CN101018677B - Coating composition for protecting pattern layer for hydraulic transfer, decorated formed article and method for production thereof - Google Patents
Coating composition for protecting pattern layer for hydraulic transfer, decorated formed article and method for production thereof Download PDFInfo
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- CN101018677B CN101018677B CN2005800309156A CN200580030915A CN101018677B CN 101018677 B CN101018677 B CN 101018677B CN 2005800309156 A CN2005800309156 A CN 2005800309156A CN 200580030915 A CN200580030915 A CN 200580030915A CN 101018677 B CN101018677 B CN 101018677B
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- China
- Prior art keywords
- polypropylene
- weight
- protection
- coating composition
- transfer
- Prior art date
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Images
Classifications
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
- C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/26—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment
- C09D123/28—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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Abstract
A coating composition for protecting a pattern layer for hydraulic transfer which uses, onto a transfer formed product obtained by the hydraulic transfer of a pattern layer having been formed through printing or application on a film base material being soluble in or swelling with water onto a polypropylene based resin formed article, a protective coating having adhesiveness to both of said polypropylene based resin formed article and said pattern layer, wherein use is made of a protective coating film obtained by curing a hydroxyl group containing resin composition (P) prepared by subjectinga resin component (A) comprising a chlorinated polypropylene based resin and a poly-ol component (B) comprising an acryl polyol selected among cyclohexyl methacrylate, t-butyl methacrylate, styrene and hydroxyethyl methacrylate to a graft polymerization, with a polyisocyanate based curing agent (Q).
Description
Technical field
The decorated formed article and the manufacture method thereof that the present invention relates to a kind of coating composition, utilize this coating composition to protect; described coating composition is on the polypropylene-based resin molding; the patterned layer that to utilize printing or coating and form on the film substrate material of water dissolution or swelling is carried out hydraulic-transfer; the transfer printing molding that relatively obtains thus produces the protection that described polypropylene-based resin molding and described patterned layer both sides are had a good adaptation and films.
The application advocate based on September 28th, 2004 to the right of priority that the spy of Japanese Patent office application is willing to 2004-282562 number, here cite its content.
Background technology
Recently, in order on the resin forming product with complex surfaces shape etc., to decorate various patterns such as ripple and grid decorative pattern, to use method of hydraulic transfer is arranged.In this method, the transfer film that will use water insoluble ingredients to be printed with the patterned layer (being also referred to as transfer printing layer) of regulation on the film of water-soluble or water-swellable floats on the water surface in the transfer groove, load the resin forming product submerged thereon, thus in the surface transfer patterned layer of resin forming product.
Use resin forming products such as ABS resin, acrylic resin, polycarbonate resin as resin forming product, but the bonding force of the relative resin forming product of patterned layer of transfer printing is insufficient, give aspect weather resistance such as chemical resistant properties such as water tolerance and alkali resistance and thermotolerance, weather proofing, wear resistance insufficient.Therefore, the protection of implementing on the patterned layer to be used to protect is filmed.Utilize this protection to film and not only make it satisfy above-mentioned many performances of enumerating, and can give patterned layer, further keep design with transparent feel and sense of fullness.
But, in recent years, with regard to the internal and external ornament accessory of automobile, consider from recirculation and cost aspect, use the polypropylene-based resin molding usually.The existing protection problem that exists of filming is; it uses acrylic acid or the like or the polyurethanes coating that ABS resin, acrylic resin, polycarbonate resin etc. are had adaptation; but its driving fit very low to polarity and the polypropylene-based resin that is difficult to adhere to is insufficient, descends as time passes or because of heat, light, temperature etc. cause its closing force.
The spy opens the 2001-232998 communique and discloses following method: will have utilize the promoting agent sensitization the transfer film of printed pattern swim on the liquid level; with respect to above-mentioned transfer film; under above-mentioned liquid level, flood transfer printing body; utilize the printed pattern on the above-mentioned transfer film of hydraulic-transfer; in transfer printing form protection on the above-mentioned transfer printing body of above-mentioned printed pattern and film; in this hydraulic-transfer method; the promoting agent of above-mentioned printed patterns sensitization is comprised give hydrophilic composition and the resin glue that forms chlorinatedpolyolefins; filming on above-mentioned transfer printing body by the centre forms above-mentioned protection and films, described centre film to above-mentioned transfer printing body and on printed patterns and the above-mentioned protection both sides that film have adaptation (with reference to patent documentation 1).
But, in this technology, use contains the promoting agent of resin glue with after the transfer film sensitization, carry out transfer printing, in transfer printing film in the middle of forming on the transfer printing body of printed pattern, described centre film contain by Tg be more than 50 ℃ contain unsaturated group vinyl monomer 5～95 weight %, Tg less than 50 ℃ contain below the unsaturated group vinyl monomer 50 weight %, graft copolymer that chlorinated polypropylene 1～50 weight % constitutes is as resin glue.Form thereon and contain the protection that acrylic polyol resin that the OH valency is 10～200mg-KOH/g and/or OH valency be the polyester polyol resin of 10～400mg-KOH/g and film.Thus, above-mentioned technology must be filmed to form to protect and be filmed by the centre.
[patent documentation 1] spy open the 2001-232998 communique (claim 1～7, embodiment)
Summary of the invention
The problem to be solved in the present invention is; the article that a kind of coating composition are provided and use its protection printing film; its coating composition can be given transparency and sense of fullness for giving the design of wanting originally on the basis that solves aforesaid problems.
The inventor has carried out research without single devotion; found that; the acrylic polyol composition that makes the Chlorinated Polypropylene III resinoid and be made of cyclohexyl methacrylate, methacrylic tert-butyl acrylate and hydroxyethyl methylacrylate carries out graft polymerization; obtain the hydroxy-containing resin composition; making this hydroxy-containing resin composition solidify to form protection with polymeric polyisocyanate class solidifying agent films; film by using this protection; the protection that can obtain polypropylene-based resin molding and patterned layer both sides are had good adaptation is filmed, so that finished the present invention.
That is; the 1st mode of the present invention provides a kind of pattern layer for hydraulic transfer protection coating composition; it is on polypropylene-based resin molding (3); the patterned layer (4) that to upward utilize printing or coating at the film substrate material (supporting carrier film) of water dissolution or swelling and form is carried out hydraulic-transfer; the relative transfer printing molding (2) that obtains thus; the protection that generation has an adaptation to this polypropylene-based resin molding (3) and this patterned layer (4) both sides film (5); it is made of hydroxy-containing resin composition (P) and polymeric polyisocyanate class solidifying agent (Q); described hydroxy-containing resin composition (P) makes resinous principle (A) and polyhydroxy reactant (B) carry out graft polymerization and forms; wherein; described resinous principle (A) comprises modified polyolefin resinoid (a) at least, and described polyhydroxy reactant (B) comprises and is selected from by acrylic polyol; polyester polyol; polycarbonate polyol; at least a in the family that polyurethane polyol constitutes.
The 2nd mode of the present invention provides a kind of protection coating composition; with in the coating composition, its modified polyolefin resinoid (a) is Chlorinated Polypropylene III, acrylic acid modified chlorinated polypropylene, maleic anhydride modified polypropylene, non-chlorination toxilic acid modified polyolefin resin and their mixture in the described protection of the 1st mode of the present invention.
The 3rd mode of the present invention provides a kind of protection coating composition; use in the coating composition in the protection of the 1st mode of the present invention; convert in solids component, its resin combination (P) is made of resinous principle (A) 1～20 weight % and polyhydroxy reactant (B) 99～80 weight % (the two adds up to 100 weight %).
The 4th mode of the present invention provides a kind of protection coating composition, uses in the coating composition in the protection of the 1st mode of the present invention, and the second-order transition temperature of its polyhydroxy reactant (B) is more than 50 ℃.
The 5th mode of the present invention provides a kind of protection coating composition; use in the coating composition in the protection of the 1st mode of the present invention; its polyhydroxy reactant (B) is an acrylic polyol, and described acrylic polyol is by (methyl) cyclohexyl acrylate (b) 5～60 weight %; (methyl) tert-butyl acrylate (c) 5～60 weight %; vinylbenzene (f) 5～60 weight %; (methyl) hydroxyalkyl acrylate (the alkyl carbon number is 2～4) (d) 3～20 weight % and other polymerizable monomer (e) 82～0 weight % (these compositions add up to 100 weight %) of adding as required constitutes.
The 6th mode of the present invention provides a kind of protection coating composition, uses in the coating composition in the protection of the 1st mode of the present invention, and the hydroxyl value of its resin combination (P) is 10～100mg-KOH/g.
The 7th mode of the present invention provides the manufacture method of a kind of decorated formed article (1); it is characterized in that; on polypropylene-based resin molding (3); the patterned layer (4) that to upward utilize printing or coating at the film substrate material (supporting carrier film) of water dissolution or swelling and form is carried out hydraulic-transfer; the relative transfer printing molding (2) that obtains thus; coating to this polypropylene-based resin molding (3) and this patterned layer (4) both have adaptation the of the present invention the 1st～6 in the described protection coating composition of arbitrary mode, and it is heating and curing.
The 8th mode of the present invention provides a kind of decorated formed article (1), it is characterized in that, it is by transfer printing molding (2) and the protection formation of filming, following the obtaining of described transfer printing molding (2): on polypropylene-based resin molding (3), will go up the patterned layer (4) of utilizing printing or coating and forming at the film substrate material (supporting carrier film) of water dissolution or swelling and carry out hydraulic-transfer; Described protection following the forming of filming: on this transfer printing molding; coating to this polypropylene-based resin molding (3) and this patterned layer (4) both sides have adaptation the of the present invention the 1st～6 in the described protection coating composition of arbitrary mode, and it is heating and curing.
According to the present invention; can obtain a kind of protection films; its can guarantee transfer printing molding that hydraulic-transfer obtains and difficult adaptation the polypropylene-based resin molding adaptation and with the adaptation of above-mentioned patterned layer, exterior qualities such as film performances such as its water tolerance, alkali resistance, oil-proofness, weather proofing, shock resistance, hardness are good, boldness, smoothness, the sense of fullness of filming are also good.
And; because protection is that resinous principle (A) and the polyhydroxy reactant (B) that contains insoluble modified polyolefin resinoid (a) carries out graft polymerization with coating composition; therefore; the intermiscibility of the two is good; its storage stability is good, viscosity is low; its result gives good design, improves exterior quality.
Description of drawings
Fig. 1 is the pie graph of the transfer printing molding of embodiment.
Fig. 2 is the pie graph of the decorated formed article of embodiment.
Label declaration
1 decorated formed article
2 transfer printing molding
3 polypropylene-based resin molding
4 patterned layer
5 protections are filmed
Embodiment
Use Fig. 1～Fig. 2 that embodiments of the present invention are described.
With regard to coating composition is used in protection of the present invention; on polypropylene-based resin molding 3; to hydraulic-transfer above-mentioned patterned layer 4 and the transfer printing molding 2 that obtains, produce the protection that above-mentioned polypropylene-based resin molding 3 and above-mentioned patterned layer 4 both sides are had a good adaptation and film 5.
(I) polypropylene-based resin molding
The polypropylene-based resin that is used for polypropylene-based resin molding 3 of the present invention, just be not particularly limited so long as be used for the polypropylene-based resin of molding, can be for example homopolymer polypropylene, with the oligopolymer of other alkene of carbon numbers 3～10 such as ethene and copolymerization straight chain shape or cyclic diene become the to grade oligopolymer more than 3 yuan of other compositions or give the polypropylene-based resin that functional group forms to these materials.These materials can be single, also can be mixtures.For these polypropylene-based resins, so long as can be used for material of the present invention, the kind of its polymerizing catalyst and the molecular weight of polymkeric substance are just without limits.
With regard to above-mentioned oligopolymer, its molecular structure is not particularly limited, and can enumerate block oligomers, random oligopolymer, block-random oligopolymer etc.
To the functional group that gives on the above-mentioned polypropylene-based resin; can enumerate carboxyl, hydroxyl, amide group, amino etc.; these functional groups both can the polymerization stage of polypropylene-based resin use can copolymerization monomer give, also can in aftertreatments such as the chemical treatment after making strand, particle or molding, burn processing, active energy beam processing, give.Be used to give the comonomer of functional group, can enumerate maleic anhydride, toxilic acid, fumaric acid, (methyl) vinylformic acid, (methyl) Hydroxyethyl acrylate, vinyl-acetic ester, (methyl) acrylamide, amino-benzene ethene etc.
(II) transfer film
Transfer film of the present invention is following formation: on the supporting carrier film (being also referred to as the support of film substrate material or patterned layer sometimes) of about 5～300 μ m of the thickness of water-soluble or water-swellable, use water insoluble ingredients, utilizing printing, coating etc. to make the patterned layer 4 of regulation is 0.1～100 μ m, is generally 1～10 μ m.
(II-1) patterned layer
The material of patterned layer 4 of the present invention has hydrophobic material as described below.
(1) by the material that is constituted by rete of hydrophobic inks that can be dissolved in organic solvent or coating,
(2) material that above-mentioned (1) form etc. is set on the substrate protective layer that constitutes by actinic energy ray curable resin or heat-curing resin.
The thickness of patterned layer 4 is not particularly limited, but when only being made of by rete printing ink or coating, its thickness is 0.1～15 μ m, preferred 1～10 μ m.When printing ink or coating were set on the substrate protective layer by rete, its thickness was 1～200 μ m, preferred 10～100 μ m.
Above-mentioned the sort of occasion no matter, when thickness is lower than above-mentioned scope when too thin, then the protection of the design of its requirement and the end is insufficient, when thickness is too thick, then is difficult to make patterned layer evenly to activate when hydraulic-transfer.The activation of patterned layer has following effect: by coating on patterned layer or distribution organic solvent, the resin that constitutes ornament layer and comprise the patterned layer of curing resin layer is as required in addition not exclusively dissolved, patterned layer can be dissolved, when hydraulic-transfer, from hydrophilic supporting carrier film (support of patterned layer or film substrate material), peel off hydrophobic patterned layer easily, simultaneously, by giving flexibility, improve servo-actuated and the adaptation of patterned layer to the three-dimension curved surface of transfer printing body to patterned layer.
Above-mentioned printing ink or coating must activate by organic solvent, the character that flexibility can be maintained the degree that pattern do not washed out is very important, can enumerate gravure printing ink, ink jet inks, epoxy polyurethane resene coating, addition polymer class coating, polycondensation polymer class coating etc.
The lacquer resin that is used for above-mentioned printing ink or coating can be enumerated thermoplastic resins such as acrylic resin, urethane resin, polyamide resin, urea resin, Resins, epoxy, vibrin, Vinylite (vinylchlorid, vinyl acetate copolymerization resin), vinylidene resin (vinylidene chloride, vinylidenefluonate), ethylene-vinyl acetate resin, polyolefin resin, chlorinated alkenes resin, ethylene-propylene acid resin, petroleum resinoid, cellulose-derived resin etc.Wherein, preferred alcohols acid resin, acrylic resin, urethane resin, cellulose-derived resin and ethylene-vinyl acetate resin.
The tinting material that is used for above-mentioned printing ink or coating can be enumerated and dye pigment, can use mineral-type to dye pigment, organic class and dye any one of pigment.And, also can use and contain the metal fragment sheet that obtains by metal cutting particle and deposited metal film metalluster printing ink as pigment.
In patterned layer, also can add defoamer, antisettling agent as required, dye pigment dispersing agent, fluidity amendment, anti-blocking agent, anti-live agent, antioxidant, photostabilizer, UV light absorber, internal curing agent, to improve the various additives etc. that scuff resistance etc. is a purpose.
(II-2) supporting carrier film (support of patterned layer or film substrate material)
The supporting carrier film that is used for transfer film is not particularly limited, and can be water-soluble substances, also can be the water-swellable material.Its material can be enumerated polyvinyl alcohol, polyvinylpyrrolidone, cellulose acetate, polyacrylamide, acetyl tributyl Mierocrystalline cellulose, gelatin, glue, sodiun alginate, Natvosol, carboxymethyl cellulose etc.In addition, be main component with these compositions, can be the material that other monomer copolymerizations such as (methyl) acrylamide are formed, also can be to make other resins such as urethane cooperate the material that forms.
(III) protection coating composition
Protection of the present invention is made of hydroxy-containing resin composition (P) and polymeric polyisocyanate class solidifying agent (Q) with coating composition.
(III-1) hydroxy-containing resin composition (P)
Above-mentioned hydroxy-containing resin composition (P) is to make the resinous principle (A) and the polyhydroxy reactant (B) that contain modified polyolefin resinoid (a) at least carry out graft polymerization formation.
Resinous principle (A)
Resinous principle (A) comprises modified polyolefin resinoid (a) at least, also can comprise other polyolefin resin (a ') as required.
As modified polyolefin resinoid (a), can enumerate chlorinated polypropylene, acrylic acid modified chlorinated polypropylene, maleic anhydride modified acrylic resin, non-chlorination toxilic acid modified polyolefin resinoid etc., these materials also can mix use more than two kinds.
As chlorinated polypropylene, specifically can enumerate trade(brand)name Si Paku synthetic fibre 892L (ス one パ one Network ロ Application 892L), Si Paku synthetic fibre 814H (ス one パ one Network ロ Application 814H) that Jujo Paper Co., Ltd makes, Si Paku synthetic fibre 822 (ス one パ one Network ロ Application 822) etc.
As acrylic acid modified chlorinated polypropylene, specifically can enumerate trade(brand)name Si Paku synthetic fibre 240H (ス one パ one Network ロ Application 240H), Si Paku synthetic fibre 223M (ス one パ one Network ロ Application 223M) etc. that Jujo Paper Co., Ltd makes.
As maleic anhydride modified acrylic resin, specifically can enumerate trade(brand)name Si Paku synthetic fibre 851L (ス one パ one Network ロ Application 851L) that Jujo Paper Co., Ltd makes, Si Paku synthetic fibre 930 (ス one パ one Network ロ Application 930) etc.
As non-chlorination toxilic acid modified polyolefin resinoid, specifically can enumerate trade(brand)name A Wuluo synthetic fibre 100 (ア ウ ロ one レ Application 100) that Nippon Paper Chemicals Co., Ltd. makes, A Wuluo synthetic fibre 200 (ア ウ ロ one レ Application 200) etc.
Convert in solids component, resin combination (P) comprises modified polypropylene resin (a) 1～20 weight %, preferred 3～18 weight %.Since when its than above-mentioned scope very little the time, can reduce the closing force of polypropylene-based resin molding produced and peel off, when it is more too many than above-mentioned scope, its glossiness can reduce greatly, can not satisfy oil-proofness, so not preferred, and, owing to influenced the design completely dissolve of boldness when it increases, it is obvious to be worn out by filming of causing of oil-proofness, so not preferred.
As other polyolefin resin (a '), can enumerate various polyethylene such as low density, extremely-low density, high-density, isotactic or syndiotactic polypropylene, propylene/ethylene block or random oligopolymer, polybutene-1, poly 3 methyl butene 1, poly-3-Methyl-1-pentene, poly(4-methyl-1-pentene), cyclenes hydro carbons etc.
Relative modified polyolefin resinoid (a) 100 weight parts, the addition of other polyolefin resin (a ') is that 0～50 weight part gets final product.
Therefore, with in the coating composition, the content of resinous principle (A) is 1～20 weight %, preferred 3～18 weight % in protection.
Polyhydroxy reactant (B)
The second-order transition temperature of polyhydroxy reactant (B) is preferably more than 50 ℃, and this condition is extremely important to the adaptation of acrylic resin molding 3 (matrix) and patterned layer 4.Polypropylene-based resin is difficult tack material, in order to make its driving fit, is the coating class that contains polypropylene-based resin, much less also needs coating strength.In this development, just insufficient to the driving fit of acrylic resin molding 3 (by containing the matrix that polypropylene-based resin forms), need remedy this deficiency with polyhydroxy reactant.
In addition, because therefore 4 pairs of acrylic resin molding of the patterned layer that is transferred 3 driving fit fully also needs to remedy this deficiency, intensity of filming and hardness become the factor of guaranteeing adaptation.
Be described in detail second-order transition temperature below, the second-order transition temperature of polyhydroxy reactant (B) is below 45 ℃ the time, because coating strength is low, so can peel off because of the initial stage adaptation produces, when its second-order transition temperature more than 45 ℃ and less than 50 ℃ the time, can because of secondary adaptations such as moisture-proof adaptation, heat-resisting adaptation produce collapse broken, peel off, not preferred.And near automotive interior trim accessory, particularly front axle, owing to be under to heat, the strict situation of light, therefore as the condition that can tolerate these, the preferred glass transition point is more than 50 ℃.
Narration is to the adaptation on the polypropylene-based resin molding 3 below.Because the supercontraction that causes because of the crosslinking reaction of filming can cause the adaptation reduction, therefore, its glass transition point is preferably more than 50 ℃, more preferably more than 60 ℃.
As above-mentioned polyhydroxy reactant (B), can enumerate at least a polyhydroxy reactant in the family that comprises formations such as being selected from acrylic polyol, polyester polyol, polycarbonate polyol, polyurethane polyol, when considering desired all performance such as cost and attractive appearance, weather proofing, chemical resistant properties, thermotolerance, preferred acrylic polyol.
Acrylic polyol is that the material that comprises the acrylic polyol that contains (methyl) vinylformic acid cycloalkyl ester (b), (methyl) vinylformic acid tertiary alkyl ester (c), vinylbenzene (f) and (methyl) hydroxyalkyl acrylate (d) gets final product.
Constituting of acrylic polyol: (methyl) vinylformic acid cycloalkyl ester (carbon number 5～8) is 5～60 weight %, preferred 10～50 weight % (b); (methyl) vinylformic acid tertiary alkyl ester (carbon number 4～8) is 5～60 weight %, preferred 10～50 weight % (c); Vinylbenzene (f) 5～60 weight %, preferred 10～50 weight %; And (methyl) hydroxyalkyl acrylate (carbon number 2～4) (d) 3～20 weight %, preferred 5～15 weight %; And other polymerizable monomer (e) the 82 weight % that add as required are following, preferred 70 weight % are following, further preferred 50 weight % following (these compositions add up to 100 weight %).
(methyl) vinylformic acid cycloalkyl ester (b)
As above-mentioned (methyl) vinylformic acid cycloalkyl ester (b), can enumerate (methyl) vinylformic acid ring pentyl ester, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid ring monooctyl ester etc., preferred (methyl) cyclohexyl acrylate.
The intermiscibility of (methyl) cyclohexyl acrylate and modified polyolefin resinoid (a) is very good, and is stable very helpful to what cause because of time lapse.Narrate above-mentioned intermiscibility below, because its polarity is very low, therefore the acrylic resin that itself and polarity are high and the intermiscibility of urethane resin are short of very much, sometimes with layer separation, gelation, generation coagulum etc., promptly enable the uniform atomizing of temporary transient mixing also spray application can't be obtained the time sometimes.In addition because its insoluble, therefore in film coated surface sometimes with the generation of pit.The quality of intermiscibility is very tangible to the influence of storage stability and screening characteristics, the formation of filming, even can not film uniformly in the rerum natura of filming, can't satisfy many performances of industrial level.And cyclohexyl methacrylate is not only guaranteed intermiscibility and stability, and the transparency that protection is filmed is good, because therefore its specific refractory power height gives sense of fullness, the smoothness that has levels and feel, even also very helpful to desired exterior quality.And, by reducing the polarity of resene greatly, also help tack to the formed products that constitutes by difficult adaptation and low polar polypropylene based material.
In addition, also very good even chemical resistant properties such as its water tolerance, alkali resistance and resistance to deterioration contain chemical preparations of ethanol etc. etc. relatively.
The content of (methyl) vinylformic acid cycloalkyl ester (b) in the polyhydroxy reactant (B) is 5～60 weight %, preferred 10～50 weight %, because transparency reduces when its less than 10 weight %, transparency disappearance can't be given design when its less than 5 weight %, so not preferred.In addition, when it is more too much than above-mentioned scope since because of filming of causing of oil-proofness aging obviously, so not preferred.
(methyl) vinylformic acid tertiary alkyl ester (c)
As above-mentioned (methyl) vinylformic acid tertiary alkyl ester (c), can enumerate (methyl) tert-butyl acrylate, (methyl) vinylformic acid uncle monooctyl ester etc., preferred (methyl) tert-butyl acrylate.
The methacrylic acid tertiary butyl and cyclohexyl methacrylate are same, and be very good with the intermiscibility of polypropylene-based resin, goes far towards because of the stability that time lapse causes, desired exterior quality.
In addition, also very good even chemical resistant properties such as its water tolerance, alkali resistance and resistance to deterioration contain chemical preparations of ethanol etc. etc. relatively.In addition, the methacrylic tert-butyl acrylate has the effect that reduces resene viscosity, the viscosity that the grafting bonding of mitigation and polyolefin resin brings rises, its result, good operability, screening characteristics in the time of can giving coating, the liquid fluidity when making the screening characteristics to coated thing, equal voltinism, coating is good.
The content of (methyl) vinylformic acid tertiary alkyl ester (c) in the polyhydroxy reactant (B) is 5～60 weight %, preferred 10～50 weight %, because transparency reduces when its less than 10 weight %, the transparency disappears when its less than 5 weight %, so not preferred.In addition, when it is more too much than above-mentioned scope since because of filming of causing of oil-proofness aging obviously, so not preferred.
Vinylbenzene (f)
Vinylbenzene is a kind of material with high refractive index.Cinnamic high refractive index is very effective in the occasion of transparency, boldness that requires of the present invention, and is helpful to exterior quality.In addition, cinnamic SP (solubility parameter) value must be very low, and the skeleton key element that is caused by phenyl ring pair has part help with the intermiscibility of acrylic resin.In addition, because of the influence of the phenyl ring in the skeleton, cinnamic thermotolerance, water tolerance, alkali resistance are good.And, because vinylbenzene is a kind of cheap raw material, thus in the coating of the polyolefin resin that contains high price of great use.In addition; for the appearance style that makes the transfer printing molding is beautiful, preferably the molecular weight of 5 resin is lower because protection is filmed, because vinylbenzene has the effect of lower molecular weightization in polymerization system; therefore can reduce polymerization starter, reduce cost also helping aspect this.
Vinylbenzene (f) content in the polyhydroxy reactant (B) is 5～60 weight %, preferred 10～50 weight %, when it is 10 weight % when following, owing to can make design reductions (exterior quality reduction) such as desired reflecting feel, boldness, so not preferred.
(methyl) acrylic acid hydroxy alkyl ester (d)
As above-mentioned (methyl) acrylic acid hydroxy alkyl ester (d), can enumerate (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 3-hydroxypropyl acrylate, (methyl) vinylformic acid 2-hydroxy butyl ester etc., preferred (methyl) vinylformic acid 2-hydroxyl ethyl ester.
The content of (methyl) acrylic acid hydroxy alkyl ester (d) in the polyhydroxy reactant (B) is 3～20 weight %, preferred 5～15 weight %, chemical resistant properties is poor after a little while than above-mentioned scope when it, when it reduces because of the cure shrinkage of filming causes adaptation for a long time than above-mentioned scope.
Other polymerizable monomer (e)
As above-mentioned other polymerizable monomer (e), can enumerate vinylbenzene, alpha-methyl styrene, (methyl) vinylformic acid, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) 2-EHA, (methyl) dodecylacrylate, (methyl) vinylformic acid stearyl, (methyl) benzyl acrylate, (methyl) isobornyl acrylate, (methyl) vinylformic acid isopentyl ester, (methyl) phenoxyethyl acrylate etc.
The content of other polymerizable monomer (e) in the polyhydroxy reactant (B) is below the 82 weight %, below the preferred 70 weight %.
The manufacture method of hydroxy-containing resin composition (P)
Hydroxy-containing resin composition (P) makes the modified polyolefin resinoid (a) that contains at least in the resinous principle (A) carry out graft polymerization with polyhydroxy reactant (B) and obtains.
Cross when low when the percentage of grafting of the polyhydroxy reactant (B) of relative modified polyolefin resinoid (a), can bring detrimentally affect storage stability.
Graft polymerization procedure is characterised in that, makes the carboxyl and the hydroxyl vinyl monomer partial reaction that derive from the maleic anhydride in the modified polyolefin resinoid, the hydroxyl that perhaps makes acrylic acid modified polyolefin resin etc. with contain unsaturated group vinyl monomer partial reaction.
Particularly, with resinous principle (A) the heating under be dissolved in solvent after, add the monomer that constitutes above-mentioned polyhydroxy reactant (B), for example: (methyl) vinylformic acid cycloalkyl ester (b), (methyl) vinylformic acid tertiary alkyl ester (c), vinylbenzene (f), (methyl) acrylic acid hydroxy alkyl ester (d) and other polymerizable monomer (e) that adds as required, after evenly stirring, by the interpolation radical polymerization initiator it is reacted and carry out graft polymerization.
In addition, graft polymerization is carried out in chlorine atom initiation reaction that also can be by utilizing polymerization starters such as superoxide etc.
The hydroxyl value of the hydroxy-containing resin composition (P) that obtains thus is 10～100mg-KOH/g, preferred 20～80mg-KOH/g.Because when hydroxyl value during less than above-mentioned scope, then can not satisfy film performances such as chemical resistant properties, weather proofing, thermotolerance, when its during greater than above-mentioned scope, then cause by curing of coating and shrink the adaptation reduction that causes, especially significantly reduce as the moisture-proof adaptation of 2 adaptations, water-fast adaptation, so not preferred.
(III-2) polymeric polyisocyanate class solidifying agent (Q)
Polymeric polyisocyanate class solidifying agent of the present invention (Q) is used to make above-mentioned hydroxy-containing resin composition (P) to solidify.
Polymeric polyisocyanate class solidifying agent (Q) is made of the amine hardener of polyisocyanate compounds and interpolation as required.
Polyisocyanate compounds for example has: aromatics such as benzylidene vulcabond, xylylene vulcabond, '-diphenylmethane diisocyanate; Fatty compoundss such as tetramethylene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate; The ester ring type compound of isophorone diisocyanate, norbornene alkyl diisocyanate and so on etc., particularly, when consider weather proofing, chemical resistant properties, when aesthetic appearance is attractive in appearance, the preferred fat compounds of group also comprises the modification body of these materials.
As the aliphatic isocyanates compound, for example have: the how anti-moral 24A-100 of trade(brand)name (デ ユ ラ ネ one ト 24A-100), how anti-moral TPA-100 (デ ユ ラ ネ one ト TPA-100), how anti-moral E402-90T (デ ユ ラ ネ one ト E402-90T) that Asahi Chemical Industry Co., Ltd makes; Firmly change this close that N-3300 (ス ミ ジ ユ one Le N-3300) of a specified duration of trade(brand)name, this close that N-3200 (ス ミ ジ ユ one Le N-3200) of a specified duration, this close that N-75 (ス ミ ジ ユ one Le N-75) of a specified duration that Bayer urethane Co., Ltd. (firmly changing バ イ エ Le ウ レ タ Application) makes; Trade(brand)name Ke Luonaide HX (コ ロ ネ one ト HX), Ke Luonaide EH (コ ロ ネ one ト EH) that Nippon Polyurethane Industry Co., Ltd. (Japanese Port リ ウ レ タ Application Industrial Co., Ltd) makes; The trade(brand)name Plutarch D-165N of anti-moral the (タ ケ ネ one ト D-165N) that Mitsui Takeda Chemical Co., Ltd makes etc.
And the ratio NCO/OH of the hydroxyl of the NCO of polymeric polyisocyanate class solidifying agent (Q) base and hydroxy-containing resin composition (P) is 0.5～2.0, preferred 0.8～1.5 than (equivalence ratio).Because then chemical resistant properties, thermotolerance obviously descend when its less than 0.8, when its be 1.5 when above then because of the over-curing contraction of filming causes the closing force reduction, so not preferred.
(IV) film
When analyzing existing transfer printing molding surperficial with electron microscope, can find to be also referred to as many holes in space, patterned layer and polypropylene-based resin molding do not have complete driving fit.
Therefore, protection of the present invention is with the purpose of coating composition, not only from patterned layer 4 self but also from being present in the many holes on the patterned layer 4, polypropylene-based resin molding 3 soaks into coating composition and makes its driving fit.
Coating composition among the present invention is 2 composition systems; as mentioned above; it not only protects the patterned layer 4 that forms on polypropylene-based resin molding 3; and further give design to patterned layer; and carry out the hydroxy-containing resin composition (P) that grafting forms and be cured crosslinked by polymeric polyisocyanate class solidifying agent (Q) in order to give transparency that desired protection films, smoothness, sense of fullness etc., make the resinous principle (A) that constitutes by aforesaid modified polyolefin resinoid (a) and polyhydroxy reactant (B).
The manufacture method of decorated formed article
Use above-mentioned transfer film, the patterned layer 4 of this transfer film of hydraulic-transfer on polypropylene-based resin molding 3 is made transfer printing molding as shown in Figure 1.When supporting carrier film swims on the interior water surface of transfer groove, because of water-soluble slowly dissolving.After the transfer printing, utilize water to clean and remove supporting carrier film remaining on the patterned layer.Then, as shown in Figure 2, apply above-mentioned protection and use coating composition, make its formation protection that is heating and curing film 5 to cover polypropylene-based resin molding 3 and patterned layer 4.
Coating method
As being used to form film 5 coating method of protection, spraying, brushing, roller coat, dip coating, electrodeposition coating etc. are arranged, consider preferred spraying from requiring the appearance looks elegant aspect.
The viscosity of mixed solution when narration applies below, the viscosity of mixed solution is 10～15 seconds in No. 4 Ford cup, preferred 11～14 seconds, mixes back with suitable organic solvent diluting with the isocyanic ester of regulation.When it is below 11 seconds the time, the depression of then on transfer film, often filming, the solution that coating is good when coated body tilts is outwards mobile from the center of coated body, and so generation picture frame phenomenon is not preferred.When it is more than 14 seconds the time, then the jet atomization reduction causes the moistening insufficient smoothness shortcoming that causes to coated body, so not preferred.
The thickness that protection was filmed when narration applied below, the thickness that protection is filmed is 10～50 μ m, preferred 20～40 μ m.Then sense of fullness slightly descends when thickness is 15～20 μ m, then can not manifest sense of fullness and can't give design when its less than 15 μ m, so not preferred.When it is that 40 μ m then can produce problems such as be full of cracks, sagging when above, so not preferred.
At room temperature placed after the coating 5～10 minutes, and carried out forced drying.Its drying conditions is following dry 10～100 minutes at 60～100 ℃, preferably following dry 20～60 minutes at 65～90 ℃, when 65 ℃ of dryings of drying temperature less than in the time of 20～60 minutes, then cross-linking density reduces, dhering strength, chemical resistant properties, thermotolerance also reduce, owing to must prolong time of drying, so not preferred.In addition, when, following the speed of response lifting and cause cure shrinkage in the time of 30～60 minutes in drying more than 90 ℃, adaptation reduces, so not preferred.
Operate as mentioned above and obtain decorated formed article 1.This decorated formed article 1 is filmed by transfer printing molding 2 and protection and 5 is constituted, wherein, described transfer printing molding 2 is following obtaining: on polypropylene-based resin molding 3, will utilize printing or coating and the patterned layer 4 that forms is carried out hydraulic-transfer on the film substrate material of water dissolution or swelling; It 5 is following obtaining that described protection is filmed: on this transfer printing molding 2, apply above-mentioned protection coating composition, so that its overlay pattern layer 4 at least, and be heating and curing.Preferably film 5 with overlay pattern layer 4 and polypropylene-based resin molding 3 both sides' mode design protection.
The main purpose of coating composition of the present invention is to give the attractive appearance with transparent feel and sense of fullness, also can utilize the painted and pigment extender of colourful transparent and so on to carry out film coated surface processing.But because the undue pigment extender that adds will cause gloss obviously to reduce, so restricted to its addition.
Below, by embodiment the present invention is described, but the present invention is not limited to these embodiment.
(manufacturing of hydroxy-containing resin composition (P), embodiment 1～2, reference example 1～8)
In four neck flasks of 1 liter capacity that has stirrer, water cooler, thermometer, monomer drop instillator, to press the composition shown in the table 1 and add (A) composition, warming while stirring to internal temperature is 85 ℃, has kept under 85 ℃ 20 minutes.Then,, after the end of instiling, add (C) composition and under 85 ℃, carry out polymerization 2 hours, obtain the solution of hydroxy-containing resin composition (P) with 2 hours (B) compositions that instil.This solution is further diluted with toluene.Need to prove that the consumption of each composition is represented with weight part in table 1.
, add as close your N-3300 (ス ミ ジ ユ one Le N-3300) of a specified duration of this of polymeric polyisocyanate class solidifying agent (Q) with dilution with toluene and carried out in the solution that viscosity adjusts at the hydroxy-containing resin composition (P) that will obtain with the amount shown in the table 1.
The manufacturing of transfer printing molding 2
On following polypropylene-based resin molding 3, use following transfer film, form patterned layer 4.
As polypropylene-based resin molding 3, the surface of using new Kobe electric (strain) the to make polypropylene PP-N-AN that is untreated is configured as the sample of 6cm (W) * 15cm (L) * 3mm (T).
As transfer film, the hydraulic-transfer printed sheet material (Ka Er Fitow (カ one Le Off イ Star ト), thick 5～10 μ m, lacquer is an alkyd based resin with resin) that uses Dai Nippon Printing's (strain) to make.
(embodiment 1～2 and reference example 1～8)
On the above-mentioned transfer printing molding 2 that obtains, use the above-mentioned coating composition that obtains, utilize spraying method, formed protection and filmed 5 so that the thickness after forming of filming is the mode of 20～40 μ m.
Aesthetic appearance, initial stage adaptation, 2 adaptations of filming about the protection of the decorated formed article 1 that obtained by embodiment 1～2 and reference example 1～8 merge the result and are shown in table 1.
(1) aesthetic appearance: with the gloss instrumentation to 60 ° gloss be that standard is judged, zero the expression more than 90, △ represents 80～90, * expression be lower than 80.
(2) adaptation: according to JIS K5400[8.5.1 texture process] carried out following driving fit test (gap 1mm cuts apart several 100).
Initial stage adaptation: form protection and film, be determined at and place 72 hours closed states afterwards under the room temperature.
2 adaptations:
(2-1) heat-resisting adaptation: form protection and film, after at room temperature placing 72 hours, be determined at 80 ℃ of closed states after following 300 hours the oven test.
(2-2) moisture-proof adaptation: form protection and film, after at room temperature placing 72 hours, be determined under 50 ℃, the environment of humidity 95%RH and carry out 500 hours closed states after the humidity test.
Initial stage adaptation, 2 adaptations are all based on following judging criterion.
The situation of the vestige of peeling off is can't see in zero expression, and it is 1 or more and less than 10/100 that △ represents to peel off, * represent to peel off be more than 10/100.
(3) oil-proofness: after at room temperature placing 72 hours again behind the formation protective membrane, in heptane, flooded 1 hour under the room temperature as low polar solvent.
Film aging can't see in zero expression, and △ represents to see some aging, and * expression is filmed obviously aging.
(4) storage stability: the dilution with toluene solution of above-mentioned hydroxy-containing resin composition (P) is placed under 0 ℃, 20 ℃, 40 ℃, 60 ℃, judges having or not of the layer separation that cause because of time lapse, gelation, condensation product with range estimation.
Table 1
(※ 1) Nippon Paper (strain), chlorinated polypropylene (trade(brand)name Si Paku synthetic fibre 892L (ス one パ one Network ロ Application 892L), chlorination rate 20%, 20% toluene solution)
(※ 2) n-butyl acrylate
(※ 3) Propenoic acid, 2-methyl, isobutyl ester
(※ 4) vinylbenzene
(※ 5) methacrylic tert-butyl acrylate
(※ 6) cyclohexyl methacrylate
(※ 7) methacrylic acid 2-hydroxyl ethyl ester
(※ 8) Diisopropyl azodicarboxylate
Need to prove that in table 1, OHV represents hydroxyl value.
As shown in Table 1, reference example 1 is because chlorinated polypropylene is few to 3 weight %, so its adaptation is insufficient.Reference example 2 since chlorinated polypropylene up to 18 weight %, so aesthetic appearance is insufficient.Reference example 3 is because hydroxyl value is a 85mg/KOH cross-linking density height, so adaptation is insufficient.Reference example 4 is because CHMA is 2.7 weight %, so cause aesthetic appearance insufficient by transparency is low.Reference example 5 is because t-BMA is 0.0%, so cause aesthetic appearance insufficient by transparency is low.Reference example 6 is because St is 0.0%, so cause aesthetic appearance insufficient by transparency is low.Reference example 7 is because second-order transition temperature is more than 50 ℃, so adaptation is insufficient.Reference example 8 is because second-order transition temperature is below 40 ℃, so adaptation is insufficient.
Utilize possibility on the industry
The present invention can provide a kind of protection to film; its relatively on the polypropylene-based resin formed products pattern layer for hydraulic transfer obtain the transfer printing formed products; can guarantee with the adaptation of the polypropylene-based resin formed products of difficult adaptation and with the adaptation of above-mentioned patterned layer; the film performances such as its resistance to water, alkali resistance, oil resistivity, weather proofing, impact resistance, hardness are good, and the exterior qualities such as its vividness, flatness, sense of fullness are also good.
Claims (8)
1. a pattern layer for hydraulic transfer protection is used coating composition; it is on the polypropylene-based resin molding; the patterned layer that to utilize printing or coating and form on the film substrate material of water dissolution or swelling is carried out hydraulic-transfer; the relative transfer printing molding that obtains thus; generation has the protection coating composition that the protection of adaptation is filmed to this polypropylene-based resin molding and this patterned layer; it is made up of hydroxy-containing resin composition (P) and polymeric polyisocyanate class solidifying agent (Q); described hydroxy-containing resin composition (P) makes resinous principle (A) and polyhydroxy reactant (B) carry out graft polymerization and forms; wherein; described resinous principle (A) comprises modified polyolefin resinoid (a) at least, and described polyhydroxy reactant (B) comprises and is selected from by acrylic polyol; polyester polyol; polycarbonate polyol; polyurethane polyol at least a.
2. protection coating composition according to claim 1; it is characterized in that modified polyolefin resinoid (a) is chlorinated polypropylene, acrylic acid modified chlorinated polypropylene, maleic anhydride modified acrylic resin, non-chlorination toxilic acid modified polyolefin resinoid or their mixture.
3. protection coating composition according to claim 1; it is characterized in that; convert in solids component; its hydroxy-containing resin composition (P) is made of resinous principle (A) 1～20 weight % and polyhydroxy reactant (B) 99～80 weight %, and the two adds up to 100 weight % described resinous principle (A) and described polyhydroxy reactant (B).
4. protection coating composition according to claim 1 is characterized in that, the second-order transition temperature of its polyhydroxy reactant (B) is more than 50 ℃.
5. protection coating composition according to claim 1; it is characterized in that; its polyhydroxy reactant (B) is an acrylic polyol; described acrylic polyol is that (methyl) hydroxyalkyl acrylate (d) 3～20 weight % of 2～4 and other polymerizable monomer (e) 82～0 weight % of adding as required constitute by (methyl) cyclohexyl acrylate (b) 5～60 weight %, (methyl) tert-butyl acrylate (c) 5～60 weight %, vinylbenzene (f) 5～60 weight %, alkyl carbon number, and these compositions add up to 100 weight %.
6. protection coating composition according to claim 1 is characterized in that, the hydroxyl value of its hydroxy-containing resin composition (P) is 10～100mg-KOH/g.
7. the manufacture method of a decorated formed article; it is characterized in that; on the polypropylene-based resin molding; the patterned layer that to utilize printing or coating and form on the film substrate material of water dissolution or swelling is carried out hydraulic-transfer; the relative transfer printing molding (2) that obtains thus; coating to this polypropylene-based resin molding and this patterned layer both sides have adaptation as each the described protection coating composition in the claim 1～6, and it is heating and curing.
8. decorated formed article, it is characterized in that, it is filmed by transfer printing molding and protection and constitutes, described transfer printing molding is following obtaining: on the polypropylene-based resin molding, will utilize printing or coating and the patterned layer that forms is carried out hydraulic-transfer on the film substrate material of water dissolution or swelling; Described protection following the forming of filming: on this transfer printing molding; coating to described polypropylene-based resin molding and described patterned layer both sides have adaptation as each the described protection coating composition in the claim 1～6, and it is heating and curing.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP282562/2004 | 2004-09-28 | ||
| JP2004282562 | 2004-09-28 | ||
| PCT/JP2005/017623 WO2006035708A1 (en) | 2004-09-28 | 2005-09-26 | Coating composition for protecting pattern layer for hydraulic transfer, decorated formed article and method for production thereof |
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| CN101018677A CN101018677A (en) | 2007-08-15 |
| CN101018677B true CN101018677B (en) | 2011-05-25 |
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| CN2005800309156A Expired - Fee Related CN101018677B (en) | 2004-09-28 | 2005-09-26 | Coating composition for protecting pattern layer for hydraulic transfer, decorated formed article and method for production thereof |
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| JP (1) | JP4510831B2 (en) |
| CN (1) | CN101018677B (en) |
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| BR112012001460A2 (en) * | 2009-07-23 | 2016-03-15 | Taica Corp | water pressure transfer method and article for water pressure transfer |
| CN102344746B (en) * | 2010-07-30 | 2014-04-30 | 比亚迪股份有限公司 | Paint as well as preparation method and use method thereof |
| US8815376B2 (en) | 2011-02-23 | 2014-08-26 | Taica Corporation | Surface treatment agent for hydraulic transfer, and hydraulic transfer method and hydraulic transfer products using same |
| CN102417787A (en) * | 2011-10-27 | 2012-04-18 | 铜陵市新泰电容电器有限责任公司 | Paint used for covering capacitor aluminum casing, and preparation method thereof |
| JP5979026B2 (en) * | 2013-01-30 | 2016-08-24 | 凸版印刷株式会社 | Transfer film for simultaneous decoration |
| WO2018062182A1 (en) * | 2016-09-28 | 2018-04-05 | 日本製紙株式会社 | Modified polyolefin resin |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1289687A (en) * | 1999-09-28 | 2001-04-04 | 株式会社艺纹技术 | Organic solvent composition for duplication and aqueous duplication method for duplicating film as external decoration by using it |
| JP2003313331A (en) * | 2002-04-25 | 2003-11-06 | Mitsubishi Chemicals Corp | Base coating composition for use in polyolefin coating |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS61255937A (en) * | 1985-05-09 | 1986-11-13 | Sanyo Chem Ind Ltd | Coating agent |
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- 2005-09-26 JP JP2006537717A patent/JP4510831B2/en not_active Expired - Fee Related
- 2005-09-26 WO PCT/JP2005/017623 patent/WO2006035708A1/en active Application Filing
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1289687A (en) * | 1999-09-28 | 2001-04-04 | 株式会社艺纹技术 | Organic solvent composition for duplication and aqueous duplication method for duplicating film as external decoration by using it |
| JP2003313331A (en) * | 2002-04-25 | 2003-11-06 | Mitsubishi Chemicals Corp | Base coating composition for use in polyolefin coating |
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| JPWO2006035708A1 (en) | 2008-05-15 |
| JP4510831B2 (en) | 2010-07-28 |
| WO2006035708A1 (en) | 2006-04-06 |
| TW200621916A (en) | 2006-07-01 |
| CN101018677A (en) | 2007-08-15 |
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