JPH03110712A - Transparent conductive resin composite - Google Patents

Abstract

PURPOSE:To obtain a resin composite with good conductivity without almost decreasing its transparency by using a charge-transfer complex which includes a tetracyanoquinodimethane derivative as an acceptor. CONSTITUTION:A charge-transfer complex, which is a tetracyanoquinodimethane derivative, is contained in a conductive metal oxide, a high polymeric resin and acceptor components. As the conductive metal oxide, a metal oxide, etc., composed mainly of tin oxide is selected on account of transparency and is mixed in a transparent conductive resin composite by 30 to 60cap.%. Acceptor components contained in the charge-transfer complex are specifically 7,7,8,8- tetracyanoquinodimethane, and any material may be used for donor components contained in the charge-transfer complex only if it forms a complex in combination with a tetracyanoquinodimethane derivative. The charge-transfer complex is preferably contained by 0.05 to 20 weight parts in the acceptor components, and also, any high polymeric resin is suitably used only if it is transparent. A resin composition excellent in conductivity and transparency is thereby obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a transparent conductive resin composition with improved conductivity and uses of the resin composition.

[Prior Art/Problems to be Solved by the Invention] In recent years, the use of transparent conductive laminates in which conductivity is imparted to transparent substrates such as glass or plastic films, and also of transparent conductive paints has been increasing.

Examples of transparent substrates made conductive include those in which the surface of the transparent substrate is coated with a paint containing carbon black or metal powder. However, this is not preferable because the substrate becomes black or gray.

Therefore, by coating a transparent substrate with a paint containing a metal oxide such as indium oxide or tin oxide, a transparent conductive laminate that is imparted with conductivity while maintaining transparency has been provided.

However, even this transparent conductive laminate does not yet have sufficient conductivity, and therefore there is a long-awaited need for a conductive laminate, a paint, and a transparent conductive resin composition for producing them that have better conductivity and transparency. has been done.

An object of the present invention is to provide a transparent conductive resin composition with excellent conductivity and transparency.

Another object of the present invention is to provide a coating material with excellent conductivity and transparency.

Still another object of the present invention is to provide a laminate with excellent conductivity and transparency.

[Means to solve the problem]

In order to solve the above-mentioned problems, the present inventors have conducted intensive research and found that a transparent material containing a conductive metal oxide, a polymer resin, and a charge transfer complex in which the acceptor component is a tetracyanoquinodimethane derivative. The present invention was completed by discovering that a conductive resin composition has extremely excellent conductivity and transparency.

That is, the present invention has the following gist.

(1) A transparent conductive resin composition comprising a conductive metal oxide, a polymer resin, and a charge transfer complex whose acceptor component is a tetracyanoquinodimethane derivative.

(2) A transparent conductive resin coating comprising the transparent conductive resin composition described in (1) above and a solvent as main components.

(3) A transparent conductive laminate obtained by laminating a layer made of the transparent conductive resin composition described in (1) above on at least one side of a transparent substrate.

Next, the present invention will be explained in detail.

Examples of the conductive metal oxide used in the present invention include Snow, In1Os, ZnO1Cd S n Oa,
Examples include metal oxides such as sb, oi, AlzOi, TiO, and composites of two or more of the above metal oxides.Metal oxides containing tin oxide as the main component (more specifically Specifically, sb-doped or Zn-doped Snow, etc.), metal oxides containing indium oxide as a main component (more specifically, sb-doped or Sn-doped InzOi, etc.) are more preferably used.

Further, the particle size of the conductive metal oxide is usually 2 μm or less, particularly 1 μm or less.

Furthermore, a conductive metal oxide obtained by coating inorganic powder such as flaky mica with the above metal oxide may be used.

The amount of the conductive metal oxide used in the present invention is preferably 10 to 70% by volume in the transparent conductive resin composition, and 3% by volume.
Particularly preferred is 0 to 60% by volume.

In the charge transfer complex used in the present invention, the acceptor component is tetracyanoquinodimethane, specifically 7,7.8
．． 8-tetracyanoquinodimethane.

The donor component in the charge transfer complex used in the present invention is not particularly limited as long as it can form a complex with the tetracyanoquinodimethane derivative, and examples include the following: ■ Isoquinolinium : N-n-butyl isoquinolinium, N-n-ethyl quinolinium.

■Quinolinium: Quinolinium, 2-methylquinolinium, N-methylquinolinium, N-n-propylquinolinium.

■ Quinaldinium: Nn-butylquinaldinium, Nn-methylquinaldinium.

■Benzoquinolinium: N-methyl-2,3-benzoquinolinium, 7°8-benzoquinolinium, N-methyl-7,8benzoquinolinium.

■Aclidinium: N-n-butylacridinium, N Ruacridinium.

■α-picolinium: N-n-butyl-α-picolinium, Hexyl-alpha-picolinium.

■Benzothiazolium: n-Methi -n- N-n-butylbenzothiazolium, Hexylbenzothiazolium.

■Pyridinium: Pyridinium, 2-styrylpyridinium, 2゛-bispyridinium.

■Tzenadinium: N-methylzenadinium, N-n-butylphenazinium.

[Stock] Ammonium: Triethylammonium, trimethylammonium.

■Phosphonium: methyltriphenylphosphonium, ethyltri phenylphosphonium, Tetraphenylphosphoni Ram.

@Sulfonium: triphenylsulfonium, tris-(dimethylamino)-sulfonium.

■Polyvinylpyridine derivatives: [Phase] Polyvinylbenzylamine derivatives: ■Polyvinylimidazole derivatives: ■Polydiallylamine derivatives: ■Polyglycidylamine derivatives: N in the structural formula of the compounds listed in the previous paragraphs ■ to ■ is hydrogen, methyl group, or ethyl. A polymer that has been substituted with a group or the like and has been quaternized.

■Others: Tetrathiafulvalene, TSF (Tetraselenaf Fe”
Examples include (3H,O), Cu', and Cu''.

The charge transfer complex is preferably contained in an amount of 0.05 parts by weight or more, more preferably 0.05 to 20 parts by weight, per 100 parts by weight of the conductive metal oxide.

The polymer resin used in the present invention is preferably any transparent one, such as polyester resin, polyurethane resin, acrylic resin, polyamide resin,
Individual, composite, or copolymers of polystyrene resins, polyolefin resins, and the like can be mentioned.

More preferably, polyester resins and polyurethane resins are used.

Here, further details of the polyester resin and the polyurethane resin will be described below.

Among the carboxylic acid components and diol components that make up polyester, the carboxylic acid components include terephthalic acid,
Aromatic dicarboxylic acids such as isophthalic acid, orthophthalic acid, 1,5-naphthalic acid, 0-oxybenzoic acid, p-(
Aromatic oxycarboxylic acids such as (hydroxyethoxy)benzoic acid; aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, and dodecane dicarboxylic acid; Examples include saturated aliphatic dicarboxylic acids, alicyclic dicarboxylic acids such as hexahydrophthalic acid, tri- and tetracarboxylic acids such as trimellitic acid, trimesic acid, and pyromellitic acid.

Glycol components constituting the polyester include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-bentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, and diethylene glycol. Propylene glycol, 2゜2.4-trimethyl-1,3-bentanediol, 1,4-cyclohexane dimetatool, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, ethylene oxide of hydrogenated bisphenol A There are diols such as adducts, propylene oxide adducts of hydrogenated bisphenol A, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Tri- and tetraols such as trimethylolethane, trimethylolpropane, glycerin, and pentaerythritol may be used in combination. In addition to the above, relatively high molecular weight diols include polyester polyols, including lactone-based polyester diols obtained by ring-opening polymerization of lactones such as ε-caprolactone.

Further, the polymer resins used in the present invention, such as the above polyester resin and the below polyurethane resin, may contain an ionic group.

For example, compounds containing ionic groups and acid groups suitable for polyester and polyurethane resins are illustrated below.

(1) -COO group (M represents hydrogen atom, alkali metal, tetraalkylammonium or tetraalkylsulfonium) Polycarboxylic acid, glyceric acid, dimethylolpropionic acid, N,N-jetanolglycine, hydroxyethyloxybenzoic acid Oxycarboxylic acids such as diaminopropionic acid, aminocarboxylic acids such as diaminobenzoic acid and their derivatives, etc.

R1 (R1-R5 are each independently a hydrogen atom, a carbon number of 1
~8 alkyl group, aryl group, aralkyl group) N-methyljetanolamine, 2-methyl-2-diethylaminomethyl-1,3-propanol, 2-methyl-2-dimethylamino-1,3- Nitrogen-containing alcohols and their derivatives, such as propatool diol.

(R1 has the same meaning as above) such as picolinic acid, dipicolinic acid, aminopyridine, diaminopyridine, hydroxypyridine, dihydroxypyridine, aminohydroxypyridine, pyridinyl dimetatool, pyridinylpropanediol, pyridinylethanol, etc. Pyridine ring-containing compounds and their derivatives, etc.

(4) -5O3M (M has the same meaning as above) Polycarboxylic acids and derivatives thereof such as 5-sodium sulfoisophthalic acid, sulfoisophthalic acid, sodium sulfosuccinic acid, sodium sulfohydroquinone and its alkylene oxide adduct, sodium Sulfobisphenol A and its alkylene oxide adducts, etc.

(5) Phosphorus-containing ionic group h- R, -0-P=O(m)-5 MI (R, is a trivalent hydrocarbon group having 3 to 10 carbon atoms, Rs is an alkyl group having 1 to 12 carbon atoms) , a cycloalkyl group, an aryl group, an alkoxy group having 1 to 12 carbon atoms, a cycloalkoxy group, or an aryloxy group (the aryl group and the aryloxy group each represent a halogen atom, a hydroxy group, and OMg Ux represents an alkali metal. ) or optionally substituted with an amino group), R6 and R? are an alkylene group, a cycloalkylene group, an arylene group having 1 to 12 carbon atoms, or a formula -←CH*ORs+-, respectively.
A group represented by (R, represents an alkylene group having 1 to 12 carbon atoms, represents a cycloalkylene group or an arylene group,
r is an integer of 1 to 4), and M represents an alkali metal atom, hydrogen, a monovalent hydrocarbon group, or an amino group] [Margin below] Ru's aO aO Polymer used in the present invention Among resins, polyurethane is produced by, for example, extending the chain of polyalkylene glycol with polyisocyanate, or extending the chain of polyester polyol (obtained by polycondensing a carboxylic acid component and a glycol component) with polyisocyanate. It is prepared by

As the polyalkylene glycol, polyethylene glycol, polybutylene glycol, polypropylene glycol, etc. are used. As the carboxylic acid component and glycol component that are raw materials for the polyester polyol, any of the carboxylic acid components and gelcol components listed in the section of polyester preparation can be used.

Examples of the polyisocyanate include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, P-phenylene diisocyanate, biphenylmethane diisocyanate, m-phenylene diisocyanate,
Hexamethylene diisocyanate, tetramethylene diisocyanate, 3,3"-dimethoxy-4,4'-biphenylene diisocyanate, 2,4-naphthalene diisocyanate, 3.3°-dimethyl-4,4'-biphenylene diisocyanate, 4,4'- Diphenylene diisocyanate, 44'-diisocyanate-diphenyl ether, 1,5'-naphthalene diisocyanate,
p-xylylene diisocyanate, m-xylylene diisocyanate, 1,3-diisocyanatemethylcyclohexane, 1,4-diisocyanatomethylcyclohexane, 4,4゛diisocyanatedicyclohexane, 4
, 4゛Diisocyanate There are diisocyanate compounds such as cyclohexylmethane and isophorone diisocyanate. These polyisocyanates may contain triisocyanate compounds such as 2.4-) lylene diisocyanate trimer and hexamethylene diisocyanate dimer in a proportion of 7 mol% or less of the total isocyanate groups. .

Polyurethane is prepared by a conventional method using each of the above components. It is also possible to use monomers with ionic groups as described in the section on polyester preparation and to incorporate these into the polyurethane backbone.

The conductive resin composition of the present invention can be used as a transparent conductive resin coating. The coating material contains the above-mentioned transparent conductive resin composition and a solvent as main components.

The solvent used in the transparent conductive resin coating may be any solvent as long as it dissolves the polymer resin of the present invention, such as ester-based, ketone-based, ether-ester-based, chlorine-based, alcohol-based, ether-based, and carbonized solvents. Organic solvents such as hydrogen-based solvents can be used. Among these, the following are exemplified as suitable specific solvents. That is, examples of ester solvents include methyl acetate, ethyl acetate, isopropyl acetate, isobutyl acetate, butyl acetate, amyl acetate, etc.
Examples of ketone solvents include methyl ethyl ketone, methyl isobutyl ketone, methyl isoamyl ketone, methyl amyl ketone, ethyl amyl ketone, isobutyl ketone, methoxymethyl pentanone, cyclohexanone, diacetone alcohol, and isophorone, and examples of ether ester solvents include acetic acid. Examples include methyl cellosolve, ethyl cellosolve acetate, butyl cellosolve acetate, 3-methoxybutyl acetate, methyl carpitol acetate, ethyl carpitol acetate, butyl carpitol acetate, and the like.

For the purpose of improving the coating properties of the transparent conductive resin paint, the transparent conductive paint may contain a fluororesin, a silicone resin, a surfactant, etc. as an additive.

Examples of methods for producing transparent conductive resin coatings include the following methods.

That is, first, a polymer resin is dissolved in a solvent to prepare a polymer resin solution. Next, a conductive metal oxide is dispersed in the polymer resin solution to prepare a transparent conductive resin coating.

Here, examples of methods for dispersing the conductive metal oxide include known methods using a paint shaker, sand mill, ball mill, homogenizer, three-roll mill, high-pressure disperser, and the like.

Moreover, a transparent conductive laminate can be manufactured by laminating a layer made of the transparent conductive resin composition of the present invention on at least one side of a transparent substrate.

As the transparent substrate used for the transparent conductive laminate, any transparent substrate is preferably used, such as glass plates, plastic sheets, plastic films, etc. Plastics are preferred because of their good productivity and flexibility. Films are preferably used.

More specifically, the plastic film includes polyester film, polyamide film, polycarbonate film, polyphenylene sulfide film,
Examples include polyetherimide film, polyethersulfone film, polyolefin film, PVA film, acrylic film, polyvinyl chloride film, etc., and appropriate materials are selected depending on the purpose and required characteristics of the transparent conductive laminate. be done.

Most commonly used for boat fishing include polyester films such as polyethylene terephthalate and polyethylene naphthalate, and polyether sulfone films.

The transparent conductive laminate can be produced by a known method such as a spray method, a barcode method, a doctor blade method, a dipping method, a roll coater method, a flow coater method, etc. For example, a method may be mentioned in which a layer made of a transparent conductive resin composition is coated on a transparent substrate.

Alternatively, a transparent conductive resin paint may be separately applied onto a release-treated substrate to produce a transparent conductive film, and this may be laminated onto the transparent substrate.

Furthermore, the transparent conductive laminate may include an anchor coat layer between the transparent substrate and the layer made of the transparent conductive resin composition for the purpose of improving adhesion and adhesion.

Furthermore, for the purpose of improving scratch resistance, a top coat layer may be provided on the layer made of the transparent conductive resin composition.

Transparent conductive laminates are used in transparent electrodes for displays such as ECDs, LCDs, and ELs, packaging materials for ICs, LSIs, magnetic tapes, magnetic cards, etc. that require protection from static electricity and electromagnetic waves, and transparent heating elements. used.

〔Example〕

EXAMPLES Hereinafter, examples will be shown to specifically explain the present invention, but the present invention is not limited thereto.

In the following examples, transparency and conductivity were evaluated as follows.

(1) Transparency Measured using a haze meter manufactured by Toyo Seiki Co., Ltd., and expressed as total light transmittance and haze (%).

0) Conductivity Measured with a surface resistance measuring device manufactured by Mitsubishi Yuka Co., Ltd., and the surface resistance (Ω
).

Example 1 Terephthalic acid 49 mol, isophthalic acid 48.5 mol, 5
- 10 parts by weight of a copolyester consisting of 2.5 moles of sodium sulfoisophthalic acid, 50 moles of ethylene glycol, and 50 moles of neopentyl glycol in a mixed solvent of methyl ethyl ketone/toluene-1 = 1 (parts by weight) 9.0 parts by weight
After dissolving in parts by weight? , 7,8.8-tetracyanoquinodimethane-N-n butylisoquinolium salt complex 0.0
5 parts by weight and 50 parts by weight of indium oxide containing tin oxide were added and dispersed using a paint shaker to prepare transparent conductive resin paint A.

Next, polyethylene terephthalate with a film thickness of 11001I)
(PET) A transparent conductive resin paint A is applied on the shim to create a film-like transparent conductive resin composition layer with a thickness of 4.5 μm, and a transparent conductive laminate 1 with excellent conductivity is produced. I got it. Table 1 shows the results of measuring the transparency and conductivity of the transparent conductive laminate 1.

Example 2 Terephthalic acid 49 mol, isophthalic acid 48.5 mol, 5
- After dissolving 10 parts by weight of a copolyester consisting of 2.5 moles of sodium sulfoisophthalic acid, 50 moles of ethylene glycol, and 50 moles of bisphenol A ethylene oxide adduct in 90 parts by weight of tetrahydrofuran,
, 0.05 parts by weight of ,7,8.8-tetracyanoquinodimethane-N-n-butylquinaldinium salt complex and 50 parts by weight of indium oxide containing tin oxide were added and dispersed with a paint shaker to form a transparent conductive resin. Paint B was produced.

Next, transparent conductive resin paint B was applied on the PET film with a thickness of 100 μm to create a film-like transparent conductive resin composition layer with a thickness of 4.5 μm. A laminate 2 was obtained. The results of the transparency and conductivity of the transparent conductive laminate 2 are shown in Table 1.

Example 3 45 mol of terephthalic acid, 50 mol of isophthalic acid of the following formula, 5 mol% of a phosphorus compound represented by 6Hs, 7 mol of ethylene glycol
10 parts by weight of a polyester polyurethane prepared by reacting a polyester diol with a molecular weight of 2,500 consisting of 0 mol and 30 mol of neopentyl glycol with 4,4''-diphenylmethane diisocyanate was mixed in a ratio of methyl ethyl ketone/toluene = 1:1 (parts by weight). After dissolving in 90 parts by weight of solvent, 7.7,8.8-tetracyanoquinodimethane-Nn-butylbenzothiazolium salt complex 0.07!
and 50 parts by weight of indium oxide containing tin oxide, and dispersed with a paint shaker to form a transparent conductive resin paint C.
was created.

Next, a transparent conductive resin paint C was applied on a PET film with a thickness of 100 μm to create a transparent conductive resin composition layer with a thickness of 4.5 μm. A laminate 3 was obtained. The results of the transparency and conductivity of the transparent conductive laminate 3 are shown in Table 1.

Example 4 Terephthalic acid 49 mol, isophthalic acid 48.5 mol, 5
- After dissolving 10 parts by weight of a copolyester consisting of 2.5 moles of sodium sulfoisophthalic acid, 50 moles of ethylene glycol, and 50 moles of bisphenol A ethylene oxide adduct in 90 parts by weight of tetrahydrofuran,
, 0.1 part by weight of 7,8.8-tetracyanoquinodimethane-N-n-butylquinaldinium salt complex and 20 parts by weight of antimony-containing tin oxide were added and dispersed with a paint shaker to form a transparent conductive resin paint. I made a new one.

Next, a transparent conductive resin paint was applied on the PET film with a thickness of 100 μm to create a film-like transparent conductive resin composition layer with a thickness of 1 μm, resulting in a transparent conductive laminate 4 with excellent conductivity.
I got it. Table 1 shows the measurement results of the transparency and conductivity of the transparent conductive laminate 4.

Comparative example 1? , 7,8.8-tetracyanoquinodimethane-N-n-
A transparent conductive laminate 5 was produced in the same manner as in Example 1 except that the butylisoquinolium complex was not added.

Table 1 shows the measurement results of the transparency and conductivity of the transparent conductive laminate 5.

Comparative Example 2 7.7,8.8-tetracyanoquinodimethane-N-n-
A transparent conductive laminate 6 was obtained in the same manner as in Example 2 except that the butylquinaldinium salt complex was not used.

Table 1 shows the measurement results of the transparency and conductivity of the transparent conductive laminate 6.

Comparative Example 3 7 A transparent conductive laminate 7 was produced in the same manner as in Example 3 except that the 78.8-tetracyanoquinodimethane-N-n-butylbenzothiazolium salt complex was not used.

The results of measuring the transparency and conductivity of the transparent conductive laminate 7 are shown in Table 1.

[Margin below]

Table 1 R: Surface resistance T: Light transmittance H2: Haze [Effects of the invention] The transparent conductive resin composition of the present invention is produced by containing a charge transfer complex whose acceptor component is a tetracyanoquinodimethane derivative. , the electrical conductivity can be significantly improved without significantly reducing its transparency.

Therefore, the paint and transparent conductive laminate obtained using the transparent conductive resin composition of the present invention have excellent transparency and conductivity.

Claims (3)

[Claims] (1) A transparent conductive resin composition comprising a conductive metal oxide, a polymer resin, and a charge transfer complex in which the acceptor component is a tetracyanoquinodimethane derivative. (2) A transparent conductive resin coating comprising the transparent conductive resin composition according to claim (1) and a solvent as main components. (3) A transparent conductive laminate comprising a layer made of the transparent conductive resin composition according to claim (1) laminated on at least one side of a transparent substrate.