CN104946117B

CN104946117B - Priming paint for the substrate with Copper thin film, the substrate with Copper thin film and its manufacturing method, conductive film and electrode film

Info

Publication number: CN104946117B
Application number: CN201510148503.8A
Authority: CN
Inventors: 山崎彰宽; 东本徹; 近藤洋平
Original assignee: Arakawa Chemical Industries Ltd
Current assignee: Arakawa Chemical Industries Ltd
Priority date: 2014-03-31
Filing date: 2015-03-31
Publication date: 2019-09-13
Anticipated expiration: 2035-03-31
Also published as: JP2015199946A; CN104946117A; TW201602262A; JP6168313B2; KR20150113912A; TWI660015B

Abstract

The object of the present invention is to provide a kind of priming paint, the priming paint is the organic polymer priming paint used in the substrate that manufacture has Copper thin film, the priming paint is capable of forming prime coat, the prime coat not only with after the initial stage good adhesion but also alkali process of plastic basis material and Copper thin film adhesiveness and acid treated that adhesiveness is also good.Priming paint for the substrate with Copper thin film of the invention contains following ingredient: (A) ingredient: taking dicarboxylic acids (a1) and dihydric alcohol (a2) as the polyester polyol of reacted constituent preparation；(B) ingredient: at least containing there are three the polyisocyanates of isocyanate group；And (C) ingredient: silane coupling agent；And as needed, contain (D) ingredient: urethanation catalyst.

Description

The system of priming paint for the substrate with Copper thin film, the substrate with Copper thin film and it Make method, conductive film and electrode film

Technical field

The present invention relates to a kind of priming paint used to form Copper thin film in various substrate surfaces, have by the priming paint shape At layer substrate with Copper thin film and its manufacturing method, using the conductive film made of the substrate with Copper thin film with And the electrode film obtained by the conductive film.

Background technique

Substrate with Copper thin film refers to forming the product of Copper thin film in various substrate surfaces.In field of electronic materials, Studying the substitute using the plastic foil with Copper thin film as tin indium oxide (ITO) conductive film.

Because the transparency and excellent conductivity of ITO conductive film, thus as touch screens such as smart phone and tablet computers Electrode film and used, however, because indium be high price rare metal, there are cost problems, and due to ITO layer again it is hard It is again crisp, it is never easily bent and deforms etc. from the perspective of processabilities, it is still problematic to need to solve.

It is well known that as the good electrode film of processability, such as can be polythiophene, polyaniline and polypyrrole etc. Pi-conjugated electroconductive polymer is coloured as conductive layer since the conductive layer exists, and there are asking on tone for the electrode film Topic.

On the other hand, as the conductive film of excellent processability, it is known that there are also other plastic foils with Copper thin film.This film Use the copper lower than ITO resistivity as conductive layer, thus electric conductivity is good, it is most important that it is cheap.It has been generally acknowledged that will Copper vapor deposition plastic foil is used as shows the electrode film of equipment such as touch screen, large screen easy to accomplish and curving.

In general, pervious copper vapor deposition plastic foil be vapor-deposited after nickel on the plastic foil as substrate, then Vapor deposition copper obtains.The nickel vapor deposition layer has the anchoring layer (ー layers of アンカ) for adhering to film and copper vapor deposition layer Function.Then, resist coating electrode pattern is used on copper vapor deposition plastic foil, (alkaline solution, acidity are molten with etching solution Liquid) processing after, by removing the resist, obtain target electrode film.

But since the nickel in copper vapor deposition plastic foil lacks alkali resistance and acid resistance, there are copper after etching process Vapor deposition layer from substrate film stripping, fall off the problem of.Although plastic foil is compared with ITO conductive film moreover, the copper is vapor-deposited It is cheap, but because nickel is than copper processing valuableness, thus this part of nickel improves price.Therefore, it has been suggested that making as anchoring layer With the method for following priming paint, which uses organic polymer as principal component (referring to patent document 1) without using nickel.It is another Aspect, using the priming paint, it is desirable that the block resistance (ロ of resistance to Block ッキ Application グ) of priming paint level.

The prior art

Patent document 1: Japanese Unexamined Patent Publication 5-28835 bulletin

Summary of the invention

The subject of the invention is to provide a kind of priming paint, the priming paint be manufacture have Copper thin film substrate when use have Machine macromolecule priming paint, the priming paint can form prime coat, and the prime coat is not only good with the initial stage adhesiveness of plastic basis material and Copper thin film Adhesiveness (hereinafter also referred to as alkaline-resisting adhesiveness), acid after good and alkali process treated adhesiveness are (hereinafter also referred to as resistance to Acid adhesion) and block resistance it is also good.

Present inventor's sharp study the result is that discovery contain following ingredient priming paint, make solve foregoing problems become can Can: make selected polyester polyol as main component；Polyisocyanates as curing agent；And as additive, The polyglycidyl compounds reacted with hydroxyl or isocyanate group.

Present invention comprises following technical solutions:

1. the priming paint for the substrate with Copper thin film, wherein the priming paint contains following component:

(A) ingredient: taking dicarboxylic acids (a1) and dihydric alcohol (a2) as the polyester polyol of reacted constituent preparation；

(B) ingredient: at least containing there are three the polyisocyanates of isocyanate group；And

(C) ingredient: silane coupling agent；And as needed, contain

(D) ingredient: urethanation catalyst.

2. the priming paint as described in aforementioned 1, wherein (A) ingredient is further at least to have the polynary of three hydroxyls Alcohol (a3) as reacted constituent, branched chain type polyester resin containing hydroxyl.

3. the priming paint as described in aforementioned 1 or 2, wherein the glass transition temperature of (A) ingredient is 80 DEG C or less.

4. the priming paint as described in aforementioned 1-3 any one, wherein the glass transition temperature of (A) ingredient is 0-75 ℃。

5. the priming paint as described in any one of aforementioned 1-4, wherein the hydroxyl value of (A) ingredient is 5-100mg KOH/ g。

6. the priming paint as described in any one of aforementioned 1-5, wherein (B) ingredient is from diisocyanate cpd Biuret body, a kind of derivative (b1) for selecting in the group that constitutes of isocyanuric acid body and addition product.

7. the priming paint as described in any one of aforementioned 1-6, wherein the hydroxyl and (B) contained in (A) ingredient The equivalent proportion (NCO/OH) of the isocyanate group contained in ingredient is 0.5-5.

8. the priming paint of the substrate as described in any one of aforementioned 1-7, wherein (C) ingredient is X- (CH₂)_n-Si (OR²)₃The silane coupling agent of expression, in above-mentioned general formula, n indicates the integer of 2-4, R²Indicate carbon number be 1-3 alkyl, X be selected from One of isocyanate group, epoxy group, the group of amino and sulfydryl composition functional group.

9. the priming paint of the substrate as described in any one of aforementioned 1-8, wherein (C) ingredient is general formula (1) X¹-Si (R¹)_a(OR²)_3-aThe reactive polyglycidyl compounds of expression, in general formula (1), X¹For the base containing following functional groups Group, the functional group react with the one kind selected from the group that hydroxyl and isocyanate group are constituted, R¹For hydrogen or carbon atom Number is the alkyl of 1-8, R²The alkyl for being 1-8 for carbon atom number, a indicate 0,1 or 2.

10. the priming paint as described in any one of aforementioned 1-9, wherein relative to 100 parts by weight of (A) ingredient (by solid The conversion of body ingredient), the usage amount of (C) ingredient is 1-20 parts by weight.

11. the priming paint as described in aforementioned 1-10, wherein (changed by solid component relative to 100 parts by weight of (A) ingredient Calculate), the usage amount of (D) ingredient is 0.1-2 parts by weight.

12. the priming paint as described in any one of aforementioned 1-11, wherein the priming paint also contains the work as (E) ingredient Property energy line polymeric compounds, (E) ingredient in the molecule at least have there are three carbon-carbon double key group.

13. the priming paint as described in aforementioned 12, wherein (changed by solid component relative to 100 parts by weight of (A) ingredient Calculate), the usage amount of (E) ingredient is 1-100 parts by weight.

14. a kind of substrate with Copper thin film, wherein the substrate with Copper thin film includes: substrate, by aforementioned 1-13 Any one of described in solidifying priming paint formed prime coat and copper film layer.

15. the substrate with Copper thin film as described in aforementioned 14, wherein the substrate is plastics.

16. the substrate with Copper thin film as described in aforementioned 15, wherein the plastics are plastic foil.

17. the substrate with Copper thin film as described in aforementioned 16, wherein the plastic foil is polyester film.

18. the substrate with Copper thin film as described in any one of aforementioned 14-17, wherein the copper film layer is copper Vapor-deposited film or copper sputtered film.

19. a kind of manufacturing method of the substrate with Copper thin film, which is characterized in that the described method comprises the following steps:

Priming paint described in any one of aforementioned 1-13 is coated on substrate surface,

Then, the substrate is heated to form solidification prime coat (1),

Then, copper film layer is formed on the solidification prime coat (1).

20. a kind of manufacturing method of the substrate with Copper thin film, which is characterized in that the described method comprises the following steps:

Then, the substrate is heated to form solidification prime coat (1 '),

Then, the solidification prime coat (1 ') is irradiated using active energy ray, so that solidification prime coat (2 ') is formed,

Then, copper film layer is formed on the solidification prime coat (2 ').

21. the manufacturing method as described in aforementioned 19, wherein form the side of copper film layer on prime coat (1) in described solidify Method is vaccum gas phase sedimentation method or sputtering method.

22. the manufacturing method as described in aforementioned 20, wherein form the side of copper film layer on prime coat (2 ') in described solidify Method is vaccum gas phase sedimentation method or sputtering method.

23. conductive film made of the substrate described in any one of aforementioned 14-18 with Copper thin film.

24. being led made of the substrate with Copper thin film that the manufacturing method described in any one of aforementioned 19-22 obtains Electrolemma.

25. the electrode film that the conductive film as described in aforementioned 23 or 24 obtains.

The effect of invention

Priming paint of the invention forms smooth film in substrate surface.Moreover, the film only under the action of heat solidification or Person solidifies under the action of heat is with active energy ray, forms prime coat, and the prime coat is not only viscous with the initial stage of substrate and Copper thin film Attached property is good and alkaline-resisting adhesiveness and two aspect of acidproof adhesiveness are good, and block resistance is good.

For the substrate with Copper thin film of the invention, due to the initial stage adhesiveness, resistance to substrate and copper vapor-deposited film Alkali adhesiveness and acidproof good adhesion, even if this has the etched liquid of the substrate of Copper thin film or acid solution processing, copper gas phase Deposition film is also not easy to fall off from substrate.In the substrate with Copper thin film, when especially substrate is plastic foil, it can be used as and replace For the conductive film of ITO conductive film.

Conductive film of the invention can be used for various electrode films, such as touch screen, IC card substrate, IC tag base The purposes such as plate, Electronic Paper substrate, flexible display substrate.Touching be especially suitable for smart phone and tablet computer etc. Touch the electrode film that screen uses.

Specific embodiment

As the preferred embodiment of the present invention, copper vapor-deposited film of the invention is with priming paint (hereinafter, also referred to as bottom Paint) be the composition containing following component: selected polyester polyol (A) (hereinafter also referred to (A) ingredient) at least contains three The polyisocyanates (B) (hereinafter also referred to (B) ingredient) of a isocyanate group and selected reactive alkoxysilyl Compound (C) (hereinafter also referred to (C) ingredient).

As (A) ingredient, various well known branched chain type polyester polyol can be used, be not particularly limited.Specifically, For example, it is preferable to dicarboxylic acids (a1) (hereinafter also referred to (a1) ingredient) and dihydric alcohol (a2) (hereinafter also referred to (a2) ingredient) Polyalcohol as neccessary composition.

As (a1) ingredient, various well known dicarboxylic acids can be used, be not particularly limited.Specifically, for example may be used To enumerate: the aromatic series of M-phthalic acid, terephthalic acid (TPA), diphenyl methane -4,4 '-dicarboxylic acids and their acid anhydrides etc. Dicarboxylic acids；Ethanedioic acid, malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, pimelic acid, suberic acid, decanedioic acid, 11 The aliphatic dicarboxylic acid of docosandioic acid, dodecanedioic acid, tridecandioic acid and their acid anhydrides etc.；Hexahydrophthalic acid, The alicyclic ring of hexahydrophthalic anhydride, 1,4- cyclohexane dicarboxylic carboxylic acid, 1,2- cyclohexane dicarboxylic carboxylic acid and their acid anhydrides etc. Race's dicarboxylic acids etc.；It is also possible to two or more combinations.Moreover, from initial stage adhesiveness, alkaline-resisting adhesiveness, acidproof adhesiveness with And from the perspective of block resistance balance, (a1) ingredient preferably comprises aromatic binary carboxylic acid.In addition, to fragrant in (a1) ingredient The usage amount of race's dicarboxylic acids is not particularly limited, usually 20-60mol% or so.In addition, binary aliphatic in (a1) ingredient The usage amount of carboxylic acid and/or Cycloaliphatic dicarboxylic acids are usually 0-5mol% or so.

As (a2) ingredient, various well known dihydric alcohols can be used, be not particularly limited.Specifically, for example can be with It enumerates: 1,2- propylene glycol, 1,3 butylene glycol, neopentyl glycol, 3- methyl-1,5- pentanediol, 2- methyl-1,3-propanediol, second two The binary aliphatics such as alcohol, diethylene glycol, triethylene glycol, 1,3- propylene glycol, 1,4- butanediol, pentanediol and 1,6-HD Alcohol；The cycloaliphatic diols such as the ethylene oxide adduct of 1,4- cyclohexanediol and hydrogenated bisphenol A；Catechol, resorcinol, Hydroquinone, benzene dimethanol, aromatic diols such as ethylene oxide adduct of bis- (hydroxy ethoxy) benzene and bisphenol-A etc.；? It can be two or more combinations.Moreover, being balanced from initial stage adhesiveness, alkaline-resisting adhesiveness, acidproof adhesiveness and block resistance From the perspective of, aliphatic dihydroxy alcohol is preferably comprised in (a2) ingredient.In addition, the use to aliphatic dihydroxy alcohol in (a2) ingredient Amount is not particularly limited, usually 20-60mol% or so.In addition, cycloaliphatic diols and/or aromatic series two in (a2) ingredient The usage amount of first alcohol is usually 0-40mol% or so.

(A) ingredient can be again and at least containing there are three any of the polyalcohol (a3) (hereinafter also referred to (a3) ingredient) of hydroxyl Reacted constituent reaction.(a3) ingredient introduces free hydroxyl and branched structure to (A) ingredient, can especially make priming paint of the invention Initial stage adhesiveness, alkaline-resisting adhesiveness, acidproof adhesiveness and the block resistance of the layer of formation improve.

As (a3) ingredient, well known any ingredient can be used, be not particularly limited.Specifically, can for example arrange It lifts: the aliphatic triol such as glycerol, trimethylolpropane, trimethylolethane, 1,2,6- hexanetriol and 1,2,4- butantriol；Ring The alicyclic triol such as hexanetriol；The aromatic series triol such as pyrogallol and phloroglucin；One contracting two glycerine, antierythrite, sorb Aliphatic tetrol such as sugar alcohol, pentaerythrite and dipentaerythritol etc.；It is also possible to two or more combinations.Moreover, from initial stage From the perspective of adhesiveness, alkaline-resisting adhesiveness, acidproof adhesiveness and block resistance balance, (a3) ingredient preferred aliphat triol And/or aliphatic tetrol.

The usage amount of (a1) ingredient, (a2) ingredient and (a3) ingredient used as needed is not particularly limited, is led to Often, from the viewpoint of initial stage adhesiveness, alkaline-resisting adhesiveness, acidproof adhesiveness and block resistance balance, it is usually preferred to following Range:

The case where without using (a3) ingredient

(a1) ingredient: 20-50mol% or so, preferably 25-45mol% or so

(a2) ingredient: 50-80mol% or so, preferably 55-75mol% or so

The case where using (a3) ingredient

(a1) ingredient: 20-50mol% or so, preferably 25-45mol% or so

(a2) ingredient: 47-77mol% or so, preferably 53-73mol% or so

(a3) ingredient: 0.1-3mol% or so, preferably 0.5-2mol% or so

Moreover, various well known polybasic carboxylic acids can be used together with (a1) ingredient, (a2) ingredient and (a3) ingredient (hereinafter also referred to (a4) ingredient).Specifically, can for example enumerate: maleic acid/maleic anhydride, O-phthalic Acid/phthalic anhydride, trimellitic acid/trimellitic anhydride, Pyromellitic Acid/pyromellitic dianhydride, hexahydro O-phthalic Acid and/or acid anhydrides of acid/hexahydrophthalic anhydride and succinic acid/succinic anhydride etc. etc.；It is also possible to two or more groups It closes.Moreover, in the case where (a1) ingredient, (a2) ingredient and (a3) ingredient add up to 100mol%, the use of (a4) ingredient Amount is usually less than 5mol%.

The manufacturing method of (A) ingredient is not particularly limited, various well known methods can be used.Specifically, for example Can enumerate: it is anti-that (a1) ingredient, (a2) ingredient and (a3) ingredient as needed and/or (a4) ingredient are carried out dehydrating condensation The one pot process answered；Make the dehydration condensation object of (a1) ingredient and (a2) ingredient and (a3) ingredient and as needed (a4) method etc. of ingredient reaction.No matter reaction temperature is all not particularly limited in which kind of situation, at 150-250 DEG C or so.And And to the reaction time it is not also specifically limited, at 5-10 hours or so.Moreover, reaction carries out under normal pressure or under reduced pressure.

When manufacturing (A) ingredient, various well known catalyst can be used.Specifically, can for example enumerate: titanium dioxide Germanium, tetraethoxy germanium, four n-butoxy germanium, antimony oxide, dibutyltin oxide, acetic acid dihydrate zinc, Mono-n-butyltin, Butyl titanate etc. is also possible to two or more combinations.Moreover, manufacture can also in the presence of aftermentioned organic solvent into Row.

The physical characteristic of (A) ingredient is not particularly limited, from initial stage adhesiveness, alkaline-resisting adhesiveness, acidproof adhesiveness with And from the perspective of block resistance balance, such as glass transition temperature (measured value based on Japanese JIS-7121 standard) is usual For 80 DEG C hereinafter, it is preferred that 0-75 DEG C or so, more preferable 30-70 DEG C or so, more preferable 40-65 DEG C or so；Hydroxyl value is (based on Japan The measured value of JIS-0070 standard) it is usually 5-100mg KOH/g or so, preferably 7-90mg KOH/g or so, more preferable 8- 75mg KOH/g or so, particularly preferred 10-60mg KOH/g or so.

As (B) ingredient, intramolecular can be used and at least contain polyisocyanates there are three isocyanate group, can be public affairs Any ingredient known, is not particularly limited.(B) ingredient is reacted with (A) ingredient by urethane, assigns bottom of the invention Paint layer is with cross-linked structure.

As the specific example of (B) ingredient, at least one selected from the group that following ingredients are constituted can be enumerated: from two At least one derivative selected in the group that biuret body, isocyanuric acid body and the addition product of isocyanate compound are constituted (b1) (hereinafter also referred to (b1) ingredient)；It is somebody's turn to do the reactant (b2) (hereinafter also referred to (b2) of (b1) ingredient and diatomic alcohol compounds Ingredient)；Tri-isocyanate compound (b3) (ingredient that removing belongs to (b1) ingredient and (b2) ingredient) (hereinafter also referred to (b3) at Point)；And other polyisocyanate compounds (hereinafter also referred to (b4) ingredient).Wherein, from initial stage adhesiveness, alkaline-resisting adherency Property, from the perspective of acidproof adhesiveness and block resistance balance, particularly preferred (b1) ingredient.

It as the diisocyanate cpd of composition (b1) ingredient, such as can enumerate: toluene di-isocyanate(TDI), hexichol first The aromatic diisocyanates such as alkane diisocyanate and eylylene diisocyanate；Hexamethylene diisocyanate, front three The aliphatic diisocyanates such as base hexamethylene diisocyanate and lysine diisocyanate；And dicyclohexyl methyl hydride two is different Cyanate, isophorone diisocyanate, 1,4- cyclohexane diisocyanate, hydrogenated xylene diisocyanate and hydrogenated toluene The ester ring types diisocyanate such as diisocyanate.

In addition, the biuret body of aforementioned diisocyanates compound is indicated with following structural formula.

[chemical formula 1]

(in formula, R³Indicate the residue of aforementioned diisocyanates compound.)

Moreover, the isocyanuric acid body of aforementioned diisocyanates compound is indicated with following structural formula.

[chemical formula 2]

(in formula, R⁴Indicate the residue of aforementioned diisocyanates compound.)

Moreover, the addition product of aforementioned diisocyanates compound is indicated with following structural formula.

[chemical formula 3]

(in formula, R⁵Indicate carbon atom number for the alkyl of 1-3 or with OCN-R⁶- HN-C (=O)-O-CH₂The function indicated Group, R⁶Indicate the residue of aforementioned diisocyanates compound.)

It to the diatomic alcohol compounds of composition (b2) ingredient, is not particularly limited, aliphatic dihydroxy alcohol preferably above-mentioned, especially It is preferred that the one kind selected from the group that following alcohol is constituted: ethylene glycol, 1,2- propylene glycol, 1,3- propylene glycol, 1,3 butylene glycol, new penta Glycol, 1,6-HD, ethohexadiol, dipropylene glycol, polyethylene glycol and polypropylene glycol etc..

(b2) ingredient can be manufactured with various well known methods.Specifically, for example, aforementioned (b1) ingredient and aforementioned binary Alcoholic compound carries out urethane under the following conditions and reacts to obtain: the isocyanate group (NCO ') of (b1) ingredient and The equivalent proportion (NCO '/OH ') of the hydroxyl (OH ') of the dihydric alcohol is usually 5-20 or so, preferably in the range of 10-20 or so It is interior, it is reacted 1-5 hours or so usually at 40-80 DEG C.Moreover, obtained (b2) ingredient, isocyanate group equivalent are usually 1-10meq/g or so, preferably 3-6meq/g or so.

As (b3) ingredient, such as can enumerate: Toluene-2,4-diisocyanate, 4,6- triisocyanates, triphenylmethane triisocyanate, It is tri o cresyl thiophosphate phenyl isocyanate, 1,6,11- hendecane triisocyanate, 1,3,6- hexa-methylene triisocyanate, bicyclic Polyisocyanates (product name " the デュラネート MHG- of the triisocyanates such as heptane triisocyanate and six functional groups 80B ", Japanese Asahi Chemical Industry chemical (strain) system) etc., it is also possible to two or more combinations.

As (b4) ingredient, such as polyisocyanates (product name " the デュラネート MHG- of six functional groups can be enumerated 80B ", Japanese Asahi Chemical Industry chemical (strain) system).

Moreover, to (B) ingredient relative to the ratio of (A) ingredient it is not also specifically limited, from initial stage adhesiveness, alkaline-resisting adherency Property, acidproof adhesiveness and block resistance balance from the perspective of, the isocyanate group of the hydroxyl and (B) ingredient of (A) ingredient Equivalent proportion (NCO/OH) is usually 0.5-5 or so, preferably 1-2 or so.

It may be reacted by (C) ingredient with (A) ingredient and/or (B) ingredient, be had by the prime coat that priming paint of the invention is formed Machine integrally combines, and can especially improve the alkaline-resisting adhesiveness of this layer.

As (C) ingredient, can be general formula is X- (CH₂)_n-Si(OR²)₃The silane coupling agent of expression, in above-mentioned general formula, n Indicate the integer of 2-4, R²Indicate that carbon number is the alkyl of 1-3, X is to form selected from isocyanate group, epoxy group, amino and sulfydryl One of group functional group, X preferably indicates isocyanate group (O=C=N-) or epoxy group, especially X are isocyanate group Substance together with (B) ingredient and in (A) ingredient hydroxyl reaction and it is integrated, it can be considered that alkaline-resisting adhesiveness becomes It is especially good.

Silane coupling agent as (C) ingredient is also possible to any general formula (1): X¹-Si(R¹)_a(OR²)_3-aThe reaction of expression Property polyglycidyl compounds, various well known substances can be used, be not particularly limited, in general formula (1), X¹For containing The group of following functional groups, the functional group react with the one kind selected from the group that hydroxyl and isocyanate group are constituted, R¹The alkyl for being 1-8 for hydrogen or carbon atom number, R²The alkyl for being 1-8 for carbon atom number, a indicate 0,1 or 2.

As the X in (C) ingredient indicated with aforementioned formula (1)¹, such as can enumerate containing from the group of following composition A kind of functional group of selection: isocyanate group, epoxy group, sulfydryl, amino and anhydride group.

As X¹In reactive functional groups be isocyanate group (C) ingredient, such as 3- isocyanate group can be enumerated Propyl trimethoxy silicane, 3- isocyanate group propyl-triethoxysilicane, 3- isocyanate group hydroxypropyl methyl dimethoxy silicon Alkane and 3- isocyanate group hydroxypropyl methyl diethoxy silane etc., are also possible to two or more combinations.

As X¹In reactive functional groups be epoxy group (C) ingredient, such as 2- (3,4- epoxy hexamethylenes can be enumerated Base) ethyl trimethoxy silane, 3- glycidyl ether oxypropyl methyl dimethoxy silane, 3- glycydoxy Three second of trimethoxy silane, 3- glycydoxy methyldiethoxysilane and 3- glycydoxy Oxysilane etc. is also possible to two or more combinations.

As X¹In reactive functional groups be sulfydryl (C) ingredient, such as 3- mercaptopropyi trimethoxy can be enumerated Silane, 3- Mercaptopropyltriethoxysilane, 3- mercapto propyl methyl dimethoxy silane and 3- mercaptopropyi methyl diethyl Oxysilane etc. is also possible to two or more combinations.

As X¹In reactive functional groups be amino (C) ingredient, such as N-2- (aminoethyl) -3- amino can be enumerated Hydroxypropyl methyl dimethoxysilane, N-2- (aminoethyl) -3- TSL 8330,3- aminopropyl trimethoxy silicon Alkane, 3-aminopropyltriethoxysilane and 3- uride propyl trialkoxy silane etc., are also possible to two or more combinations.

As X¹In reactive functional groups be anhydride group (C) ingredient, such as 3- trimethoxy first silicon substrate can be enumerated Propyl succinimide acid anhydrides.

As (C) ingredient, from the viewpoint of initial stage adhesiveness, alkaline-resisting adhesiveness, acidproof adhesiveness and block resistance balance It sets out, preferably X¹In functional group be the compound of isocyanate group and/or the compound of epoxy group.

The usage amount of (C) ingredient is not particularly limited, in general, (pressing solid component relative to 100 parts by weight of (A) ingredient Conversion), the usage amount of (C) ingredient is 1-20 parts by weight or so, preferably 5-15 parts by weight or so.

As needed, priming paint of the invention can also containing urethanation catalyst (D) (hereinafter also referred to (D) at Point).Should (D) ingredient accelerate (A) ingredient and (B) ingredient curing reaction, make priming paint of the invention initial stage adhesiveness, it is alkaline-resisting glue Attached property, acidproof adhesiveness and block resistance improve.

As (D) ingredient, specifically, can for example enumerate three (2- ethyl -1- caproic acid) butyl tins, monobutyl oxidation Tin, two isooctyl acid tin, dibutyl tin dilaurate, tin dilaurate dioctyl tin, distearyl acid dioctyl tin, oxidation dioctyl Tin, diethyl acyl-oxygen dioctyl tin salt (ジオ Network チ Le tin ジアセテート) and two new caprinoyl oxygen tin (ジオ Network チ of dioctyl Le Xi バーサテート) etc. tin urethane catalyst；The bismuths system amino such as Bismuth Octoate, three Bismuth Octoates/tri- isooctyl acid bismuths Formic acid esterification catalyst；Diazabicyclooctane, dimethyl cyclohexyl amine, 4-methyl-diaminopropane, ethyl morpholine, dimethyl ethanol Organic amines urethane catalyst such as amine, triethylamine and triethylenediamine etc.；It is also possible to two or more groups It closes.

The usage amount of (D) ingredient is not particularly limited, for (A) ingredient, (B) ingredient and (C) at 100 weight of subtotaling Part (converting by solid component) is measured, the usage amount of (D) ingredient is usually 0.1-2 parts by weight or so, preferably 0.5-1.5 parts by weight.

The case where for being suitable for film base material, priming paint of the invention can also contain active energy ray polymeric compounds (E) (hereinafter also referred to (E) ingredient), (E) ingredient at least have the group there are three carbon-carbon double key in the molecule.Contain Should the priming paint of (E) ingredient solidify under the action of heat and both active energy rays, to obtain excellent initial stage adhesiveness, alkaline-resisting Adhesiveness and acidproof adhesiveness, moreover, also assigning prime coat excellent block resistance.

The group of carbon-carbon double key as (E) ingredient, for example, can enumerate vinyl, acrylic, acryloyl group and Methylacryloyl etc..Moreover, the specific example as (E) ingredient can be enumerated: trimethylolpropane tris (methyl) acrylic acid Trimethylolpropane tris (the first of ester, ethylene-oxide-modified trimethylolpropane tris (methyl) acrylate, epoxy pronane modification Base) acrylate, pentaerythrite monohydroxy three (methyl) acrylate, dipentaerythritol six (methyl) acrylate, two seasons penta Tetrol monohydroxy five (methyl) acrylate, dipentaerythritol five (methyl) acrylate, double trimethylolpropane four (methyl) Acrylate and glycerine three (methyl) acrylate etc. are at least containing there are three the compounds of (methyl) acryloyl group；Ji Wusi Alcohol monohydroxy triallyl ether and citric acid triallyl etc. are at least containing there are three the compounds etc. of vinyl；It is also possible to two Kind or more combination.Wherein, from the angle of the hardness of priming paint epithelium, the group of carbon-carbon double key preferably (methyl) propylene Acyl group, and its number is 3-6.

The usage amount of (E) ingredient is not particularly limited, from initial stage adhesiveness, alkaline-resisting adhesiveness, acidproof adhesiveness and From the perspective of block resistance balance, in general, (E) ingredient is 0-100 parts by weight or so relative to 100 parts by weight of (A) ingredient, It is preferred that 20-70 parts by weight or so (converting by solid component).

Moreover, other various well known (methyl) acrylate can be shared with (E) ingredient.Specifically, for example can be with It enumerates: 1,3 butylene glycol two (methyl) acrylate, 1,4- butanediol two (methyl) acrylate, 1,6-HD two (methyl) Acrylate, diethylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate and bisphenol-A ethylene oxide Two (methyl) acrylate such as two modified (methyl) acrylate；Polyurethane polyureas (methyl) acrylate and the poly- (first of polyester Base) oligomer such as acrylate；(methyl) 2-EHA, (methyl) isodecyl acrylate, (methyl) acrylic acid are different Monooctyl ester, (methyl) benzyl acrylate, (methyl) acrylic acid ring pentyl ester, (methyl) cyclohexyl acrylate, (methyl) acrylic acid two Cyclopentene ester, (methyl) isobornyl acrylate；Vinyltrimethoxysilane, styryltrimethoxysilane, 3- (first Base) acryloxypropyl dimethoxysilane, 3- (methyl) acryloyloxypropyltrimethoxysilane, 3- (methyl) Acryloyloxy propyl methyl diethoxysilane and 3- (methyl) acryloxypropyl triethoxysilane etc.；It can also be with It is two or more combinations.

Moreover, priming paint of the invention can also contain Photoepolymerizationinitiater initiater (F) (hereinafter also referred to (F) ingredient).It is specific and Speech, such as benzophenone, 4 '-methyl mercapto-α-morpholinyl-Alpha-Methyl propiophenone, 2 can be enumerated, 4,6- tri-methyl benzophenones, Methyl o-benzoylbenzoate, 4- phenyl benzophenone, tert-butyl anthraquinone, 2- ethyl hydrazine, diethoxy acetophenone, 2- hydroxyl Base-2- methyl-1-phenyl-1- acetone, oligomerization { 2- hydroxy-2-methyl-1- [4- (1- methyl ethylene) phenyl] acetone }, benzene are even Acyl dimethyl ketal, 1- hydroxycyclohexyl phenyl ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl Butyl ether, 2- methyl-[4- (methyl mercapto) phenyl] -2- morpholinyl -1- acetone, 2- benzyl -2- dimethylamino -1- (4- morpholinyl benzene Base) -1- butanone, 2- dimethylamino -2- (4- methylbenzyl) -1- (4- morpholine -4- base-phenyl) -1- butanone, diethyl thioxanthene Ketone, isopropyl thioxanthone, 2,4,6- trimethyl benzoyl diphenyl base phosphine oxide, bis- (2,6- Dimethoxybenzoyls)- 2,4,4- trimethylpentylphosphine oxide, bis- (2,4,6- trimethylbenzoyl) phenyl phosphine oxides, 2- hydroxyl -1- { 4- [4- (2- Hydroxy-2-methyl propiono) benzyl] phenyl } -2- methylpropane -1- ketone, methyl benzoylformate, phenylglyoxalates methyl esters, 4, 4 '-bis- (lignocaine) benzophenone, 2- benzyl -2- dimethylamino -4- morpholine phenyl propyl ketone, 2,2- dimethoxy -2- phenyl benzene Ethyl ketone, 2- methyl-1-phenyl-2- morpholino propane-1- ketone, 2- methyl-1-(4- hexyl phenyl)-2- morpholino propane-1- ketone, The light that 2- ethyl -2- dimethylamino -1- (4- morphlinophenyl) -1- butanone and Japanese Unexamined Patent Publication 2014-1390 bulletin are recorded Polymerization initiator etc. is also possible to two or more combinations.Moreover, Irgacure can be used for example as (F) ingredient 907、Irgacure 369、Irgacure 379、Irgacure 651、Irgacure 184、Irgacure 500、Irgacure 1000, the commercial goods such as Irgacure 149, Irgacure 261 and Darocur 1173.

The usage amount of (F) ingredient is not particularly limited, in general, relative to 100 parts by weight of (E) ingredient, (F) ingredient is 0.1-3 parts by weight or so, preferably 0.5-2 parts by weight or so (convert by solid component).

Moreover, the auxiliary agent as (F) ingredient, can enumerate triethanolamine, triisopropanolamine, 4,4 '-Dimethylaminobenzene first Ketone (michaelis ketone), 4,4 '-lignocaine Benzophenones, 2- dimethyl ethyl aminobenzoate, 4- dimethyl ethyl aminobenzoate, 4- bis- Methylamino acid n-butoxy ethyl ester, 4- dimethylaminobenzoic acid isopentyl ester, 4- dimethylaminobenzoic acid 2- ethylhexyl, 2, 4- diethyl thioxanthone, 2,4- diisopropyl thioxanthone etc., are also possible to two or more combinations.

Moreover, priming paint of the invention can also contain inorganic particulate for example in the case where being suitable for plastic film substrate.By The cured layer of priming paint of the invention is imparted in the inorganic particulate with slickness appropriate, the base material film with the cured layer is made to exist Do not allow to be also easy to produce abnormal sound and film defect when batching.

As the inorganic particulate, such as silica, titanium dioxide, aluminium oxide, zinc oxide, tin oxide, oxygen can be enumerated Change the particles such as zirconium, tin indium oxide (ITO), antimony tin (ATO), aluminium hydroxide, calcium hydroxide and magnesium hydroxide, is also possible to Two or more combinations.And, wherein from the viewpoint of aforementioned slickness, particularly preferred silica and/or aluminium oxide. Moreover, the particle surface can apply various processing.Moreover, the median particle diameter (d50) to the particle is not particularly limited, usually It is 10nm-5 μm or so.

The usage amount of the inorganic particulate is not particularly limited, in general, relative to 100 parts by weight of (A) ingredient, the inorganic grain The usage amount of son is 0-20 parts by weight or so, preferably 5-10 parts by weight or so (all converting by solid component).

Moreover, as needed, priming paint of the invention can contain the compound with sulfydryl.Specifically, for example can be with It enumerates: 1,3,5- tri- (3- sulfydryl butyryl acyloxy ethyl) -1,3,5- triazine -2,4,6 (1H, 3H, 5H)-triketone, bis- (the 3- mercaptos of 1,4- Base butyryl acyloxy) butane, trimethylolpropane tris (3- mercaptobutylate), trimethylolethane trimethacrylate (3- mercaptobutylate), season Penta tetrol four (3- mercaptobutylate) and dipentaerythritol six (3- mercaptobutylate) etc., are also possible to two or more groups It closes.

The usage amount of the compound with sulfydryl is not particularly limited, in general, relative to 100 parts by weight of (A) ingredient, The usage amount of compound with sulfydryl is 0-20 parts by weight or so, and preferably 5-10 parts by weight or so (are all changed by solid component It calculates).

Moreover, in the case where stating the compound with sulfydryl in use, when in line with the storage for extending priming paint of the present invention Between purpose, can be applied in combination with various well known alkene-thiol reaction inhibitor.Specifically, can for example enumerate: triphen The phosphorus series compounds such as base phosphine and triphenyl phosphite；P methoxy phenol, hydroquinone, pyrogallol, naphthylamines, tert-butyl o Benzenediol, stannous chloride, DBPC 2,6 ditertiary butyl p cresol, 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol)s, 2,2 '-Asias Methyl bis- (4- methyl-6-tert-butylphenols), the N- nitroso-radical polymerizations such as N-Phenylhydroxylamine aluminium salt and diphenyl nitrosamine Close inhibitor；Benzyl dimethylamine, 2- (dimethylaminomethyl) phenol, (bis aminomethyl) phenol of 2,4,6- tri- and 1,8- bis- The tertiary amines such as 11 carbon -7- alkene of azabicyclo [5.4.0]；And 2-methylimidazole, 2-ethyl-4-methylimidazole, 2- ethylhexyl Imidazoles such as imidazoles, 2- undecylimidazole and 1- cyano ethyl -2-methylimidazole etc.；It is also possible to two or more combinations.It is right The usage amount of the inhibitor is not particularly limited, and can suitably set.

Priming paint of the invention is made by aforementioned (A) ingredient, (B) ingredient, (C) ingredient and other compositions used as needed It is mixed to get with various well known means.

When mixing, various well known organic solvents (G) (hereinafter also referred to (G) ingredient) can be used as needed.Specifically For, such as can enumerate: the lower ketones such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK)；The aromatic hydrocarbons such as toluene；The alcohol such as ethyl alcohol, propyl alcohol；Third The ether-ethers such as glycol monomethyl ether acetate, ethylene glycol ether acetate (エチ Le セロソ Le Block アセテート)；Ethyl acetate； Chloroform；Dimethylformamide etc.；It is also possible to two or more combinations.Moreover, the usage amount of the ingredient is usually to make this Range of the concentration of the solid component of invention priming paint in 1-60 weight % or so.Wherein, the case where substrate is plastic foil Under, particularly preferred lower ketones.

Moreover, priming paint of the invention can containing levelling agent, antioxidant, polymerization inhibitor, ultraviolet absorbing agent etc. its His additive.

Substrate with Copper thin film of the invention is layered product, comprising: various substrates, solidifying priming paint of the invention are formed Prime coat and copper film layer.

Substrate is not particularly limited, as long as surface can form Copper thin film, various well known substrates can be used.Tool For body, such as plastics, metal, cellulosic material, glass can be enumerated etc..As the plastics, for example, can enumerate polyester, Polyvinyl chloride, polyamide, polyimides, polycarbonate, polyethylene and polypropylene etc..Moreover, as the cellulosic material, Such as paper, nano-cellulose paper and timber can be enumerated etc..

Substrate shapes are not particularly limited.Such as it can be spherical, cylindric, rectangular-shape, plate, membranaceous.Moreover, Part or all of substrate surface can have concave-convex either curved surface.Substrate with Copper thin film of the invention is as conduction In the case where film use, consider from heat resistance and optical characteristics etc., as the preferred plastic foil of substrate, particularly preferred polyester Film.Moreover, the thickness to the base material film is it is not also specifically limited, usually 50-200 μm or so.Moreover, to the thickness of prime coat It is not particularly limited, usually 0.1-5 μm or so.

As copper film layer above-mentioned, such as copper vapor-deposited film, copper sputtered film, copper chemical vapor deposition can be enumerated (CVD) film etc..Film with Copper thin film of the invention is in the case where being used for electrode film, as the Copper thin film, particularly preferred copper Vapor-deposited film or copper sputtered film.Moreover, the thickness of the copper vapor-deposited film or copper sputtered film is not particularly limited, usually 0.1-2 μm or so.

The preparation method of substrate with Copper thin film of the invention is not particularly limited, such as can generally take following system Method.

The case where without using (E) ingredient

On aforementioned substrates surface, it is coated with priming paint of the invention (without (E) ingredient), then the substrate is heated to be formed Solidify prime coat (1), then forms the method for copper film layer on the solidification prime coat (1).

The case where using (E) ingredient

On aforementioned substrates surface, it is coated with priming paint of the invention (containing (E) ingredient), then the substrate is heated to be formed Solidify prime coat (1 '), then then exists to solidification prime coat irradiation active energy ray to form solidification prime coat (2 ') The method of copper film layer is formed on the solidification prime coat (2 ').

Application conditions are not particularly limited, as spreading implement, such as sprayer, roll coater, reverse roll can be enumerated Painting machine, intaglio plate roll coater, knife type coater, rod coater, point type coating machine etc., and coating weight is not also limited especially System, usually as drying solid ingredient in 0.01-10g/m²Left and right.

To heating condition it is not also specifically limited, typical temperature is at 80-150 DEG C or so, the time was at -2 minutes or so 10 seconds. May the processing enable (A) ingredient, (B) ingredient and (C) ingredient is organic integrally reacts, assign prime coat (1) with Excellent initial stage adhesiveness, alkaline-resisting adhesiveness, acidproof adhesiveness and block resistance.

To active energy ray irradiation condition it is not also specifically limited, usually as active energy ray, such as purple can be enumerated Outside line and electron ray.Moreover, the supply source as ultraviolet light, such as high-pressure sodium lamp and metal halide lamp can be enumerated Deng its irradiation energy is usually in 100-2,000mJ/cm²Left and right.Moreover, the supply mode as electron ray, such as can be with The irradiation of scanning electron beam, the irradiation of curtain electron beam etc. are enumerated, its irradiation energy is usually 10-200kGy or so.It may be through The processing is crossed, Raolical polymerizable occurs between each other as (E) ingredient in solidification prime coat (1 ') and forms cross-linked structure As a result, make it is described solidify prime coat (2 ') not only have excellent initial stage adhesiveness, alkaline-resisting adhesiveness and acidproof adhesiveness Block resistance, and there is excellent block resistance.

For being not particularly limited in the means for solidifying prime coat (1) or solidify and being formed on prime coat (2 ') copper film layer, It is preferred that so-called dry-coated method.Specifically, the physical method such as can enumerate vaccum gas phase sedimentation method or sputtering method, chemical gaseous phase Deposit chemical methodes (chemical gas phase reaction etc.) such as (CVD) etc..The film with Copper thin film that the manufacturing method of the present invention obtains exists In the case where for electrode film, preferably vaccum gas phase sedimentation method or sputtering method.

Electrode film of the invention is the electronic component obtained by conductive film of the invention.Particularly, conductive film of the invention In plastic foil is vapor-deposited by copper or electrode film that copper sputtered film obtains may be used as the substitution of the electrode film using ITO conductive film Product.

The resist of conductive film of the invention is coated with according to electrode pattern, with etching solution (alkaline solution, acid solution) After processing, the resist is removed, obtains electrode film of the invention.The shape of electrode pattern is not particularly limited, Ke Yilie Lift thin-line-shaped, dotted, netted, sheet etc..

Embodiment

Next, being illustrated in further detail by embodiment and comparative example to the present invention, but model of the invention It encloses and is not limited to these embodiments.Moreover, " part " in embodiment is to indicate according to weight basis.Moreover, hydroxyl value and acid value are Value according to Japan's JIS-0070 standard test.Moreover, glass transition temperature is to use commercially available measuring instrument (product name " DSC8230B ", Rigaku motor (strain) system) measurement value.

Production Example 1

(A) manufacture of ingredient

Terephthalic acid (TPA) two is added to the flask with blender, thermometer, nitrogen ingress pipe and reflux dewatering device 2843.4 parts of methyl esters (TPhDM), 1382.2 parts of ethylene glycol (EG), 449.7 parts of 1,6-HD (1,6HD), neopentyl glycol (NPG) 1189 parts and 51.1 parts of trimethylolpropane (TMP) are added 0.79 part of zinc acetate as ester exchange catalyst.Then, it heats Raw material carries out ester exchange reaction 2 hours at 195 DEG C while distilling the methanol of generation to outside reaction system.

Then, 2043.8 parts of M-phthalic acid (IPhA), 440.9 parts of azelaic acid (AzA) is added, in the water that will be generated to anti- While answering system to distill outside, carried out dehydration condensation 3 hours at 200 DEG C.The acid value of reaction solution is 11.2mg KOH/g.

Then, reflux unit is changed into vacuum decompression device, is added 0.42 part of butyl titanate, 240 DEG C, 0.3kPa with Under carry out decompression 2 hours.Then, 2300.4 parts of methyl iso-butyl ketone (MIBK), 6901 parts of methyl ethyl ketone, 219.8 parts of acetylacetone,2,4-pentanedione are added, and Mixing.

Thus it obtains polyester polyol (A-1), the nonvolatile component of the polyester polyol is 40%, hydroxyl value 17mg KOH/g, glass transition temperature are 47 DEG C.

Production Example 2

Into flask same as Production Example 1,452.2 parts of terephthalic acid (TPA) (TPhA), M-phthalic acid (IPhA) is added 839.9 parts, 94.1 parts of ethylene glycol (EG), 368.3 parts of neopentyl glycol (NPG), bis- (4- polyoxyethylene-oxygen phenyl) propane of 2,2- (BA-P) 1745.5 parts.Then, while heating melting removes the water that distillation generates to outside reaction system, by reaction system 250 DEG C are slowly ramped to, then keeps the temperature 3 hours.Then, which is connect with vacuum decompression device, adds butyl titanate After 0.18 part, heat preservation 30 minutes, carried out depressurization condensation reaction 1 hour at 1.3hPa.Then 100 parts of resin are transferred to has Thermometer, nitrogen ingress pipe, cooling tube and agitating device flask, 75 parts of methyl iso-butyl ketone (MIBK), 75 parts of methyl ethyl ketone is added, One dissolution.Thus polyester polyol (A-2) is obtained, the nonvolatile component of the polyester polyol is 40%, hydroxyl value is 20mg KOH/ G, glass transition temperature is 60 DEG C.

Production Example 3

Terephthalic acid (TPA) two is added to the flask with blender, thermometer, nitrogen ingress pipe and reflux dewatering device 2843.4 parts of methyl esters (TPhDM), 1382.2 parts of ethylene glycol (EG), 1638.7 parts of neopentyl glycol (NPG) and trimethylolpropane (TMP) 51.1 parts, 0.79 part of zinc acetate is added as ester exchange catalyst.Then, raw material is heated, in the methanol that will be generated to anti- While answering system to distill outside, carried out ester exchange reaction 2 hours at 195 DEG C.Then, M-phthalic acid (IPhA) is added It 2484.7 parts, while distilling the water of generation to outside reaction system, is carried out dehydration condensation 3 hours at 200 DEG C.Instead The acid value for answering liquid is 11mg KOH/g.Then, reflux unit is changed into vacuum decompression device, is added 0.42 part of butyl titanate, Decompression 2 hours is carried out in 240 DEG C, 0.3kPa or less.Then, 2520.2 parts of methyl iso-butyl ketone (MIBK), 6901 parts of methyl ethyl ketone are added, and Mixing.Thus obtain polyester polyol (A-3), the nonvolatile component of the polyester polyol is 40%, hydroxyl value be 55mg KOH/g, Glass transition temperature is 50 DEG C.

Production Example 4

Into flask same as Production Example 1,328 parts of terephthalic acid (TPA) (TPhA), M-phthalic acid (IPhA) 328 is added Part, 182 parts of ethylene glycol (EG), bis- (4- polyoxyethylene-oxygen phenyl) 762 parts of the propane (BA-P) of 2,2-.Then, it is incited somebody to action in heating melting While the water that distillation generates is removed to outside reaction system, reaction system is slowly ramped to 250 DEG C, then keep the temperature 3 hours.So Afterwards, which is connect with vacuum decompression device, after adding 0.18 part of butyl titanate, heat preservation 30 minutes, at 1.3hPa It carries out depressurization condensation reaction 1 hour.Then, by 100 parts of resin be transferred to thermometer, nitrogen ingress pipe, cooling tube and 75 parts of methyl iso-butyl ketone (MIBK), 75 parts of methyl ethyl ketone, uniform dissolution is added in the flask of agitating device.Thus polyester polyol (A- is obtained 4), the nonvolatile component of the polyester polyol is 40%, hydroxyl value is 5mg KOH/g, glass transition temperature is 70 DEG C.

Production Example 5

Into flask same as Production Example 1,479 parts of terephthalic acid (TPA) (TPhA), M-phthalic acid (IPhA) 402 is added Part, 87 parts of azelaic acid (AzA), 256 parts of ethylene glycol (EG), 221 parts of 1,6-HD (1,6HD), 148 parts of neopentyl glycol (NPG) And 7 parts of trimethylolpropane (TMP).Then, while heating melting removes the water that distillation generates to outside reaction system, Reaction system is slowly ramped to 250 DEG C, then keeps the temperature 3 hours.Then, which is connect with vacuum decompression device, is added After 0.18 part of butyl titanate, heat preservation 30 minutes, carried out depressurization condensation reaction 1 hour at 1.3hPa.Then, by resin 100 Part is transferred to the flask with thermometer, nitrogen ingress pipe, cooling tube and agitating device, be added 75 parts of methyl iso-butyl ketone (MIBK), 75 parts of methyl ethyl ketone, uniform dissolution.Thus it obtains polyester polyol (A-5), the nonvolatile component of the polyester polyol is 40%, hydroxyl Value is 21mg KOH/g, glass transition temperature is 31 DEG C.

Production Example 6

Into flask same as Production Example 1,479 parts of terephthalic acid (TPA) (TPhA), M-phthalic acid (IPhA) 402 is added Part, 87 parts of azelaic acid (AzA), 256 parts of ethylene glycol (EG), 354 parts of 1,6-HD (1,6HD) and 23 parts of glycerol (GLY).So Afterwards, while heating melting removes the water that distillation generates to outside reaction system, reaction system is slowly ramped to 250 DEG C, 3 hours are kept the temperature again.Then, which is connect with vacuum decompression device, adds 0.18 part of butyl titanate, keep the temperature 30 minutes Afterwards, it is carried out depressurization condensation reaction 1 hour at 1.3hPa.Then, 100 parts of resin are transferred to thermometer, nitrogen importing 75 parts of methyl iso-butyl ketone (MIBK), 75 parts of methyl ethyl ketone, uniform dissolution is added in the flask of pipe, cooling tube and agitating device.Thus it obtains Polyester polyol (A-6), the nonvolatile component of the polyester polyol is 40%, hydroxyl value is 45mg KOH/g, glass transition temperature Degree is 17 DEG C.

Production Example 7

Into flask same as Production Example 1,386 parts of terephthalic acid (TPA) (TPhA), M-phthalic acid (IPhA) 292 is added Part, 300 parts of azelaic acid (AzA), 251 parts of ethylene glycol (EG), 348 parts of 1,6-HD (1,6HD) and 23 parts of glycerol (GLY). Then, while heating melting removes the water that distillation generates to outside reaction system, reaction system is slowly ramped to 250 DEG C, then keep the temperature 3 hours.Then, which is connect with vacuum decompression device, adds 0.18 part of butyl titanate, heat preservation 30 After minute, carried out depressurization condensation reaction 1 hour at 1.3hPa.Then, 100 parts of resin are transferred to thermometer, nitrogen 75 parts of methyl iso-butyl ketone (MIBK), 75 parts of methyl ethyl ketone, uniform dissolution is added in the flask of ingress pipe, cooling tube and agitating device.Thus Polyester polyol (A-7) is obtained, the nonvolatile component of the polyester polyol is 40%, hydroxyl value is 30mg KOH/g, vitrifying turns Temperature is 8 DEG C.

Comparison manufacturing example 1

Into flask same as Production Example 1,300 parts of terephthalic acid (TPA) (TPhA), 81 parts of ethylene glycol (EG), the third two are added 3 parts of 216 parts of alcohol (PG) and trimethylolpropane (TMP).Then, the water generated will be distilled to outside reaction system in heating melting While removal, reaction system is slowly ramped to 250 DEG C, then keeps the temperature 3 hours.Then, by the flask and vacuum decompression device Connection carries out depressurization condensation reaction 1 hour at 1.3hPa after adding 0.18 part of butyl titanate, heat preservation 30 minutes.So Afterwards, it is transferred to the flask with thermometer, nitrogen ingress pipe, cooling tube and agitating device by 100 parts of resin, it is different that methyl is added 75 parts of butyl ketone, 75 parts of methyl ethyl ketone, uniform dissolution.Thus polyester polyol (α), the nonvolatile component of the polyester polyol are obtained It is 5mg KOH/g for 40%, hydroxyl value, glass transition temperature is 84 DEG C.

The modulation of priming paint

Embodiment 1

By the isocyanuric acid of 100 parts of (A-1) ingredient of Production Example 1 and the hexamethylene diisocyanate as (B) ingredient 7.8 parts of body (trade name " U ロネート (CORONATE) HX ", Nippon Polyurethane Industry (Ltd.)) and as (C) ingredient 10 parts of silane coupling agent (trade name " KBE-9007 ", Japanese SHIN-ETSU HANTOTAI's silicone resin (strain) system) and conduct containing isocyanate group (D) commercially available tin system catalysts for polyurethanes (tin dilaurate dioctyl tin, trade name " ネオスタ Application (NEOSTANN) U- of ingredient 810 ", day east is melted into (strain) system) 1.0 parts be uniformly mixed, be modulated into priming paint.

Embodiment 2

Using 100 parts of (A-1) ingredient of Production Example 1 and 7.8 parts of U ロネート (CORONATE) HX as (B) ingredient, 10 Silane coupling agent (trade name " サイラエース (Sila-Ace) 510 ", Japanese JNC (strain) system) conduct of part containing epoxy group (C) ingredient and 1.0 parts of ネオスタ Application U-810 are uniformly mixed as (D) ingredient, are modulated into priming paint.

Embodiment 3

Using 100 parts of (A-1) ingredient of Production Example 1 with 7.8 parts of U ロネート (CORONATE) HX as (B) ingredient, 10 parts KBE-9007 is used as (C) ingredient and 1.0 parts of commercially available tin system catalysts for polyurethanes (the new caprinoyl oxygen tin of dioctyl two, trade names " ネオスタ Application (NEOSTANN) U-830 ", Japanese day east chemical conversion (strain) system) it is uniformly mixed as (D) ingredient, it is modulated into bottom Paint.

Embodiment 4

Using 100 parts of Production Example 1 (A-2) ingredient with 7.8 parts of U ロネート (CORONATE) HX as (B) ingredient, 10 parts KBE-9007 is uniformly mixed as (C) ingredient and 1.0 parts of ネオスタ Application (NEOSTANN) U-830 as (D) ingredient, modulation At priming paint.

Embodiment 5

Using 100 parts of (A-1) ingredient of Production Example 1 with 7.8 parts of U ロネート (CORONATE) HX as (B) ingredient, 10 parts KBE-9007 is used as (C) ingredient and 1.0 parts of commercially available bismuth system catalysts for polyurethanes (three Bismuth Octoates, trade name " ネオスタ Application (NEOSTANN) U-600H ", Japanese day east chemical conversion (strain) system) it is uniformly mixed as (D) ingredient, it is modulated into priming paint.

Embodiment 6

By isocyanuric acid body (trade name " the U ロ of 100 parts of (A-2) ingredient of Production Example 2 and 10 parts of toluene di-isocyanate(TDI)s ネート (CORONATE) 2030 ", Nippon Polyurethane Industry (Ltd.)) it is used as (B) ingredient, 10 parts of KBE-9007 to be used as (C) ingredient And 1.0 parts of ネオスタ Application (NEOSTANN) U-600H are uniformly mixed as (D) ingredient, are modulated into priming paint.

Embodiment 7

By the biuret body (trade name " デ of 100 parts of (A-1) ingredient of Production Example 1 and 6 parts of hexamethylene diisocyanates ュラネート (DURANATE) 24A-100 ", Japanese Asahi Chemical Industry's (strain) (Asahi Chemical Industry ケミカ Le ズ (strain)) system) as (B) at Divide, 10 parts of KBE-9007 are mixed as (C) ingredient and 1.0 parts of ネオスタ Application (NEOSTANN) U-810 as (D) ingredient It is even, it is modulated into priming paint.

Embodiment 8

By the biuret body (trade name of 100 parts of (A-1) ingredient of Production Example 1 and 11.3 parts of hexamethylene diisocyanates " デュラネート (DURANATE) P301-75E ", Japanese Asahi Chemical Industry's (strain) system) it is used as (B) ingredient, 10 parts of KBE-9007 conducts (C) ingredient and 1.0 parts of ネオスタ Application (NEOSTANN) U-810 are uniformly mixed as (D) ingredient, are modulated into priming paint.

Embodiment 9

Using 100 parts of (A-1) ingredient of Production Example 1 with 7.8 parts of U ロネート (CORONATE) HX as (B) ingredient, 10 parts Silane coupling agent (trade name " KBM-803 ", Japanese SHIN-ETSU HANTOTAI's silicone resin (strain) system) containing sulfydryl is used as (C) ingredient and 1.0 parts ネオスタ Application (NEOSTANN) U-810 is uniformly mixed as (D) ingredient, is modulated into priming paint.

Embodiment 10

Using 100 parts of (A-3) ingredient of Production Example 1 with 25 parts of U ロネート (CORONATE) HX as (B) ingredient, 10 parts KBE-9007 is uniformly mixed as (C) ingredient and 1.0 parts of ネオスタ Application (NEOSTANN) U-810 as (D) ingredient, modulation At priming paint.

Embodiment 11

Using 100 parts of (A-4) ingredient of Production Example 1 and 2 parts of デュラネート (DURANATE) 24A-100 as (B) at Divide, 10 parts of KBE-9007 are mixed as (C) ingredient and 1.0 parts of ネオスタ Application (NEOSTANN) U-810 as (D) ingredient It is even, it is modulated into priming paint.

Embodiment 12

Using 100 parts of (A-5) ingredient of Production Example 1 with 8 parts of U ロネート (CORONATE) HX as (B) ingredient, 10 parts KBE-9007 is uniformly mixed as (C) ingredient and 1.0 parts of ネオスタ Application (NEOSTANN) U-810 as (D) ingredient, modulation At priming paint.

Embodiment 13

Using 100 parts of (A-6) ingredient of Production Example 1 with 20 parts of U ロネート (CORONATE) HX as (B) ingredient, 10 parts KBE-9007 as (C) ingredient, 1.0 parts of ネオスタ Application (NEOSTANN) U-810 as (D) ingredients, 12 parts of pentaerythrites with Condensation product (trade name " ビスコート (Biscoat) 300 ", Osaka, Japan Organic Chemical Industry (strain) system) conduct of acrylic acid (E) ingredient and 0.3 part of Photoepolymerizationinitiater initiater (trade name " Irg907 ", チバジャパ Application (strain) system) are uniformly mixed, and adjust Priming paint is made.

Embodiment 14

Using 100 parts of (A-7) ingredient of Production Example 7 with 13.7 parts of U ロネート (CORONATE) HX as (B) ingredient, 10 Part KBE-9007 is uniformly mixed as (C) ingredient and 1.0 parts of ネオスタ Application (NEOSTANN) U-810 as (D) ingredient, is adjusted Priming paint is made.

Embodiment 15

Using 100 parts of (A-7) ingredient of Production Example 7 with 13.7 parts of U ロネート (CORONATE) HX as (B) ingredient, 10 Part KBE-9007 is used as (D) ingredient, 12 parts of ビスコート as (C) ingredient, 1.0 parts of ネオスタ Application (NEOSTANN) U-810 (Biscoat) it 300 is uniformly mixed as (E) ingredient and 0.3 part of Irg907, is modulated into priming paint.

Comparative example 1

Except being 0 especially that other are same as Example 1, are modulated into priming paint containing KBE-9007.

Comparative example 2

Using 100 parts of (α) ingredient of comparison manufacturing example 1 with 3 parts of U ロネート (CORONATE) HX as (B) ingredient, 10 parts KBE-9007 is uniformly mixed as (C) ingredient and 1.0 parts of ネオスタ Application (NEOSTANN) U-810 as (D) ingredient, modulation At priming paint.

Comparative example 3

By 100 parts of (A-1) ingredient of Production Example 2,10 parts of melamine series curing agent (trade name " サ of (B) ingredient are substituted イメ Le (CYMEL) 303LF ", methylated melamine resins, Japan are profound new (strain) (オ Le ネ Network スジャパ Application (strain)) System), 10 parts of KBE-9007 as (C) ingredient and substitution (D) ingredient 0.3 part of p-methyl benzenesulfonic acid (PTS) as catalyst It is uniformly mixed, is modulated into priming paint.

Comparative example 4

By 100 parts of (A-1) ingredient of Production Example 2,10 parts of melamine series curing agent (trade name " サ of (B) ingredient are substituted イメ Le (CYMEL) 303LF ", methylated melamine resins, Japan profound new (strain) system), 10 parts of サイラエース (Sila- Ace) S510 is uniformly mixed as 0.3 part of p-methyl benzenesulfonic acid (PTS) as catalyst of (C) ingredient and substitution (D) ingredient, It is modulated into priming paint.

(1) production has the substrate of prime coat (state for not using (E) ingredient)

The priming paint of embodiment 1 is in commercially available polyester film (trade name " Le ミラ-(Lumirror) U48 ", toray (strain) (eastern レ (strain)) system, 150 μ m-thicks) on, it is coated with rod coater, makes desciccator diaphragm thickness at 1.0 μm or so, at 130 DEG C through 1 point Clock is dry to be made with the substrate for solidifying prime coat.

(2) copper vapor-deposited film is made

Then, on the priming paint face of the substrate, commercially available vapor phase growing apparatus (product name " NS-1875-Z ", day are used This Western Hills makes institute (strain) (Western Hills make institute (strain)) system), it is vapor-deposited to obtain (about 100nm is thick) copper vapor deposition by copper Film.The priming paint of embodiment 2-12,14 and comparative example 1-4, which similarly operate, obtains copper vapor-deposited film.

(3) production has the substrate of prime coat (state for using (E) ingredient)

The priming paint of embodiment 13 is coated on aforementioned commercially available polyester film using rod coater, makes 1.0 μ of dry film thickness M or so is 1 minute dry at 130 DEG C.Then, by obtained coated film in atmosphere in high-pressure sodium lamp (300mJ/cm²) under lead to It crosses, thus production has the substrate for solidifying prime coat.

(4) copper vapor-deposited film is made

Then in the priming paint face of the substrate, using commercially available vapor phase growing apparatus above-mentioned, (about by copper vapor deposition 100nm is thick), obtain copper vapor-deposited film.The priming paint of embodiment 15 similarly operates and obtains copper vapor-deposited film.

(5) initial stage adhesiveness

100 pieces of checkerboard grids are cut into cutter in the copper vapor deposition face for the copper vapor-deposited film that embodiment 1 obtains, are pasted After adhesive tape (trade name " Cellotape " (registered trademark), Japanese day make with (strain) (ニチバ Application (strain))), from vertical direction Traction removing, to evaluate the adhesiveness of copper vapor deposition layer.Copper gas phase involved in embodiment 12-15 and comparative example 1-4 Deposition film similarly carries out the evaluation of initial stage adhesiveness.

(6) alkaline-resisting adhesiveness

The copper vapor-deposited film that embodiment 1 obtains is impregnated 5 minutes in 4% sodium hydrate aqueous solution for being heated up to 40 DEG C Afterwards, with it is aforementioned it is same with checkerboard network test evaluation copper vapor deposition layer adhesiveness.Embodiment 12-15 and comparative example 1- Copper vapor-deposited film involved in 4 similarly carries out the evaluation of alkaline-resisting adhesiveness.

(7) acidproof adhesiveness

The copper vapor-deposited film that embodiment 1 obtains is impregnated after five minutes in 4% aqueous hydrochloric acid solution for being heated up to 40 DEG C, With the aforementioned same adhesiveness with checkerboard network test evaluation copper vapor deposition layer.Embodiment 12-15 and comparative example 1-4 institute The copper vapor-deposited film being related to similarly carries out the evaluation of acidproof adhesiveness.

(8) block resistance

Using the priming paint of embodiment 1-12, embodiment 14 and comparative example 1-4, made according to the method for aforementioned project (1) With the substrate for solidifying prime coat.Then, which is overlapped with aforementioned polyester film, is applying 8kg/cm²Loading under, 7 days are stood under 40 DEG C of environment.Then, release-coated film and uncoated film implement block resistance evaluation.Specifically, when removing Observe apply film stripping be denoted as ×, when removing, which does not observe, to be applied film stripping, slightly resists sense and be denoted as △, and film is not removed when removing Zero △ is denoted as almost without sense is resisted, and film, which is not removed, when removing is also denoted as zero without resisting sense.

By the priming paint of embodiment 13 and embodiment 15 according to the method for aforementioned project (3), the base with prime coat is made Material.Then, according to the method for aforementioned project (8), block resistance is evaluated.

Claims

(C) ingredient: silane coupling agent；And as needed, contain

(D) ingredient: urethanation catalyst；

(E) ingredient: active energy ray polymeric compounds, and at least there are three contain carbon-to-carbon for tool in the molecule for (E) ingredient The group of double bond.

2. priming paint as described in claim 1, wherein (A) ingredient is further at least to have the polynary of three hydroxyls Alcohol (a3) as reacted constituent, branched chain type polyester resin containing hydroxyl.

3. priming paint as claimed in claim 1 or 2, wherein the glass transition temperature of (A) ingredient is 80 DEG C or less.

4. priming paint as claimed in claim 1 or 2, wherein the glass transition temperature of (A) ingredient is 0-75 DEG C.

5. priming paint as claimed in claim 1 or 2, wherein the hydroxyl value of (A) ingredient is 5-100mg KOH/g.

6. priming paint as claimed in claim 1 or 2, wherein (B) ingredient is the biuret from diisocyanate cpd A kind of derivative (b1) selected in the group that body, isocyanuric acid body and addition product are constituted.

7. priming paint as claimed in claim 1 or 2, wherein (C) ingredient is X- (CH₂)_n-Si(OR²)₃The silane of expression is even Join agent, in above-mentioned general formula, n indicates the integer of 2-4, R²Indicate that carbon number is the alkyl of 1-3, X is selected from isocyanate group, epoxy One of the group of base, amino and sulfydryl composition functional group.

8. priming paint as claimed in claim 1 or 2, wherein (C) ingredient is general formula (1) X¹-Si(R¹)_a(OR²)_3-aIt indicates Reactive polyglycidyl compounds, in general formula (1), X¹For the group containing following functional groups, the functional group with from The one kind selected in the group that hydroxyl and isocyanate group are constituted reacts, R¹The alkyl for being 1-8 for hydrogen or carbon atom number, R²For Carbon atom number is the alkyl of 1-8, and a indicates 0,1 or 2.

9. priming paint as claimed in claim 1 or 2, wherein convert by solid component, relative to 100 weight of (A) ingredient Part, the usage amount of (C) ingredient is 1-20 parts by weight.

10. priming paint as claimed in claim 1 or 2, wherein convert by solid component, relative to 100 weight of (A) ingredient Part, the usage amount of (D) ingredient is 0.1-2 parts by weight.

11. priming paint as claimed in claim 1 or 2, wherein convert by solid component, relative to 100 weight of (A) ingredient Part, the usage amount of (E) ingredient is 1-100 parts by weight.

12. a kind of substrate with Copper thin film, wherein the substrate with Copper thin film includes: substrate, by claim 1-11 Any one of described in solidifying priming paint formed prime coat and copper film layer.

13. as claimed in claim 12 with the substrate of Copper thin film, wherein the substrate is plastics.

14. as claimed in claim 13 with the substrate of Copper thin film, wherein the plastics are plastic foil.

15. as claimed in claim 14 with the substrate of Copper thin film, wherein the plastic foil is polyester film.

16. the substrate with Copper thin film as described in any one of claim 12-15, wherein the copper film layer is copper Vapor-deposited film or copper sputtered film.

17. a kind of manufacturing method of the substrate with Copper thin film, which is characterized in that the described method comprises the following steps:

Priming paint described in any one of claim 1-11 is coated on substrate surface,

Then, the substrate is heated to form solidification prime coat (1),

Then, copper film layer is formed on the solidification prime coat (1).

18. a kind of manufacturing method of the substrate with Copper thin film, which is characterized in that the described method comprises the following steps:

Then, the substrate is heated to form solidification prime coat (1 '),

Then, copper film layer is formed on the solidification prime coat (2 ').

19. manufacturing method as claimed in claim 17, wherein form the side of copper film layer on prime coat (1) in described solidify Method is vaccum gas phase sedimentation method or sputtering method.

20. manufacturing method as claimed in claim 18, wherein form the side of copper film layer on prime coat (2 ') in described solidify Method is vaccum gas phase sedimentation method or sputtering method.

21. conductive film made of the substrate described in any one of claim 12-16 with Copper thin film.

22. being led made of the substrate with Copper thin film that the manufacturing method described in any one of claim 17-20 obtains Electrolemma.

23. the electrode film that the conductive film as described in claim 21 or 22 obtains.