JPWO2017094264A1 - Substrate with conductive film - Google Patents

Abstract

An object of this invention is to provide the base material with an electrically conductive film which has the favorable adhesiveness of a plastic base material and an electrically conductive film irrespective of the kind of electrically conductive ink, and has the electrically conductive film with the nonuniformity on the surface. A base material with a conductive film having a base film and a conductive film in this order on the surface of the base material, wherein the base film has the formula (I) (wherein Ar has an electron donating group) An optionally substituted aryl group of C6 to C10, X represents a single bond, etc. Y represents a polymerizable functional group, Z represents a carbon atom or a silicon atom, R2 represents a hydrogen atom, or the like. Wherein each Ar may be the same or different, and a compound represented by the formula (II) R4Si (R3) 3 (II) (wherein R4 represents an epoxy group or the like). R3 represents a hydroxyl group or a hydrolyzable group.) A substrate with a conductive film, which is a film that is a cured product of a coating agent containing a condensate of an organosilane compound represented by: [Chemical 1]

Description

The present invention relates to a substrate with a conductive film in which a conductive film is formed on the surface of a plastic substrate with good adhesion.
This application claims priority with respect to the Japan patent application 2015-236366 for which it applied on December 3, 2015, and uses the content here.

  2. Description of the Related Art Conventionally, a conductive film formed using a conductive ink or paste containing metal particles or a conductive polymer has been widely used to form electrodes and circuits of electronic components, electromagnetic wave shields, and the like. Further, due to recent demands for miniaturization of devices and circuits, for example, it has been attempted to form a conductive film wiring on a plastic substrate so that the substrate can be stored in a folded state.

  However, such a substrate has low heat resistance, and it is necessary to bake the conductive ink at a low temperature when forming the conductive film. In particular, when a conductive film is formed by applying and firing a conductive ink or paste containing metal fine particles on a substrate, there is also a problem that the conductive film is easily peeled off from the substrate because the adhesion between the conductive film and the substrate is low. .

Therefore, a method is known in which a base film is formed on the surface of the substrate to improve the adhesion between the substrate and the conductive film laminated thereon. For example, in Patent Document 1, an overcoat agent containing vinyl chloride / acrylic / polycarbonate as a primer composition is applied on a plastic substrate, and then dried at 80 ° C. for 30 minutes to form a base film, and It describes a method for obtaining a substrate with a conductive film by applying a conductive composition comprising silver oxide and a fatty acid silver salt on a base film, followed by heating at 180 ° C. for 3 minutes.
In Patent Document 2, a base film containing an organic salt or an inorganic salt and a binder resin such as polyvinyl alcohol is formed on a glass substrate whose surface has been subjected to oxygen plasma treatment, and further, a quencher is formed on the base film. A method for forming a conductive film having no unevenness and good adhesion to a substrate by forming a circular dot pattern of silver nanoink containing sodium acid as a dispersant with an inkjet device and drying at 150 ° C. for 30 minutes is described. Yes.

  On the other hand, a coating agent containing a compound represented by the following formula (A), which is excellent in adhesion to a plastic substrate, is known. (See Patent Document 3)

In the formula, A represents a phenyl group or a naphthyl group which may have an electron donating group as a substituent. Z is a carbon atom or silicon atom, R ² is a hydrogen atom, a hydroxyl group, a linear or branched alkyl group, a linear or branched alkoxy group, a cyclic alkyl group, or a cyclic alkoxy group, and X is a single bond; An oxygen atom, a sulfur atom, a selenium atom, -NR-, a divalent aliphatic ring group, an arylene group, an amide structure or a C1-C20 alkylene group which may contain a urethane structure; a divalent aliphatic ring group; Or an arylene group, Y is a polymerizable functional group, n is an integer of 2 or 3, m is an integer of 1 or 2, l is an integer of 0 or 1, and n + m + 1 = 4. When n is an integer of 2 or 3, A may be the same or different.

JP 2009-252494 A JP 2010-272402 A International Publication No. WO2014 / 115210 Pamphlet

  In the base film described in Patent Document 1, the conductive composition is limited to a composition containing silver oxide and a fatty acid silver salt, and is not a general-purpose one that can be used for conductive ink in general. In addition, the method described in Patent Document 2 is a method for forming a conductive pattern by an ink jet method, in which the conductive film has a uniform film thickness in the case of combining a metal particle-containing ink having specific physical properties and a primer layer having specific properties. And the effect of adhesion to the substrate can be obtained.

  The present invention has been made in view of the above circumstances, and has a conductive film having a conductive film that has good adhesion between the plastic substrate and the conductive film regardless of the type of the conductive ink, and has no unevenness on the surface. An object is to provide a substrate.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have laminated a conductive film on a base material provided with a base film formed from a specific coating agent on the surface. The present invention was completed by finding that a substrate with a conductive film having good adhesion was obtained and the surface of the conductive film was not uneven.

（式中、Ａｒは、電子供与性基を有していてもよいＣ６〜Ｃ１０のアリール基を示す。
Ｘは、単結合；酸素原子、硫黄原子、セレン原子、−ＮＲ^１−（式中、Ｒ^１は水素原子又はＣ１〜Ｃ６のアルキル基を表す。）、Ｃ３〜Ｃ６の２価の脂肪族環基、Ｃ６〜Ｃ１０のアリーレン基、アミド構造若しくはウレタン構造を含んでいてもよいＣ１〜Ｃ２０のアルキレン基；Ｃ３〜Ｃ６の２価の脂肪族環基；又はＣ６〜Ｃ１０のアリーレン基を示す。
Ｙは、重合可能な官能基を示し、
Ｚは、炭素原子又はケイ素原子を示す。
Ｒ^２は、水素原子、水酸基、Ｃ１〜Ｃ６のアルキル基、Ｃ１〜Ｃ６のアルコキシ基、Ｃ３〜Ｃ６のシクロアルキル基、Ｃ３〜Ｃ６のシクロアルコキシ基、電子供与性基を有していてもよいＣ６〜Ｃ１０のアリール基、又は式：−Ｘ−Ｙで表される基を示す。
ここで、各Ａｒは、同一でも相異なっていてもよい。）
で表される化合物と、
式（ＩＩ）
Ｒ^４Ｓｉ（Ｒ^３）_３ （ＩＩ）
（式中、Ｒ^４は、エポキシ基、グリシジルオキシ基若しくは（メタ）アクリロキシ基で置換されていても良いＣ１〜Ｃ３０のアルキル基、Ｃ２〜Ｃ８のアルケニル基、又はＣ６〜Ｃ１０のアリール基を示す。Ｒ^３は、水酸基又は加水分解性基を示す。）で表される有機シラン化合物の縮合物を含有するコーティング剤の硬化物である膜である、導電膜付き基材、
（２）下地膜に用いるコーティング剤に、更に金属化合物を含有することを特徴とする（１）に記載の導電膜付き基材、
（３）前記基材がプラスチック基材である、（１）又は（２）に記載の導電膜付き基材、
（４）前記導電膜が金属微粒子の焼結体を含有する、（１）〜（３）のいずれかに記載の導電膜付き基材、
（５）前記金属微粒子の焼結体が銀微粒子の焼結体である、（４）に記載の導電膜付き基材、及び、
（６）前記導電膜が、溶媒又は樹脂に分散した金属微粒子を含む導電性インク又は導電性ペーストの焼成物である膜である、（１）〜（５）のいずれかに記載の導電膜付き基材
に関する。That is, the present invention
(1) A base material with a conductive film having a base film and a conductive film in this order on the surface of the base material, wherein the base film has the formula (I)

(In formula, Ar shows the C6-C10 aryl group which may have an electron-donating group.
X is a single bond; an oxygen atom, a sulfur atom, a selenium atom, —NR ¹ — (wherein R ¹ represents a hydrogen atom or a C1-C6 alkyl group), a C3-C6 divalent aliphatic ring. A C1-C20 alkylene group which may contain a group, a C6-C10 arylene group, an amide structure or a urethane structure; a C3-C6 divalent aliphatic ring group; or a C6-C10 arylene group.
Y represents a polymerizable functional group,
Z represents a carbon atom or a silicon atom.
R ² may have a hydrogen atom, a hydroxyl group, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C3-C6 cycloalkyl group, a C3-C6 cycloalkoxy group, or an electron-donating group. A C6-C10 aryl group or a group represented by the formula: -X-Y is shown.
Here, each Ar may be the same or different. )
A compound represented by
Formula (II)
R ⁴ Si (R ³ ) ₃ (II)
Wherein R ⁴ represents a C1-C30 alkyl group, a C2-C8 alkenyl group, or a C6-C10 aryl group optionally substituted with an epoxy group, a glycidyloxy group or a (meth) acryloxy group. R ³ represents a hydroxyl group or a hydrolyzable group.) A substrate with a conductive film, which is a cured product of a coating agent containing a condensate of an organosilane compound represented by:
(2) The base material with a conductive film according to (1), wherein the coating agent used for the base film further contains a metal compound,
(3) The substrate with a conductive film according to (1) or (2), wherein the substrate is a plastic substrate,
(4) The base material with a conductive film according to any one of (1) to (3), wherein the conductive film contains a sintered body of metal fine particles.
(5) The base material with a conductive film according to (4), wherein the metal fine particle sintered body is a silver fine particle sintered body, and
(6) The conductive film with a conductive film according to any one of (1) to (5), wherein the conductive film is a film that is a fired product of conductive ink or conductive paste containing metal fine particles dispersed in a solvent or resin. It relates to a substrate.

  According to the present invention, by providing a base film obtained by applying a specific coating agent on a base material in advance, the adhesiveness with a plastic base material is good regardless of the type of the conductive composition. A substrate with a conductive film having a conductive film with no unevenness on the surface can be obtained.

[1] Undercoat Film The undercoat film of the present invention is formed on the surface of the base material, and the adhesion between the conductive film and the base material and the film formability of the conductive film are improved by modifying the base material surface like glass. It is a film formed for the purpose of improvement.

First, the coating agent used for forming the base film will be described in detail.
(1) Coating agent (a) Compound represented by formula (I) The coating agent used in the present invention contains a compound represented by the following formula (I). The compound represented by the formula (I) may be only one kind or a mixture of two or more kinds.

In the formula, Ar represents a C6-C10 aryl group optionally having an electron-donating group.
X is a single bond; an oxygen atom, a sulfur atom, a selenium atom, —NR ¹ — (wherein R ¹ represents a hydrogen atom or a C1-C6 alkyl group), a C3-C6 divalent aliphatic ring. A C1-C20 alkylene group which may contain a group, a C6-C10 arylene group, an amide structure or a urethane structure; a C3-C6 divalent aliphatic ring group; or a C6-C10 arylene group.
Y represents a polymerizable functional group.
Z represents a carbon atom or a silicon atom.
R ² may have a hydrogen atom, a hydroxyl group, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C3-C6 cycloalkyl group, a C3-C6 cycloalkoxy group, or an electron-donating group. A C6-C10 aryl group or a group represented by the formula: -X-Y is shown.
Here, each Ar may be the same or different.

(Ar)
Examples of the “C6-C10 aryl group” in Ar include a phenyl group and a naphthyl group.
Examples of the electron donating group in Ar include a hydroxyl group, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C6 alkylthio group, a C6-C10 aryl group, and a C6-C10 aryloxy group.

Specific examples of the electron donating group are as follows.
Examples of the “C1-C6 alkyl group” include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, i-butyl group, t-butyl group, and n-pentyl. Group, n-hexyl group and the like.
Examples of the “C1-C6 alkoxy group” include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, s-butoxy group, i-butoxy group, t-butoxy group, and n-pentoxy group. Group, n-hexoxy group and the like.
Examples of the “C1-C6 alkylthio group” include methylthio group, ethylthio group, n-propylthio group, i-propylthio group, n-butylthio group, s-butylthio group, i-butylthio group, t-butylthio group, and n-pentylthio group. Group, n-hexylthio group and the like.
Examples of the “C6-C10 aryl group” include a phenyl group and a naphthyl group.
Examples of the “C6-C10 aryloxy group” include a phenoxy group and a naphthoxy group.

(X)
X is a single bond; an oxygen atom, a sulfur atom, a selenium atom, —NR ¹ — (wherein R ¹ represents a hydrogen atom or a C1-C6 alkyl group), a C3-C6 divalent aliphatic ring. A C1-C20 alkylene group which may contain a group, a C6-C10 arylene group, an amide structure or a urethane structure; a C3-C6 divalent aliphatic ring group; or a C6-C10 arylene group.
Here, “an oxygen atom, a sulfur atom, a selenium atom, —NR ¹ — (wherein R ¹ represents a hydrogen atom or a C1-C6 alkyl group), a C3-C6 divalent aliphatic cyclic group, The phrase “may contain a C6-C10 arylene group, amide structure or urethane structure” means “may contain one or more of these groups”.

Specific examples of X are as follows.
“C1-C20 alkylene group” is a divalent hydrocarbon group, for example, methylene group, dimethylene group, trimethylene group, methyldimethylene group, tetramethylene group, 1,2-dimethyldimethylene group, pentamethylene group. Group, 1-methyltetramethylene group, 2-methyltetramethylene group, hexamethylene group, octamethylene group, decamethylene group, icosamethylene group and the like.
As the “C1-C6 alkyl group” of R ^{1 in} —NR ¹ —, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, i-butyl group , T-butyl group, n-pentyl group, n-hexyl group and the like.
Examples of the “C3-C6 divalent aliphatic cyclic group” include 1,1-cyclopropylene group, 1,2-cyclopropylene group, 1,2-cyclobutylene group, 1,3-cyclobutylene group, 1, Examples include 2-cyclohexylene group and 1,4-cyclohexylene group.
Examples of the “C6-C10 arylene group” include 1,2-phenylene group, 1,4-phenylene group, 1,2-naphthylene group, 1,5-naphthylene group and the like.
The oxygen atom, sulfur atom and selenium atom include, for example, the case of —O— and —CO— in the case of an oxygen atom.

“Oxygen atom, sulfur atom, selenium atom, —NR ¹ — (wherein R ¹ represents a hydrogen atom or a C1-C6 alkyl group), C3-C6 divalent aliphatic cyclic group, C6-C10 Specific examples of X that is a “C1-C20 alkylene group optionally having an arylene group, an amide structure or a urethane structure” include the following.
First, examples of X including an oxygen atom, a sulfur atom, a selenium atom, —NR ¹ —, a C6-C10 arylene group, an amide structure or a urethane structure include the following structures.

  In the above structure,

The structure represented by these is preferable. Examples of X containing a biphenylene group or a naphthylene group include the following structures.

  In the above structure,

The structure represented by these is preferable. Examples of X containing a C3-C6 divalent aliphatic ring group include the following structures.

Here, R ⁵ and R ⁶ represent an electron donating group, and are a hydroxyl group, a C1 to C6 alkyl group, a C1 to C6 alkoxy group, a C1 to C6 alkylthio group, a C6 to C10 aryl group, and a C6 to C10. Of the aryloxy group.

Specific examples of the electron donating groups of R ⁵ and R ⁶ are as follows.
Examples of the “C1-C6 alkyl group” include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, i-butyl group, t-butyl group, and n-pentyl. Group, n-hexyl group and the like.
Examples of the “C1-C6 alkoxy group” include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, s-butoxy group, i-butoxy group, t-butoxy group, and n-pentoxy group. Group, n-hexoxy group and the like.
Examples of the “C1-C6 alkylthio group” include methylthio group, ethylthio group, n-propylthio group, i-propylthio group, n-butylthio group, s-butylthio group, i-butylthio group, t-butylthio group, and n-pentylthio group. Group, n-hexylthio group and the like.
Examples of the “C6-C10 aryl group” include a phenyl group and a naphthyl group.
Examples of the “C6-C10 aryloxy group” include a phenoxy group and a naphthoxy group.

A ″ and a ′ ″ are each independently an integer of 0 to 4, preferably 0 or 1, and n1 is an integer of 1 to 20, preferably an integer of 1 to 10. More preferably, it is an integer of 1-5.
n2 is an integer of 1 to 10, preferably an integer of 1 to 5, and more preferably an integer of 1 to 2.
n3 and n4 are independently an integer of 1 to 10, preferably an integer of 1 to 5.
m1 is an integer of 0 or 1.

(Y)
Y represents a polymerizable functional group, and examples of the polymerizable functional group include acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, vinyloxycarbonyloxy group, vinyl group, allyloxy group, allyloxycarbonyloxy group. And epoxy groups.
Furthermore, the functional group etc. which are used in order to form polyester, a polyurethane, polyisocyanate, or a polycarbonate shown below are mentioned.

(Z)
Z represents a carbon atom or a silicon atom. As a compound represented by the formula (I), Z is preferably a carbon atom.

(R ² )
R ² may have a hydrogen atom, a hydroxyl group, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C3-C6 cycloalkyl group, a C3-C6 cycloalkoxy group, or an electron-donating group. A C6-C10 aryl group or a group represented by the formula: -X-Y is shown.

"C1-C6 alkyl group", "C1-C6 alkoxy group", "C6-C10 aryl group optionally having an electron-donating group" are the groups exemplified for Ar and X above. Similar groups apply.
X and Y in the “group represented by the formula: —X—Y” are the same as those exemplified for X and Y above.

Examples of the “C3-C6 cycloalkyl group” include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like.
Examples of the “C3-C6 cycloalkoxy group” include a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, a cyclohexyloxy group, and the like.

Here, as R ^2, an aryl group as an electron-donating group may have a C6~C10 are preferred.

Table 1 below shows particularly preferred compounds for the compound represented by formula (I) used in the present invention.
The symbols Ar, R ² , Z, X, and Y in the table correspond to each of the formula (I). * In the structure indicating X represents a position where Y is bonded.
The structures of R ² in Compound 23 and Compound 24 represent the following formula (* 1).

  Although the compound represented by the formula (I) used in the present invention can be produced by a known method, it can be produced, for example, by the method described in WO2014 / 115210 pamphlet.

(B) Condensate of organosilane compound The coating agent used in the present invention further contains a condensate of an organosilane compound represented by the following formula (II). By containing a condensate of an organosilane compound, improvement in adhesion can be expected.
The organic silane compound represented by the formula (II) may be only one type or a mixture of two or more types.

R ⁴ Si (R ³ ) ₃ (II)

In the formula, R ⁴ represents a C1-C30 alkyl group, a C2-C8 alkenyl group, or a C6-C10 aryl group which may be substituted with an epoxy group, a glycidyloxy group or a (meth) acryloxy group.
R ³ represents a hydroxyl group or a hydrolyzable group.

Examples of the C1-C30 alkyl group in R ⁴ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-pentyl group, and isopentyl group. Group, neopentyl group, 2-methylbutyl group, 2,2-dimethylpropyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, nonyl group, isononyl group, decyl group, lauryl group, tridecyl group , Myristyl group, pentadecyl group, palmityl group, heptadecyl group, stearyl group and the like.
Examples of the C2-C8 alkenyl group include a vinyl group, an allyl group, and a 2-propenyl group.
Examples of the C6-C10 aryl group include a phenyl group and a naphthyl group.

The hydrolyzable group of R ³ is, for example, a group that can be hydrolyzed to produce a silanol group by heating at 25 ° C. to 100 ° C. in the presence of non-catalyst and excess water, or siloxane condensation It means a group that can form a product, and specific examples include an alkoxy group, an acyloxy group, a halogeno group, and an isocyanate group, and a C1-C4 alkoxy group or a C1-C6 acyloxy group is preferable. .

  Here, examples of the C1-C4 alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a t-butoxy group, and the like, and a C1-C6 acyloxy group. Examples thereof include an acetyloxy group and a benzoyloxy group. Examples of the halogeno group include a fluoro group, a chloro group, a bromo group, and an iodo group.

  Specific examples of the organosilicon compound represented by the formula (II) include methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriisopropoxysilane, ethyl Tributoxysilane, butyltrimethoxysilane, pentafluorophenyltrimethoxysilane, phenyltrimethoxysilane, trifluoromethyltrimethoxysilane, vinyltrimethoxysilane, 3- (meth) acryloxy-n-propyltrimethoxysilane, 3- ( 3-methyl-3-oxetanemethoxy) -n-propyltrimethoxysilane, 4-oxacyclohexyltrimethoxysilane, methyltris [(meth) acryloxy] silane, methyltris [2- (meth) acryloxyate Si] silane, methyl-triglycidyloxysilane, methyltris (3-methyl-3-oxetanemethoxy) silane, vinyltrichlorosilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3- Examples thereof include glycidoxy-n-propyltrimethoxysilane, 3-glycidoxy-n-propyltriethoxysilane, p-styryltrimethoxysilane, and 3-methacryloxypropyltriethoxysilane.

  In a preferred embodiment of the condensate of the organic silane compound used in the present invention, at least one organic silane compound represented by the formula (II-1) in an amount satisfying the following formula (1) and the formula (II-2): Is a condensate with at least one of the organosilane compounds represented by

R ⁴¹ Si (R ³ ) ₃ (II-1)
R ⁴² Si (R ³ ) ₃ (II-2)

  30 mol% ≦ {[compound of formula (II-1)]} / {[compound of formula (II-1)] + [compound of formula (II-2)]} × 100 <100 mol%. 1)

In formula (II-1), R ⁴¹ represents a C2-C8 alkenyl group.
Wherein ^{(II-2), R 42} represents an epoxy group, a glycidyl group, or (meth) acryloxy alkyl group may be substituted C1~C30 groups.

  The above mathematical formula (1) is a combination of the organic silane compound represented by the formula (II-1) and the organic silane compound represented by the formula (II-2) when preparing the condensate of the organic silane compound. Indicates the ratio.

  Specific examples of the compound represented by the formula (II-1) include vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltributoxysilane, vinyltriisopropoxysilane, allyltrimethoxysilane, 3 -Butenyltrimethoxysilane, allylethyltriethoxysilane, etc. are mentioned.

  Specific examples of the compound represented by the formula (II-2) include methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriisopropoxysilane, and ethyl. Tributoxysilane, n-butyltrimethoxysilane, trimethylchlorosilane, 3- (meth) acryloxy-n-propyltrimethoxysilane, 3-glycidoxy-n-propyltrimethoxysilane, 3- (3-methyl-3-oxetanemethoxy ) -N-propyltrimethoxysilane, oxacyclohexyltrimethoxysilane and the like.

  When organic silane compounds are used in combination, for example, a combination of vinyltrimethoxysilane and 3-methacryloxy-n-propyltrimethoxysilane, a combination of vinyltrimethoxysilane and 3-glycidoxy-n-propyltrimethoxysilane, and the like are preferable.

The condensate of an organic silane compound is a dimer or the like in which organic silane compounds are condensed or hydrolytically condensed to form a siloxane bond.
The condensate of the organic silane compound may be obtained by condensing or hydrolyzing one kind of the organic silane compound represented by the formula (II), or condensing or hydrolyzing two or more kinds of the organosilane compound represented by the formula (II). It may be condensed.

The condensate of the organic silane compound can be obtained by heating to 25 ° C. to 100 ° C. in the presence of excess water even if it is non-catalyzed, but may be condensed using a silanol condensation catalyst.
The silanol condensation catalyst is not particularly limited as long as it hydrolyzes a hydrolyzable group in the compound represented by the formula (II) and condenses silanol to form a siloxane bond. Organic metal, organic acid metal Examples thereof include salts, metal hydroxides, acids, bases, and metal chelate compounds. Moreover, those hydrolysates and those condensates can also be used.
The silanol condensation catalyst can be used alone or in combination of two or more.

  Examples of the organic metal include alkyl metal compounds such as tetramethyltitanium and tetrapropylzirconium; metal propoxide, metal isopropoxide, metal n-butoxide, specifically metal alcoholates such as tetraisopropoxytitanium and tetrabutoxyzirconium Etc.

  The organic acid metal salt is a compound composed of a salt obtained from a metal ion and an organic acid. Examples of the organic acid include carboxylic acids such as acetic acid, oxalic acid, tartaric acid and benzoic acid; and sulfur-containing organic materials such as sulfonic acid and sulfinic acid. Examples include acids, phenolic compounds, enol compounds, oxime compounds, imide compounds, aromatic sulfonamides, and the like. Specific examples include carboxylic acid metal salts, sulfonic acid metal salts, phenol metal salts, and the like.

  A metal hydroxide is a metal compound having a hydroxide ion as an anion.

  The metal chelate compound is preferably a metal chelate compound having a hydroxyl group or a hydrolyzable group, and more preferably a metal chelate compound having two or more hydroxyl groups or hydrolyzable groups. In addition, having two or more hydroxyl groups or hydrolyzable groups means that the sum of hydrolyzable groups and hydroxyl groups is 2 or more. Examples of the hydrolyzable group include an alkoxy group, an acyloxy group, a halogeno group, and an isocyanate group, and a C1-C4 alkoxy group and a C1-C4 acyloxy group are preferable.

  Further, as the metal chelate compound, β-ketocarbonyl compounds, β-ketoester compounds, and α-hydroxyester compounds are preferable, and specifically, acetylacetone, hexane-2,4-dione, heptane-2,4. Β-diketones such as dione, heptane-3,5-dione, octane-2,4-dione, nonane-2,4-dione, 5-methyl-hexane-2,4-dione; methyl acetoacetate; Β-ketoesters such as n-propyl acetoacetate, isopropyl acetoacetate, n-butyl acetoacetate, sec-butyl acetoacetate, t-butyl acetoacetate; α-hydroxycarboxylic acids such as glycolic acid and lactic acid coordinated Compounds.

  In addition, as metals in these organic metals, organic acid metal salts, metal hydroxides, and metal chelate compounds, titanium (Ti), zirconium (Zr), aluminum (Al), silicon (Si), germanium (Ge), indium (In), tin (Sn), tantalum (Ta), zinc (Zn), tungsten (W), lead (Pb), etc. Among them, titanium (Ti), zirconium (Zr), aluminum (Al) Tin (Sn) is preferable, and titanium (Ti) is particularly preferable. These may be used alone or in combination of two or more.

Examples of the acid include organic acids and mineral acids. Specifically, examples of the organic acid include acetic acid, formic acid, oxalic acid, carbonic acid, phthalic acid, trifluoroacetic acid, p-toluenesulfonic acid, methanesulfonic acid, and the like. Examples of the mineral acid include hydrochloric acid, nitric acid, boric acid, borohydrofluoric acid, and the like.
Examples of the base include strong bases such as tetramethylguanidine and tetramethylguanidylpropyltrimethoxysilane; organic amines, carboxylic acid neutralized salts of organic amines, quaternary ammonium salts and the like.

The condensate of the organic silane compound can be prepared by appropriately mixing a silanol condensation catalyst, water, and an organic solvent in addition to the organic silane compound. When the silanol condensation catalyst is blended, the blending ratio is 1:99 to 99: 1, preferably 1:99 to 50:50 with respect to the mass of the organosilane compound.
When the coating agent used in the present invention is mixed with a condensate of an organic silane compound, it is preferable to use a condensate of the organic silane compound prepared in advance by the above method.

(C) Other components (organic solvent)
The coating agent used in the present invention can contain an organic solvent. Typical organic solvents that can be used include alcohols, ethers, esters, aliphatic hydrocarbons, aromatic hydrocarbons, ketones, and organic halides. Alcohol-based, ether-based, ester-based and aliphatic hydrocarbon-based are preferable. Alcohol solvents include methanol, ethanol, n-propanol, isopropanol; ether solvents include diethyl ether, dipropyl ether, dibutyl ether, diamyl ether; ester solvents include ethyl acetate, propyl acetate, butyl Acetate, amyl acetate, heptyl acetate, ethyl butyrate, isoamyl isovalerate; normal hexane, normal heptane, cyclohexane as aliphatic hydrocarbon solvent; toluene, xylene as aromatic solvent; ketone solvent As methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and organic halide solvents include trichloroethane and trichloroethylene.

(Polymerization initiator)
The coating agent used in the present invention may contain a polymerization initiator. Here, examples of the polymerization reaction include a photopolymerization reaction and a thermal polymerization reaction, but a photopolymerization reaction that does not require consideration of the thermal influence on the plastic substrate is more preferable. Examples of light used for the photopolymerization reaction include ultraviolet light and visible light, and ultraviolet light is preferred because of its high polymerization rate.

  Examples of the photopolymerization initiator include (a) a compound that generates a cationic species by light irradiation, and (b) a compound that generates an active radical species by light irradiation.

Examples of the compound that generates a cationic species by light irradiation include, for example, a cation moiety of sulfonium, iodonium, diazonium, ammonium, (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -Fe cation. And the anion moiety is composed of BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , [BX ₄ ] ⁻ (where X is a phenyl group substituted with at least two fluorine or trifluoromethyl groups). Onium salts.

  Examples of compounds that generate active radical species by light irradiation include acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, xanthone, fluorenone, and benzaldehyde. Fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, benzoinpropyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1 -(4-Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxa , Diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1 -(4-morpholinophenyl) -butanone-1,4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2 , 6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone) and the like. .

  It is preferable to mix | blend 0.01-20 mass% with respect to the total amount of all the polymeric compounds, and, as for the compounding quantity of the polymerization initiator used in this invention, 0.1-10 mass% is further more preferable.

(Other copolymerizable compounds)
The coating agent used for this invention may contain other copolymerizable compounds other than the compound represented by Formula (I). Other copolymerizable compounds other than the compound represented by the formula (I) may be appropriately selected according to the purpose of adjustment such as melting point, viscosity or refractive index, and are not particularly limited. Things.

  Methyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, bromophenyl (meth) acrylate, ethylene glycol di (meth) acrylate, cyclohexyl (meth) acrylate, tris (2- (meth) acryloxyethyl) (Meth) acrylic acid esters such as isocyanate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, allyl esters such as diethylene glycol bisallyl carbonate, triallyl cyanurate, triallyl isocyanurate, styrene, chlorostyrene, bromostyrene, etc. And aromatic olefins.

(Metal compound)
A metal compound can be added to the coating agent used in the present invention for the purpose of increasing the refractive index and hardness of the underlying film to be formed. Examples of the metal compound include the organic silane compounds described above, and organic metals exemplified as silanol condensation catalysts, organic acid metal salts, metal hydroxides, and metal chelate compounds. Other metal compounds include metal oxides. Specific examples include silicon dioxide, titanium oxide, aluminum oxide, chromium oxide, manganese oxide, iron oxide, zirconium oxide (zirconia), cobalt oxide metal oxide particles, and the like. Zirconium oxide is particularly preferable.
Examples of the shape of the particles include a spherical shape, a porous powder, a scale shape, and a fiber shape, and a porous powder shape is more preferable.
Colloidal metal oxide particles can also be used as the metal oxide particles. Specific examples include colloidal silica and colloidal zirconium, and water-dispersed colloidal or organic solvent-dispersed colloidal metal oxide particles such as methanol or isopropyl alcohol.

[2] Base Material The base material with a conductive film of the present invention is obtained by directly coating a base material coated with a coating agent used in the present invention and cured.
The base material used in the present invention is preferably a plastic base material, for example, cycloolefin resin, polycarbonate resin, acrylic resin, polyimide resin, polyester resin, epoxy resin, liquid crystal polymer resin, polyether sulfone, A cycloolefin resin is preferably used.
The shape may be any shape such as a film shape, a sheet shape, and a plate shape, but a film shape is particularly preferable. The film-like substrate may be made of an unstretched film or may be made of a stretched film. Moreover, even if it is a single layer film, the laminated film which laminated | stacked two or more layers by means, such as a lamination and a coating, may be sufficient.
Although the thickness of a film-form base material is not specifically limited, Usually, it is 1-1000 micrometers, Preferably it is 3-500 micrometers. It is preferable to have flexibility enough to handle a roll-to-roll process.

[3] Formation of base film (1) Preparation of coating agent The coating agent used in the present invention is usually a compound represented by the above formula (I) and an organosilane compound represented by the above formula (II) in an organic solvent. In addition to the condensate, a photopolymerization initiator, a metal compound and the like are mixed as necessary.
Examples of the solvent to be used include the organic solvents described above. These solvents can be used alone or in combination of two or more.
As solid content in the coating agent used for this invention, it is preferable that it is 1-90 mass%, and it is more preferable that it is 5-60 mass%. The compounding amount of the condensate of the compound represented by formula (I) and the organosilane compound represented by formula (II) is the compound represented by formula (I) / condensate of organosilane compound represented by formula (II) = 95/5 to 50/50 (mass ratio).

(2) Formation of base film In the case of using a photopolymerization initiator, the base film in the present invention includes (A) a step of applying the above-mentioned coating agent on a substrate and drying, and (B) an ultraviolet ray. It can be manufactured by irradiating light and passing through a step of curing the coating agent.
The base film in the present invention undergoes the step (B), whereby the compound represented by the formula (I) is polymerized, and the condensation product of the organosilane compound represented by the formula (II) is concentrated on the film surface. Thus, the carbon atom content in the surface portion of the film is less than the carbon atom content in the inside of the film (near the joint with the base material).

As a coating method of the coating agent, a known coating method can be used, for example, dipping method, spray method, bar coating method, roll coating method, spin coating method, curtain coating method, gravure printing method, silk screen method, An ink jet method can be used.
Further, the film thickness of the base film to be formed is not particularly limited and is, for example, about 0.1 to 200 μm.
As a drying process of the base film after application | coating, it is preferable to carry out for about 0.5 to 120 minutes at 40-200 degreeC, for example, and it is more preferable to carry out for about 1 to 60 minutes at 60-120 degreeC.
Irradiation with ultraviolet rays can be performed using a known apparatus such as a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, or an excimer lamp.

[4] Conductive Film (1) Conductive Ink The conductive film in the present invention is provided on a substrate having a base film formed on the surface, and is obtained by applying conductive ink and heating or sintering. It is a film. Preferably, a sintered body of metal fine particles is included.

  Although it does not restrict | limit especially as an electroconductive ink used for this invention, It is preferable to use an organic material, for example, the ink containing electroconductive polymer compounds, such as polyethylenedioxythiophene (PEDOT) / polystyrene sulfonic acid (PSS), Examples thereof include inks and pastes in which metal fine particles are dispersed in a solvent or resin. Among these, it is preferable to use an ink in which metal fine particles are dispersed.

  Examples of the metal fine particles contained in the conductive ink include gold, silver, platinum, palladium, rhodium, osmium, ruthenium, iridium, copper, nickel, cobalt, iron, tin, chromium, titanium, tantalum, tungsten, and indium. A metal or an alloy thereof can be used, and it is particularly preferable to use gold, silver, palladium, or copper. The shape and size of the metal fine particles are not particularly limited, but those having an average particle diameter of 1 nm to 100 nm are preferably used.

  Examples of the conductive ink include water-based conductive inks and organic-based conductive inks, and organic-based conductive inks in which metal fine particles are dispersed in an organic dispersion medium are particularly preferable. The content of the metal fine particles in the conductive ink is 10 to 60% by mass, and contains a dispersant, a resin, a solvent, or the like as other components as necessary.

(2) Formation of conductive film The conductive film in the present invention is obtained by laminating a coating film made of a conductive ink on a base material provided with the base film on the surface, and heating or sintering the coating film. It is done. The coating film made of a conductive ink can be formed using a known coating method such as screen printing, ink jet printing, spin coating, roll coating, spray coating or the like.
The atmosphere for heating or sintering may be an atmospheric pressure oxidizing atmosphere (for example, air). The heating or sintering temperature is in the range of 100 ° C to 300 ° C, preferably in the range of 100 ° C to 200 ° C. The heating or sintering time is 30 seconds to 24 hours, preferably 10 minutes to 10 hours.
The thickness of the conductive film is preferably 2000 nm or less, more preferably 1000 nm or less, and most preferably 500 nm or less.

The base material with a conductive film of the present invention can be suitably used for, for example, production of circuits such as electronic circuits and antennas, electromagnetic wave absorbers, light reflectors, and the like.
The present invention will be described in more detail with reference to the following examples, but the technical scope of the present invention is not limited to these examples.

(1) Preparation of coating agent (A) Step 1
4 g of cyclohexane was dissolved in 1 g of 2- (4- (triphenylmethyl) phenoxy) ethyl acrylate and stirred until it was completely dissolved. Then, photopolymerization initiator Irgacure (registered trademark) 907 (manufactured by BASF, UV polymerization initiator, 2-methyl-1- [4- (methylthio) phenyl])-2-morpholino-propan-1-one) 04 g was added to obtain a composition (A-1).

(B) Step 2
After dissolving 303.03 g of diisopropoxybisacetylacetonate titanium (manufactured by Nippon Soda, T-50, solid content in terms of titanium oxide: 16.5% by weight) in 584.21 g of ethanol, ion-exchanged water 112. 76 g was added. The solution was hydrolyzed by stirring for 2 hours while warming to 40 ° C. Next, the solution was filtered to obtain a yellow transparent titanium oxide nanodispersion (B-1) having a titanium oxide equivalent concentration of 5% by weight. The average particle size of titanium oxide was 4.1 nm and was monodispersed.
As organic silane compounds, vinyltrimethoxysilane 264.76 g (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-1003) and 3-methacryloxypropyltrimethoxysilane 190.19 g (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-503) ( A liquid (C-1) mixed with vinyltrimethoxysilane / 3-methacryloxypropyltrimethoxysilane = 70/30: molar ratio was used.
Next, 453.09 g of (B-1) and 454.95 g of (C-1) were mixed so that the element ratio (Ti / Si = 1/9) was obtained, and 91.96 g of ion-exchanged water was further added. A liquid (D-1) stirred for an hour was produced.

(C) Preparation of coating agent [A-2] The above-mentioned [D-1] liquid and [A-1] liquid so that the ratio of solid content may be 10 wt% / 90 wt% = D-1 / A-1. Were mixed to prepare a coating agent [A-2].

(2) Formation of base film A cycloolefin polymer (COP) substrate having a thickness of 188 μm was cut into 20 mm × 20 mm, and the coating agent [A-2] was formed by bar coating. The coated substrate is dried in an oven (130 ° C., 3 minutes), and a condensing high-pressure mercury lamp (UV light mainly composed of 365 nm, 313 nm, and 254 nm wavelength light, manufactured by IGRAPHFIX, 120 W / cm, lamp A substrate (E-1) with a base film was obtained by irradiating ultraviolet rays with a cumulative irradiation amount of 400 mJ / cm ^{2 at} a height of 9.8 cm and a conveyor speed of 5 m / min.

(3) Formation of silver conductive film A silver ink (product name “SR6000”, manufactured by Bando Chemical Co., Ltd., 40% by mass of tetradecane dispersion) is spin-coated on a substrate (E-1) with a base film (rotation speed 1500 rpm, 60). Second) and then dried in an oven (100 ° C., 60 minutes) to obtain a substrate (F-1) with a silver conductive film.

(4) Evaluation of adhesion The cross-cut peel test of the obtained substrate with silver conductive film (F-1) was performed according to the cross-cut tape peel test method described in JIS K-5400 (1999). The silver conductive film on the COP resin substrate was cross-cut into a 1 mm × 1 mm grid pattern, and a peel test was performed using a transparent adhesive tape. When the silver conductive film of each grid was evaluated with an optical microscope, the number of non-peeling / number of tests was 90/100. Therefore, it was found that the COP substrate and the silver conductive film were in good contact.
For comparison, a similar cross-cut tape peeling test was performed on a substrate in which a silver conductive film was formed on a COP substrate on which a base film was not formed, and more peeling was observed (non-peeling number / test Number = 30/100).

Claims (6)

On the surface of the base material, the base film and the conductive film, in this order, a base material with a conductive film,
The undercoat film has the formula (I)

(In formula, Ar shows the C6-C10 aryl group which may have an electron-donating group.
X is a single bond; an oxygen atom, a sulfur atom, a selenium atom, —NR ¹ — (wherein R ¹ represents a hydrogen atom or a C1-C6 alkyl group), a C3-C6 divalent aliphatic ring. A C1-C20 alkylene group which may contain a group, a C6-C10 arylene group, an amide structure or a urethane structure; a C3-C6 divalent aliphatic ring group; or a C6-C10 arylene group.
Y represents a polymerizable functional group,
Z represents a carbon atom or a silicon atom.
R ² may have a hydrogen atom, a hydroxyl group, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C3-C6 cycloalkyl group, a C3-C6 cycloalkoxy group, or an electron-donating group. A C6-C10 aryl group or a group represented by the formula: -X-Y is shown.
Here, each Ar may be the same or different. )
A compound represented by
Formula (II)
R ⁴ Si (R ³ ) ₃ (II)
Wherein R ⁴ represents a C1-C30 alkyl group, a C2-C8 alkenyl group, or a C6-C10 aryl group optionally substituted with an epoxy group, a glycidyloxy group or a (meth) acryloxy group. R ³ represents a hydroxyl group or a hydrolyzable group.   The base material with a conductive film according to claim 1, wherein the coating agent used for the base film further contains a metal compound.   The base material with a conductive film according to claim 1 or 2, wherein the base material is a plastic base material.   The base material with a electrically conductive film in any one of Claims 1-3 in which the said electrically conductive film contains the sintered compact of a metal microparticle.   The base material with an electrically conductive film of Claim 4 whose sintered compact of the said metal fine particle is a sintered compact of silver fine particles. The base material with a conductive film according to any one of claims 1 to 5, wherein the conductive film is a film that is a fired product of a conductive ink or a conductive paste containing metal fine particles dispersed in a solvent or a resin.