CN104946117A - An undercoat agent for a substrate with thin copper film, a substrate with thin copper film and the method for producing same, a conductive film, and an electrode film - Google Patents
An undercoat agent for a substrate with thin copper film, a substrate with thin copper film and the method for producing same, a conductive film, and an electrode film Download PDFInfo
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- CN104946117A CN104946117A CN201510148503.8A CN201510148503A CN104946117A CN 104946117 A CN104946117 A CN 104946117A CN 201510148503 A CN201510148503 A CN 201510148503A CN 104946117 A CN104946117 A CN 104946117A
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Abstract
The invention aims at providing an undercoat agent which is the organic polymer undercoat agent used in the manufacture of a substrate having a thin copper film. The undercoat agent can form an undercoat agent layer, wherein the undercoat agent layer has good initial adhesion performance with a plastic substrate and the thin copper film, and also has good adhesion performance after alkali treatment and acid treatment. The undercoat agent for the substrate with the thin copper film comprises polyester polyol (A) prepared by dicarboxylic acids (a1) and diols (a2); polyisocyanate (B) including at least three isocyanate groups; and silane coupling agents (C). Esterification catalysts (D) for carbamic acid are also included in the undercoat agent as needed.
Description
Technical field
The present invention relates to a kind of in order to the priming paint used, the base material with Copper thin film with the layer formed by this priming paint and its manufacture method, the conducting film using the base material having Copper thin film by this to make and the electrode film obtained by this conducting film at various substrate surface formation Copper thin film.
Background technology
The base material with Copper thin film refers to the product forming Copper thin film at various substrate surface.In field of electronic materials, studying to have the substitute of plastic film as tin indium oxide (ITO) conducting film of Copper thin film.
Because the transparency of ITO conducting film and excellent conductivity, thus as the touch-screen such as smart mobile phone and panel computer electrode film and used, but, because indium is the rare metal of high price, there is Cost Problems, and due to ITO layer not only hard but also crisp, from the angle being not easy the processibilities such as bending and distortion, still have problem to need to solve.
As everyone knows, as the electrode film that processibility is good, can be such as the pi-conjugated electroconductive polymer of Polythiophene, polyaniline and polypyrrole etc. as conductive layer, but existing painted due to this conductive layer, there is the problem on tone in this electrode film.
On the other hand, as the conducting film of excellent processability, known also have other plastic films with Copper thin film.This film uses the copper lower than ITO resistivity as conductive layer, and thus electroconductibility is good, the most important thing is cheap.It has been generally acknowledged that electrode film copper vapour deposition plastic film being used as the display equipment such as such as touch-screen, easily realize large screen and curving.
In general, former copper vapour deposition plastic film is after as vapour deposition nickel on the plastic film of base material, then vapour deposition copper obtains.This nickel vapor deposition layer has the function of the anchoring layer (ア ン カ ー Layer) film and copper vapor deposition layer adhered to.Then, with resist coating electrode pattern on copper vapour deposition plastic film, after etching solution (basic solution, acidic solution) process, by removing this resist, target electrode film is obtained.
But, because the nickel in this copper vapour deposition plastic film lacks alkali resistance and acid resistance, the problem that after there is etch processes, copper vapor deposition layer is peeled off from base material film, come off.And, although this copper vapour deposition plastic film is cheap compared with ITO conducting film, because nickel is more expensive than copper processing, thus nickel this part improve price.Therefore, someone proposes the method using following priming paint as anchoring layer, and this priming paint does not use nickel and uses organic polymer as principal constituent (with reference to patent documentation 1).On the other hand, when using this priming paint, the block resistance (ロ of resistance to Block ッ キ Application グ) of priming paint aspect is required.
Prior art
Patent documentation 1: Japanese Unexamined Patent Publication 5-28835 publication
Summary of the invention
Problem of the present invention is to provide a kind of priming paint, described priming paint is the organic polymer priming paint used when manufacturing and having the base material of Copper thin film, this priming paint can form prime coat, this prime coat not only with the initial stage good adhesion of plastic basis material and Copper thin film but also alkaline purification after adhesivity (following, also referred to as alkaline-resisting adhesivity), adhesivity (hereinafter also referred to as acidproof adhesivity) after acid treatment and block resistance also good.
The result that present inventor studies with keen determination finds, containing, for example the priming paint of lower composition, to make solution foregoing problems become possibility: as main component the polyester polyol selected; As the polymeric polyisocyanate of solidifying agent; And as additive, with the polyglycidyl compounds of hydroxyl or isocyanic ester radical reaction.
Present invention comprises following technical scheme:
1. for having the priming paint of the base material of Copper thin film, wherein, described priming paint contains following composition:
(A) composition: the polyester polyol prepared for reacted constituent with di-carboxylic acid (a1) and dibasic alcohol (a2);
(B) composition: the polymeric polyisocyanate at least containing three isocyanate group; And,
(C) composition: silane coupling agent; And as required, contain
(D) composition: urethanation catalyst.
2. the priming paint as described in aforementioned 1, wherein, described (A) composition is further using the polyvalent alcohol (a3) at least with three hydroxyls as reacted constituent, containing hydroxyl branched chain type vibrin.
3. the priming paint as described in aforementioned 1 or 2, wherein, the second-order transition temperature of described (A) composition is less than 80 DEG C.
4. the priming paint as described in aforementioned 1-3 any one, wherein, the second-order transition temperature of described (A) composition is 0-75 DEG C.
5. as the priming paint in aforementioned 1-4 as described in any one, wherein, the hydroxyl value of described (A) composition is 5-100mg KOH/g.
6. as the priming paint in aforementioned 1-5 as described in any one, wherein, described (B) composition is a kind of derivative (b1) selected from the group that the biuret body of diisocyanate cpd, isocyanuric acid body and adduct are formed.
7. the equivalence ratio (NCO/OH) of the isocyanate group contained in the hydroxyl as the priming paint in aforementioned 1-6 as described in any one, wherein, contained in described (A) composition and described (B) composition is 0.5-5.
8. as the priming paint of the base material in aforementioned 1-7 as described in any one, wherein, described (C) composition is X-(CH
2)
n-Si (OR
2)
3the silane coupling agent represented, in above-mentioned general formula, n represents the integer of 2-4, R
2represent that carbon number is the alkyl of 1-3, X is selected from a kind of functional group in the group of isocyanate group, epoxy group(ing), amino and sulfydryl composition.
9. as the priming paint of the base material in aforementioned 1-8 as described in any one, wherein, described (C) composition is general formula (1) X
1-Si (R
1)
a(OR
2)
3-athe reactive polyglycidyl compounds represented, in general formula (1), X
1for the group containing following functional group, described functional group and the one selected from the group that hydroxyl and isocyanate group are formed react, R
1for hydrogen or carbonatoms are the alkyl of 1-8, R
2for carbonatoms is the alkyl of 1-8, a represents 0,1 or 2.
10. as the priming paint in aforementioned 1-9 as described in any one, wherein, relative to described (A) composition 100 weight part (converting by solids component), the usage quantity of described (C) composition is 1-20 weight part.
11. priming paint as described in aforementioned 1-10, wherein, relative to described (A) composition 100 weight part (converting by solids component), the usage quantity of described (D) composition is 0.1-2 weight part.
12. as the priming paint in aforementioned 1-11 as described in any one, and wherein, described priming paint is also containing the active energy ray polymeric compounds as (E) composition, and described (E) composition at least has the group of three carbon-carbon double keys in molecule.
13. priming paint as described in aforementioned 12, wherein, relative to described (A) composition 100 weight part (converting by solids component), the usage quantity of described (E) composition is 1-100 weight part.
14. 1 kinds of base materials with Copper thin film, wherein, described in there is Copper thin film base material comprise: base material, the prime coat formed by the solidifying priming paint in aforementioned 1-13 described in any one and copper film layer.
15. base materials with Copper thin film as described in aforementioned 14, wherein, described base material is plastics.
16. base materials with Copper thin film as described in aforementioned 15, wherein, described plastics are plastic film.
17. base materials with Copper thin film as described in aforementioned 16, wherein, described plastic film is polyester film.
18. as the base material with Copper thin film in aforementioned 14-17 as described in any one, and wherein, described copper film layer is copper vapor-deposited film or copper sputtered film.
19. 1 kinds of manufacture method with the base material of Copper thin film, is characterized in that, said method comprising the steps of:
Priming paint in aforementioned 1-13 described in any one is coated on substrate surface,
Then, by described base material heating thus formed cured base enamelled coating (1),
Then, described cured base enamelled coating (1) forms copper film layer.
20. 1 kinds of manufacture method with the base material of Copper thin film, is characterized in that, said method comprising the steps of:
Priming paint in aforementioned 1-13 described in any one is coated on substrate surface,
Then, by described base material heating thus formed cured base enamelled coating (1 '),
Then, use active energy ray to irradiate to described cured base enamelled coating (1 '), thus form cured base enamelled coating (2 '),
Then, described cured base enamelled coating (2 ') forms copper film layer.
21. manufacture method as described in aforementioned 19 wherein, are vaccum gas phase sedimentation method or sputtering method in the upper method forming copper film layer of described cured base enamelled coating (1).
22. manufacture method as described in aforementioned 20 wherein, are vaccum gas phase sedimentation method or sputtering method in the upper method forming copper film layer of described cured base enamelled coating (2 ').
23. conducting films be made up of the base material with Copper thin film in aforementioned 14-18 described in any one.
The conducting film that 24. base materials with Copper thin film obtained by the manufacture method in aforementioned 19-22 described in any one are made.
25. electrode films obtained by the conducting film described in aforementioned 23 or 24.
The effect of invention
Priming paint of the present invention forms level and smooth film at substrate surface.And, this film only solidifies under the action of heat or solidifies under heat with the effect of active energy ray, form prime coat, this prime coat not only with the initial stage good adhesion of base material and Copper thin film but also alkaline-resisting adhesivity and acidproof adhesivity two aspect all good, and block resistance is good.
For the base material with Copper thin film of the present invention, due to the initial stage adhesivity of base material and copper vapor-deposited film, alkaline-resisting adhesivity and acidproof good adhesion, even if this base material with Copper thin film is through etching solution or acidic solution process, copper vapor-deposited film is also not easy to come off from base material.This has in the base material of Copper thin film, when particularly base material is plastic film, and can the conducting film of ITO conducting film as an alternative.
Conducting film of the present invention may be used for various electrode film, such as, for purposes such as touch-screen, IC-card substrate, IC tag substrate, Electronic Paper substrate, flexible display substrates.The electrode film that the touch-screen being especially suitable for use as smart mobile phone and panel computer etc. uses.
Embodiment
As the preferred embodiment of the present invention, copper vapor-deposited film priming paint of the present invention (following, also referred to as priming paint) be the composition containing following composition: select polyester polyol (A) (hereinafter also referred to (A) composition), the polymeric polyisocyanate (B) (hereinafter also referred to (B) composition) at least containing three isocyanate group and the reactive polyglycidyl compounds (C) (hereinafter also referred to (C) composition) selected.
As (A) composition, various known branched chain type polyester polyol can be used, be not particularly limited.Specifically, such as, preferably using di-carboxylic acid (a1) (hereinafter also referred to (a1) composition) and dibasic alcohol (a2) (hereinafter also referred to (a2) composition) as the polyvalent alcohol of neccessary composition.
As (a1) composition, various known di-carboxylic acid can be used, be not particularly limited.Specifically, such as can enumerate: the aromatic binary carboxylic acid of m-phthalic acid, terephthalic acid, ditan-4,4 '-di-carboxylic acid and their acid anhydrides etc.; The aliphatic dicarboxylic acid of oxalic acid, propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, nonane diacid, pimelic acid, suberic acid, sebacic acid, undecane diacid, dodecanedioic acid, undecane dicarboxylic acid and their acid anhydrides etc.; The Cycloaliphatic dicarboxylic acids etc. of hexahydrophthalic acid, hexahydrophthalic anhydride, Isosorbide-5-Nitrae-cyclohexane dicarboxylic carboxylic acid, 1,2-cyclohexane dicarboxylic carboxylic acid and their acid anhydrides etc.; Also can be two or more combinations.And from the view point of initial stage adhesivity, alkaline-resisting adhesivity, acidproof adhesivity and block resistance balance, (a1) composition is preferably containing aromatic binary carboxylic acid.In addition, the usage quantity of aromatic binary carboxylic acid in (a1) composition is not particularly limited, is generally about 20-60mol%.In addition, in (a1) composition, the usage quantity of aliphatic dicarboxylic acid and/or Cycloaliphatic dicarboxylic acids is generally about 0-5mol%.
As (a2) composition, various known dibasic alcohol can be used, be not particularly limited.Specifically, such as can enumerate: 1,2-propylene glycol, 1,3-butyleneglycol, neopentyl glycol, 3-methyl isophthalic acid, 5-pentanediol, 2-methyl isophthalic acid, ammediol, ethylene glycol, Diethylene Glycol, triethylene glycol, 1,3-PD, 1, the aliphatic dihydroxy alcohols such as 4-butyleneglycol, pentanediol and 1,6-hexylene glycol; The cycloaliphatic diols such as the ethylene oxide adduct of Isosorbide-5-Nitrae-cyclohexanediol and Hydrogenated Bisphenol A; The aromatic diols etc. such as the ethylene oxide adduct of pyrocatechol, Resorcinol, Resorcinol, xylyl alcohol, two (hydroxy ethoxy) benzene and dihydroxyphenyl propane; Also can be two or more combinations.And, from the view point of initial stage adhesivity, alkaline-resisting adhesivity, acidproof adhesivity and block resistance balance, preferably containing aliphatic dihydroxy alcohol in (a2) composition.In addition, the usage quantity of aliphatic dihydroxy alcohol in (a2) composition is not particularly limited, is generally about 20-60mol%.In addition, in (a2) composition, the usage quantity of cycloaliphatic diols and/or aromatic diol is generally about 0-40mol%.
(A) composition can react with any reacted constituent of the polyvalent alcohol (a3) (hereinafter also referred to (a3) composition) at least containing three hydroxyls again.(a3) composition introduces free hydroxyl and branched structure to (A) composition, and the initial stage adhesivity of the layer that priming paint of the present invention especially can be made to be formed, alkaline-resisting adhesivity, acidproof adhesivity and block resistance improve.
As (a3) composition, known any composition can be used, be not particularly limited.Specifically, such as can enumerate: the aliphatics triols such as glycerine, TriMethylolPropane(TMP), trimethylolethane, 1,2,6-hexanetriol and BT; The alicyclic triol such as phloroglucite; The aromatic series such as pyrogallol and Phloroglucinol triol; The aliphatics tetrols etc. such as one contracting two glycerol, erythritol, Sorbitol Powder, tetramethylolmethane and Dipentaerythritol; Also can be two or more combinations.And, from the view point of initial stage adhesivity, alkaline-resisting adhesivity, acidproof adhesivity and block resistance balance, (a3) composition preferred aliphat triol and/or aliphatics tetrol.
(a1) composition, (a2) composition and the usage quantity of (a3) composition that uses as required are not particularly limited, usually, from the view point of initial stage adhesivity, alkaline-resisting adhesivity, acidproof adhesivity and block resistance balance, usual preferred following scope:
Do not use the situation of (a3) composition
(a1) composition: about 20-50mol%, preferred about 25-45mol%
(a2) composition: about 50-80mol%, preferred about 55-75mol%
Use the situation of (a3) composition
(a1) composition: about 20-50mol%, preferred about 25-45mol%
(a2) composition: about 47-77mol%, preferred about 53-73mol%
(a3) composition: about 0.1-3mol%, preferred about 0.5-2mol%
And, together with (a1) composition, (a2) composition and (a3) composition, various known polycarboxylic acid (hereinafter also referred to (a4) composition) can be used.Specifically, such as can enumerate: the acid of maleic acid/MALEIC ANHYDRIDE, phthalic acid/Tetra hydro Phthalic anhydride, trimellitic acid/trimellitic anhydride, Pyromellitic Acid/pyromellitic dianhydride, hexahydrophthalic acid/hexahydrophthalic anhydride and succinic acid/Succinic anhydried etc. and/or acid anhydrides etc.; Also can be two or more combinations.And when (a1) composition, (a2) composition and (a3) composition add up to 100mol%, the usage quantity of (a4) composition is usually less than 5mol%.
The manufacture method of (A) composition is not particularly limited, various known method can be used.Specifically, such as can enumerate: the one pot process (a1) composition, (a2) composition and (a3) composition as required and/or (a4) composition being carried out dehydration condensation; Make the method etc. that the dehydration condensation thing of (a1) composition and (a2) composition reacts with (a3) composition and (a4) composition as required.Which kind of situation is all not particularly limited temperature of reaction, at about 150-250 DEG C.And, the reaction times is also not particularly limited, at 5-10 hours.And reaction is carried out at ambient pressure or under decompression.
When manufacturing (A) composition, various known catalyzer can be used.Specifically, such as, can enumerate: germanium dioxide, tetraethoxy germanium, four n-butoxy germanium, antimonous oxide, dibutyltin oxide, two acetate hydrate zinc, Mono-n-butyltin, tetrabutyl titanate etc. also can be two or more combinations.And, manufacture and also can carry out under organic solvent described later exists.
The physical property of (A) composition is not particularly limited, balance from the view point of initial stage adhesivity, alkaline-resisting adhesivity, acidproof adhesivity and block resistance, such as second-order transition temperature (measured value based on Japanese JIS-7121 standard) is generally less than 80 DEG C, about preferred 0-75 DEG C, more preferably about 30-70 DEG C, more preferably about 40-65 DEG C; Hydroxyl value (measured value based on Japanese JIS-0070 standard) is generally 5-100mg about KOH/g, preferred 7-90mg about KOH/g, more preferably 8-75mg about KOH/g, particularly preferably 10-60mg about KOH/g.
As (B) composition, the polymeric polyisocyanate at least containing three isocyanate group in molecule can be used, can be known any composition, be not particularly limited.(B) composition and (A) composition are reacted by urethane, give prime coat of the present invention with crosslinking structure.
As the object lesson of (B) composition, at least one selected the group formed from following ingredients can be enumerated: at least one derivative (b1) (hereinafter also referred to (b1) composition) selected from the group that the biuret body of diisocyanate cpd, isocyanuric acid body and affixture are formed; Be somebody's turn to do the reactant (b2) (hereinafter also referred to (b2) composition) of (b1) composition and diatomic alcohol compounds; Tri-isocyanate compound (b3) (composition of removing belongs to (b1) composition and (b2) composition) (hereinafter also referred to (b3) composition); And other polyisocyanate compounds (hereinafter also referred to (b4) composition).Wherein, from the view point of initial stage adhesivity, alkaline-resisting adhesivity, acidproof adhesivity and block resistance balance, particularly preferably (b1) composition.
As the diisocyanate cpd forming (b1) composition, such as, can enumerate: the aromatic diisocyanates such as tolylene diisocyanate, '-diphenylmethane diisocyanate and eylylene diisocyanate; The aliphatic diisocyanates such as hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate and 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 aforementioned diisocyanates compound represents with structural formula below.
[chemical formula 1]
(in formula, R
3represent the residue of aforementioned diisocyanates compound.)
And the isocyanuric acid body of aforementioned diisocyanates compound represents with structural formula below.
[chemical formula 2]
(in formula, R
4represent the residue of aforementioned diisocyanates compound.)
And the affixture of aforementioned diisocyanates compound represents with structural formula below.
[chemical formula 3]
(in formula, R
5represent carbonatoms be 1-3 alkyl or with OCN-R
6-HN-C (=O)-O-CH
2the functional group of-expression, R
6represent the residue of aforementioned diisocyanates compound.)
To the diatomic alcohol compounds forming (b2) composition, be not particularly limited, preferred aforesaid aliphatic dihydroxy alcohol, the one particularly preferably selected from the group that following alcohol is formed: ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,3 butylene glycol, neopentyl glycol, 1,6-hexylene glycol, ethohexadiol, dipropylene glycol, polyoxyethylene glycol and polypropylene glycol etc.
(b2) composition can with various known method manufacture.Specifically, such as, aforementioned (b1) composition and aforementioned diatomic alcohol compounds carry out urethane under the following conditions and are obtained by reacting: and the equivalence ratio of the hydroxyl of the isocyanate group of described (b1) composition (NCO ') and described dibasic alcohol (OH ') (NCO '/OH ') be generally about 5-20, preferably in the scope of about 10-20, usually at 40-80 DEG C, react 1-5 hours.And (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 phenyl isocyanate, 1,6,11-undecane triisocyanate, 1,3, polymeric polyisocyanate (the goods name " デ ュ ラ ネ ー ト MHG-80B " of the triisocyanates such as 6-hexa-methylene triisocyanate, norbornane triisocyanate and six functional groups, Asahi Chemical Industry's chemistry of Japan (strain) system) etc., also can be two or more combinations.
As (b4) composition, such as, can enumerate the polymeric polyisocyanate (goods name " デ ュ ラ ネ ー ト MHG-80B ", Japanese Asahi Chemical Industry chemistry (strain) makes) of six functional groups.
And, the ratio of (B) composition relative to (A) composition is also not particularly limited, from the view point of initial stage adhesivity, alkaline-resisting adhesivity, acidproof adhesivity and block resistance balance, the equivalence ratio (NCO/OH) of the hydroxyl of (A) composition and the isocyanate group of (B) composition is generally about 0.5-5, preferably about 1-2.
Can react by (C) composition and (A) composition and/or (B) composition, the prime coat formed by priming paint of the present invention is organic to be combined integratedly, can improve the alkaline-resisting adhesivity of this layer especially.
As (C) composition, can be general formula be X-(CH
2)
n-Si (OR
2)
3the silane coupling agent represented, in above-mentioned general formula, n represents the integer of 2-4, R
2represent that carbon number is the alkyl of 1-3, X is selected from a kind of functional group in the group of isocyanate group, epoxy group(ing), amino and sulfydryl composition, X preferably represents isocyanate group (O=C=N-) or epoxy group(ing), particularly X is hydroxyl reaction together and in (A) composition of material and described (B) composition of isocyanate group and integrated, therefore can think that alkaline-resisting adhesivity becomes good especially.
Silane coupling agent as (C) composition also can be any general formula (1): X
1-Si (R
1)
a(OR
2)
3-athe reactive polyglycidyl compounds represented, can use various known material, be not particularly limited, in general formula (1), and X
1for the group containing following functional group, described functional group and the one selected from the group that hydroxyl and isocyanate group are formed react, R
1for hydrogen or carbonatoms are the alkyl of 1-8, R
2for carbonatoms is the alkyl of 1-8, a represents 0,1 or 2.
As the X in (C) composition represented with aforementioned formula (1)
1, such as, can enumerate a kind of functional group containing selecting from the group of following formation: isocyanate group, epoxy group(ing), sulfydryl, amino and anhydride group.
As X
1in reactive functional groups be isocyanate group (C) composition, such as can enumerate 3-isocyanate group propyl trimethoxy silicane, 3-isocyanate group propyl-triethoxysilicane, 3-isocyanate group hydroxypropyl methyl dimethoxysilane and 3-isocyanate group hydroxypropyl methyl diethoxy silane etc., also can be two or more combinations.
As X
1in reactive functional groups be epoxy group(ing) (C) composition, such as can enumerate 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3-glycydoxy methyl dimethoxysilane, 3-glycydoxy Trimethoxy silane, 3-glycydoxy methyldiethoxysilane and 3-glycydoxy triethoxyl silane etc. also can be two or more combinations.
As X
1in reactive functional groups be sulfydryl (C) composition, such as can enumerate 3-mercaptopropyi Trimethoxy silane, 3-Mercaptopropyltriethoxysilane, 3-mercaptopropyi methyl dimethoxysilane and 3-mercaptopropyi methyldiethoxysilane etc., also can be two or more combinations.
As X
1in reactive functional groups be amino (C) composition, such as can enumerate N-2-(aminoethyl)-3-amino propyl methyl dimethoxysilane, N-2-(aminoethyl)-3-TSL 8330,3-TSL 8330, APTES and 3-uride propyl trialkoxy silane etc., also can be two or more combinations.
As X
1in reactive functional groups be anhydride group (C) composition, such as can enumerate the silica-based propyl succinimide acid anhydrides of 3-trimethoxy first.
As (C) composition, from the view point of initial stage adhesivity, alkaline-resisting adhesivity, acidproof adhesivity and block resistance balance, preferred X
1in functional group be the compound of isocyanate group and/or the compound of epoxy group(ing).
The usage quantity of (C) composition is not particularly limited, usually, relative to (A) composition 100 weight part (converting by solids component), the usage quantity of (C) composition is about 1-20 weight part, about preferred 5-15 weight part.
As required, priming paint of the present invention can also contain urethanation catalyst (D) (hereinafter also referred to (D) composition).(A) composition and the curing reaction of (B) composition should be accelerated by (D) composition, the initial stage adhesivity of priming paint of the present invention, alkaline-resisting adhesivity, acidproof adhesivity and block resistance are improved.
As (D) composition, specifically, the tin urethane catalyzer such as three (2-ethyl-1-caproic acid) butyl tin, Mono-n-butyltin, two isocaprylic acid tin, dibutyl tin laurate, tin dilaurate dioctyl tin, the new caprinoyl oxygen tin (ジ オ Network チ Le Tin バ ー サ テ ー ト) of distearyl acid dioctyl tin, di-n-octyltin oxide, diethyl acyl-oxygen dioctyl tin salt (ジ オ Network チ Le Tin ジ ア セ テ ー ト) and dioctyl two can such as be enumerated; The bismuth urethane catalyzer such as Bismuth Octoate, three Bismuth Octoate/tri-isocaprylic acid bismuths; The organic amine urethane catalyzer etc. such as diazabicyclooctane, dimethylcyclohexylamine, 4-methyl-diaminopropane, ethyl morpholine, dimethylethanolamine, triethylamine and triethylenediamine; Also can be two or more combinations.
The usage quantity of (D) composition is not particularly limited, subtotaling 100 weight part (converting by solids component) is become for (A) composition, (B) composition and (C), (D) about the usage quantity of composition is generally 0.1-2 weight part, preferred 0.5-1.5 weight part.
For the situation being applicable to film base material, priming paint of the present invention can also contain active energy ray polymeric compounds (E) (hereinafter also referred to (E) composition), and described (E) composition at least has the group of three carbon-carbon double keys in molecule.Containing should the priming paint of (E) composition solidify under the effect of heat and active energy ray, thus obtain excellent initial stage adhesivity, alkaline-resisting adhesivity and acidproof adhesivity, and, the block resistance that also imparting prime coat is excellent.
As the group of the carbon-carbon double key of (E) composition, such as, can enumerate vinyl, propenyl, acryl and methacryloyl etc.And, object lesson as (E) composition can be enumerated: trimethylolpropane tris (methyl) acrylate, ethylene-oxide-modified trimethylolpropane tris (methyl) acrylate, trimethylolpropane tris (methyl) acrylate of epoxy pronane modification, tetramethylolmethane monohydroxy three (methyl) acrylate, own (methyl) acrylate of Dipentaerythritol, Dipentaerythritol monohydroxy five (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, the compound at least containing three (methyl) acryls such as ditrimethylolpropane four (methyl) acrylate and glycerol three (methyl) acrylate, the compound etc. at least containing three vinyl such as tetramethylolmethane monohydroxy triallyl ether and citric acid triallyl, also can be two or more combinations.Wherein, from the angle of the hardness of priming paint epithelium, group preferably (methyl) acryl of carbon-carbon double key, and its number is 3-6.
The usage quantity of (E) composition is not particularly limited, balance from the view point of initial stage adhesivity, alkaline-resisting adhesivity, acidproof adhesivity and block resistance, usually, relative to (A) composition 100 weight part, (E) composition is about 0-100 weight part, (all converts by solids component) about preferred 20-70 weight part.
And other various known (methyl) acrylate can share with (E) composition.Specifically, such as can enumerate: 1,3-butyleneglycol two (methyl) acrylate, 1, two (methyl) acrylate 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 and dihydroxyphenyl propane; The oligopolymer such as polyurethane polyureas (methyl) acrylate and poly-(methyl) acrylate of polyester; (methyl) 2-EHA, (methyl) isodecyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) benzyl acrylate, (methyl) vinylformic acid ring pentyl ester, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid dicyclopentenyl ester, (methyl) isobornyl acrylate; Vinyltrimethoxy silane, styryl Trimethoxy silane, 3-(methyl) acryloxypropyl dimethoxysilane, 3-(methyl) acryloxypropyl Trimethoxy silane, 3-(methyl) acryloxypropyl diethoxy silane and 3-(methyl) acryloxypropyl triethoxyl silane etc.; Also can be two or more combinations.
And priming paint of the present invention can also contain Photoepolymerizationinitiater initiater (F) (hereinafter also referred to (F) composition).Specifically, such as benzophenone can be enumerated, 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-phenyl-1-acetone, 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-morpholine-4-base-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 Japanese Unexamined Patent Publication 2014-1390 publication are recorded also can be two or more combination.And, as (F) composition, such as, can use the commercial goods such as Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 651, Irgacure 184, Irgacure 500, Irgacure 1000, Irgacure 149, Irgacure 261 and Darocur 1173.
Be not particularly limited the usage quantity of (F) composition, usually, relative to (E) composition 100 weight part, (F) composition is about 0.1-3 weight part, (all converts by solids component) about preferred 0.5-2 weight part.
And, as the auxiliary agent of (F) composition, trolamine, tri-isopropanolamine, 4 can be enumerated, 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. also can be two or more combinations.
And such as when being applicable to plastic film substrate, priming paint of the present invention can also contain inorganic particulate.Because this inorganic particulate imparts the cured layer of priming paint of the present invention with suitable slipperiness, the base material film with this cured layer is made to be not easy when take-up to produce abnormal sound and film defect.
As this inorganic particulate, 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 and magnesium hydroxide, also can be two or more combinations.And, wherein, from the view point of aforementioned slipperiness, particularly preferably silicon-dioxide and/or aluminum oxide.And this particle surface can apply various process.And, the median particle diameter (d50) of this particle is not particularly limited, is generally about 10nm-5 μm.
Be not particularly limited the usage quantity of this inorganic particulate, usually, relative to (A) composition 100 weight part, the usage quantity of this inorganic particulate is about 0-20 weight part, (all presses solids component to convert) about preferred 5-10 weight part.
And as required, priming paint of the present invention can containing the compound with sulfydryl.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) and Dipentaerythritols six (3-mercaptobutylate) etc. also can be two or more combinations.
The usage quantity that this has the compound of sulfydryl is not particularly limited, usually, relative to (A) composition 100 weight part, the usage quantity with the compound of sulfydryl is about 0-20 weight part, (all presses solids component to convert) about preferred 5-10 weight part.
And, when using above-mentioned this to have the compound of sulfydryl, in line with the object of the pot life of prolongation priming paint of the present invention, can combinationally use with various known alkene-thiol reactant inhibitor.Specifically, such as can enumerate: the phosphorus series compound such as triphenylphosphine and triphenyl phosphite; P methoxy phenol, Resorcinol, pyrogallol, naphthylamines, tert-butyl catechol, cuprous chloride, 2,6-ditertbutylparacresol, 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol), 2,2 '-methylene-bis (4-methyl-6-tert-butylphenol), N-nitroso-group-radical polymerization inhibitor such as N-Phenylhydroxylamine aluminium salt and phenylbenzene nitrosamine; The tertiary amines such as benzyldimethylamine, 2-(dimethylaminomethyl) phenol, 2,4,6-tri-(bis aminomethyl) phenol and 1,8-diazabicyclo [5.4.0] 11 carbon-7-alkene; And the imidazoles etc. such as glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-ethylhexyl imidazoles, 2-undecylimidazole and 1-cyano ethyl-glyoxal ethyline; Also can be two or more combinations.The usage quantity of this inhibitor is not particularly limited, can suitably sets.
Priming paint of the present invention uses various known means to be mixed to get by aforementioned (A) composition, (B) composition, (C) composition and other compositions of using as required.
During mixing, various known organic solvent (G) (hereinafter also referred to (G) composition) can be used as required.Specifically, such as can enumerate: the lower ketones such as methylethylketone, methyl iso-butyl ketone (MIBK); The aromatic hydrocarbonss such as toluene; The alcohol such as ethanol, propyl alcohol; The ether-ethers such as propylene glycol monomethyl ether acetate, ethylene glycol ether acetate (エ チ Le セ ロ ソ Le Block ア セ テ ー ト); Ethyl acetate; Trichloromethane; Dimethyl formamide etc.; Also can be two or more combinations.And the usage quantity of this composition is generally the scope of concentration at 1-60 about % by weight of the solids component making priming paint of the present invention.Wherein, when base material is plastic film, particularly preferably lower ketones.
And priming paint of the present invention can contain other additives such as flow agent, antioxidant, polymerization retarder, UV light absorber.
The base material with Copper thin film of the present invention is layered product, has: the prime coat that various base material, solidifying priming paint of the present invention are formed and copper film layer.
Base material is not particularly limited, as long as surface energy forms Copper thin film, various known base material can be used.Specifically, such as plastics, metal, cellulose materials, glass etc. can be enumerated.As described plastics, such as, can enumerate polyester, polyvinyl chloride, polymeric amide, polyimide, polycarbonate, polyethylene and polypropylene etc.And, as described cellulose materials, such as, can enumerate paper, nano-cellulose paper and timber etc.
Substrate shapes is not particularly limited.It can be such as spherical, cylindric, rectangular-shaped, tabular, membranaceous.And part or all of substrate surface can have concavo-convex or curved surface.The base material with Copper thin film of the present invention when using as conducting film, from the viewpoint of thermotolerance and optical characteristics etc., as the preferred plastic film of base material, particularly preferably polyester film.And, the thickness of this base material film is also not particularly limited, is generally about 50-200 μm.And, the thickness of prime coat is not particularly limited, is generally about 0.1-5 μm.
As aforesaid copper film layer, such as, can enumerate copper vapor-deposited film, copper sputtered film, copper chemical vapour deposition (CVD) film etc.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.And, the thickness of this copper vapor-deposited film or copper sputtered film is not particularly limited, is generally about 0.1-2 μm.
The method for making with the base material of Copper thin film of the present invention is not particularly limited, such as, generally can takes following method for making.
Do not use the situation of (E) composition
On aforementioned substrates surface, be coated with priming paint of the present invention (not containing (E) composition), then cured base enamelled coating (1) is formed, then in the upper method forming copper film layer of this cured base enamelled coating (1) to this base material heating.
Use the situation of (E) composition
On aforementioned substrates surface, be coated with priming paint of the present invention (containing (E) composition), then to this base material heating thus formed cured base enamelled coating (1 '), then irradiate active energy ray to this cured base enamelled coating thus form cured base enamelled coating (2 '), then in the upper method forming copper film layer of this cured base enamelled coating (2 ').
Application conditions is not particularly limited, as spreading implement, such as can enumerate atomizer, roller coating machine, reverse roller coating machine, intaglio plate roller coating machine, knife coater, rod coater, point type coating machine etc., and glue spread is also not particularly limited, usually used as drying solid composition at 0.01-10g/m
2left and right.
Also be not particularly limited heating condition, typical temperature is at about 80-150 DEG C, and the time was at 10 seconds about-2 minutes.May (A) composition, (B) composition and (C) composition organicly can be reacted described process integratedly, give prime coat (1) with excellent initial stage adhesivity, alkaline-resisting adhesivity, acidproof adhesivity and block resistance.
Active energy ray illuminate condition is also not particularly limited, usually used as active energy ray, such as, can enumerates ultraviolet and electron rays.Such as, and as ultraviolet supply source, can enumerate high voltage mercury lamp and metal halide lamp etc., its irradiation energy is usually at 100-2,000mJ/cm
2left and right.Such as, and as the supply mode of electron rays, can enumerate the irradiation of scanning electron bundle, curtain electron beam irradiation etc., its irradiation energy is generally about 10-200kGy.May through described process, the result that Raolical polymerizable forms crosslinking structure is there is each other as (E) composition in cured base enamelled coating (1 '), make described cured base enamelled coating (2 ') not only have excellent initial stage adhesivity, alkaline-resisting adhesivity and acidproof adhesivity block resistance, and there is excellent block resistance.
Be not particularly limited at cured base enamelled coating (1) or the upper means forming copper film layer of cured base enamelled coating (2 '), preferred so-called dry-coated method.Specifically, the chemical process such as the physical method such as vaccum gas phase sedimentation method or sputtering method, chemical vapour deposition (CVD) (chemical gas phase reaction etc.) etc. can such as be enumerated.What manufacture method of the present invention obtained has the film of Copper thin film when for electrode film, preferred vaccum gas phase sedimentation method or sputtering method.
Electrode film of the present invention is the electronic unit obtained by conducting film of the present invention.Especially, the electrode film obtained by copper vapour deposition plastic film or copper sputtered film in conducting film of the present invention can be used as the substitute of the electrode film using ITO conducting film.
The resist of conducting film of the present invention is coated with according to electrode pattern, after etching solution (basic solution, acidic solution) process, removes described resist, obtain electrode film of the present invention.The shape of electrode pattern is not particularly limited, thin-line-shaped, point-like, netted, sheet etc. can be enumerated.
Embodiment
Next, by embodiment and comparative example, the present invention is illustrated in further detail, but scope of the present invention is not limited to these embodiments.And " part " in embodiment is for represent according to weight basis.And hydroxyl value and acid number are the value according to Japanese JIS-0070 standard test.And second-order transition temperature is the value using commercially available measuring instrument (goods name " DSC8230B ", Rigaku motor (strain) is made) to measure.
Production Example 1
(A) manufacture of composition
Dimethyl terephthalate (DMT) (TPhDM) 2843.4 parts, ethylene glycol (EG) 1382.2 parts, 1 is added to the flask with agitator, thermometer, nitrogen ingress pipe and reflux dewatering device, 6-hexylene glycol (1,6HD) 449.7 parts, neopentyl glycol (NPG) 1189 parts and TriMethylolPropane(TMP) (TMP) 51.1 parts, add zinc acetate 0.79 part as transesterification catalyst.Then, heating raw, while being distilled outside reaction system by the methyl alcohol of generation, carries out transesterification reaction 2 hours at 195 DEG C.
Then, add m-phthalic acid (IPhA) 2043.8 parts, nonane diacid (AzA) 440.9 parts, while being distilled outside reaction system by the water of generation, at 200 DEG C, carry out dehydration condensation 3 hours.The acid number of reaction solution is 11.2mg KOH/g.
Then, reflux is changed into vacuum decompression device, adds tetrabutyl titanate 0.42 part, 240 DEG C, below 0.3kPa carries out decompression 2 hours.Then, add methyl iso-butyl ketone (MIBK) 2300.4 parts, methylethylketone 6901 parts, methyl ethyl diketone 219.8 parts, and mix.
Obtain polyester polyol (A-1) thus, the nonvolatile component of this polyester polyol is 40%, hydroxyl value is 17mg KOH/g, second-order transition temperature is 47 DEG C.
Production Example 2
To in the flask same with Production Example 1, add terephthalic acid (TPhA) 452.2 parts, m-phthalic acid (IPhA) 839.9 parts, ethylene glycol (EG) 94.1 parts, neopentyl glycol (NPG) 368.3 parts, 2,2-two (4-polyoxyethylene-oxygen phenyl) 1745.5 parts, propane (BA-P).Then, while the water that distillation generates is removed by heating and melting outside reaction system, reaction system is slowly warming up to 250 DEG C, then is incubated 3 hours.Then, this flask is connected with vacuum decompression device, then adds tetrabutyl titanate 0.18 part, be incubated after 30 minutes, under 1.3hPa, carry out decompression polycondensation 1 hour.Then resin 100 parts is transferred to the flask with thermometer, nitrogen ingress pipe, cooling tube and whipping appts, adds methyl iso-butyl ketone (MIBK) 75 parts, methylethylketone 75 parts, homogeneous dissolving.Obtain polyester polyol (A-2) thus, the nonvolatile component of this polyester polyol is 40%, hydroxyl value is 20mg KOH/g, second-order transition temperature is 60 DEG C.
Production Example 3
Add dimethyl terephthalate (DMT) (TPhDM) 2843.4 parts, ethylene glycol (EG) 1382.2 parts, neopentyl glycol (NPG) 1638.7 parts and TriMethylolPropane(TMP) (TMP) 51.1 parts to the flask with agitator, thermometer, nitrogen ingress pipe and reflux dewatering device, add zinc acetate 0.79 part as transesterification catalyst.Then, heating raw, while being distilled outside reaction system by the methyl alcohol of generation, carries out transesterification reaction 2 hours at 195 DEG C.Then, add m-phthalic acid (IPhA) 2484.7 parts, while being distilled outside reaction system by the water of generation, at 200 DEG C, carry out dehydration condensation 3 hours.The acid number of reaction solution is 11mg KOH/g.Then, reflux is changed into vacuum decompression device, adds tetrabutyl titanate 0.42 part, 240 DEG C, below 0.3kPa carries out decompression 2 hours.Then, add methyl iso-butyl ketone (MIBK) 2520.2 parts, methylethylketone 6901 parts, and mix.Obtain polyester polyol (A-3) thus, the nonvolatile component of this polyester polyol is 40%, hydroxyl value is 55mg KOH/g, second-order transition temperature is 50 DEG C.
Production Example 4
To in the flask same with Production Example 1, add terephthalic acid (TPhA) 328 parts, m-phthalic acid (IPhA) 328 parts, ethylene glycol (EG) 182 parts, 2,2-two (4-polyoxyethylene-oxygen phenyl) 762 parts, propane (BA-P).Then, while the water that distillation generates is removed by heating and melting outside reaction system, reaction system is slowly warming up to 250 DEG C, then is incubated 3 hours.Then, this flask is connected with vacuum decompression device, then adds tetrabutyl titanate 0.18 part, be incubated after 30 minutes, under 1.3hPa, carry out decompression polycondensation 1 hour.Then, resin 100 parts is transferred to the flask with thermometer, nitrogen ingress pipe, cooling tube and whipping appts, adds methyl iso-butyl ketone (MIBK) 75 parts, methylethylketone 75 parts, homogeneous dissolving.Obtain polyester polyol (A-4) thus, the nonvolatile component of this polyester polyol is 40%, hydroxyl value is 5mg KOH/g, second-order transition temperature is 70 DEG C.
Production Example 5
To in the flask same with Production Example 1, add terephthalic acid (TPhA) 479 parts, m-phthalic acid (IPhA) 402 parts, nonane diacid (AzA) 87 parts, ethylene glycol (EG) 256 parts, 1,6-hexylene glycol (1,6HD) 221 parts, neopentyl glycol (NPG) 148 parts and TriMethylolPropane(TMP) (TMP) 7 parts.Then, while the water that distillation generates is removed by heating and melting outside reaction system, reaction system is slowly warming up to 250 DEG C, then is incubated 3 hours.Then, this flask is connected with vacuum decompression device, then adds tetrabutyl titanate 0.18 part, be incubated after 30 minutes, under 1.3hPa, carry out decompression polycondensation 1 hour.Then, resin 100 parts is transferred to the flask with thermometer, nitrogen ingress pipe, cooling tube and whipping appts, adds methyl iso-butyl ketone (MIBK) 75 parts, methylethylketone 75 parts, homogeneous dissolving.Obtain polyester polyol (A-5) thus, the nonvolatile component of this polyester polyol is 40%, hydroxyl value is 21mg KOH/g, second-order transition temperature is 31 DEG C.
Production Example 6
To in the flask same with Production Example 1, add terephthalic acid (TPhA) 479 parts, m-phthalic acid (IPhA) 402 parts, nonane diacid (AzA) 87 parts, ethylene glycol (EG) 256 parts, 1,6-hexylene glycol (1,6HD) 354 parts and glycerine (GLY) 23 parts.Then, while the water that distillation generates is removed by heating and melting outside reaction system, reaction system is slowly warming up to 250 DEG C, then is incubated 3 hours.Then, this flask is connected with vacuum decompression device, then adds tetrabutyl titanate 0.18 part, be incubated after 30 minutes, under 1.3hPa, carry out decompression polycondensation 1 hour.Then, resin 100 parts is transferred to the flask with thermometer, nitrogen ingress pipe, cooling tube and whipping appts, adds methyl iso-butyl ketone (MIBK) 75 parts, methylethylketone 75 parts, homogeneous dissolving.Obtain polyester polyol (A-6) thus, the nonvolatile component of this polyester polyol is 40%, hydroxyl value is 45mg KOH/g, second-order transition temperature is 17 DEG C.
Production Example 7
To in the flask same with Production Example 1, add terephthalic acid (TPhA) 386 parts, m-phthalic acid (IPhA) 292 parts, nonane diacid (AzA) 300 parts, ethylene glycol (EG) 251 parts, 1,6-hexylene glycol (1,6HD) 348 parts and glycerine (GLY) 23 parts.Then, while the water that distillation generates is removed by heating and melting outside reaction system, reaction system is slowly warming up to 250 DEG C, then is incubated 3 hours.Then, this flask is connected with vacuum decompression device, then adds tetrabutyl titanate 0.18 part, be incubated after 30 minutes, under 1.3hPa, carry out decompression polycondensation 1 hour.Then, resin 100 parts is transferred to the flask with thermometer, nitrogen ingress pipe, cooling tube and whipping appts, adds methyl iso-butyl ketone (MIBK) 75 parts, methylethylketone 75 parts, homogeneous dissolving.Obtain polyester polyol (A-7) thus, the nonvolatile component of this polyester polyol is 40%, hydroxyl value is 30mg KOH/g, second-order transition temperature is 8 DEG C.
Relatively Production Example 1
To in the flask same with Production Example 1, add terephthalic acid (TPhA) 300 parts, ethylene glycol (EG) 81 parts, propylene glycol (PG) 216 parts and TriMethylolPropane(TMP) (TMP) 3 parts.Then, while the water that distillation generates is removed by heating and melting outside reaction system, reaction system is slowly warming up to 250 DEG C, then is incubated 3 hours.Then, this flask is connected with vacuum decompression device, then adds tetrabutyl titanate 0.18 part, be incubated after 30 minutes, under 1.3hPa, carry out decompression polycondensation 1 hour.Then, resin 100 parts is transferred to the flask with thermometer, nitrogen ingress pipe, cooling tube and whipping appts, adds methyl iso-butyl ketone (MIBK) 75 parts, methylethylketone 75 parts, homogeneous dissolving.Obtain polyester polyol (α) thus, the nonvolatile component of this polyester polyol is 40%, hydroxyl value is 5mg KOH/g, second-order transition temperature is 84 DEG C.
The modulation of priming paint
Embodiment 1
Using the isocyanuric acid body (trade(brand)name " コ ロ ネ ー ト (CORONATE) HX " of (A-1) composition 100 parts of Production Example 1 with the hexamethylene diisocyanate as (B) composition, Nippon Polyurethane Industry (Ltd.)) 7.8 parts and the silane coupling agent (trade(brand)name " KBE-9007 " containing isocyanate group as (C) composition, SHIN-ETSU HANTOTAI's silicone resin of Japan (strain) system) 10 parts and commercially available tin system catalysts for polyurethanes (tin dilaurate dioctyl tin as (D) composition, trade(brand)name " ネ オ ス タ Application (NEOSTANN) U-810 ", day east changes into (strain) system) 1.0 parts mix, be modulated into priming paint.
Embodiment 2
Using (A-1) composition 100 parts of Production Example 1 and 7.8 parts of コ ロ ネ ー ト (CORONATE) HX as (B) composition, 10 parts of silane coupling agent (trade(brand)names " サ イ ラ エ ー ス (Sila-Ace) 510 " containing epoxy group(ing), Japan JNC (strain) system) mix as (D) composition as (C) composition and 1.0 parts of ネ オ ス タ Application U-810, be modulated into priming paint.
Embodiment 3
Using (A-1) composition 100 parts of Production Example 1 and 7.8 parts of コ ロ ネ ー ト (CORONATE) HX as (B) composition, 10 parts of KBE-9007 as (C) composition and 1.0 parts of commercially available tin system catalysts for polyurethanes (new caprinoyl oxygen tin of dioctyl two, trade(brand)name " ネ オ ス タ Application (NEOSTANN) U-830 ", Japan day east changes into (strain) system) mix as (D) composition, be modulated into priming paint.
Embodiment 4
Production Example 1 (A-2) composition 100 parts is mixed as (D) composition as (C) composition and 1.0 parts of ネ オ ス タ Application (NEOSTANN) U-830 as (B) composition, 10 parts of KBE-9007 with 7.8 parts of コ ロ ネ ー ト (CORONATE) HX, is modulated into priming paint.
Embodiment 5
Using (A-1) composition 100 parts of Production Example 1 and 7.8 parts of コ ロ ネ ー ト (CORONATE) HX as (B) composition, 10 parts of KBE-9007 as (C) composition and 1.0 parts of commercially available bismuth system catalysts for polyurethanes (three Bismuth Octoates, trade(brand)name " ネ オ ス タ Application (NEOSTANN) U-600H ", Japan day east changes into (strain) system) mix as (D) composition, be modulated into priming paint.
Embodiment 6
By the tricarbimide body (trade(brand)name " コ ロ ネ ー ト (CORONATE) 2030 " of (A-2) composition 100 parts of Production Example 2 with 10 parts of tolylene diisocyanates, Nippon Polyurethane Industry (Ltd.)) mix as (D) composition as (C) composition and 1.0 parts of ネ オ ス タ Application (NEOSTANN) U-600H as (B) composition, 10 parts of KBE-9007, be modulated into priming paint.
Embodiment 7
By the biuret body (trade(brand)name " デ ュ ラ ネ ー ト (DURANATE) 24A-100 " of (A-1) composition 100 parts of Production Example 1 with 6 parts of hexamethylene diisocyanates, Japan Asahi Chemical Industry (strain) (Asahi Chemical Industry ケ ミ カ Le ズ (strain)) system) mix as (D) composition as (C) composition and 1.0 parts of ネ オ ス タ Application (NEOSTANN) U-810 as (B) composition, 10 parts of KBE-9007, be modulated into priming paint.
Embodiment 8
By the biuret body (trade(brand)name " デ ュ ラ ネ ー ト (DURANATE) P301-75E " of (A-1) composition 100 parts of Production Example 1 with 11.3 parts of hexamethylene diisocyanates, Asahi Chemical Industry of Japan (strain) system) as (B) composition, 10 parts of KBE-9007 mix as (D) composition as (C) composition and 1.0 parts of ネ オ ス タ Application (NEOSTANN) U-810, are modulated into priming paint.
Embodiment 9
Using (A-1) composition 100 parts of Production Example 1 and 7.8 parts of コ ロ ネ ー ト (CORONATE) HX as (B) composition, 10 parts of silane coupling agent (trade(brand)names " KBM-803 " containing sulfydryl, SHIN-ETSU HANTOTAI's silicone resin of Japan (strain) system) mix as (D) composition as (C) composition and 1.0 parts of ネ オ ス タ Application (NEOSTANN) U-810, be modulated into priming paint.
Embodiment 10
(A-3) composition 100 parts of Production Example 1 is mixed as (D) composition as (C) composition and 1.0 parts of ネ オ ス タ Application (NEOSTANN) U-810 as (B) composition, 10 parts of KBE-9007 with 25 parts of コ ロ ネ ー ト (CORONATE) HX, is modulated into priming paint.
Embodiment 11
(A-4) composition 100 parts of Production Example 1 is mixed as (D) composition as (C) composition and 1.0 parts of ネ オ ス タ Application (NEOSTANN) U-810 as (B) composition, 10 parts of KBE-9007 with 2 parts of デ ュ ラ ネ ー ト (DURANATE) 24A-100, is modulated into priming paint.
Embodiment 12
(A-5) composition 100 parts of Production Example 1 is mixed as (D) composition as (C) composition and 1.0 parts of ネ オ ス タ Application (NEOSTANN) U-810 as (B) composition, 10 parts of KBE-9007 with 8 parts of コ ロ ネ ー ト (CORONATE) HX, is modulated into priming paint.
Embodiment 13
Using (A-6) composition 100 parts of Production Example 1 and 20 parts of コ ロ ネ ー ト (CORONATE) HX as (B) composition, 10 parts of KBE-9007 are as (C) composition, 1.0 parts of ネ オ ス タ Application (NEOSTANN) U-810 are as (D) composition, 12 parts of tetramethylolmethanes and acrylic acid condenses (trade(brand)name " PVC ス コ ー ト (Biscoat) 300 ", Osaka, Japan Organic Chemical Industry (strain) is made) as (E) composition and 0.3 part of Photoepolymerizationinitiater initiater (trade(brand)name " Irg907 ", チ バ ジ ャ パ Application (strain) makes) mix, be modulated into priming paint.
Embodiment 14
(A-7) composition 100 parts of Production Example 7 is mixed as (D) composition as (C) composition and 1.0 parts of ネ オ ス タ Application (NEOSTANN) U-810 as (B) composition, 10 parts of KBE-9007 with 13.7 parts of コ ロ ネ ー ト (CORONATE) HX, is modulated into priming paint.
Embodiment 15
(A-7) composition 100 parts of Production Example 7 is mixed as (E) composition and 0.3 part of Irg907 as (D) composition, 12 parts of PVC ス コ ー ト (Biscoat) 300 as (C) composition, 1.0 parts of ネ オ ス タ Application (NEOSTANN) U-810 as (B) composition, 10 parts of KBE-9007 with 13.7 parts of コ ロ ネ ー ト (CORONATE) HX, is modulated into priming paint.
Comparative example 1
Except being 0 especially containing KBE-9007, other are identical with embodiment 1, are modulated into priming paint.Comparative example 2
(α) composition 100 parts comparing Production Example 1 is mixed as (D) composition as (C) composition and 1.0 parts of ネ オ ス タ Application (NEOSTANN) U-810 as (B) composition, 10 parts of KBE-9007 with 3 parts of コ ロ ネ ー ト (CORONATE) HX, is modulated into priming paint.
Comparative example 3
By (A-1) composition 100 parts of Production Example 2, substitute 10 parts of melamine series solidifying agent (trade(brand)name " サ イ メ Le (CYMEL) 303LF " of (B) composition, methylated melamine resins, profound new (strain) (オ Le ネ Network ス ジ ャ パ Application (the strain)) system of Japan), 10 parts of KBE-9007 mix as (C) composition and 0.3 part of tosic acid (PTS) as catalyzer of substituting (D) composition, are modulated into priming paint.
Comparative example 4
By (A-1) composition 100 parts of Production Example 2, substitute 10 parts of melamine series solidifying agent (trade(brand)name " サ イ メ Le (CYMEL) 303LF " of (B) composition, methylated melamine resins, Japan's profound new (strain) system), 10 parts of サ イ ラ エ ー ス (Sila-Ace) S510 mix as (C) composition and 0.3 part of tosic acid (PTS) as catalyzer of substituting (D) composition, are modulated into priming paint.
(1) base material with prime coat (not using the state of (E) composition) is made
The priming paint of embodiment 1 is in commercially available polyester film (trade(brand)name " Le ミ ラ-(Lumirror) U48 ", toray (strain) (East レ (strain)) system, 150 μm are thick) on, be coated with rod coater, make desciccator diaphragm thickness at about 1.0 μm, make the base material with cured base enamelled coating at 130 DEG C through drying in 1 minute.
(2) copper vapor-deposited film is made
Then, this base material priming paint face on, use commercially available vapor phase growing apparatus (goods name " NS-1875-Z ", Japan's Western Hills make institute's (strain) (Xi Shan System and do institute's (strain)) system), obtain (about 100nm is thick) copper vapor-deposited film by copper vapour deposition.Embodiment 2-12,14 and the priming paint of comparative example 1-4 operate too and obtain copper vapor-deposited film.
(3) base material with prime coat (using the state of (E) composition) is made
Use rod coater to be coated on aforementioned commercially available polyester film by the priming paint of embodiment 13, make dry film thickness about 1.0 μm, 130 DEG C of dryings 1 minute.Then, by the coated film that obtains in air at high voltage mercury lamp (300mJ/cm
2) under pass through, make thus and there is the base material of cured base enamelled coating.
(4) copper vapor-deposited film is made
Then in the priming paint face of this base material, use aforesaid commercially available vapor phase growing apparatus, by copper vapour deposition (about 100nm is thick), obtain copper vapor-deposited film.The priming paint of embodiment 15 operates too and obtains copper vapor-deposited film.
(5) initial stage adhesivity
The copper vapour deposition face cutting knife of the copper vapor-deposited film obtained in embodiment 1 is cut into 100 pieces of checkerboard grids, stick adhesive tape (trade(brand)name " Cellotape " (registered trademark), Japan day companion (strain) (ニ チ バ Application (strain)) system) after, peel off from vertical direction traction, thus evaluate the adhesivity of copper vapor deposition layer.Embodiment 12-15 and the copper vapor-deposited film involved by comparative example 1-4 carry out initial stage adhering evaluation too.
(6) alkaline-resisting adhesivity
Copper vapor-deposited film embodiment 1 obtained after 5 minutes, evaluates the adhesivity of copper vapor deposition layer with aforementioned same checkerboard network test at dipping to 4% aqueous sodium hydroxide solution of 40 DEG C of heating.Embodiment 12-15 and the copper vapor-deposited film involved by comparative example 1-4 carry out alkaline-resisting adhering evaluation too.
(7) acidproof adhesivity
Copper vapor-deposited film embodiment 1 obtained after 5 minutes, evaluates the adhesivity of copper vapor deposition layer with aforementioned same checkerboard network test at dipping to 4% aqueous hydrochloric acid of 40 DEG C of heating.Embodiment 12-15 and the copper vapor-deposited film involved by comparative example 1-4 carry out acidproof adhering evaluation too.
(8) block resistance
Use the priming paint of embodiment 1-12, embodiment 14 and comparative example 1-4, make the base material with cured base enamelled coating according to the method for aforementioned project (1).Then, this priming paint face is overlapped with previous polyesters film, at applying 8kg/cm
2loading under, under 40 DEG C of environment leave standstill 7 days.Then, release-coated film and uncoated film, implement block resistance evaluation.Specifically, observe during stripping film peel off be designated as ×, do not observe film during stripping and peel off, slightly resist sense and be designated as △, during stripping, film is not peeled off and is not almost resisted sense and be designated as zero △, and during stripping, film is not peeled off and do not resisted sense yet and be designated as zero.
By the method for the priming paint of embodiment 13 and embodiment 15 according to aforementioned project (3), make the base material with prime coat.Then, according to the method for aforementioned project (8), evaluate block resistance.
Claims (6)
1. for having the priming paint of the base material of Copper thin film, wherein, described priming paint contains following composition:
(A) composition: the polyester polyol prepared for reacted constituent with di-carboxylic acid (a1) and dibasic alcohol (a2);
(B) composition: the polymeric polyisocyanate at least containing three isocyanate group; And,
(C) composition: silane coupling agent; And as required, contain
(D) composition: urethanation catalyst.
2. priming paint as claimed in claim 1, wherein, described (A) composition is further using the polyvalent alcohol (a3) at least with three hydroxyls as reacted constituent, containing hydroxyl branched chain type vibrin.
3. the priming paint of base material as claimed in claim 1 or 2, wherein, described (C) composition is X-(CH
2)
n-Si (OR
2)
3the silane coupling agent represented, in above-mentioned general formula, n represents the integer of 2-4, R
2represent that carbon number is the alkyl of 1-3, X is selected from a kind of functional group in the group of isocyanate group, epoxy group(ing), amino and sulfydryl composition.
4. there is a base material for Copper thin film, wherein, described in there is Copper thin film base material comprise: base material, the prime coat formed by the solidifying priming paint in claim 1-3 described in any one and copper film layer.
5. have the base material of Copper thin film as claimed in claim 4, wherein, described base material is polyester film.
6. the conducting film be made up of the base material with Copper thin film described in claim 4 or 5.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014-071263 | 2014-03-31 | ||
| JP2014071263 | 2014-03-31 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104946117A true CN104946117A (en) | 2015-09-30 |
| CN104946117B CN104946117B (en) | 2019-09-13 |
Family
ID=54161197
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510148503.8A Expired - Fee Related CN104946117B (en) | 2014-03-31 | 2015-03-31 | Priming paint for the substrate with Copper thin film, the substrate with Copper thin film and its manufacturing method, conductive film and electrode film |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6168313B2 (en) |
| KR (1) | KR20150113912A (en) |
| CN (1) | CN104946117B (en) |
| TW (1) | TWI660015B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110062522A (en) * | 2018-01-18 | 2019-07-26 | 施赖纳集团两合公司 | Flexible circuit with the connection between the conductive structural detail of energy |
| CN111902445A (en) * | 2018-02-02 | 2020-11-06 | Ddp特种电子材料美国公司 | Adhesive useful for mounting vehicle windows |
| 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 |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017150663A1 (en) * | 2016-03-04 | 2017-09-08 | 三菱ケミカル株式会社 | Actinic-ray-curable coating material composition and layered product |
| KR102009424B1 (en) | 2018-05-17 | 2019-08-12 | 주식회사 도프 | Manufacturing method of flexible transparent copper films having ultra-high conductivity and the copper films made therefrom |
| JP2020070368A (en) * | 2018-10-31 | 2020-05-07 | 日本ペイント・オートモーティブコーティングス株式会社 | Coating composition for discontinuous metal thin film top coat and coating composition for discontinuous metal thin film undercoat |
| 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 |
| WO2023048049A1 (en) * | 2021-09-21 | 2023-03-30 | 東洋インキＳｃホールディングス株式会社 | Active energy ray curable undercoat agent, undercoat layer, laminate, and metal film-attached base material |
| 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 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0484956A2 (en) * | 1990-11-08 | 1992-05-13 | Diafoil Hoechst Co., Ltd | Polyester film capacitor element |
| JPH0528835A (en) * | 1990-09-12 | 1993-02-05 | Kakogawa Plast Kk | Filmy copper-evaporated base material |
| JPH0995654A (en) * | 1995-09-29 | 1997-04-08 | Asahi Glass Co Ltd | Adhesive for bonding glass to non-rigid vinyl-based resin |
| JP2002201453A (en) * | 2000-12-28 | 2002-07-19 | Toyobo Co Ltd | Adhesive for inorganic vapor deposited film |
| CN102408823A (en) * | 2010-09-21 | 2012-04-11 | 荒川化学工业株式会社 | Non-water-based for plastic film provided with active energy line curing film and plastic film provided with active energy line curing film |
| CN103282459A (en) * | 2010-12-28 | 2013-09-04 | 汉高股份有限及两合公司 | Outdoor urethane adhesive agent |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5397938A (en) * | 1977-02-09 | 1978-08-26 | Fujikura Kasei Kk | Undercoating for vacuum deposition |
| JPS5811904B2 (en) * | 1978-02-16 | 1983-03-05 | 藤倉化成株式会社 | Undercoat paint for vacuum deposition |
| JP2605816B2 (en) * | 1988-08-12 | 1997-04-30 | 東洋紡績株式会社 | Evaporated polyester film |
| JPH0793242B2 (en) * | 1991-05-16 | 1995-10-09 | ダイアホイルヘキスト株式会社 | Metal evaporated polyester film capacitor |
| JP2005305379A (en) * | 2004-04-26 | 2005-11-04 | Nippon Kasei Chem Co Ltd | Coating method and bonded structure |
| JP3903067B1 (en) * | 2005-06-03 | 2007-04-11 | 横浜ゴム株式会社 | Primer composition |
| JP5690583B2 (en) * | 2010-12-28 | 2015-03-25 | ヘンケルジャパン株式会社 | Adhesive for solar battery backsheet |
-
2015
- 2015-03-31 TW TW104110512A patent/TWI660015B/en not_active IP Right Cessation
- 2015-03-31 CN CN201510148503.8A patent/CN104946117B/en not_active Expired - Fee Related
- 2015-03-31 JP JP2015074190A patent/JP6168313B2/en not_active Expired - Fee Related
- 2015-03-31 KR KR1020150044855A patent/KR20150113912A/en unknown
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0528835A (en) * | 1990-09-12 | 1993-02-05 | Kakogawa Plast Kk | Filmy copper-evaporated base material |
| EP0484956A2 (en) * | 1990-11-08 | 1992-05-13 | Diafoil Hoechst Co., Ltd | Polyester film capacitor element |
| JPH0995654A (en) * | 1995-09-29 | 1997-04-08 | Asahi Glass Co Ltd | Adhesive for bonding glass to non-rigid vinyl-based resin |
| JP2002201453A (en) * | 2000-12-28 | 2002-07-19 | Toyobo Co Ltd | Adhesive for inorganic vapor deposited film |
| CN102408823A (en) * | 2010-09-21 | 2012-04-11 | 荒川化学工业株式会社 | Non-water-based for plastic film provided with active energy line curing film and plastic film provided with active energy line curing film |
| CN103282459A (en) * | 2010-12-28 | 2013-09-04 | 汉高股份有限及两合公司 | Outdoor urethane adhesive agent |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110062522A (en) * | 2018-01-18 | 2019-07-26 | 施赖纳集团两合公司 | Flexible circuit with the connection between the conductive structural detail of energy |
| CN111902445A (en) * | 2018-02-02 | 2020-11-06 | Ddp特种电子材料美国公司 | Adhesive useful for mounting vehicle windows |
| CN111902445B (en) * | 2018-02-02 | 2022-06-17 | Ddp特种电子材料美国公司 | Adhesive useful for mounting vehicle windows |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20150113912A (en) | 2015-10-08 |
| JP6168313B2 (en) | 2017-07-26 |
| TWI660015B (en) | 2019-05-21 |
| TW201602262A (en) | 2016-01-16 |
| CN104946117B (en) | 2019-09-13 |
| JP2015199946A (en) | 2015-11-12 |
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