CN105462468A - Undercoat used for base material with copper film, base material with copper film, manufacturing method for base material with copper film, and conductive film - Google Patents
Undercoat used for base material with copper film, base material with copper film, manufacturing method for base material with copper film, and conductive film Download PDFInfo
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Abstract
An objective of the invention is to provide an undercoat. The undercoat has excellent initial-stage adhesion, acid-resisting adhesion, and alkali-resisting adhesion with a base material and a copper film. The invention relates to an undercoat of a base material with a copper film. The undercoat contains acrylic copolymer (A) with hydroxyl, alkyl ester groups, nitrile groups, and required primary amide groups, polyisocyanates (B) at least containing three isocyanate groups, an active energy line aggregate compound (C) at least containing three carbon-carbon double bond groups, and a reactive alkoxy silyl group compound (D) represented by a formula (1): X1-Si(R1)a(OR2)3-A, wherein in the formula (1), X1 is a group containing the following functional groups, the functional groups react with at least a group selected from a group formed by hydroxyl, isocyanate groups, and groups containing polymeric carbon-carbon double bonds, R1 represents hydroxyl with 1-9 hydrogen or carbon number, R2 represents hydroxyl with 1-8 carbon number, and a represents 0, 1, or 2.
Description
Technical field
The present invention relates in order to the conducting film forming Copper thin film and the priming paint used, the base material with Copper thin film with the layer formed by this priming paint and manufacture method thereof on the surface of various base material and use the base material having Copper thin film by this to be formed.
Background technology
" having the base material of Copper thin film " in this specification sheets refers to the product forming Copper thin film on the surface of the various base materials such as formed products and plastic film, metal, glass, paper, nanofiber paper, timber.Below, enumerate as the film on surface with the conductive layer formed by tin indium oxide (ITO) (hereinafter referred to as, ito film) substitute occupy a tiny space, have on surface the conductive layer formed by copper vapor-deposited film film (hereinafter referred to as, copper vapour deposition plastic film) example, background technology is described.
Because the transparency of ito film and excellent electric conductivity, thus people like the electrode film that it can be used as the touch-screen such as smart mobile phone and panel computer to use.But, because indium is the rare metal of high price, so have problems in cost, in addition, because ITO layer is general not only hard but also crisp, so bending and be out of shape existing problems in the processibility such as poor.
In this field, someone attempts the organic conductive polymer (such as, Polythiophene, polyaniline and polypyrrole etc.) with film-forming properties to use as electro-conductive material with alternative ITO.But, because organic conductive polymer is general strong painted, so they are applied to the conducting film of conductive layer or electrode film has problems in tone.In this, in order to improve tone, the high molecular usage quantity of organic conductive can be reduced, but can electroconductibility be lost.
On the other hand, in this field, someone studies and substitutes ito film with copper vapour deposition plastic film.Because this film uses the copper lower than ITO resistivity, so show the electroconductibility no less than ito film, excellent in workability in addition, the most important thing is cheap.Therefore, be useful by the electrode film that copper vapour deposition plastic film is used as various electronics, such as, can consider the more large screen, interactive digital label etc. expecting it to be effectively used in touch-screen.
In general, copper vapour deposition plastic film be by after as the face vacuum vapor deposition nickel of base material, vacuum vapor deposition copper and obtaining again thereon.This nickel vapor deposition layer plays a role as the anchoring layer for making film and copper vapor deposition layer adhere more strongly.Then, painting erosion resistant agent on the copper vapour deposition plastic film obtained, after describing electrode pattern, is immersed in etching solution (basic solution and/or acidic solution), by removing resist, obtains electrode film.
But because in above-mentioned copper vapour deposition plastic film, nickel lacks alkali resistance and acid resistance, so after there is etch processes, copper vapor deposition layer is peeled off from base material film, the problem such as come off.
In addition, can say that copper vapour deposition plastic film is cheap compared with ito film as mentioned above, because the nickel forming anchoring layer is more expensive than copper processing, so correspondingly improve price.In this field, have people in research using organic polymer as the priming paint of main component as the copper vapour deposition plastic film (with reference to patent documentation 1) of anchoring layer.
Prior art document
Patent documentation
Patent documentation 1: flat No. 5-28835 of Japanese Laid-Open Patent Publication
Summary of the invention
The technical problem that invention will solve
Major subjects of the present invention is to provide a kind of new priming paint, all there is between this priming paint and base material and between this priming paint and Copper thin film excellent initial stage adhesivity, moreover, after with alkaline solution and acid solution process, this has the base material of Copper thin film, this priming paint and base material and still all there is between this priming paint and Copper thin film excellent adhesivity (alkaline-resisting adhesivity, acidproof adhesivity).
Present inventor studies repeatedly with keen determination, found that, using the selected acrylic copolymer containing hydroxyl as main component, using selected polyisocyanates as in the composition of solidifying agent, further mixing the active energy ray-curable compound selected and reactive polyglycidyl compounds formed, the priming paint that solidifies under effect in two of heat and active energy ray, can solve the problems of the technologies described above.
That is, the present invention relates to a kind of priming paint of the base material for having Copper thin film, described priming paint contains: the acrylic copolymer (A) with hydroxyl, alkyl ester group, itrile group and primary amide base as required; At least there is the polyisocyanates (B) of 3 isocyanate group; At least there is the active energy ray polymeric compounds (C) of 3 carbon-carbon double bonds groups; And with general formula (1): X
1-Si (R
1)
a(OR
2)
3-a(in formula (1), X
1for the group containing following functional group, described functional group reacts with at least one group be selected from by selecting in hydroxyl, isocyanate group and the group that forms containing the group of polymerizability carbon-carbon double bond; R
1represent the alkyl of hydrogen or carbon number 1-8; R
2represent the alkyl of carbon number 1-8; A represents 0,1 or 2) the reactive polyglycidyl compounds (D) that represents.
In addition, the conducting film that the present invention relates to the base material with Copper thin film with the layer formed by this priming paint and manufacture method thereof and use this base material with Copper thin film to be formed.
The effect of invention
As mentioned above, priming paint of the present invention is the composition of the type be cured by heat and active energy ray two aspect, thus, initial stage adhesivity between the various base materials such as described priming paint and plastics and between described priming paint and Copper thin film is excellent, moreover, alkaline-resisting adhesivity and acidproof adhesivity become and well (only they are referred to adhesivity below).In addition, because containing the composition be cured by active energy ray in this priming paint, so priming paint tunic can be given with the hardness of excellence.
In addition, particularly, the alkaline-resisting adhesivity of the base material with Copper thin film using priming paint of the present invention to obtain and acidproof good adhesion.Therefore, even if the base material this with Copper thin film is immersed in etching solution, Copper thin film is also difficult to come off.In addition, because this base material with Copper thin film can give prime coat with the hardness of excellence, so in the manufacturing process of this base material, the scuff resistance in Copper thin film face is good, and in addition, when this Copper thin film face is mesh shape, defect becomes and is difficult to occur.
Copper thin film plastic film of the present invention may be used for various uses, but wherein particularly the film etc. of the very thin films of copper vapor-deposited film, use sputtering method formation copper is suitable as the electrode film replacing ito film.In addition, this electrode film such as may be used for smart mobile phone, tablet terminal, notebook computer, integrated computer, digital signage etc.
Embodiment
The base material priming paint (hereinafter referred to as, priming paint) with Copper thin film of the present invention is the composition of the non-water system containing following composition: the acrylic copolymer (A) (hereinafter referred to as (A) composition) with hydroxyl, alkyl ester group, itrile group and primary amide base as required; At least there is the polyisocyanates (B) (hereinafter referred to as (B) composition) of 3 isocyanate group; At least there is the active energy ray polymeric compounds (C) (hereinafter referred to as (C) composition) of 3 carbon-carbon double bonds groups; And with the reactive polyglycidyl compounds (D) of the chemical formulation of defined (hereinafter referred to as (D) composition).
Because (A) composition has hydroxyl and itrile group as polar group in molecule, so impart above-mentioned adhesivity, particularly above-mentioned acidproof adhesivity and alkaline-resisting adhesivity.In addition, when introducing primary amide base further in (A) composition, above-mentioned acidproof adhesivity and alkaline-resisting adhesivity improve further.
As (A) composition, various known composition can be used, be not particularly limited.Such as, preferably using material that following compositions obtains as reacted constituent: (methyl) acrylic acid hydroxy alkyl ester (a1) (hereinafter referred to as (a1) composition), (methyl) alkyl acrylate (a2) (except the composition with hydroxyl) (hereinafter referred to as (a2) composition), (methyl) vinyl cyanide (a3) (hereinafter referred to as (a3) composition) and (methyl) acrylamide as required (hereinafter referred to as (a4) composition).
(a1) composition introduces hydroxyl in as (A) composition of main component, using (a1) composition to react to make itself and special (B) composition, in prime coat, introducing crosslinking structure.Introducing the result of crosslinking structure is the adhesivity and hardness that this prime coat are become reach expectation.
As (a1) composition, as long as have the compound of (methyl) acryl and hydroxyalkyl ester group in molecule, various known composition can be used, be not particularly limited.Specifically, such as can enumerate: (methyl) acrylate, (methyl) Hydroxyethyl acrylate, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 2-hydroxy butyl ester, (methyl) vinylformic acid 3-hydroxy butyl ester, (methyl) vinylformic acid 4-hydroxy butyl ester, (methyl) dihydroxypropyl cyclohexyl etc.These compositions can be used alone one, also can be used in combination of two or more.
As (a2) composition, as long as at the compound in molecule with (methyl) acryl and alkyl ester group (except hydroxyalkyl), various known composition can be used, be not particularly limited.Specifically, such as can enumerate: (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) Octyl acrylate, (methyl) 2-EHA, (methyl) aliphatic acrylate, (methyl) dodecylacrylate, (methyl) octadecyl acrylate, (methyl) vinylformic acid eicosyl ester, (methyl) behenyl base ester, (methyl) vinylformic acid ring pentyl ester, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid cyclopentenes ester, (methyl) isobornyl acrylate etc.These compositions can be used alone one, also can be used in combination of two or more.In these compositions, from the viewpoint of adhering, the carbon number of preferred alkyl ester group is the composition of about 1-6.
As (a3) composition, specifically, such as can enumerate: vinyl cyanide and/or methacrylonitrile.
As (a4) composition, specifically, such as can enumerate: acrylamide, Methacrylamide, N hydroxymethyl acrylamide and N-methylol methacrylamide etc.
The usage quantity of above-mentioned each composition is not particularly limited, but, from the viewpoint of adhesivity etc., usually can in following scope.
The situation > of < does not use (a4) composition
(a1) composition: about 5-35 % by mole usually, about preferred 8-25 % by mole
(a2) composition: about 10-95 % by mole usually, about preferred 30-70 % by mole
(a3) composition: about 5-80 % by mole usually, about preferred 15-65 % by mole
< uses the situation > of (a4) composition
(a1) composition: about 5-35 % by mole usually, about preferred 8-25 % by mole
(a2) composition: about 10-87 % by mole usually, about preferred 30-70 % by mole
(a3) composition: about 5-80 % by mole usually, about preferred 15-65 % by mole
(a4) composition: about 3-55 % by mole usually, about preferred 5-40 % by mole
In addition, in the present invention, the vinyl monomer beyond above-mentioned (a1) composition to (a4) composition can be covered in the reacted constituent of (A) composition.Specifically, such as can enumerate: the alpha-olefines such as 2,4,4-trimethylammonium-1-amylene, 3-methyl-1-butene, 3-Methyl-1-pentene, 1-hexene, vinyl cyclohexane, 2-ethylene methacrylic butylcyclohexane; The unsaturated alcohols such as (methyl) vinyl carbinol, 4-amylene-1-ol, 1-methyl-3-butene-1-alcohol, 5-hexen-1-ol; The styrenics such as vinylbenzene, alpha-methyl styrene, t-butyl styrene; (methyl) benzyl acrylate classes such as (methyl) phenyl acrylate, (methyl) benzyl acrylate, (methyl) vinylformic acid 4-methyl benzyl ester; (methyl) propenoic acid dialkyl aminoalkyl ester class and their salts such as (methyl) dimethylaminoethyl acrylate, (methyl) acrylate propyl ester, (methyl) vinylformic acid lignocaine ethyl ester, (methyl) vinylformic acid diethylin propyl ester; Dialkyl aminoalkyl (methyl) acrylamide and their salts such as dimethylaminoethyl (methyl) acrylamide, diethyllaminoethyl (methyl) acrylamide, dimethylamino-propyl (methyl) acrylamide, diethylin propyl group (methyl) acrylamide; The chain tra nsfer monomer classes such as N, N-dimethyl (methyl) acrylamide, diacetone (methyl) acrylamide, sec.-propyl (methyl) acrylamide, 2-(methyl) acrylamide-2-methylpro panesulfonic acid, 2-(methyl) acrylamido-2-methylpropane formic acid (acid of 2-(メ タ) ア Network リ Le ア ミ De-2-メ チ Le プ ロ パ Application カ Le ボ Application) and their salt; Other Monofunctional monomers's classes such as vinyl-amine, (methyl) acrylate, allyl sulfhydrate, (methyl) glycidyl acrylate; Two (methyl) acrylic amides such as two (methyl) acrylamides of methylene-bis (methyl) acrylamide, ethylenebis (methyl) acrylamide, hexa-methylene; Two (methyl) esters of acrylic acids such as ethylene glycol bisthioglycolate (methyl) acrylate, Diethylene Glycol two (methyl) acrylate; The divinyl ester classes such as vinyl hexanediacetate, sebacic acid divinyl; Two monomer's classes such as diallyl dimethyl ammonium, Phthalic acid, diallyl ester, diallyl chlorendate DAC, Vinylstyrene; The trifunctional monomer classes such as 1,3,5-triacryl, six hydrogen-1,3,5-triazines, triallyl isocyanurate, triallylamine, triallyltrimelitate, N, N-diallyl acrylamide; Tetramethylol methane tetraacrylate, pyromellitic acid four allyl ester, N, N, N ', the four-functional group monomer classes etc. such as N '-tetraallyl-1,4-Diaminobutane.These compositions can be used alone one, also can be used in combination of two or more.In addition, their usage quantity is not particularly limited, but usually, relative to above-mentioned (a1) composition ~ (a4) composition, the usage quantity of these compositions is less than 10 % by mole.
(A) composition can use various known method manufacture.Specifically, such as can be obtained by following method: by (a1) composition, (a2) composition, (a3) composition and (a4) composition as required and other monomer solvent-free lower or in organic solvent described later (G), usually under the existence of radical polymerization initiator, at about 80-180 DEG C, make it copolyreaction 1-10 hours occurs.In addition, the usage quantity of organic solvent (G) is generally the solids by weight of the solution made containing (A) composition in the scope of 10-50 about % by weight.
As radical polymerization initiator, can enumerate: hydrogen peroxide, ammonium persulphate, Potassium Persulphate, peroxidized t-butyl perbenzoate, dicumyl peroxide, lauroyl peroxide (ラ ウ リ ル パ ー オ キ サ イ De), 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two (2,4-methyl pentane nitrile) (ABN-V), 2,2 '-azo-bis-iso-dimethyl etc.These compositions can be used alone one, also can be used in combination of two or more.In addition, relative to the gross weight of the reacted constituent of formation (A) composition, the usage quantity of radical polymerization initiator is usually in the scope of 0.1-2 about % by weight.
The physical property of (A) composition is not particularly limited, but from the viewpoint of initial stage adhesivity, acidproof adhesivity, alkaline-resisting adhesivity and hardness of film, usual hydroxyl value is about 30-150mgKOH/g, further, second-order transition temperature is about 0-100 DEG C; Particularly preferably hydroxyl value is about 50-100mgKOH/g, and second-order transition temperature is about 10-70 DEG C.
(B) composition is the composition worked as the solidifying agent of main component (A) composition, as long as at least have the polyisocyanates of isocyanate group in 3 molecules, can use various known composition, not be particularly limited.In addition, (B) composition and following (C) composition react with the composition with isocyanate-reactive functional group (hydroxyl, amino etc.) in (D), give prime coat of the present invention with crosslinking structure.
As the specific examples of (B) composition, at least one selected from the group of following ingredients composition can be enumerated: a kind of derivative (b1) (hereinafter referred to as (b1) composition) selected from the group of the biuret body of diisocyanate cpd, isocyanuric acid body and affixture composition; Be somebody's turn to do the reaction product (b2) (hereinafter referred to as (b2) composition) of (b1) composition and diatomic alcohol compounds; Tri-isocyanate compound (b3) (composition except belonging to (b1) composition and (b2) composition) (hereinafter referred to as (b3) composition); And other polyisocyanate compound (hereinafter referred to as (b4) composition).
As the diisocyanate cpd forming (b1) composition, such as, can enumerate: the aromatic diisocyanates such as tolylene diisocyanate, '-diphenylmethane diisocyanate, xylylene diisocyanate (キ シ リ レ Application ジ イ ソ シ ア ネ ー ト); The aliphatic diisocyanates such as hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, lysinediisocyanate; And the ester ring type vulcabond such as dicyclohexyl methane diisocyanate, isophorone diisocyanate, Isosorbide-5-Nitrae-cyclohexyl diisocyanate, hydrogenated xylene diisocyanate and hydrogenated tolylene diisocyanate.
In addition, the biuret body of above-mentioned diisocyanate cpd represents with following structural formula.
(in formula, R
3represent the residue of above-mentioned diisocyanate cpd)
In addition, the isocyanuric acid body of above-mentioned diisocyanate cpd represents with following structural formula.
[changing 1]
(in formula, R
4represent the residue of above-mentioned diisocyanate cpd)
In addition, the affixture of above-mentioned diisocyanate cpd represents with following structural formula.
[changing 2]
(in formula, R
5represent carbon number 1-3 alkyl or with OCN-R
6-HN-C (=O)-O-CH
2the functional group of-expression, R
6represent the residue of above-mentioned diisocyanate cpd).
To the diatomic alcohol compounds forming (b2) composition, be not particularly limited, such as, can enumerate: ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,3 butylene glycol, neopentyl glycol, 1,6-hexylene glycol, ethohexadiol, dipropylene glycol, polyoxyethylene glycol, polypropylene glycol etc.These compositions can be used alone one, also can be used in combination of two or more.Wherein, carbon number can be about 2-20, preferred about 4-8.
(b2) composition can by various known method manufacture.Specifically, such as, can be obtained by reacting by above-mentioned (b1) composition and above-mentioned diatomic alcohol compounds are carried out urethane reaction (the anti-ying of ウ レ タ Applicationization) under the following conditions: the equivalence ratio of the hydroxyl of the isocyanate group of described (b1) composition (NCO ') and described diatomic alcohol compounds (OH ') (NCO '/OH ') usually in the scope of about 5-20, preferably in the scope of about 10-20, usually react 1-5 hours at 40-80 DEG C.In addition, (b2) composition obtained, its isocyanate group equivalent is generally about 1-10meq/g, preferred about 3-6meq/g.
As (b3) composition, such as can enumerate: Toluene-2,4-diisocyanate, 4,6-triisocyanate, triphenylmethane triisocyanate, tri o cresyl thiophosphate (phenylcarbimide), 1,6,11-undecane triisocyanate, 1,3, the polyisocyanates (goods name " デ ュ ラ ネ ー ト MHG-80B ", Japanese Asahi Chemical Industry chemistry (strain) makes) etc. of the triisocyanates such as 6-hexa-methylene triisocyanate, norbornane triisocyanate and six functional groups.
As (B) composition, from the viewpoint of above-mentioned initial stage adhesivity, acidproof adhesivity and alkaline-resisting adhesivity balance, above-mentioned (b1) composition (b1) composition particularly preferably using above-mentioned aliphatic diisocyanate as constituent.
In addition, the ratio of (A) composition with the usage quantity of (B) composition is not particularly limited, from the viewpoint such as adhesivity and hardness of film, the mol ratio (NCO/OH) of the hydroxyl of (A) composition and the isocyanate group of (B) composition is generally about 0.2-5, preferably about 1-2.
As (C) composition, as long as at least have the active energy ray polymeric compounds of 3 carbon-carbon double bonds groups in molecule, various known composition can be used, be not particularly limited.In addition, as this carbon-carbon double bonds group, such as, can enumerate: vinyl, propenyl, acryl, methacryloyl etc.
As the preferred concrete kind of (C) composition, at least one selected from the group of following compositions composition can be enumerated: there is 3-6 (methyl) acryl in molecule and there is the active energy ray polymeric compounds (C1) (hereinafter referred to as (C1) composition) of at least 1 hydroxyl; There is 3-6 (methyl) acryl in molecule and not there is the active energy ray polymeric compounds (C2) (hereinafter referred to as (C2) composition) of hydroxyl; There is 3-6 allyl group in molecule and there is the active energy ray polymeric compounds (C3) (hereinafter referred to as (C3) composition) of at least 1 hydroxyl; There is 3-6 allyl group in molecule and not there is the active energy ray polymeric compounds (C4) (hereinafter referred to as (C4) composition) of hydroxyl.Even have the composition of hydroxyl in these compositions, in the composition of this hydroxyl and above-mentioned (B) composition and aftermentioned (D), carry out chemical bonding with the composition of hydroxyl reaction, prime coat of the present invention forms crosslinking structure, and its hardness of result strengthens, and is therefore more preferably.
As (C1) composition, such as, can enumerate: (methyl) acrylic compound containing hydroxyl such as TriMethylolPropane(TMP) two (methyl) acrylate, glycerine two (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, tetramethylolmethane monohydroxy three (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane two (methyl) acrylate, Dipentaerythritol monohydroxy five (methyl) acrylate, Dipentaerythritol four (methyl) acrylate.
As (C2) composition, such as, can enumerate: (methyl) acrylic compound not containing hydroxyl such as trimethylolpropane tris (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, ditrimethylolpropane four (methyl) acrylate, glycerol three (methyl) acrylate of trimethylolpropane tris (methyl) acrylate, ethylene-oxide-modified trimethylolpropane tris (methyl) acrylate, epoxy pronane modification.
As (C3) composition, such as, can enumerate tetramethylolmethane monohydroxy triallyl ether.In addition, as (C4) composition, such as, the vinyl compounds such as citric acid triallyl can be enumerated.
The usage quantity of (C) composition is not particularly limited, usually, when by (A) composition and (B) composition as 100 weight parts (converting by solids component), usually, in the scope about 10-500 weight part, (all press solids component to convert) in the scope preferably about 30-300 weight part.
In addition, following compositions can combinationally use together with (C) composition: 1,3-butyleneglycol two (methyl) acrylate, 1, two (methyl) esters of acrylic acids such as ethylene-oxide-modified two (methyl) acrylate of 4-butyleneglycol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, dihydroxyphenyl propane; The oligopolymer such as poly-(methyl) acrylate of polyurethane polyureas (methyl) acrylate, polyester; Single (methyl) esters of acrylic acid such as (methyl) 2-EHA, (methyl) isodecyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) benzyl acrylate, (methyl) vinylformic acid cyclopentenes ester, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid dicyclopentenyl ester, (methyl) isobornyl acrylate.
(D) composition is with general formula (1): X
1-Si (R
1)
a(OR
2)
3-athe reactive polyglycidyl compounds represented, in formula (1), X
1represent containing the group of following functional group, described functional group reacts with at least one group be selected from the group that is made up of hydroxyl, isocyanate group and the group containing polymerizability carbon-carbon double bond; R
1represent the alkyl of hydrogen or carbon number 1-8; R
2represent the alkyl of carbon number 1-8; A represents 0,1 or 2.
As the X in (D) composition that above-mentioned general formula (1) represents
1in functional group, such as can enumerate a kind of functional group of selecting from the group of following radicals composition: isocyanate group, sulfydryl, amino, epoxy group(ing), anhydride group and vinyl.
As X
1in functional group be the compound of isocyanate group, such as can enumerate: 3-isocyanate group propyl trimethoxy silicane, 3-isocyanate group propyl-triethoxysilicane, 3-isocyanate group hydroxypropyl methyl dimethoxysilane, 3-isocyanate group hydroxypropyl methyl diethoxy silane etc.
As X
1in functional group be the compound of sulfydryl, such as can enumerate: 3-mercaptopropyi Trimethoxy silane, 3-Mercaptopropyltriethoxysilane, 3-mercaptopropyi methyl dimethoxysilane, 3-mercaptopropyi methyldiethoxysilane etc.
As X
1in functional group be amino compound, such as can enumerate: N-2-(amino-ethyl)-3-amino propyl methyl dimethoxysilane, N-2-(amino-ethyl)-3-TSL 8330,3-TSL 8330, APTES, 3-urea propyl trialkoxy silane etc.
As X
1in functional group be the compound of epoxy group(ing), such as can enumerate: 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3-glycydoxy methyl dimethoxysilane, 3-glycydoxy Trimethoxy silane, 3-glycydoxy methyldiethoxysilane, 3-glycydoxy triethoxyl silane etc.
As X
1in functional group be the compound of anhydride group, such as can enumerate: the silica-based propyl succinimide acid anhydrides of 3-trimethoxy first.
As X
1in functional group be the compound of vinyl, such as can enumerate: vinyltrimethoxy silane, vinyltriethoxysilane, styryl Trimethoxy silane, 3-(methyl) acryloxypropyl dimethoxysilane, 3-(methyl) acryloxypropyl Trimethoxy silane, 3-(methyl) acryloxypropyl diethoxy silane, 3-(methyl) acryloxypropyl triethoxyl silane etc.
The usage quantity of (D) composition is not particularly limited, usually, when by (A) composition and (B) composition as 100 weight parts (converting by solids component), usually in the scope about 5-50 weight part, in the scope preferably about 20-40 weight part.
As required, priming paint of the present invention can contain various known inorganic particulate (E) (hereinafter referred to as (E) composition).Specifically, such as can enumerate: the particles such as silicon-dioxide, titanium dioxide, aluminum oxide, zinc oxide, stannic oxide, zirconium white, tin indium oxide (ITO), antimony tin (ATO), aluminium hydroxide, calcium hydroxide, magnesium hydroxide.These compositions can be used alone one, also can be used in combination of two or more.Wherein, particularly preferably silicon-dioxide and/or aluminum oxide.In addition, various process can be applied to the surface of (E) composition.In addition, the median particle diameter (d50) of (E) composition is not particularly limited, is generally about 10nm-5 μm.
The usage quantity of (E) composition is not particularly limited, usually, when by (A) composition and (B) composition as 100 weight parts (converting by solids component), usually in the scope about 1-20 weight part, in the scope preferably about 5-10 weight part.
Priming paint of the present invention can contain Photoepolymerizationinitiater initiater (F) (hereinafter referred to as (F) composition) further.
As the concrete kind of (F) composition, such as, can enumerate: benzophenone, 4 '-methylthio group-α-morpholinyl-Alpha-Methyl Propiophenone, 2,4,6-tri-methyl benzophenone, methyl o-benzoylbenzoate, 4-phenyl benzophenone, tertiary butyl anthraquinone, 2-ethyl-anthraquinone, diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenylpropyl alcohol alkane-1-ketone, oligomerization { 2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] acetone }, benzil dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoin methyl ether, Benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2-methyl-[4-(methylthio group) phenyl]-2-morpholinyl-1-acetone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-1-butanone, 2-dimethylamino-2-(4-methyl-benzyl)-1-[4-(4-morpholinyl) phenyl]-1-butanone, diethyl thioxanthone, isopropyl thioxanthone, TMDPO, two (2,6-Dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, two (2,4,6-trimethylbenzoyl) phenyl phosphine oxide, 2-hydroxyl-1-{4-[4-(2-hydroxy-2-methyl propionyl) benzyl] phenyl }-2-methylpropane-1-ketone, methyl benzoylformate, phenylglyoxalates methyl esters, 4,4 '-bis-(diethylin) benzophenone, 2-benzyl-2-dimethylamino-4-morpholine phenyl propyl ketone, 2,2-dimethoxy-2-phenyl acetophenone, 2-methyl isophthalic acid-phenyl-2-morpholino propane-1-ketone, 2-methyl isophthalic acid-(4-hexyl phenyl)-2-morpholino propane-1-ketone, the Photoepolymerizationinitiater initiater etc. that 2-ethyl-2-dimethylamino-1-(4-morphlinophenyl)-1-butanone and No. 2014-1390, Japanese Laid-Open Patent Publication are recorded.These compositions can be used alone one, also can be used in combination of two or more.In addition, as (F) composition, such as, the commercial goods such as Irgacure907, Irgacure369, Irgacure379, Irgacure651, Irgacure184, Irgacure500, Irgacure1000, Irgacure149, Irgacure261, Darocure1173 can be used.In addition, these compositions can be used alone one, also can be used in combination of two or more.
The usage quantity of (F) composition is not particularly limited, usually, when by (C) composition as 100 weight parts (by solids component convert), (F) in the scope of the usage quantity of composition usually about 0.1-10 weight part, in the scope preferably about 1-5 weight part.
In addition, as the auxiliary agent of (F) composition, following compositions can be combinationally used: trolamine, tri-isopropanolamine, 4,4 '-dimethylamino benzophenone (michaelis ketone), 4,4 '-diethylin benzophenone, 2-dimethyl ethyl aminobenzoate, 4-dimethyl ethyl aminobenzoate, 4-dimethylaminobenzoic acid (n-butoxy) ethyl ester, 4-dimethylaminobenzoic acid isopentyl ester, 4-dimethylaminobenzoic acid-2-ethylhexyl, 2,4-diethyl thioxanthone, 2,4-di-isopropyl thioxanthones etc.In addition, these compositions can be used alone one, also can be used in combination of two or more.
In priming paint of the present invention, organic solvent (G) (hereinafter referred to as (G) composition) can be contained further.Specifically, such as can enumerate: the rudimentary ketone such as methylethylketone, mibk; Toluene etc. are aromatic hydrocarbon based; The alcohols such as ethanol, propyl alcohol; The ether-ether such as propylene glycol methyl ether acetate, ethyl cellosolve acetate class; Ethyl acetate; Trichloromethane; Dimethyl formamide etc.These compositions can be used alone one, also can be used in combination of two or more.
The usage quantity of (G) composition is not particularly limited.But the usage quantity of (G) composition normally makes the solid component concentration of priming paint of the present invention become in the scope of 1-60 about % by weight.
In priming paint of the present invention, urethanation catalyst can be contained further.Specifically, such as can enumerate: the organo-metallic catalysts such as dibutyl tin laurate, tin dilaurate dioctyl tin, Bismuth Octoate; The organic amine series catalysts etc. such as diazabicyclooctane, dimethylcyclohexylamine, 4-methyl-diaminopropane, ethyl morpholine, dimethylethanolamine, triethylamine, triethylenediamine.These compositions can be used alone one, also can be used in combination of two or more.In addition, the usage quantity of this urethanation catalyst is not particularly limited, but, when by (A) composition and (B) composition as 100 weight parts (converting by solids component), in the usage quantity of this catalyzer scope usually about 0.01-0.5 weight part, in the scope preferably about 0.05-0.2 weight part.
In addition, as required, priming paint of the present invention can contain many sulfhydryl compounds.Specifically, such as can enumerate: 1,3,5-tri-(3-sulfydryl butyryl acyloxy ethyl)-1,3,5-triazine-2,4,6 (1H, 3H, 5H)-triketone, Isosorbide-5-Nitrae-bis-(3-sulfydryl butyryl acyloxy) butane, trimethylolpropane tris (3-mercaptobutylate), trimethylolethane trimethacrylate (3-mercaptobutylate), tetramethylolmethane four (3-mercaptobutylate), Dipentaerythritol six (3-mercaptobutylate) etc.These compositions can be used alone one, also can be used in combination of two or more.The usage quantity of this many sulfhydryl compound is not particularly limited, when by (A) composition and (B) composition as 100 weight parts (converting by solids component), in the usage quantity of this many sulfhydryl compound scope usually about 1-20 weight part, in the scope about preferred 5-10 weight part.
In addition, when using many sulfhydryl compounds, in order to extend the pot life of priming paint of the present invention, various known mercaptan-alkene reaction suppressor can be used.Specifically, such as can enumerate: the phosphine such as triphenylphosphine, triphenyl phosphite based compound; P methoxy phenol, Resorcinol, pyrogallol, naphthylamines, tert-butyl catechol, cuprous chloride, 2,6-ditertbutylparacresol, 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol), 2, the radical polymerization inhibitors such as 2 '-methylene-bis (4-methyl-6-tert-butylphenol), N-nitroso-group-N-Phenylhydroxylamine aluminium salt, phenylbenzene nitrosamine; The tertiary amines such as benzyldimethylamine, 2-(dimethylamino methyl) phenol, 2,4,6-tri-(bis aminomethyl) phenol, 1,8-diazabicyclo [5.4.0] 11 carbon-7-alkene; The imidazoles etc. such as glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-ethylhexyl imidazoles, 2-undecylimidazole, 1-cyano ethyl-glyoxal ethyline.These compositions can be used alone one, also can be used in combination of two or more.
In priming paint of the present invention, other additives such as flow agent, antioxidant, polymerization retarder, UV light absorber can also be contained.
The base material with Copper thin film of the present invention is on the surface of various base material, the composite base material be laminated in the following order: the prime coat of solidifying priming paint of the present invention; And copper film layer.
As above-mentioned base material, such as, can enumerate: not only have the plastic materials such as polyester, polyvinyl chloride, polymeric amide, polyimide, polycarbonate, polyethylene, polypropylene, also have the non-plastic materials such as metal, glass, paper, nano-cellulose paper, timber.In addition, not being particularly limited the shape of these base materials, such as, can be spherical, cylindric, rectangular-shaped, tabular, membranaceous; In addition, the part on their surface can have the existence such as concavo-convex and curved surface.When the base material with Copper thin film of the present invention uses as conducting film, from the viewpoint of thermotolerance and optical characteristics etc., the preferred plastic film of base material, particularly preferably polyester film.In addition, the thickness of this base material film is not also particularly limited, is generally about 50-200 μm.
In addition, the thickness of above-mentioned cured base enamelled coating is not particularly limited, is generally about 0.1-5 μm.
As above-mentioned copper film layer, such as, can enumerate: copper vapor-deposited film, copper sputtered film, copper cvd film.The film with Copper thin film of the present invention when for electrode film, as this Copper thin film, particularly preferably copper vapor-deposited film or copper sputtered film.In addition, the thickness of this copper film layer is not particularly limited, is generally about 0.1-2 μm.
The manufacture method with the base material of Copper thin film of the present invention is not particularly limited.Such as can enumerate the embodiment comprising following operation: (I) is coated with priming paint of the present invention on the surface (base material is such as membranaceous, is one or two sides) of base material; (II) by after this base material heating; (III) by irradiating active energy ray further, cured base enamelled coating is formed; (IV) on this cured base enamelled coating, copper film layer is formed.
About operation (I), to the surface at above-mentioned base material, (base material is such as membranaceous words, for one or two sides) condition that is coated with priming paint of the present invention is not particularly limited, as coating apparatus, such as, can enumerate: spraying machine, roller coating machine, reverse roller coating machine, intaglio plate roller coating machine, blade coating machine, rod coater, point type coating machine etc.In addition, not also being particularly limited glue spread, usually, is 0.01-10g/m as drying solid composition
2left and right.
About operation (II), be not particularly limited condition during this base material heating, typical temperature is about 80-150 DEG C, and the time is 10 seconds to about 2 minutes.By this process, when with an organic solvent (G), organic solvent is volatilized from the prime coat of semicure, in this layer simultaneously, (A) composition and the reaction of (B) composition generation urethane, form crosslinking structure.In addition, in the reaction of this urethane, the composition such as with hydroxyl, amino, sulfydryl, isocyanate group etc. in (C) composition and (D) composition also participates in reaction.
About operation (III), the condition when prime coat of subtend semicure irradiates active energy ray is not particularly limited.As active energy ray, such as, can enumerate: ultraviolet, electron beam etc.As ultraviolet supply source, such as, can enumerate: high voltage mercury lamp, metal halide lamp etc., its irradiation energy is generally 100-2,000mJ/cm
2left and right.As the supply mode of electron beam, such as, can enumerate: the irradiation of scanning electron bundle, curtain electron beam irradiation etc., its irradiation energy is generally about 10-200kGy.By this process, in the prime coat be heating and curing, there is Raolical polymerizable between (C) composition itself is mutual, form crosslinking structure.In this polyreaction, the composition with active energy ray polymerizable functional group in (D) composition also participates in reaction.
About operation (IV), the method that this cured base enamelled coating is formed copper film layer is not particularly limited, preferred so-called dry-coated method.Specifically, such as can enumerate: the physical method such as vaccum gas phase sedimentation method or sputtering method; The chemical processes such as CVD (chemical gas phase reaction etc.) etc.
Conducting film of the present invention is the film using the base material with Copper thin film of the present invention to be formed.Particularly, this has the film obtained by copper vapour deposition plastic film or copper sputtered film in the base material of Copper thin film, and the substitute as ito film is useful.
The method for making of this conducting film is not particularly limited, but, when it can be used as electrode film to use, following methods can be enumerated: on above-mentioned copper vapour deposition plastic film or copper sputtered film, be coated with various resist, after describing electrode pattern, be immersed in etching solution (basic solution), removing resist.The shape of electrode pattern can be following any shape: thin-line-shaped, point-like, netted, planar etc.
Embodiment
Next, by embodiment and comparative example, the present invention is described in further detail, but scope of the present invention is not made by these embodiments and being limited.In addition, " part " in embodiment represents weight standard.In addition, hydroxyl value is the value according to JIS-0070 standard test.In addition, second-order transition temperature is the value using commercially available determining instrument (goods name " DSC8230B ", Rigaku motor (strain) is made) to measure.
The manufacture > of < (A) composition
Production Example 1
To having agitator, thermometer, reflux condensing tube, in the reaction vessel of dropping funnel and nitrogen ingress pipe, be mixed into the Hydroxyethyl acrylate (HEA) 40.8 parts (13.6 % by mole) as (a1) composition, as methyl methacrylate (MMA) 72.0 parts (about 27.7 % by mole) and the butyl acrylate (BA) 79.2 parts (about 23.8 % by mole) of (a2) composition, as the vinyl cyanide (AN) 48.0 parts (34.9 % by mole) of (a3) composition and the ethyl acetate 445.7 parts as (G) composition, reaction system is set in 70 DEG C.Then, be mixed into 2,2 '-azo two (2,4-methyl pentane nitrile) (ABN-V) 1.2 parts, near 70 DEG C, be incubated 6 hours.Then, be mixed into ABN-V2.4 part, reaction system is incubated 6 hours again near uniform temp.Afterwards, reaction system is cooled to room temperature, thus obtains the solution of acrylic copolymer (A-1), its second-order transition temperature is 13 DEG C, and hydroxyl value is 80mgKOH/g.
Production Example 2
To in the reaction vessel same with Production Example 1, be mixed into the HEA51.0 part (13.3 % by mole) as (a1) composition, MMA72.0 part (about 21.8 % by mole) as (a2) composition and BA102.0 part (about 24.1 % by mole), as (a3) composition AN60.0 part (about 34.3 % by mole), as the acrylamide (AM) 15.0 parts (about 6.4 % by mole) of (a4) composition and the ethyl acetate 557.1 parts as (G) composition, reaction system is set in 70 DEG C.Then, be mixed into ABN-V1.5 part, near 70 DEG C, be incubated 6 hours.Then, be mixed into ABN-V3.0 part, reaction system is incubated 6 hours again near uniform temp.Afterwards, reaction system is cooled to room temperature, thus obtains the solution of acrylic copolymer (A-2), its second-order transition temperature is 13 DEG C, and hydroxyl value is 80mgKOH/g.
Production Example 3
To in the reaction vessel same with Production Example 1, be mixed into the hydroxyethyl methylacrylate (HEMA) 59.2 parts (12.5 % by mole) as (a1) composition, MMA196.8 part (about 54.2 % by mole) as (a2) composition, as AN64.0 part (about 33.3 % by mole) of (a3) composition and the ethyl acetate 564.3 parts as (G) composition, reaction system be set in 70 DEG C.Then, be mixed into ABN-V3.2 part, near 70 DEG C, be incubated 6 hours.Then, be mixed into ABN-V3.2 part, reaction system is incubated 6 hours again near uniform temp.Afterwards, reaction system is cooled to room temperature, thus obtains the solution of acrylic copolymer (A-3), its second-order transition temperature is 92 DEG C, and hydroxyl value is 80mgKOH/g.
Production Example 4
To in the reaction vessel same with Production Example 1, be mixed into the HEA25.5 part (6.8 % by mole) as (a1) composition, MMA99.0 part (about 30.5 % by mole) and BA115.5 part (about 27.8 % by mole) as (a2) composition, as AN60.0 part (about 34.9 % by mole) of (a3) composition and the ethyl acetate 557.1 parts as (G) composition, reaction system be set in 70 DEG C.Then, be mixed into ABN-V1.5 part, near 70 DEG C, be incubated 6 hours.Then, be mixed into ABN-V3.0 part, reaction system is incubated 6 hours again near uniform temp.Afterwards, reaction system is cooled to room temperature, thus obtains the solution of acrylic copolymer (A-4), its second-order transition temperature is 13 DEG C, and hydroxyl value is 40mgKOH/g.
Production Example 5
To in the reaction vessel same with Production Example 1, be mixed into the HEA76.5 part (18.1 % by mole) as (a1) composition, MMA37.5 part (about 10.3 % by mole) and BA81.0 part (about 17.3 % by mole) as (a2) composition, as AN105.0 part (about 54.3 % by mole) of (a3) composition and the ethyl acetate 557.1 parts as (G) composition, reaction system be set in 70 DEG C.Then, be mixed into ABN-V1.5 part, near 70 DEG C, be incubated 6 hours.Then, be mixed into ABN-V3.0 part, reaction system is incubated 6 hours again near uniform temp.Afterwards, reaction system is cooled to room temperature, thus obtains the solution of acrylic copolymer (A-5), its second-order transition temperature is 13 DEG C, and hydroxyl value is 120mgKOH/g.
Relatively Production Example 1
To in the reaction vessel same with Production Example 1, be mixed into the HEA40.8 part (15.1 % by mole) as (a1) composition, MMA192.0 part (about 82.5 % by mole) as (a2) composition and BA7.2 part (about 2.4 % by mole) and the methylethylketone 445.7 parts as (G) composition, reaction system be set in 80 DEG C.Then, be mixed into 2,2 '-Diisopropyl azodicarboxylate (AIBN) 1.2 parts, near 80 DEG C, be incubated 5 hours.Then, be mixed into AIBN2.4 part, reaction system is incubated 4 hours again near uniform temp.Afterwards, reaction system is cooled to room temperature, thus obtains the solution of acrylic copolymer (A '), its second-order transition temperature is 70 DEG C, and hydroxyl value is 80mgKOH/g.
[table 1]
The preparation > of < priming paint
Embodiment 1
By the solution 286.0 parts of (A-1) composition, as the biuret body (trade(brand)name " デ ュ ラ ネ ー ト 24A-100 " of the hexamethylene diisocyanate of (B) composition, Asahi Chemical Industry's chemistry of Japan (strain) system) 25.7 parts, as the pentaerythritol triacrylate of (C1) composition and the mixture (trade(brand)name " PVC ス コ ー ト #300 " of tetramethylol methane tetraacrylate, Osaka, Japan Organic Chemical Industry (strain) is made) 50.0 parts, as the 3-isocyanate group propyl-triethoxysilicane (trade(brand)name " KBE-9007 " of (D) composition, SHIN-ETSU HANTOTAI シ リ コ ー Application of Japan (strain) system) 40.0 parts, as the aluminium oxide particles dispersion agent (trade(brand)name " NANOBYK3610 " of (E) composition, Japan's PVC ッ Network ケ ミ ー ジ ャ パ Application (strain) system) 5.0 parts and Photoepolymerizationinitiater initiater (trade(brand)name " Irg907 " as (F) composition, Japan チ バ ジ ャ パ Application (strain) system) 2.5 parts of fully mixing, preparation priming paint.
Embodiment 2
The solution 286.0 parts of (A-1) composition, デ ュ ラ ネ ー ト 24A-10025.7 part, PVC ス コ ー ト #300100.0 part, KBE-900740.0 part, NANOBYK36105.0 part and Irg9075.0 part are fully mixed, preparation priming paint.
Embodiment 3
The solution 286.0 parts of (A-1) composition, デ ュ ラ ネ ー ト 24A-10025.7 part, PVC ス コ ー ト #300150.0 part, KBE-900740.0 part, NANOBYK36105.0 part and Irg9077.5 part are fully mixed, preparation priming paint.
Embodiment 4
By the solution 286.0 parts of (A-1) composition, デ ュ ラ ネ ー ト 24A-10025.7 part, PVC ス コ ー ト #300150.0 part, 3-mercaptopropyi Trimethoxy silane (trade(brand)name " KBM-803 " as (D) composition, SHIN-ETSU HANTOTAI シ リ コ ー Application of Japan (strain) system) 40.0 parts, NANOBYK36105.0 part and Irg9077.5 part fully mixes, preparation priming paint.
Embodiment 5
The solution 286.0 parts of (A-1) composition, デ ュ ラ ネ ー ト 24A-10025.7 part, PVC ス コ ー ト #300200.0 part, KBM-80340.0 part, NANOBYK36105.0 part and Irg90710.0 part are fully mixed, preparation priming paint.
Embodiment 6
The solution 286.0 parts of (A-2) composition, デ ュ ラ ネ ー ト 24A-10025.7 part, PVC ス コ ー ト #300100.0 part, KBE-900740.0 part, NANOBYK36105.0 part and Irg9075.0 part are fully mixed, preparation priming paint.
Embodiment 7
The solution 286.0 parts of (A-3) composition, デ ュ ラ ネ ー ト 24A-10025.7 part, PVC ス コ ー ト #300100.0 part, KBE-900740.0 part, NANOBYK36105.0 part and Irg9075.0 part are fully mixed, preparation priming paint.
Embodiment 8
The solution 286.0 parts of (A-4) composition, デ ュ ラ ネ ー ト 24A-10025.7 part, PVC ス コ ー ト #300100.0 part, KBE-900740.0 part, NANOBYK36105.0 part and Irg9075.0 part are fully mixed, preparation priming paint.
Embodiment 9
The solution 286.0 parts of (A-5) composition, デ ュ ラ ネ ー ト 24A-10025.7 part, PVC ス コ ー ト #30050.0 part, KBE-900740.0 part, NANOBYK36105.0 part and Irg9072.5 part are fully mixed, preparation priming paint.
Embodiment 10
By the isocyanuric acid body (trade(brand)name " コ ロ ネ ー ト HX " of the solution 286.0 parts of (A-1) composition, hexamethylene diisocyanate, Nippon Polyurethane Industry (Ltd.)) 28.4 parts, PVC ス コ ー ト #300100.0 part, KBE-900740.0 part, NANOBYK36105.0 part and Irg9075.0 part fully mixes, preparation priming paint.
Embodiment 11
By the solution 286.0 parts of (A-1) composition, デ ュ ラ ネ ー ト 24A-10025.7 part, the many acrylate of Dipentaerythritol (trade(brand)name " NK エ ス テ Le A-9550W ", Japan's Xin Zhong village chemical industry (strain) system) 100.0 parts, KBE-900740.0 part, NANOBYK36105.0 part and Irg9075.0 part fully mixes, preparation priming paint.
Embodiment 12
The solution 286.0 parts of (A-1) composition, デ ュ ラ ネ ー ト 24A-10025.7 part, NK エ ス テ Le A-9550W50.0 part, KBE-900740.0 part, NANOBYK36105.0 part and Irg9072.5 part are fully mixed, preparation priming paint.
Embodiment 13
By the solution 286.0 parts of (A-1) composition, デ ュ ラ ネ ー ト 24A-10025.7 part, Viscoat 295 (trade(brand)name " PVC ス コ ー ト #295 " as (C2) composition, Osaka, Japan Organic Chemical Industry (strain) is made) 100.0 parts, KBE-900740.0 part, NANOBYK36105.0 part and Irg9075.0 part fully mixes, preparation priming paint.
Embodiment 14
The solution 286.0 parts of (A-1) composition, デ ュ ラ ネ ー ト 24A-10025.7 part, PVC ス コ ー ト #29550.0 part, KBE-900740.0 part, NANOBYK36105.0 part and Irg9072.5 part are fully mixed, preparation priming paint.
Embodiment 15
By the solution 286.0 parts of (A-1) composition, デ ュ ラ ネ ー ト 24A-10025.7 part, PVC ス コ ー ト #300100.0 part, 3-acryloxypropyl Trimethoxy silane (trade(brand)name " KBM-5103 " as (D) composition, SHIN-ETSU HANTOTAI シ リ コ ー Application of Japan (strain) system) 40.0 parts, NANOBYK36105.0 part and Irg9075.0 part fully mixes, preparation priming paint.
Embodiment 16
By the solution 286.0 parts of (A-1) composition, デ ュ ラ ネ ー ト 24A-10025.7 part, PVC ス コ ー ト #300100.0 part, 3-methacryloxypropyl trimethoxy silane (trade(brand)name " サ イ ラ エ ー ス S710 " as (D) composition, Japan チ ッ ソ (strain) system) 40.0 parts, NANOBYK36105.0 part and Irg9075.0 part fully mixes, preparation priming paint.
Embodiment 17
By the solution 286.0 parts of (A-1) composition, デ ュ ラ ネ ー ト 24A-10025.7 part, PVC ス コ ー ト #300100.0 part, 3-glycydoxy Trimethoxy silane (trade(brand)name " サ イ ラ エ ー ス S510 " as (D) composition, Japan チ ッ ソ (strain) system) 40.0 parts, NANOBYK36105.0 part and Irg9075.0 part fully mixes, preparation priming paint.
Comparative example 1
The solution 286.0 parts of (A ') composition, デ ュ ラ ネ ー ト 24A-10025.7 part, PVC ス コ ー ト #300100.0 part, KBE-900740.0 part, NANOBYK36105.0 part and Irg9075.0 part are fully mixed, has prepared priming paint.
Comparative example 2
The solution 286.0 parts of (A-1) composition, デ ュ ラ ネ ー ト 24A-10025.7 part, PVC ス コ ー ト #300150.0 part, NANOBYK36105.0 part and Irg9077.5 part are fully mixed, has prepared the priming paint not containing (D) composition.
Comparative example 3
The solution 286.0 parts of (A-1) composition, デ ュ ラ ネ ー ト 24A-10025.7 part, PVC ス コ ー ト #300200.0 part, NANOBYK36105.0 part and Irg90710.0 part are fully mixed, has prepared the priming paint not containing (D) composition.
The making > of < copper vapour deposition plastic film
On commercially available polyester film (trade(brand)name " Le ミ ラ ー U48 ", toray (strain) is made, and 100 μm thick), the priming paint rod coater of embodiment 1 is coated with, makes dry film thickness be about 1.0 μm, 120 DEG C of dryings 1 minute.Then 300mJ/cm is used
2carry out UV solidification, thus obtain the coated film possessing cured base enamelled coating.For the priming paint of other embodiment and comparative example, operate equally, obtain coated film.
Then, this coated film priming paint aspect on, use commercially available vapor phase growing apparatus (goods name " NS-1875-Z ", Japanese Western Hills make institute's (strain) system), obtain (thickness is about 100nm) copper vapour deposition plastic film by vapour deposition copper.For the priming paint of other embodiment and comparative example, operate equally, obtain copper vapour deposition plastic film.
1. the hardness test of cured base enamelled coating
The pencil hardness of the cured base enamelled coating of each coated film of embodiment and comparative example, evaluates according to JISK5600-5-4 standard.Result is shown in table 1.
2. initial stage adhesivity
For each copper vapor-deposited film that embodiment and comparative example obtain, according to JISK5600-5-6 standard, implement cross cutting test.Specifically, cutting knife is used to be cut into 100 pieces of grids in this copper vapour deposition face, after sticking adhesive tape (trade(brand)name " セ ロ テ ー プ " (registered trademark), Japan's day companion (strain) system), drawing stripping in the vertical direction, counting there is no the grid number peeled off.Initial stage adhesivity be have rated equally to the copper vapor-deposited film of other embodiment and comparative example.Result is shown in table 1.In addition, under unstripped grid number is 100 and relies on the four perfectly smooth situations in limit of visual arbitrary grid, be judged as that adhesivity is best, so the signalment symbol (as follows) of " * " in Table 1.
3. acidproof adhesivity
Copper vapor-deposited film embodiment and comparative example obtained is flooded after 5 minutes in 4% aqueous hydrochloric acid being heated to 40 DEG C, as described above, have rated the adhesivity of copper vapor-deposited film.
4. alkaline-resisting adhesivity
Copper vapor-deposited film embodiment and comparative example obtained, floods after 5 minutes, as described above, have rated the adhesivity of copper vapor-deposited film in 4% aqueous sodium hydroxide solution being heated to 40 DEG C.
[table 3]
Claims (17)
1. for having a priming paint for the base material of Copper thin film, wherein, described priming paint contains:
There is the acrylic copolymer (A) of hydroxyl, alkyl ester group, itrile group and primary amide base as required;
At least have 3 isocyanate group polyisocyanates (B);
At least there is the active energy ray polymeric compounds (C) of 3 carbon-carbon double bonds groups; And
With general formula (1): X
1-Si (R
1)
a(OR
2)
3-athe reactive polyglycidyl compounds (D) represented, in formula (1), X
1for the group containing following functional group, described functional group reacts with at least one group be selected from by hydroxyl, isocyanate group and the group that forms containing the group of polymerizability carbon-carbon double bond; R
1represent the alkyl of hydrogen or carbon number 1-8; R
2represent the alkyl of carbon number 1-8; A represents 0,1 or 2.
2. priming paint according to claim 1, wherein, (A) composition is for making the reacted material of following compositions: (methyl) acrylic acid hydroxy alkyl ester (a1), (methyl) alkyl acrylate (a2) (except the composition with hydroxyl), (methyl) vinyl cyanide (a3) and (methyl) acrylamide (a4) as required.
3. priming paint according to claim 1 and 2, wherein, the hydroxyl value of described (A) composition is 30-150mgKOH/g, and second-order transition temperature is 0-100 DEG C.
4. according to the priming paint in claim 1-3 described in any one, wherein, a kind of derivative (b1) of (B) composition for selecting from the group formed from the biuret body of diisocyanate cpd, isocyanuric acid body and adduct.
5. the equivalence ratio NCO/OH of the isocyanate group contained in the hydroxyl according to the priming paint in claim 1-4 described in any one, wherein, contained in described (A) composition and described (B) composition is 0.2-5.
6. according to the priming paint in claim 1-5 described in any one, wherein, described (C) composition is: the active energy ray polymeric compounds (C1) in molecule with 3-6 (methyl) acryl and at least 1 hydroxyl; And/or there is 3-6 (methyl) acryl in molecule and not there is the active energy ray polymeric compounds (C2) of hydroxyl.
7. according to the priming paint in claim 1-6 described in any one, wherein, represent the X of the above-mentioned general formula (1) of (D) composition
1in functional group be a kind of functional group selected from the group that following group forms: isocyanate group, sulfydryl, amino, epoxy group(ing), anhydride group and vinyl.
8. according to the priming paint in claim 1-7 described in any one, wherein, described priming paint comprises inorganic particulate (E) further.
9. according to the priming paint in claim 1-8 described in any one, wherein, described priming paint comprises Photoepolymerizationinitiater initiater (F) further.
10. according to the priming paint in claim 1-9 described in any one, wherein, described priming paint comprises organic solvent (G) further.
11. base materials with Copper thin film be laminated on the surface of base material in the following order: the prime coat of the solidifying priming paint in by claim 1-10 described in any one; And copper film layer.
12. base materials with Copper thin film according to claim 11, wherein, described base material is plastics.
13. base materials with Copper thin film according to claim 12, wherein, described plastics are plastic film.
14. base materials with Copper thin film according to claim 13, wherein, described plastic film is polyester film.
15. manufacture method with the base material of Copper thin film, is characterized in that:
On the surface of base material, be coated with according to the priming paint in claim 1-10 described in any one;
After this base material heating, by irradiating active energy ray further, form cured base enamelled coating;
This cured base enamelled coating forms copper film layer.
16. manufacture method according to claim 15, wherein, the method that described cured base enamelled coating is formed copper film layer is vaccum gas phase sedimentation method or sputtering method.
17. conducting films using the following base material with Copper thin film to be formed: according to the base material with Copper thin film in claim 11-14 described in any one; Or by the base material with Copper thin film obtained according to the manufacture method in claim 15-16 described in any one.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014199934 | 2014-09-30 | ||
| JP2014-199934 | 2014-09-30 |
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| Publication Number | Publication Date |
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| CN105462468A true CN105462468A (en) | 2016-04-06 |
| CN105462468B CN105462468B (en) | 2019-04-05 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510641042.8A Active CN105462468B (en) | 2014-09-30 | 2015-09-30 | Substrate priming paint with Copper thin film, the substrate with Copper thin film, the manufacturing method of the substrate with Copper thin film and conductive film |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6011895B2 (en) |
| KR (1) | KR102392743B1 (en) |
| CN (1) | CN105462468B (en) |
| TW (1) | TWI661015B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113493574A (en) * | 2020-03-19 | 2021-10-12 | 荒川化学工业株式会社 | Primer for substrate with metal thin film, cured product, substrate with metal thin film and method for producing same, and film |
| CN116406391A (en) * | 2020-12-21 | 2023-07-07 | 东洋油墨Sc控股株式会社 | Active energy ray-curable hard coating agent, hard coating layer, and laminate |
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| JP5641321B2 (en) * | 2009-11-30 | 2014-12-17 | 荒川化学工業株式会社 | Undercoat agent for plastic with inorganic thin film, plastic with inorganic thin film, and decorative film for in-mold or insert molding |
| JP7081151B2 (en) * | 2016-03-04 | 2022-06-07 | 三菱ケミカル株式会社 | Active energy ray-curable coating material composition and laminate |
| JP6862705B2 (en) * | 2016-07-22 | 2021-04-21 | 荒川化学工業株式会社 | Non-aqueous oligomer bleed inhibitor for polyester film, and oligomer bleed prevention method for polyester film |
| JP6943117B2 (en) * | 2016-10-07 | 2021-09-29 | 三菱ケミカル株式会社 | Undercoating agent composition for metal thin film, undercoating agent for metal thin film, base film with undercoat layer and laminated film with metal thin film layer |
| KR102186080B1 (en) * | 2017-06-27 | 2020-12-03 | 주식회사 엘지화학 | Adhesive composition, protective film and polarizing plate comprising adhesive layer comprising the same and display device comprising the same |
| KR20240048541A (en) | 2021-09-21 | 2024-04-15 | 아티엔스 가부시키가이샤 | Active energy ray-curable undercoat agent, undercoat layer, laminate, and metal film attachment substrate |
| JP7136299B1 (en) | 2021-09-21 | 2022-09-13 | 東洋インキＳｃホールディングス株式会社 | Active energy ray-curable undercoating agent, undercoating layer, laminate, and substrate with metal film |
| JP7214946B1 (en) * | 2022-06-02 | 2023-01-31 | 東洋インキＳｃホールディングス株式会社 | Active energy ray-curable hard coating agents, hard coating layers, laminates, and substrates with inorganic oxide films |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2016069653A (en) | 2016-05-09 |
| KR20160038853A (en) | 2016-04-07 |
| TW201627434A (en) | 2016-08-01 |
| TWI661015B (en) | 2019-06-01 |
| JP6011895B2 (en) | 2016-10-25 |
| KR102392743B1 (en) | 2022-04-28 |
| CN105462468B (en) | 2019-04-05 |
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