency, solvent resistance and scratch resistance, is particularly preferable, and its mass average molecular weight is 30,000 to 300,000, preferably 150,000 to 300,000. Is.

The curable resin layer (T2) containing the active energy ray curable resin is preferably non-sticky, and the urethane (meth) acrylate and the non-adhesive thermoplastic resin are poly (meth) having a Tg of 70 ° C. or higher. A combination of acrylates is preferred. Further, the non-adhesive thermoplastic resin is preferably a poly (meth) acrylate containing 90% or more of polymethylmethacrylate, and particularly a urethane acrylate having three or more (meth) acrylic groups in one molecule. And the mass average molecular weight is 3
Those containing 10,000 to 300,000 poly (meth) acrylate are preferable, and it is preferable to use 30 to 70 parts by mass of urethane acrylate having three or more (meth) acrylic groups in one molecule.

Next, the primer layer (P) covering the surface of the molded product used in the present invention will be described. The primer layer (P) used in the present invention contains, in particular, a diglycidyl ether (P1) of (poly) alkylene glycol and a phosphorus compound (P2) having at least one P—OH bond. Diglycidyl ether (P
With respect to 1 equivalent of the epoxy group of 1), a phosphorus compound (P
It is preferable that the resin composition obtained by the phosphoric acid esterification reaction is 2) at a ratio of 0.05 to 1.0 equivalent of hydroxyl groups.

As the diglycidyl ether (P1) of (poly) alkylene glycol constituting the primer layer (P) of the present invention, various conventionally known compounds can be used. Specifically, diglycidyl ether of bisphenol A oxyalkylene adduct, diglycidyl ether of bisphenol AD oxyalkylene adduct, diglycidyl ether of bisphenol F oxyalkylene adduct, diglycidyl ether of hydrogenated bisphenol A oxyalkylene adduct. ,

Of diglycidyl ether of oxyalkylene adduct of phenol novolac, diglycidyl ether of oxyalkylene adduct of cresol novolac type resin, diglycidyl ether of polyhydric phenoloxyalkylene adduct, diglycidyl ether of aromatic polyhydric alcohol. Diglycidyl ether of aromatic (poly) alkylene glycol such as diglycidyl ether of oxyalkylene adduct and diglycidyl ether of oxyalkylene adduct of aromatic nitrogen-containing heterocyclic compound (P1
a),

Diglycidyl ethers of aliphatic (poly) alkylene glycols (P1b) such as diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, diglycidyl ether of polytetramethylene glycol, and the like, among which aromatic ( Diglycidyl ethers of poly) alkylene glycols (P1a) are preferred. Particularly, a diglycidyl ether of an oxyalkylene adduct of bisphenol is preferable, and a diglycidyl ether of an oxyalkylene adduct of bisphenol A is more preferable.

Examples of the (poly) alkylene glycol of the diglycidyl ether (P1) of (poly) alkylene glycol used in the present invention include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol and polytetramethylene glycol. Any one will do,
Any combination of ethylene glycol or polyethylene glycol, propylene glycol or polypropylene glycol, tetramethylene glycol and polytetramethylene glycol can be used.

Specifically, diglycidyl ether of bisphenol A oxyethylene 2 mol adduct, for example,
Diglycidyl ether of bisphenol A oxypropylene 2 mol adduct of Chemical formula 1 whose structural formula is exemplified below

[0059]

[Chemical 1]

Bisphenol A oxyethylene 2 mol
Diglycidyl ether of oxypropylene 3 mol adduct, bisphenol A oxyethylene 5 mol oxypropylene 4 mol adduct diglycidyl ether, bisphenol AD oxyethylene 2 mol oxy adduct diglycidyl ether, bisphenol F oxypropylene 5 mol adduct diglycidyl ether, Diglycidyl ether of hydrogenated bisphenol A oxypropylene 3 mol adduct, diglycidyl ether of phenol novolac oxyethylene 6 mol adduct,

Diglycidyl ether of oxypropylene 4 mol adduct of cresol novolac type resin, diglycidyl ether of polyhydric phenol oxypropylene 2 mol adduct, diglycidyl ether of aromatic polyhydric alcohol oxypropylene 2 mol adduct, aromatic Examples thereof include diglycidyl ether of an oxypropylene 2 mol adduct of a nitrogen-containing heterocyclic compound, and diglycidyl ether of a bisphenol oxypropylene 2 mol adduct is particularly preferable.

The phosphorus compound (P2) having at least one P—OH bond used in the present invention is a monoester of orthophosphoric acid. Suitable examples of phosphoric acid monoesters are monobutyl phosphate, monoamyl phosphate, monononyl phosphate, monocetyl phosphate, monophenyl phosphate, and monobenzyl phosphate.

Phosphorus compounds useful herein include hydrated phosphoric acid to pure phosphoric acid, ie, from about 70% to about 100%.
% Phosphoric acid, preferably about 85% phosphoric acid. The reason is that it is industrially easily available. Various condensed forms of phosphoric acid equivalents are used, such as polymerized partial anhydrides or esters of phosphoric acid, pyrophosphoric acid, triphosphoric acid and the like.

These phosphorus compounds (P2) and diglycidyl ether of (poly) alkylene glycol (P2)
In the reaction with 1), the ratio of the reactants can be selected in any ratio, but the hydroxyl group of the phosphorus compound (P2) is 0.05 equivalent or more and 1.0 equivalent to 1 equivalent of the epoxy group.
It is preferably equal to or less than the equivalent. When the amount is less than 0.05 equivalent, the compound itself is unstable. On the contrary, when the amount is more than 1.0, particularly when a diglycidyl ether (P1) of (poly) alkylene glycol having an epoxy equivalent of 240 or less is used,
It is not preferable because the reaction becomes difficult to control.

Further, a part of the epoxy group of the diglycidyl ether of (poly) alkylene glycol (P1) may be reacted with the monobasic acid, and then reacted with the phosphorus compound (P2). Examples of the monobasic acid used here include acetic acid, propionic acid, butyric acid, neodecanoic acid (versatic acid), alkyl (C1-C18) monocarboxylic acids such as stearic acid, acrylic acid, methacrylic acid, animal and vegetable oil fatty acids. And alkenyl (C2-C18) monocarboxylic acids, hydroxyalkyl monocarboxylic acids such as lactic acid, and aromatic monocarboxylic acids such as benzoic acid.

The reaction temperature is 25 ° C to 150 ° C, preferably 50 ° C to 100 ° C. If the reaction temperature is lower than 25 ° C, the reaction is slow, while if it exceeds 150 ° C, it becomes difficult to control the reaction. This reaction is usually performed in the presence of an inert solvent.

Examples of the solvent used include aromatic solvents such as benzene, toluene and xylene, ketone solvents such as methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone and isophorone, hydrocarbon solvents such as hexane, heptane and cyclohexane, diethyl ether and tetrahydrofuran. , Ether compounds such as dioxane and propylene glycol monopropyl ether, esters such as ethyl acetate, isopropyl acetate and butyl diglycol acetate, and solvents containing no active hydrogen such as halogen solvents.

The amount of the inert solvent used is 0.1 to 20 times, preferably 0.5 to 2 times the diglycidyl ether of (poly) alkylene glycol (P1). When the amount used is less than 0.1 times, the substrate concentration is high, and it is difficult to control the reaction. On the other hand, when it exceeds 20 times, it is uneconomical, which is not preferable.

When carrying out the reaction, the order of charging is not limited, but preferably phosphoric acid is added dropwise to a mixture of the diglycidyl ether (P1) of (poly) alkylene glycol and an inert solvent, and the temperature is raised to the above temperature. . The end point of the reaction can be confirmed by, for example, titration to find that substantially no oxirane oxygen remains.

The diglycidyl ether of (poly) alkylene glycol (P1) used in the present invention and the phosphorus compound (P2) having at least one P-OH bond are combined with the diglycidyl ether of (poly) alkylene glycol (P1).
With respect to 1 equivalent of the epoxy group of 1), a phosphorus compound (P
The resin composition obtained by the phosphoric acid esterification reaction at a ratio in which the hydroxyl group of 2) is 0.05 equivalent or more and 1.0 equivalent or less has a stickiness without being cured by irradiation with active energy rays or heating. In other words, the primer layer exhibits sufficient adhesion to the transferred material and the curable resin layer or the decorative layer.

These resin compositions for the primer layer (P) are used for aluminum plate, tin-plated steel plate, zinc-plated steel plate,
It is particularly useful as a coating material for metal plates such as steel, and metal plates obtained by treating these plate materials with organic / inorganic compounds, but in addition to these, coating non-metal base materials such as wood and plastics. It is also useful as a material.

The method of coating the molded product to be the transferred material with the resin composition for the primer layer (P) of the present invention is a conventionally known method, that is, spraying, brush coating, curtain coater, bar coater, die coater, roll. Any method such as a coater is used. It is not particularly limited. The dry film thickness of the primer layer (P) is 0.5 to 50 μm.
Is preferable, and more preferably 1 to 30 μm.
m.

The most preferable applications of the decorative molded article having these primer layers are home electric appliances, automobile interior parts and the like. The coating film of the decorative molded article of the present invention has water resistance, solvent resistance, no elution of low molecular weight compounds from the coating film to the outer surface, and high impermeability of the coating film, so long-term contact, etc. As a result, there is no concern that a trace amount of harmful substances will corrode the human body, and there is little risk of eroding the coated metal.

The resin composition for a primer layer of the present invention comprises
Depending on the application, a suitable rust preventive agent, defoaming agent, as long as it does not impair the desired physical properties such as sufficient adhesion to the transferred material or the decorative layer,
Anti-settling agent, pigment, pigment dispersant, fluidity modifier, anti-blocking agent, antistatic agent, antioxidant, light stabilizer,
An ultraviolet absorber, an internal curing agent, various additives for the purpose of improving scratch resistance, etc. may be added.

Next, the layer structure of the hydraulic transfer film of the present invention and the laminating method thereof will be described. The film thickness of the curable resin layer (T2) is not particularly limited, but is 3
It is preferably about 200 μm. More preferably, it is 5 to 150 μm. This is because if it is less than 3 μm, it is difficult to impart a sufficient surface protection function, and if it exceeds 200 μm, the film thickness is too large to make uniform activation at the time of hydraulic transfer difficult. The dry film thickness of the decorative layer (T1) is preferably 0.5 to 15 μm, more preferably 1 to 7 μm. The decorative layer in the present invention also includes a clear varnish layer containing no pigment or pattern.

The decorative layer (T1) and the curable resin layer (T2) are not limited to one-time printing and coating, but two
It may be formed by printing or coating a plurality of times or more. For example, multi-layer printing may be performed within a range possible with a multicolor printing machine or the like. In gravure printing, since the viscosity of printing ink is low, the film thickness that can be laminated at one time is limited, and overlay printing by a multicolor printing machine is required. Especially the curable resin layer (T
Since 2) preferably has a thickness of 3 μm or more, it is laminated to a desired film thickness by a plurality of overprints.

On the other hand, in a coater capable of thick coating, such as a comma coater, the desired film thickness can be obtained by coating only once. Also in the decorative layer (T1) to be overprinted, it is general that the solid layer and the pattern layer are overprinted and laminated.

The coating method of the decorative layer and the curable resin layer of the hydraulic transfer film is carried out by 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. It can also be applied by spray painting. However, when a pattern is printed, gravure printing, flexographic printing, offset printing, silk printing, etc. are preferable. Further, it is necessary to pay attention to the drying temperature, but since many of them generally have low drying properties, a printing machine or coater having a wide drying temperature range and a long drying oven length is suitable.

As long as the effects of the present invention such as designability, spreadability, and adhesiveness are not impaired, defoaming and sedimentation prevention are prevented in the resin composition constituting the decorative layer (T1) and the curable resin layer (T2). Various additives for the purpose of pigment dispersion, fluidity modification, anti-blocking, anti-static, anti-oxidation, light stability, UV absorption, internal crosslinking and the like may be added.

Next, a method for producing a decorative molded article in which the transfer layer (B) is hydraulically transferred from the above-mentioned hydraulic transfer film onto the coating film surface of the transfer target having a primer layer will be described.
The hydraulic transfer method itself of the present invention is the same as the conventional hydraulic transfer method, and its outline is as follows.

(1) The hydraulic transfer film is floated on water in a water tank with the support film (F) made of a hydrophilic resin facing down, and the support film (F) is dissolved or swollen with water. (2) The transfer layer (B) is activated by applying or spraying an organic solvent onto the transfer layer (B) of the hydraulic transfer film. (3) While the transfer target is pressed against the transfer layer (B) surface of the hydraulic transfer film, the transfer target and the hydraulic transfer film are immersed in water, and the transfer layer is brought into close contact with the transfer target by hydraulic pressure. Transcribe.

(4) The transferred material taken out from water is dried. (5) When the transfer layer (B) includes the curable resin layer (T2), the curable resin layer (T2) of the transferred transfer layer is cured by at least one of irradiation with active energy rays and heating.

In the production method in which the transfer layer (B) of the film for hydraulic transfer which is the second embodiment of the present invention includes the curable resin layer (T2), spray coating after hydraulic transfer is performed as compared with the conventional hydraulic transfer method. Since the process is omitted, the manufacturing time can be shortened,
Further, there is an advantage in terms of equipment that does not require a paint booth at the manufacturing site.

The water in the water tank used for the hydraulic transfer is the hydraulic transfer film when transferring the decorative layer and the curable resin layer.
In addition to acting as a hydraulic medium for adhering the decorative layer and the curable resin layer to the transferred material, it also swells or dissolves the support film (F) made of a hydrophilic resin that is sufficiently flexible to be adhered to the transferred material. Specifically, water such as tap water, distilled water, or ion-exchanged water may be used, and depending on the support film used, water may contain inorganic salts such as boric acid or alcohols within 10%. It may be dissolved in.

It is important that the organic solvent used to activate the transfer layer does not evaporate until the hydraulic transfer step is complete.
The organic solvent used for the hydraulic transfer film having the curable resin layer of the present invention may be the same as that used in the conventional hydraulic transfer method, and specifically, toluene, xylene, butyl cellosolve, butyl carbyl can be used. Examples include tall acetate, carbitol, carbitol acetate, cellosolve acetate, methyl isobutyl ketone, ethyl acetate, isobutyl acetate, isobutyl alcohol, isopropyl alcohol, n-butanol and mixtures thereof.

A small amount of resin component may be contained in the organic solvent in order to enhance the adhesion between the printing ink or the coating material and the transferred material. For example, by including 1 to 10% of a binder, which has a structure similar to that of the ink binder, such as polyurethane, acrylic resin, or epoxy resin, the adhesion may be increased.

After the transfer layer is transferred to the transfer-receiving member, the support film is dissolved in water or peeled off by washing or physical / chemical means. As for the washing and dissolving methods, the support film is dissolved and peeled off with a water stream, preferably a water jet, as in the conventional hydraulic transfer method.

In the step of drying the transferred material after the hydraulic transfer, the transfer layer (B) is a curable resin layer (T) made of a thermosetting resin.
When 2) is included, the curable resin layer can be cured together with drying. The curing time depends on the composition and the kind of the curing agent, but it is preferable that curing proceeds within a few minutes to an hour in terms of the process.

On the other hand, when the transfer layer (B) includes a curable resin layer (T2) made of an active energy ray curable resin,
After drying, the active energy ray is irradiated to cure the curable resin layer. At this time, the curing step can be shortened by using an ultraviolet or electron beam irradiator that simultaneously irradiates far infrared rays to proceed with curing while drying.

The present invention is particularly useful when the transferred material is a metal. Specific application examples of the decorated metal molding obtained by the manufacturing method of the present invention include televisions, VCRs, radio cassettes, personal computers, liquid crystal displays, plasma displays, printers, fax machines, telephones, and magneto-optical disk drives. , Hard disk drive, CD / DVD drive, scanner, speaker, radio / TV tuner, stereo component, portable CD player, portable MD player, portable cassette player, BS antenna,

Mobile phones, refrigerators, air conditioner gas fan heaters, oil fan heaters, ceramic heaters, humidifiers, air purifiers, furniture kotatsu, table lamps, home lighting equipment, digital cameras, video cameras, washing machines,
Clothes dryer, iron, coffee maker, dishwasher, microwave oven, toaster oven, electric kettle, rice cooker, vacuum cleaner, juicer mixer clock, shaving machine, dryer, weight scale, sphygmomanometer, massager, toilet seat for hot water washing, etc. The metal parts of home appliances in.

Also, chairs, tables, bookshelves, chests,
It can also be applied to furniture members such as columns and benches, and building members such as bathtubs, system kitchens, doors, window frames, and rims. Further, those having high surface properties can be used for automobile interior panels, automobile exterior plates, aluminum wheels and the like.

[0093]

The present invention will be described in more detail with reference to examples. In the following,% and parts are based on mass unless otherwise specified.

(Production Example 1) Non-curable resin composition (P-
1) Synthesis of bisphenol A oxypropylene 2 mol adduct diglycidyl ether (Epolite 3002 manufactured by Kyoeisha Kagaku Co., Ltd.) and 240 g of methyl ethyl ketone were charged in a four-neck flask in which nitrogen gas was replaced, and the temperature was raised to 65 ° C while stirring and dissolving. . While keeping the liquid temperature at 65 ° C,
A solution prepared by mixing and dissolving 25 g of 85% phosphoric acid, 15.4 g of distilled water and 43 g of methyl ethyl ketone therein was gradually added dropwise over 1 hour. After the dropping is completed, the temperature is further 6
The mixture was stirred for an hour to obtain a resin composition (P-1) having a solid content of 65%. The obtained resin composition has an acid value of 24 and a number average molecular weight of about 4
It was 000.

(Production Example 2) Non-curable resin composition (P-
2) Synthetic polypropylene glycol (number average molecular weight 400) 400 parts of diglycidyl ether (Epolite 400P manufactured by Kyoeisha Chemical Co., Ltd.) and 230 g of methyl ethyl ketone were placed in a four-neck flask in which nitrogen gas was replaced, and heated to 65 ° C. while stirring and dissolving. did. While keeping the liquid temperature at 65 ° C., 1.5 g of a mixture of 25 g of 85% phosphoric acid, 15.4 g of distilled water and 43 g of methyl ethyl ketone was dissolved in the solution.
It was dripped gradually over time. After completion of dropping, the mixture was further stirred at the same temperature for 8 hours to obtain a resin composition (P-2) having a solid content of 65%. The resulting resin composition had an acid value of 22 and a number average molecular weight of about 500.

(Production Example 3) Production of transferred material (X1) with primer layer Chromate-treated galvanized steel sheet (material thickness 0.6 m
m, galvanized amount 60 g / m ² ) Molded product (petroleum fan heater housing) was mixed with ethyl acetate / toluene mixed solvent (mixing ratio = 1/1) for Fordcup # 4 for 18 seconds (25 ° C) Non-curable resin composition (P-
After spray coating of 1) so that the dry coating thickness would be 7 μm, it was dried in an oven at 80 ° C. for 2 minutes to obtain a transferred body (X1).

(Manufacturing Example 4) Manufacture of the transferred material (X2) with a primer layer Chromate-treated galvanized steel sheet (material thickness 0.6 m
m, galvanized coating amount 60 g / m ² ) on a molded product (model car), mixed solvent of ethyl acetate / toluene (mixing ratio = 1
/ 1) and the viscosity of the non-curable resin composition was adjusted to 18 seconds (25 ° C) with Fordcup # 4 (mixing ratio: P-1 / P-2 =
9/1) was spray-coated so that the dry coating film thickness was 7 μm, and then dried in an oven at 80 ° C. for 2 minutes to obtain a transferred body (X2).

(Production Example 5) Production of transferred material (X3) with primer layer Aluminium-treated molded article (petroleum fan heater housing) having a thickness of 6 μ was coated with ethyl acetate /
Fordcup # using toluene mixed solvent (mixing ratio = 1/1)
The non-curable resin composition (P-1) whose viscosity was adjusted to 4 seconds for 18 seconds (25 ° C.) was spray-coated to a dry coating film thickness of 7 μm, and then dried in an 80 ° C. oven for 2 minutes. ,
A transferred material (X3) was obtained.

(Production Example 6) Production of transferred material with primer layer (X4) Fordcup # 4 was prepared using a steel molded product (petroleum fan heater housing) with an ethyl acetate / toluene mixed solvent (mixing ratio = 1/1). After spray-coating the non-curable resin composition (P-1) whose viscosity was adjusted to 18 seconds (25 ° C.) with a dry coating film thickness of 7 μm, it was dried in an oven at 80 ° C. for 2 minutes, A transferred material (X4) was obtained.

(Production Example 7) Production of transferred material (X5) with primer layer Chromate-treated galvanized steel sheet (material thickness 0.6 m
m, galvanized coating amount 60 g / m ² ) on a molded product (model car), mixed solvent of ethyl acetate / toluene (mixing ratio = 1
/ 1) and the viscosity of the non-curable resin composition was adjusted to 18 seconds (25 ° C) with Fordcup # 4 (mixing ratio: P-1 / P-2 =
7/3) was spray-coated so that the dry coating film thickness was 7 μm, and then dried in an oven at 80 ° C. for 2 minutes to obtain a transferred body (X5).

(Production Example 8) Production of transferred material (X6) with primer layer Chromate-treated galvanized steel sheet (material thickness 0.6 m
m, galvanized coating amount 60 g / m ² ) Epoxy resin type thermosetting primer (AR Bt-100 black manufactured by Takashi Kubo Paint Co., Ltd.) on a molded product (automobile model).
Was spray-coated so that the layer thickness after drying would be 7 μm, and then heat-cured for 2 minutes in an oven at 150 ° C. to obtain a transferred material (X having a semi-cured primer layer).
6) was obtained.

(Production Example 9) Production of transferred material (X7) with primer layer Steel molded product (petroleum fan heater housing)
Then, an epoxy resin thermosetting primer (AR Bt-100 black manufactured by Takashi Kubo Paint Co., Ltd.) was spray-coated so that the layer thickness after drying was 7 μm, and then 1
Heat transfer treatment was carried out for 20 minutes in a 50 ° C. oven to obtain a transferred body (X7).

(Production Example 10) Production of UV-curable resin composition (H1) Polyisocyanate obtained by reacting toluylene diisocyanate with trimethylolpropane in an amount of 3 per molecule, and hydroxyethyl methacrylate in an amount of 3 in each molecule. Esterified trifunctional urethane acrylate 40
As a non-adhesive thermoplastic resin, 60 parts by weight of polymethyl methacrylate having a weight average molecular weight of 200,000 is used as a mixed solvent of ethyl acetate and methyl ethyl ketone (1
It melt | dissolved in / 1) and obtained the ultraviolet curable resin composition (H1) whose solid content rate is 30%.

(Production Example 11) Thermosetting resin composition (H
2) Production Acrylic polyol obtained by copolymerizing hydroxyethyl methacrylate, methyl methacrylate, ethyl acrylate, butyl acrylate and styrene in a molar ratio of 20/30/15/15/20 (mass average molecular weight 25.0).
00) To 85 parts by mass, 19 parts by mass of a mixture of a xylylene diisocyanate phenol adduct having an isocyanate value almost equivalent to the hydroxyl value of the acrylic polyol and a phenol adduct of a trimer of xylylene diisocyanate was mixed with toluene and ethyl acetate. It was dissolved in a mixed solvent of (1/1) to obtain a thermosetting resin composition (H2) having a solid content of 25%.

(Production Example 12) Film for hydraulic transfer (Z
Production of 1) On the surface of a polyvinyl alcohol resin film having a thickness of 35 μm, printing ink A having the following formulation is gravure-printed.
A pattern and a solid having a thickness of g (solid content) / m ² were printed on the third plate.

<Composition of printing ink A, black, brown, white> Polyurethane (Bernock EZL67 manufactured by Dainippon Ink and Chemicals, Inc.
6): 20 parts by mass Pigment (black, brown, white): 10 parts by mass Ethyl acetate / toluene (1/1): 60 parts by mass Additives such as wax: 10 parts by mass

(Production Example 13) Film for hydraulic transfer (Z
Production of 2) An ultraviolet curable resin composition having the following composition was printed on the surface of a polyvinyl alcohol resin film having a thickness of 35 μm by gravure printing so as to have a solid content of 10 g (solid content) / m ² with 4 plates.

(Composition of curable resin composition) UV curable resin composition (H1): 99 parts by mass Irgacure 184: 1 part by mass

(Production Example 14) Film for hydraulic transfer (Z
Production of 3) An ultraviolet curable resin composition having the following composition was printed on the surface of a polyvinyl alcohol resin film having a thickness of 35 μm by gravure printing so as to be 10 g (solid content) / m ² with a solid 4 plate, and then the following: 4g of printing ink of the prescription
The pattern and solid were printed on the 3rd plate so that the thickness was (solid content) / m ² .

(Composition of curable resin composition) UV curable resin composition (H1): 99 parts by mass Irgacure 184: 1 part by mass

(Ink composition (red, blue)) Polyurethane (Polyurethane 2569 manufactured by Arakawa Chemical Co., Ltd.):
20 parts by mass Pigment (red, blue): 10 parts by mass Ethyl acetate / toluene (1/1): 60 parts by mass Additives such as wax: 10 parts by mass

(Production Example 15) Film for hydraulic transfer (Z
Production of 4) A curable resin composition having the following composition was printed on the surface of a polyvinyl alcohol resin film having a thickness of 35 μm by gravure printing so as to be 10 g (solid content) / m ² with a solid 4 plate, and then the following: Prescription printing ink 4g (solid content) / m
^The pattern and solid were printed on the 3rd plate so that the thickness was ² .

(Composition of curable resin composition) UV curable resin composition (H1): 49.5 parts by mass Irgacure 184: 0.5 parts by mass Thermosetting resin composition (H2): 50 parts by mass

(Ink composition (red, blue)) Polyurethane (Polyurethane 2569 manufactured by Arakawa Chemical Co., Ltd.):
20 parts by mass Pigment (red, blue): 10 parts by mass Ethyl acetate / toluene (1/1): 60 parts by mass Additives such as wax: 10 parts by mass

(Example 1) Hydrostatic transfer to transferred material (X1) with primer layer The prepared film for hydraulic transfer (Z1) was floated in a water bath at 30 ° C with the ink side facing upward and left for 2 minutes. rear,
Activator (main component methyl isobutyl ketone) 20 g / m ²
Was sprinkled on the film. After leaving it for another 10 seconds, the transfer target with a primer layer (X1) is pressed from the vertical direction,
I transferred the pattern. After transfer, wash the molded product with water, and at 15
A pattern was decorated on the surface of the molded product by drying for a minute.

(Example 2) Hydraulic Transfer to Transferred Material with Primer Layer (X2) Implementation was carried out except that the transferred material with a primer layer (X1) in Example 1 was replaced with the transferred material with a primer layer (X2). In the same manner as in Example 1, a pattern was decorated on the surface of the molded product of the transfer material with a primer layer (X2).

(Example 3) Hydraulic Transfer to Transferred Material with Primer Layer (X3) Implementation was carried out except that the transferred material with a primer layer (X1) in Example 1 was replaced with the transferred material with a primer layer (X3). In the same manner as in Example 1, a pattern was decorated on the surface of the molded product of the transfer material with a primer layer (X3).

(Example 4) Hydraulic Transfer to Transferred Material with Primer Layer (X4) Implementation was carried out except that the transferred material with a primer layer (X1) in Example 1 was replaced with the transferred material with a primer layer (X4). In the same manner as in Example 1, a pattern was decorated on the surface of the molded product of the transfer material with a primer layer (X4).

(Example 5) Hydrostatic transfer to transferred material (X1) with primer layer The prepared film for hydraulic transfer (Z2) was floated in a water bath at 30 ° C with the ink side facing upward, and left for 2 minutes. , Activator (main component methyl isobutyl ketone) 30 g / m ² was sprinkled on the film. After being left for 10 seconds, the transfer target with a primer layer (X1) was pressed from the vertical direction to transfer the decorative layer. After transfer, wash the molded product with water, and at 15
It was dried for a minute. Next, UV irradiation device (output 80 kW / m,
The sample was passed once at a conveyor speed of 10 m / min) to obtain a glossy cured film on the surface of the molded article of the primer layer-transferred body (X1).

(Example 6) Hydraulic Transfer to Transferred Material with Primer Layer (X3) The transferred material with a primer layer (X1) in Example 5 was replaced with the transferred material with a primer layer (X3). By the same method as in Example 5, a glossy cured coating film was obtained on the surface of the molded article of the transferred material (X3) with the primer layer.

(Example 7) Hydraulic Transfer to Transferred Material with Primer Layer (X4) Except that the transferred material with a primer layer (X1) in Example 5 was replaced with the transferred material with a primer layer (X4). By the same method as in Example 5, a glossy cured film was obtained on the surface of the molded product of the primer layer-transferred body (X4).

(Example 8) Hydrostatic transfer to transferred material (X2) with primer layer The prepared film for hydraulic transfer (Z3) was floated in a water bath at 30 ° C with the ink surface facing upward, and left for 2 minutes. , Activator (main component methyl isobutyl ketone) 30 g / m ² was sprinkled on the film. After standing for another 10 seconds, a molded product (automobile interior part) using the transfer target with a primer layer (X2) was pressed from the vertical direction to transfer the pattern with the curable resin layer. After the transfer, the molded product was washed with water and dried at 80 ° C. for 30 minutes. Next, UV irradiation device (output 80kW / m, 1
The pattern with a glossy cured coating was decorated on the surface of the molded product by passing the sample once through the conveyor (0 m / min conveyor speed).

(Example 9) Hydrostatic transfer to transferred material (X3) with primer layer The prepared film for hydraulic transfer (Z4) was floated in a water bath at 30 ° C with the ink side facing upward, and left for 2 minutes. , Activator (main component methyl isobutyl ketone) 30 g / m ² was sprinkled on the film. After standing for further 10 seconds, a molded product (petroleum fan heater housing) using the transferred material with a primer layer (X3) was pressed from the vertical direction to transfer the pattern with the curable resin layer. After transfer, wash the molded product with water,
It was dried at 90 ° C. for 10 minutes and further dried and cured at 120 ° C. for 30 minutes. Next, UV irradiation device (output 80 kW / m, 10
The pattern with a glossy cured film was decorated on the surface of the molded product by passing the sample once through the conveyor (m / min conveyor speed).

(Example 10) Hydrostatic transfer to transferred material (X5) with primer layer The prepared film for hydraulic transfer (Z1) was floated in a water bath at 30 ° C with the ink surface facing upward, and left for 2 minutes. , Activator (main component methyl isobutyl ketone) 30 g / m ² was sprinkled on the film. After left for 10 seconds, a pattern was transferred from the vertical direction by pressing a molded product (automobile interior part) using the transfer target with a primer layer (X5). The pattern was transferred onto the surface of the molded product by washing the molded product with water and drying at 90 ° C. for 15 minutes.

(Comparative Example 1) Hydrostatic Transfer to Transfer Target (X6) with Primer Layer The prepared film for hydraulic transfer (Z1) was floated in a water bath at 30 ° C with the ink surface facing upward, and left for 2 minutes. , Activator (main component methyl isobutyl ketone) 30 g / m ² was sprinkled on the film. After further standing for 10 seconds, a pattern was transferred by pressing a molded product (automobile interior part) using the transfer target with a primer layer (X6) from the vertical direction. The pattern was transferred onto the surface of the molded product by washing the molded product with water and drying at 90 ° C. for 15 minutes.

(Comparative Example 2) Hydraulic Transfer to Transferred Material with Primer Layer (X7) Comparative Example 1 except that the transferred material with a primer layer (X6) in Comparative Example 1 was replaced with the transferred material with a primer layer (X7). A pattern was transferred to the surface of the molded product by the same method as in Example 1.

The inventors of the present invention have disclosed the Japanese Patent Publication No. 07-037196.
However, since the publication does not describe the manufacturer name and coating composition of the epoxy melamine coating material provided on the transferred material, the same coating material should be tested. I couldn't. Therefore, of the commercially available primers, we searched for paints that have sufficient adhesion to metal materials such as aluminum and galvanized steel plates, and that almost satisfied the baking conditions and layer thickness settings, and then used epoxy resin-based paints that meet these conditions. AR made by Takashi Kubo Paint Co., Ltd.
Using Bt-100, the hydraulic transferability was evaluated for the incomplete curing of Comparative Example 1 and the complete curing of Comparative Example 2. Comparative Example 1 in which transfer is performed by incomplete curing is more preferable than Comparative Example 2 in which complete transfer is performed.
Showed better performance than.

(Evaluation of Transferability) Regarding the transferability of the transfer layer (T) in the three-dimensional molded product of the hydraulic transfer sample, the reproducibility of the film pattern on the three-dimensional molded product was visually evaluated as follows. Then, the transferability was evaluated. ◯: Pattern reproduction area ratio of 98% or more (transferability is good) Δ: Pattern reproduction area ratio of 80% to less than 98% (transferability is slightly good) ×: Pattern reproduction area ratio of less than 80% (transferability is poor)

(Evaluation of Adhesion of Coating Film) A sample obtained by hydraulically transferring each of the hydraulic transfer films onto a flat plate of a transfer material with a primer layer prepared separately was coated according to the cross-cut tape method (JIS K5400). Evaluation of adhesion (1
I got 0 points.

(Adhesion after Hot Water Treatment) A flat plate evaluation sample similar to that used for evaluation of coating film adhesion was treated in hot water (water temperature 98 ° C.) for 30 minutes and then coated. After making 100 crosses of 1 × 1 mm on the film with a cutter and sticking an adhesive tape on the part, the adhesive tape was rapidly peeled off, and the peeled state of the coating film was visually observed to give the following 3 It was evaluated in stages.

[0131] ◯: No peeling is observed Δ: 1 to 30% of the whole peeled off X: 31 to 100% of the whole was peeled off

[0132]

[Table 1]

[0133]

[Table 2]

[0134]

EFFECTS OF THE INVENTION The present invention provides a method for producing a decorative molded article, which has good adhesiveness to the decorative layer and excellent heat resistance even on the transferred material having poor adhesion to the decorative layer such as metal. The first aspect of the present invention does not require a curing step of the primer layer of the transferred material,
And a method for producing a decorative molded article having excellent adhesiveness to a decorative layer, and the second aspect of the present invention is, in addition to the above effects, a step of coating a curable resin layer on a transfer target after hydraulic transfer. A method for producing a decorative molded article that does not require

Continued front page    F term (reference) 3B005 EB01 EB09 EC03 EC22 FA13                       FB13 FC08Y FC20Y FE04                       FG02X GA28                 4J038 CB001 CB051 CB061 CB171                       CD081 CD111 CF021 CG001                       CR011 DA141 DB001 DB031                       DD121 DG001 JC20 PB02                       PC02 PC08                 4J039 AB02 AD01 AD04 AD08 AD09                       AD18 AE04 AE05 AE06 AE08                       EA03 EA04 FA01 FA02 GA05                 4K044 AA01 BA21 BB04 BB15 BC04                       BC09 CA04 CA16

Claims (5)

[Claims] 1. A hydraulic transfer film comprising a support film (F) made of a hydrophilic resin and a hydrophobic transfer layer (T) which is soluble in an organic solvent and is provided on the support film. A method for producing a decorative molded article, which comprises hydraulically transferring a transfer layer to a transfer target covered with a primer layer (P), wherein the transfer layer comprises a decorative layer (T1) comprising a printing ink film or a paint film, A resin composition obtained by subjecting a primer layer (P) to a phosphoric acid esterification reaction of a diglycidyl ether (P1) of (poly) alkylene glycol and a phosphorus compound (P2) having at least one P—OH bond A method for producing a decorative molded article, comprising: 2. A hydraulic transfer film comprising a support film (F) made of a hydrophilic resin and a hydrophobic transfer layer (T) provided on the support film and soluble in an organic solvent. A method for producing a decorative molded article, which comprises hydraulically transferring a transfer layer to a transfer target coated with a primer layer (P), comprising: activating the transfer layer (T) on the support film; A transparent curable resin layer (T2) curable by at least one kind of heating and a decorative layer (T1) composed of a printing ink film or a paint film, wherein the primer layer (P) is diglycidyl of (poly) alkylene glycol. A decorative molding comprising a resin composition obtained by subjecting an ether (P1) and a phosphorus compound (P2) having at least one P-OH bond to a phosphoric acid esterification reaction. Method of manufacturing things. 3. The primer layer (P) comprises a diglycidyl ether of (poly) alkylene glycol (P1) and P-.
Phosphorus compound having at least one OH bond (P2)
And a phosphoric ester at a ratio such that the hydroxyl group of the phosphorus compound (P2) is 0.05 equivalent or more and 1.0 equivalent or less with respect to 1 equivalent of the epoxy group of the diglycidyl ether of (poly) alkylene glycol (P1). The method for producing a decorative molded article according to claim 1, which is obtained by a chemical reaction. 4. The decoration according to claim 3, wherein the diglycidyl ether (P1) of (poly) alkylene glycol contains 80% or more of diglycidyl ether (P1a) of aromatic (poly) alkylene glycol in terms of solid content. Molded article manufacturing method. 5. The method for producing a decorative molded article according to claim 1, wherein the transferred material is made of metal.