Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B44—DECORATIVE ARTS
  • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
  • B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
  • B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
  • B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
  • B44C1/175—Transfer using solvent
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S428/00—Stock material or miscellaneous articles
  • Y10S428/914—Transfer or decalcomania
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
  • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31511—Of epoxy ether
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31855—Of addition polymer from unsaturated monomers
  • Y10T428/31938—Polymer of monoethylenically unsaturated hydrocarbon

Definitions

• the present invention relates to a hydraulic transfer film having a curable resin layer, a method of manufacturing the hydraulic transfer film, and a hydraulic transfer body having the cured resin layer or the cured resin layer and the decorative layer using the hydraulic transfer film. And a method for producing the same.
• the hydraulic transfer method is a method in which a decorative layer rich in design can be applied to a complicated three-dimensional molded product.After the hydraulic transfer, the decorative layer that has been hydraulically transferred is spray-coated with a curable resin as a protective layer. There is a need. For this reason, the production of molded articles by the hydraulic transfer method is costly because the production process is complicated and requires painting equipment in addition to the hydraulic transfer equipment. Molded articles produced by the hydraulic transfer method are expensive. Was limited to goods.
• Japanese Patent Application Laid-Open Publication No. Japanese Patent Publication No. Hei 7-29084 discloses a hydraulic transfer sheet having a resin coating layer which is cured by irradiation of ionizing radiation or heat, and a sheet to be transferred using the hydraulic transfer sheet.
• a method for producing a molded article having a cured resin layer in which after the coating layer is transferred, the coating layer is cured by ionizing radiation or heat.
• the film for hydraulic transfer described in the publication is manufactured even if the curable resin layer is not tacky at room temperature in addition to the fact that the resin used for the curable resin layer is limited. If the hydraulic transfer film is wound up in a wool shape and stored for a long time, blocking occurs between the curable resin layer and the support film or between the decorative layer and the support film. Disclosure of the invention
• the problem to be solved by the present invention is to provide a hydraulic transfer film which has a transfer layer capable of forming a cured resin layer having excellent surface characteristics on a hydraulic transfer body and is less likely to cause blocking. To provide a system.
• Another object of the present invention is to provide a method for producing a hydraulic transfer film capable of transferring a cured resin layer and a clear decorative layer to a transfer object.
• Another object of the present invention is to provide a method for producing a hydraulic transfer body having a cured resin layer free from surface defects due to transfer failure of the transfer layer.
• the present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found the following findings.
• curable resin layer and the decorative layer are formed on the support film and the peelable film, respectively, and the two films are laminated by dry lamination to form a clear pattern on the curable resin layer. Can be formed.
• the present invention has been completed based on the above findings.
• the present invention comprises a support film made of a water-soluble or water-swellable resin, and a hydrophobic transfer layer provided on the support film and dissolvable in an organic solvent, wherein the transfer layer is an active energy ray.
• a hydraulic transfer film having a curable resin layer curable by at least one of irradiation and heating, comprising a release film on the transfer layer, which is peelable at an interface with the transfer layer. Provide hydraulic transfer film.
• a hydrophobic curable resin layer soluble in an organic solvent curable by at least one of active energy ray irradiation and heating is provided on a support film made of a water-soluble or water-swellable resin.
• a film (I) and a film (II) provided with a hydrophobic decorative layer soluble on an organic solvent comprising a printing ink film or a paint film on a peelable film are cured by curing the film (I).
• the resin layer and the film (II) A method for producing a film for hydraulic transfer, characterized in that the film is overlapped so as to face a decorative layer and bonded by dry lamination.
• the present invention provides the hydraulic transfer film, after peeling off the peelable film from the film, floating the support film on water with the support film downward, and vigorously activating the transfer layer with an organic solvent. Transferring a transfer layer to a transfer object, removing a support film, and curing the transfer layer by at least one of active energy ray irradiation and heating in the next step. I do. BEST MODE FOR CARRYING OUT THE INVENTION
• the support film containing a water-soluble or water-swellable resin used for the hydraulic transfer film of the present invention is a film containing a resin that is soluble or swellable with water.
• a support film containing a water-soluble or water-swellable resin examples include, for example, PVA (polyvinyl alcohol), polyvinylpyrrolidone, acetinolecellulose, polyacrylamide, and acrylamide. Films such as cetyl butyl senorellose, gelatin, glue, sodium alginate, hydroxyshethyl cellulose, and carboxymethyl senorellose can be used. Above all, a PVA film generally used as a film for hydraulic transfer is easily dissolved in water, easily available, and suitable for printing a curable resin layer, and is particularly preferable. The thickness of the support film to be used is preferably about 10 to 200 inches.
• the transfer layer is a hydrophobic layer that can be solubilized by an organic solvent.
• the organic solvent is the same as the activator used in general hydraulic transfer.
• a hydrophobic layer that can be solubilized by either butanol or sorbit acetate, or a mixture thereof, can be used.
• the transfer layer has a curable resin layer (hereinafter, abbreviated as a curable resin layer) that is transparent and can be cured by at least one of active energy ray irradiation and heating.
• the transfer layer may have a decorative layer (hereinafter, abbreviated as a decorative layer) formed of a printing ink film or a paint film provided on the curable resin layer together with the curable resin layer.
• the curable resin layer is preferably transparent because the decorative layer of the obtained hydraulic transfer body can exhibit good designability. However, depending on the required characteristics of the hydraulic transfer member, it is basically sufficient if the color and pattern of the decorative layer of the obtained hydraulic transfer member can be seen through, and the curable resin layer does not need to be completely transparent. Including transparent to translucent ones. Also, it may be colored.
• the curable resin layer contains a resin curable by at least one of irradiation with active energy rays and heating, and specific examples thereof include the following (1) to (6).
• a curable resin layer containing an active energy ray-curable resin (1) A curable resin layer containing an active energy ray-curable resin.
• a curable resin layer containing an active energy ray-curable resin and a non-polymerizable thermoplastic resin (2) A curable resin layer containing an active energy ray-curable resin and a non-polymerizable thermoplastic resin.
• a curable resin layer containing a thermosetting resin and a non-polymerizable thermoplastic resin (4) A curable resin layer containing a thermosetting resin and a non-polymerizable thermoplastic resin.
• a curable resin layer containing an active energy ray-curable resin and a thermosetting resin containing an active energy ray-curable resin and a thermosetting resin.
• a curable resin layer containing an active energy ray-curable resin, a thermosetting resin, and a non-polymerizable thermoplastic resin is a curable resin layer containing an active energy ray-curable resin, a thermosetting resin, and a non-polymerizable thermoplastic resin.
• the hydraulic transfer film of the present invention comprises a support film and a peelable film coated or printed with a cured green resin layer thereon, or a support film coated or printed with a curable resin layer thereon and a decoration.
• the curable resin layer is manufactured by laminating a peelable film with a layer coated or printed on it by dry lamination (dry lamination method). From the viewpoint of workability and the difficulty of blocking during film storage, those having no tackiness at room temperature are preferred.
• a support film such as a PVA film generally has low heat resistance, and when laminated at a temperature exceeding 120 ° C, shrinkage and laminar wrinkling of the film are likely to occur.
• Temperature should be 40 ° C or more and 120 ° C or less Preferably, it is more preferably 40 ° C to 100 ° C.
• adheresion initiation temperature refers to a film obtained by coating a resin on a PET film having a thickness of 100 ⁇ m with a bar coater so as to have a solid content of 10 ⁇ . After drying at 10 ° C for 10 minutes to evaporate the solvent, cool it down to room temperature, put it in a hot air dryer, raise the temperature by 5 ° C from room temperature, and confirm by finger touch at each temperature. The lowest temperature at which fingerprints remain.
• the active energy ray-curable resin is an oligomer and a polymer having a polymerizable group or a structural unit curable by an active energy ray in one molecule.
• the active energy rays referred to here are ultraviolet rays and electron beams, and any of oligomers and polymers which are cured by these can be used, and ultraviolet curable resins are particularly preferable.
• Low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, etc. are used as the ultraviolet light source.
• Examples of polymerizable groups and structural units that can be cured by active energy rays include groups having a polymerizable unsaturated double bond such as (meth) acryloyl group, styryl group, butyl ester, bierether, and maleimide group. Structural units are mentioned, and among them, a (meth) atalyloyl group is preferable. Among them, an active energy linear curable oligomer or polymer having three or more (meth) atalyleinole groups in one molecule is preferable. More specifically, active energy ray curing having a mass average molecular weight of three to three or more (meth) acryloyl groups in one molecule of 300 to 10,000, more preferably 300 to 500,000. Oligomer or polymer is preferably used.
• the oligomer or polymer having a (meth) acryloyl group can be used without any problem as long as it is used as a coating resin.
• Specific examples include polyurethane (meth) acrylate and polyester (meth). Acrylate, polyacryl (meth) acrylate, epoxy (meth) acrylate, polyalkylene glycol poly (meth) acrylate, polyether (meth) acrylate, etc., among which polyurethane (meth) acrylate, polyester (meth) Acrylates and epoxy (meth) acrylates are preferably used.
• a polyurethane (meth) acrylate obtained as a reaction product of a polyol, a hydroxyl group-containing (meth) acrylate and a polyisocyanate is preferable because of its excellent surface properties.
• polyols include ethylene diglycol, diethylene glycol, triethylene glycol cornole, polyethylene glycol cornole, polypropylene glycol cornole, dipropylene glycol cornole, 1,2-butanediole, 1,3-butanediol, 1,4-butanediole, Polybutylene glycol, 1,3-pentanediol, neopentinole glycolone, 1, 6 1, hexanediene, sieve, hexadimethanol, bisdimethanol, bisphenol A, hydrogenated bisphenol A And ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, glycerin, and trimethylolpropane.
• hydroxyl group-containing (meth) acrylates include (meth) acrylic acid 2-hydroxyalkyl esters of acrylic acid or methacrylic acid, such as 2-hydroxyhexyl methacrylate and hydroxybutylinole methacrylate.
• a monoester of a polyether polyol such as polypropylene dalicol and an unsaturated carboxylic acid such as acrylic acid or methacrylic acid; a polyether polyol such as polyethylene glycol and a hydroxyl group-containing unsaturated monomer such as 2-hydroxylethyl allylate; Monoesters of maleic anhydride; monoesters or diesters of an acid anhydride group-containing unsaturated compound such as maleic anhydride and itaconic anhydride with dalicols such as ethylene glycol; hydroxy such as vinyl ether vinyl ether Alkyl butyl ethers; adducts of o, —unsaturated carboxylic acids with monoepoxy compounds such as ⁇ -olephine epoxide; glycidyl atalylate or glycidyl methacrylate with acetic acid, propionic acid, ⁇ -tert-butyl benzoic acid, Adducts with monobasic acids such
• polyisocyanate a compound having two or more (divalent) isocyanate groups in one molecule may be used, and a compound having three or more isocyanate groups (trivalent) in one molecule of diisocyanate may be used. Can be.
• diisocyanates include, for example, hexamethylene diisocyanate.
• Aliphatic diisocyanates such as trimethylhexamethylene diisocyanate, dimer diisocyanate, and lysine diisocyanate; hydrogenated xylylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, etc.
• Cycloaliphatic diisocyanates; and aromatic diisocyanates such as tolylene disocyanate and naphthalene disocyanate.
• polyisocyanate having a valency of 3 or more examples include aliphatic triisocyanates such as 2-isocyanatoethyl-2,6-diisocyanatocaproate and 1,3,5-triisocyanatocyclohexane; Aromatic triisocyanates such as 1,3,5-triisocyanatobenzene and 2,4,6-triisocyanatonaphthalene; having a so-called isocyanurate ring structure obtained by cyclizing and trimerizing diisocyanates And polyisocyanates.
• aliphatic triisocyanates such as 2-isocyanatoethyl-2,6-diisocyanatocaproate and 1,3,5-triisocyanatocyclohexane
• Aromatic triisocyanates such as 1,3,5-triisocyanatobenzene and 2,4,6-triisocyanatonaphthalene
• isocyanurate ring structure obtained by cyclizing and trimer
• trivalent or higher polyisocyanate examples include dimers or trimers of divalent or higher polyisocyanates; these divalent or trivalent or higher polyisocyanates, polyhydric alcohols, and low molecular weight polyester resins. Or adducts obtained by reacting water or the like with an excess of isocyanate groups; polyisocyanates having a pellet structure obtained by reacting polyisocyanates with water; and the like.
• a homopolymer of a vinyl monomer having an isocyanate group such as 2-isocyanatoethyl (meth) atalylate, 3- ⁇ f soprodinyl mono-, ct-dimethylbenzyl isocyanate or (meth) acryloyl isocyanate;
• these isocyanate group-containing vinyl monomers can be copolymerized with (meth) acrylic, butyl ester, butyl ether, aromatic vinyl or fluorinated butyl monomers which are copolymerizable therewith.
• Polyurethane (meth) acrylate obtained by reacting an isocyanate group-containing vinyl copolymer with the hydroxyl group-containing (meth) acrylate obtained by polymerization can also be used.
• the ultraviolet curable type having three or more (meth) atalyloyl groups in one molecule obtained as described above and having a mass average molecular weight of from 300 to 10,000, more preferably from 300 to 500,000.
• Polyurethane (meth) acrylate is particularly preferably used as the active energy ray-curable resin.
• the curable resin layer containing these active energy ray-curable resins may contain a conventional photopolymerization initiator or photosensitizer as necessary.
• Photopolymerization initiators include acetophenone-based compounds such as jetethoxyacetophenone and 1-hydroxycyclohexynole-phenylene ketone; and benzine and benzoinisopropyl ether.
• Benzophenone-based compounds such as 2,4-dimethylthioxanthone; thioxanthone-based compounds such as 2,4-dimethylthioxanthone; 4,4′-dimethylaminobenzo-phenone-based amino-benzophenone-based compounds; polyether-based maleimide carboxylic acid ester compounds; These can be used in combination.
• the amount of the photopolymerization initiator to be used is generally 0.1 to 15% by mass, preferably 0.5 to 8% by mass, based on the active energy ray-curable resin used.
• the photosensitizer include amines such as triethanolanolamine and ethyl 4-dimethylaminobenzoate.
• onium salts such as benzylsulfonium salt, benzylpyridinium salt, arylsulfonium salt and the like are known as light-powered thione initiators, and these initiators can be used. It can be used in combination with the above photopolymerization initiator.
• the curable resin layer containing the active energy ray-curable resin and the non-polymerizable thermoplastic resin contains the above-described active energy ray-curable resin and the non-polymerizable thermoplastic resin.
• the use of a non-polymerizable thermoplastic resin in combination with an active energy ray-curable resin reduces the adhesiveness of the curable resin layer, improves the glass transition temperature (Tg), and reduces the cohesive fracture strength of the curable resin layer. It is extremely effective for improvement. However, if the amount of the thermoplastic resin contained in the curable resin layer is large, the curing reaction of the curable resin is inhibited, so that the thermoplastic resin is contained in 100 parts by mass of the total amount of the curable resin layer. It is preferable to add in an amount not exceeding 70 parts by mass.
• Non-polymerizable thermoplastic resin is compatible with the active energy ray-curable resin used.
• Specific examples thereof include polymetaarylate, polystyrene, polyvinyl chloride, polyvinyl chloride vinylidene, polyvinyl acetate, and polyester. These may be homopolymers or copolymers of a plurality of monomers.
• polystyrene and polymethacrylate are preferable because they have a high Tg and are suitable for reducing the tackiness of the curable resin layer.
• Particularly, polymethaacrylate having polymethyl methacrylate as a main component is preferable. It is preferable because it has excellent transparency, solvent resistance and scratch resistance.
• the molecular weight and Tg of the thermoplastic resin have a great influence on the ability to form a coating film.
• the mass average molecular weight of the thermoplastic resin is preferably 3,000,000 to 400,000, It is more preferably 10,000 to 200,000, and the Tg is preferably 35 ° C to 200 ° C, more preferably 35 ° C to 150 ° C.
• the thermoplastic resin preferably has a mass average molecular weight of 100,000 or more.
• the curable resin layer containing the active energy ray-curable resin and the non-polymerizable thermoplastic resin among these, a mass average having three or more (meth) ataliroynole groups in one molecule.
• An active energy ray-curable resin having a molecular weight of from 300 to 10,000, more preferably from 300 to 500, and a T g compatible with the active energy ray-curable resin of from 35 ° C. to 20 ° C.
• a hard resin containing a non-polymerizable thermoplastic resin having a weight average molecular weight of 0 ° C, preferably 35 ° C to 150 ° C, and a weight average molecular weight of 30000 to 400000, preferably 10,000 to 200,000.
• a plasticizable resin layer is preferred.
• the active energy ray-curable resin is a polyurethane (meth) acrylate having three or more (meth) acryloyl groups in one molecule
• the non-polymerizable thermoplastic resin is polymethacrylate, particularly polymethylmethacrylate. Curable resin layers that are acrylates are particularly preferred.
• thermosetting resin is a compound in which a molecule having a functional group that polymerizes by the action of heat or a catalyst in the molecule, or a thermosetting compound serving as a main component and a thermoreactive compound serving as a curing agent are blended.
• functional groups that are polymerized by the action of heat or a catalyst include N-methylol group, N-alkoxymethyl group, epoxy group, and methylol Group, acid anhydride, carbon-carbon double bond and the like.
• Curable resins that have a carbon-carbon double bond in the molecule and can undergo a cross-linking reaction by polymerization can use the same kind of curable resin as the active energy ray-curable resin. It can be used as a thermosetting resin by combining it with a thermal polymerization initiator that generates water. As the thermal polymerization initiator at this time, an ordinary thermal polymerization initiator such as benzoyl peroxide and azobisisobutyronitrile is used.
• the combination of the main agent and the curing agent include, for example, a main resin having a hydroxyl group or an amino group and an isocyanate as a curing agent; a main resin having a hydroxyl group or a carboxyl group and an N-methylol or a N-methylol as a curing agent.
• Amino resins such as alkoxymethylated melamine and benzoguanamine; base resins having epoxy groups and hydroxyl groups; and acid anhydrides such as phthalic anhydride as curing agents; carboxyl groups, carbon-carbon double bonds, nitrile groups, and epoxy groups.
• a phenol resin can be used as the main resin and the curing agent, and a main resin having a carboxyl group or an amino group and an epoxy group-containing compound can be used as the curing agent.
• thermosetting resins the curing reaction gradually proceeds during storage even at room temperature. If the curing reaction proceeds during the preservation period, the activation of the transfer layer by the organic solvent is not sufficiently performed, which causes a transfer failure. For this reason, among the thermosetting resins, a system using a polyol as a main component and a block isocyanate as a curing agent is preferable.
• the block isocyanate those in which the isocyanate group is protected with a general-purpose blocking agent can be used, and these conventional blocking agents include phenol, cresol, aromatic secondary amine, tertiary alcohol, ratatum, and oxime. And the like.
• the block isocyanate may be selected from those having a suitable block group desorption temperature in accordance with the heat resistance of the decorative layer and the heat resistance of the transfer object.
• polystyrene examples include acrylic polyol, poly (p-hydroxystyrene), polyester polyol, and polyethylene vinyl alcohol copolymer.
• acrylic polyol is preferable, and among them, the mass average molecular weight is preferably from 3,000 to 1,000.
• Preferred is 100,000 acrylyl polyol, more preferably 10,000 to 70,000 acrylyl polyol.
• the thermosetting resin also needs printability or coatability, the molecular weight of the resin before curing is preferably higher, and the weight average molecular weight is preferably 100,000 to 100,000. Preferably it is 30,000 to 30,000.
• a polyol having a weight average molecular weight of 30,000 to 100,000, more preferably 10,000 to 70,000 (particularly preferably an acrylic polyol) is used as a main component, and a block isocyanate is used as a curing agent. What is included as is preferably used.
• the curable resin layer containing the thermosetting resin and the non-polymerizable thermoplastic resin includes the thermosetting resin described in (3) and the non-polymerizable thermoplastic resin described in (2). is there. ⁇
• thermosetting resin used is the same as the thermosetting resin described in (3), and the preferred thermosetting resins are also a block isocyanate and a polyol as in (3), and particularly, the polyol is acrylyl polyol. Among them, those having a mass average molecular weight of 30,000 to 100,000, more preferably 10,000 to 70,000.
• the amount of the non-polymerizable thermoplastic resin used in combination may be small since the polyol generally has a film forming ability.
• the non-polymerizable thermoplastic resin to be used must be compatible with the thermosetting resin to be used.
• block isocyanate and polyol are used as the thermosetting resin, the non-polymerizable thermoplastic resin soluble in the polyol is used. Is preferred.
• the non-polymerizable thermoplastic resin has a Tg of 35 ° C to 200 ° C, more preferably a Tg of 35 ° C to 150 ° C, and a weight average molecular weight of 300 ° C. Up to 400,000 non-polymerizable thermoplastic resins are preferably used, and among them, polymethacrylate, especially polymethyl methacrylate, is preferable.
• Curable resin layer containing active energy ray-curable resin and thermosetting resin The curable resin layers containing active energy ray-curable resin and thermosetting resin are described in (1), respectively.
• An active energy ray-curable resin and the thermosetting resin described in (3) can be used.
• it includes a (meth) acrylate having three or more (meth) acryloyl groups in one molecule, a block isocyanate and a polyol.
• active energy ray-curable resin described in (1) and the thermosetting resin described in (3) each of which contains a preferred resin.
• Curable resin layer containing active energy ray-curable resin, thermosetting resin and non-polymerizable thermoplastic resin
• the curable resin layer containing the active energy ray-curable resin, the thermosetting resin, and the non-polymerizable thermoplastic resin comprises the active energy ray-curable resin described in (1) and the heat-curable resin described in (3).
• the above-mentioned curable resin layer has a greater surface protection effect of the obtained hydraulic transfer body as the dried film thickness is larger, and also has an excellent gloss of the molded article due to a large effect of absorbing irregularities of the decoration layer. It is preferable because it can be performed.
• the dry film thickness is too large, the activation (solubilization) of the curable resin layer by the organic solvent tends to be insufficient. Therefore, in order to sufficiently activate the curable resin layer by the organic solvent, and to satisfy the function as the protective layer and the effect of absorbing the unevenness of the decorative layer, the dry thickness of the curable resin layer should be 3 times. M200 m, more preferably 10 ⁇ 70 ⁇ . Next, the decorative layer will be described.
• the printing ink or paint used for forming the decorative layer of the present invention is a printing ink or paint that can be printed or applied to a peelable film, has a low peeling force with the peelable film, and is activated by an organic solvent. It is preferable that sufficient flexibility is obtained when the transfer layer is transferred to the transfer object by being subjected to the printing, and a Dalavia printing ink is particularly preferable. Further, a colored layer having no pattern can be formed by coating. Varnish resins used in 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 mouth lid). , Vie 2003/008233
• Thermoplastic resins such as 13-denidenfluorate), ethylene-butyl acetate resin, polyolefin resin, chlorinated olefin resin, ethylene-acrylic resin, petroleum resin, and cellulose derivative resin are preferably used.
• the coloring agent in the decorative layer is preferably a pigment, and any of an inorganic pigment and an organic pigment can be used. It is also possible to use a metallic luster ink containing pigment as a paste of metal cutting particles or metal flakes obtained from a vapor-deposited metal film. As these metals, aluminum, gold, silver, brass, titanium, chromium, nickel, nickel chrome and stainless steel are preferably used. These metal flakes may be surface-treated with a cellulose derivative such as epoxy resin, polyurethane, acrylic resin, or nitrocellulose to improve dispersibility, antioxidation, and strength of the ink layer (decorative layer).
• a cellulose derivative such as epoxy resin, polyurethane, acrylic resin, or nitrocellulose to improve dispersibility, antioxidation, and strength of the ink layer (decorative layer).
• the decorative layer in addition to gravure printing, offset printing, screen printing, ink jet printing, thermal transfer printing, and the like can be used.
• a dry film of the decoration layer, inkjet printing, thermal transfer printing, or the like can be used.
• the dry thickness of the decorative layer is preferably from 0.5 to 15 ⁇ , more preferably from 1 to 7 ⁇ .
• Various conventional additives such as light stabilizers and ultraviolet absorbers may be added.
• the peelable film of the present invention at the time of hydraulic transfer, the peelable film needs to be peeled from the transfer layer including the curable resin layer or the cured resin layer and the decorative layer, and the peelable film is It is necessary that it can be peeled off at the transfer layer interface. Accordingly, the release film used for the hydraulic transfer film preferably has a low release force at the interface of the transfer layer.
• the hydraulic transfer film of the present invention is obtained by coating a support film coated or printed with a curable resin layer thereon and a peelable film, or by coating a curable resin layer thereon.
• the processed or printed support film and the peelable film coated or printed with the decorative layer are coated by dry lamination (dry lamination method). Since the decorative film is coated or printed, the decorative film is also applied or printed, and the decorative layer is fixed on the peelable film with a peeling force that does not cause the decorative layer to peel off during work such as film feeding or handling. Need to be. Therefore, the peeling force of the peelable film at the interface with the transfer layer is measured, and a preferable combination of the peelable film and the transfer layer is selected.
• the peeling force (F1) between the peelable film and the transfer layer must be at least as high as the peeling test specified in JIS K6854, because the peeling force between the peelable film and the transfer layer must be equal to or greater than the peeling force at which the decorative layer does not peel off during work or handling such as film feeding. It is preferable that the peeling force measured at 0.7 g / cm or more. If the peeling force (F 1) is too large, the peeling force (F 1) is 60 gZcm, since a streak pattern is formed on the transfer layer surface when the peelable film is peeled from the transfer layer. It is preferably less than. Therefore, the peeling force (F1) between the peelable film and the transfer layer is preferably from 0.7 gZcm to 60 g / cm, and more preferably from 3 gZcm to 40 g / cm.
• peelable film specifically, a film made of a material such as polypropylene, polyethylene, polyester, nylon, or polyvinyl chloride can be used, and a film having a thickness of 20 ⁇ to 250 ⁇ is preferable.
• the peeling force of the peelable film at the interface between the peelable film and the transfer layer to be used may be measured to select a preferable combination of the peelable film and the transfer layer. Further, if necessary, the peeling force (F1) can be further reduced by further performing a surface treatment on the peelable film.
• the method for producing a film for hydraulic transfer according to the present invention is characterized in that a hydrophobic film which can be dissolved in an organic solvent curable by at least one of active energy ray irradiation and heating on a support film containing a water-soluble or water-swellable resin.
• the curable resin layer of (I) and the decorative layer of the film (II) are superposed so as to face each other and bonded by dry lamination (dry lamination method).
• the production of the hydraulic transfer film of the present invention can be performed using a dry laminator. preferable. That is, the support film is mounted on one of the rolls (first feeding roll) of the dry laminator, and the decoration of the pattern is applied to the peeling film in advance on the other feeding roll (second feeding roll). Mount the film (II) with the printed layer.
• the curable resin layer of the film (I) and the decorative layer of the film (II) unwound from the second unwinding roll are overlapped so as to face each other, bonded by a heat-pressing roll, and wound around a take-up roll.
• the film for hydraulic transfer of the present invention is manufactured.
• the production of a film ( ⁇ ) having a decorative layer on a peelable film may be performed by coating, but is preferably performed by printing. In particular, when a pattern is printed, gravure printing, flexo printing, offset printing or silk printing is preferable. . After applying or printing a decorative layer on the peelable film, it is dried to obtain a film (II).
• a support such as a PVA film is used.
• Low heat resistance of film 130.
• the above-described curable resin is used until the production of the film (I) in which the curable resin layer is formed on the support film. This is the same as the production of a hydraulic transfer film having a layer and a decorative layer.
• the curable resin layer of the produced film (I) and the second operation 3 008233 is used until the production of the film (I) in which the curable resin layer is formed on the support film. This is the same as the production of a hydraulic transfer film having a layer and a decorative layer.
• the obtained hydraulic transfer film of the present invention is wound on a roll, covered with light-shielding paper, and stored in a warehouse or other place so that the curing reaction does not proceed unnecessarily, and the film is blocked during storage. It does not generate water, it is good to be fed from a roll at the time of hydraulic transfer, and it is capable of clear transfer of the decorative layer with hydraulic pressure, and has sufficient marketability unless it is actively exposed to ultraviolet rays or sunlight. It has.
• the hydraulic transfer film of the present invention is prepared by peeling the release film, floating the support film on water with the support film facing down, and curing the resin layer or the decorative layer with an organic solvent. Activate the transfer layer consisting of the resin and the curable resin layer, transfer the transfer layer to the transfer object, remove the support film, and then cure the curable resin layer of the transfer layer by at least one of active energy ray irradiation and heating. It is a way to make it.
• hydraulic transfer can be performed by the same method as the conventional hydraulic transfer of the conventional hydraulic transfer film.
• the outline of the method of manufacturing a hydraulic transfer body using these hydraulic transfer films is as follows.
• the curable resin layer or the transfer layer composed of the curable resin layer and the decoration layer is activated.
• the activation of the transfer layer with the organic solvent may be performed before floating the film on water.
• the support film is removed from the transfer object discharged from the water, and the curable resin layer of the transfer layer transferred to the transfer object is cured by at least one of active energy ray irradiation and heating, and the cured resin is cured.
• the curable resin layer of the transfer layer transferred to the transfer object is cured by at least one of active energy ray irradiation and heating, and the cured resin is cured.
• the transfer layer consisting of the curable resin layer or the cured individual resin layer and the decorative layer needs to be activated with an organic solvent to be sprayed before being hydraulically transferred and sufficiently solubilized or softened. is there.
• activation means that the resin constituting the transfer layer is solubilized without completely dissolving it by applying or spraying an organic solvent on the transfer layer. This means that the hydrophobic transfer layer is easily peeled off from the substrate, and that the flexibility of the transfer layer is improved so that the followability of the transfer layer to the three-dimensional curved surface and the adhesion of the transfer layer are improved.
• This activation may be performed to such an extent that when the transfer layer is transferred from the hydraulic transfer film to the object to be transferred, these transfer layers are softened and can sufficiently follow the three-dimensional curved surface of the object to be transferred.
• the water in the water tank in the hydraulic transfer acts as a hydraulic medium for bringing the curable resin layer or the curable resin layer of the hydraulic transfer film and the decorative layer into close contact with the three-dimensional curved surface of the transfer object when transferring the transfer layer.
• it swells or dissolves the support film.
• water such as tap water, distilled water, or ion-exchanged water may be used, and depending on the support film used, inorganic salts such as boric acid may be added to the water. 10% or less, or 50% or less of alcohols.
• the activator used in the present invention is an organic solvent that solubilizes the curable resin layer or the curable resin layer and the decoration layer.
• the activator used in the present invention can be the same as the activator used for general hydraulic transfer. Specifically, toluene, xylene, butyl sorbitol, butyl carbitol acetate, carbitol Tall, carbitol acetate, cellosonolev acetate, methyl isobutyl ketone, ethyl benzoate, isobutyl acetate, isobutynole alcohol, isopropinole alcohol, n-butanol, sorbit acetate, and mixtures thereof.
• a slight resin component may be contained in the activator.
• a structure similar to an ink binder such as polyurethane, acrylic resin, or epoxy resin, the adhesion may be improved.
• the support film is removed by dissolving or peeling with water, and then dried. Removal of the support film from the transfer object The support film is dissolved or peeled off with a water flow in the same manner as in the hydraulic transfer method.
• the hydraulic transfer member is dried and then irradiated with active energy rays to cure the curable resin layer. If the curable luster layer contains a thermosetting resin, the curable resin layer can be cured together with drying.
• the curable resin layer is uncured at the stage of transfer, it is easy to activate the curable resin layer of the film for hydraulic transfer. Further, at least one of irradiation with active energy rays and heating after transfer is performed. It cures depending on the species, and exhibits sufficient surface protection performance and gloss.
• a curable resin layer and a decorative layer are sufficiently adhered to the surface of the transfer object, and a primer layer is provided on the surface of the transfer object as needed.
• a commonly used resin for the primer layer can be used without particular limitation, and examples thereof include a urethane resin, an epoxy resin, and an acrylic resin.
• no primer treatment is required for a transfer target made of a resin component having high solvent absorption such as ABS resin and SBS rubber having good adhesion.
• the material of the transferred object may be any of metal, plastic, wood, pulp mold, glass, etc., as long as it is waterproof as long as it is submerged by applying a waterproof treatment so that its shape does not collapse even if submerged. There is no particular limitation.
• hydraulic transfer member to which the present invention can be applied include: home appliances such as televisions, videos, air conditioners, radio cassettes, mobile phones, refrigerators; OA equipment such as personal computers, faxes and printers; fan heaters and cameras Household parts of household products such as table; Furniture materials such as table, chest, and pillars; Building materials such as bathtub, system kitchen, doors, window frames, etc .; miscellaneous goods such as calculators and electronic organizers; Exterior and interior parts such as outer plates, wheel caps, ski carriers, and carrier bags for automobiles; sports equipment such as golf clubs, skis, snowboards, helmets, and goggles; stereoscopic images for advertising, signboards, monuments, etc.
• home appliances such as televisions, videos, air conditioners, radio cassettes, mobile phones, refrigerators
• OA equipment such as personal computers, faxes and printers
• fan heaters and cameras Household parts of household products such as table; Furniture materials such as table, chest, and pillars; Building materials such as bathtub, system kitchen, doors,
• the resin was applied to a PET film having a thickness of 100 m with a bar coater at a solid content film thickness of 10 ⁇ . After drying the coated film at 70 ° C for 10 minutes to evaporate the solvent, cool it down to room temperature, put it in a hot air dryer, raise it from room temperature by 5 ° C, and confirm by touch at each temperature Then, the lowest temperature at which a fingerprint mark remains was defined as the adhesion start temperature. (Judgment of winding property of hydraulic transfer film)
• a 1 Om hydraulic transfer film was stored in a rolled state in a constant temperature room at 20 ° C and 60% RH. Three months later, the film was pulled out and evaluated for film blocking. A sample without blocking was marked with a ⁇ , and a film with a remarkably increased film pull-out force due to blocking was marked with X. (Method of measuring adhesion of hydraulic transfer body)
• the scratch resistance of the hydraulic transfer member was measured in accordance with JIS K5401 “Pencil drawing tester for coating film”.
• the length of the core used was 3 mm, the angle to the coating surface was 45 degrees, the load was 1 kg, the drawing speed was 0.5 mmZ, the drawing length was 3 mm, and the pencil used was Mitsubishi Mitsubishi.
• the 60-degree specular gloss (JIS K5400) of the hydraulic transfer member was measured. (Method of measuring scratch resistance of hydraulic transfer body)
• a rubbing tester is used for rubbing a hydraulic transfer body that has been hydraulically transferred to a primed galvanized steel plate (flat plate: 100 mm x 100 mm x 0.5 mm) or an ABS resin plate (flat plate: 100 mm x 100 mm x 3 mm). 800 g) to evaluate the surface gloss retention after 100 dry wipings.
• the hydraulic transfer body is heated and held in hot water (water temperature of 98 ° C) for 30 minutes, and then 100 cuts of 1 X lmm are cut on the transfer layer with a cutter in accordance with the checkerboard tape method (JIS K5400). After applying an adhesive tape to the portion, the adhesive tape was rapidly peeled off, and the peeling state of the coating film was visually observed to evaluate the ink adhesion on a scale of 10 out of 10 points. (Measurement method of gloss retention after hydrothermal treatment of hydraulic transfer body)
• Arakawa Chemical Beam Set 575 (6-functional polyurethane acrylate, weight average molecular weight 1000) 60 parts, Dainippon Ink & Chemicals DP A-720 (ester acrylate, molecular weight 410) 10 parts and Rohm and Haas Acrylic resin paraloid B-72 (Tg 40 ° C, weight average molecular weight 105,000) 40 parts and a mixed solvent of ethyl acetate and toluene (mixing ratio 1 Z 1) with a curability of 45% solids. Fat A2 was produced. The adhesion start temperature of the resin component was 40 ° C.
• Production Example 1 'average 40 parts of 6-functional urethane acrylate (UA1), 30 parts of Arakawa Chemical Co., Ltd. beam set 575 (6-functional polyurethane acrylate) and Toyobo Co., Ltd. Pylon 500 (polyester, Tg 40 °) C, a curable resin A3 having a solid content of 50% was produced using 30 parts of a mass average molecular weight of 25,000) and a mixed solvent of ethyl acetate and toluene (mixing ratio: 1: 1). The adhesion start temperature of the resin component was 40 ° C.
• Acryl polyol (a) obtained by copolymerizing hydroxyshethyl methacrylate, methyl methacrylate, ethyl acrylate, butyl acrylate and styrene at a molar ratio of 20: 30: 15: 15: 20 (mass average molecular weight (25,000) 81 parts, with respect to the hydroxyl value of the acrylic polyol 1.1 times equivalent of the hexamethylene diisocyanate adduct and the trimer of hexamethylene diisocyanate having an isocyanate value of 1 equivalent.
• Acrylic polyol (b) obtained by copolymerizing hydroxyshethyl methacrylate, methyl methacrylate, ethyl acrylate, butyl acrylate, butyl fumarate and styrene at a molar ratio of 20: 30: 20: 10: 10: 10 (Amount of 20,000) For 50 parts, for hydroxyl value of acrylic polyol 1.
• PP film non-stretched 50- ⁇ m-thick polypropylene film manufactured by Toyobo Co., Ltd. was used as the release film, and urethane ink (trade name: Univia A) was used for the film on a gravure four-color printing machine.
• Decorative film (II) B1 was produced by printing a wood pattern with a thickness of 3 ⁇ .
• a 50 ⁇ m-thick stretched polypropylene film (hereinafter abbreviated as “ ⁇ ⁇ ”) manufactured by Toyobo Co., Ltd. was used as the peelable film.
• the decorative film ( ⁇ ) B2 was manufactured by printing a 4 m abstract pattern. (Ink composition, black, brown, white)
• Polyurethane (Polyurethane 2569 manufactured by Arakawa Chemical Co., Ltd.) 20 parts
• the PP film was peeled off from the hydraulic transfer film C1.
• the peeling force between the curable resin layer and the OPP film was sufficiently low at 25 gcm, and no wrinkles or streaks remained in the curable resin layer.
• the curable resin A1 of Production Example 1 was applied to a 30 ⁇ m thick PVA film manufactured by Aicello Chemical Co., Ltd. using a lip coater to a solid content of 20 inches per month, and then dried at 60 for 2 minutes.
• a film (I) The curable resin layer of the film (I) and the ink layer (decorative layer) of the decorative film (II) B1 were laminated at 60 ° C with facing each other.
• the laminated film was wound up as it was to produce a hydraulic transfer film C2.
• Hot water at 30 ° C was placed in a water tank, and the PP film was peeled off, and the hydraulic transfer film C7 was floated on the water surface with the ink layer (decorative layer) side up.
• Activator xylene: MI BK: butyl acetate: isopropanol, 5: 2: 2: 1
• the oil fan heater housing made of steel plate with primer was inserted from the ink surface to the water surface, and water pressure was applied. Transcribed. Heating was performed at 120 ° C for 30 minutes to dry the activator and cure the thermosetting resin layer.
• UV irradiation was performed twice at an irradiation amount of 20 OmjZcm 2 to completely cure the ultraviolet curable resin.
• a decorative hydraulic transfer member provided with a cured resin layer having excellent surface gloss and a print layer was obtained.
• Example 8 Example 9
• Example 10 Example 11 1 For hydraulic transfer
• a curable resin A2 was applied to a 30 ⁇ thick PVA film manufactured by Aicello Chemical Co., Ltd. using a lip ter to a solid content of 20 ⁇ . After drying at 60 ° C for 2 minutes, the film was wound up without laminating a release film, but the film was blocked and hydraulic transfer could not be performed. 200
• the curable resin A 6 was coated to a solid content of thickness 2 0 lip coater P VA film Aicello Chemical Co., Ltd. having a thickness of 3 0. After drying at 60 ° C for 2 minutes, a film (I) was produced and wound up. Without laminating the release film, this film was stored at a temperature of 20 ° (60% humidity for 1 month.) The cured resin layer and the PVA film blocked, and when the film was pulled out, the cured resin layer became PVA. (Comparative Example 3) Production of hydraulic transfer film with UV-curable resin layer
• a curable resin A2 was applied to a 30 // in thick PVA film manufactured by Aicello Chemical Co. using a lip coater so as to have a solid content of 20 m .
• the film was dried at 60 ° C for 2 minutes to produce a film (I).
• an attempt was made to print a printing layer on the curable resin layer of the film (I) by gravure printing, but the wound film was blocked and could not be marked.
• the hydraulic transfer film having the curable resin layer without the peelable film has poor winding property of the produced film, difficulty in printing the decorative layer, or The wound film caused blocking after storage for one month.
• the hydraulic transfer film of the present invention has good winding and unwinding properties of the film, and can be rolled up in a roll and stored for 3 months or more. No blocking occurred, and the release film was easily peeled off.
• the hydraulic transfer member obtained by transferring the curable resin layer or the curable resin layer and the decoration layer using the hydraulic transfer film of the present invention has a surface gloss, abrasion resistance, and adhesion after hot water treatment. And the glossiness was both excellent. Industrial applicability
• the film for hydraulic transfer according to the present invention is provided with a peelable film on the curable resin layer or the decorative layer, thereby forming a film between the curable resin layer or the decorative layer and the support film. Since it can prevent locking, it has excellent roll winding properties and storage stability.
• the method for producing a film for hydraulic transfer of the present invention is characterized in that the curable resin layer formed on the support film and the decorative layer formed on the peelable film are bonded by dry lamination.
• a clear decorative layer can be formed on the substrate.
• the method for producing a hydraulic transfer body of the present invention uses a pressure transfer film having good film payout properties and no occurrence of transfer failure, a cured resin layer having excellent surface characteristics and a clear picture pattern can be obtained. Can be manufactured.
• the hydraulic transfer film of the present invention enables the manufacture of a hydraulic transfer body having excellent surface properties such as solvent resistance, chemical resistance, and surface hardness and design properties, and is required to have design properties and surface strength. It is particularly useful in the production of decorative hydraulic transfer media for home appliances, building components, automotive components and the like.

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• 2002
  • 2002-07-01 JP JP2002191992A patent/JP3691030B2/ja not_active Expired - Lifetime
• 2003
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