JPH03134906A - Transparent and conductive resin composition, paint and laminate - Google Patents

Abstract

PURPOSE:To improve transparency by using polyester and polyurethan a macromolecular resin as main ingredients of transparent and conductive resin composition together with conductive metallic oxide. CONSTITUTION:A conductive metallic oxide, macromolecular resin such as polyurethane resin and polyester bases resin having ion radicals in their straight and side chains as main ingredients provides a highly transparent conductive composition. Transparent, conductive paint and transparent, conductive laminate using said composition are highly transparent and have high commercial values.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a conductive resin composition with improved transparency, a transparent conductive paint and a transparent conductive laminate using this resin composition. be.

[Prior Art] Recently, the use of transparent conductive laminates in which conductivity is imparted to a transparent substrate such as glass or a transparent plastic film has been increasing. As a method of imparting conductivity to a transparent substrate, there is a method of applying a paint mixed with a small amount of conductive powder such as carbon black or fine metal powder to the transparent substrate. However, this method has a drawback in that the conductive laminate is colored black or gray depending on the characteristics of the conductive fine powder.

Therefore, a method has been proposed to provide conductivity without reducing transparency by replacing it with fine metal oxide powder such as indium oxide or tin oxide, but this has not necessarily resulted in satisfactory transparency. .

[Problems to be Solved by the Invention] The present invention has been made in view of the above circumstances, and its purpose is to provide a conductive composition with excellent transparency. Another object of the present invention is to provide a useful transparent conductive paint and a transparent conductive laminate using the transparent conductive composition.

[Means for Solving the Problems] The structure of the present invention that has solved the above problems is that, in a transparent conductive resin composition containing a conductive metal oxide and a polymer resin as main components, ions are used as the polymer resin. This transparent conductive resin composition can be prepared by dissolving or dispersing it in an appropriate solvent, or by adding other auxiliary raw materials as necessary. It can be used as a transparent conductive resin paint, and it can also be used as a transparent conductive laminate by laminating it on at least one side of a transparent substrate such as glass or plastic.

[Function] As the conductive metal oxide used in the present invention, SnO
2, I n20:+, ZnO, CdSnO4゜Sb2
o3. 1 ff of metal oxide powder such as A120s, TiO or their composite powder! Alternatively, two or more types may be used, but from the viewpoint of transparency, particularly preferred are a metal oxide powder containing tin oxide as a main component and a metal oxide powder containing indium oxide as a main component. These conductive metal oxide powders have a particle size of 2 μm to improve transparency.
Hereinafter, fine powder of 1 μm or less is more preferably used.

The conductive metal oxide described above can also be used as a coating on an inorganic powder such as flaky mica.

Further, as the polymer resin containing an ionic group used in the present invention, a polyester resin and/or a polyurethane resin having an ionic group in the main chain and/or side chain is used. Examples include carboxylic acid groups, sulfonic acid groups, phosphoric acid groups, ammonium groups, and the like.

Hereinafter, the polyester resin, polyurethane resin, and ionic group used in the present invention will be explained in more detail.

First, among the carboxylic acid components and diol components that constitute polyester, the carboxylic acid components include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, and 1,5-naphthalic acid;
- Aromatic oxycarboxylic acids such as (hydroxyethoxy)benzoic acid; Aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid; fumaric acid, maleic acid, itaconic acid, tetrahydrophthalic acid, etc. Unsaturated aliphatic dicarboxylic acids such as hexahydrophthalic acid; alicyclic dicarboxylic acids such as hexahydrophthalic acid; tri- or tetracarboxylic acids such as trimellitic acid, trimesic acid, and pyromellitic acid.

In addition, the glycol component that makes up polyester is
Ethylene glycol, propylene glycol, 1,3-
Propanediol, 1.4-butanediol, 1.5-
Bentanediol, 1゜6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 2,2,4-trimethyl-1,3-bentanediol, 1,4-cyclohexane dimetatool,
Diols such as propylene oxide adducts of bisphenol A, propylene oxide adducts of bisphenol A, ethylene oxide adducts of hydrogenated bisphenol A, propylene oxide adducts of hydrogenated bisphenol A, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. is exemplified,
These may be used alone or in combination of two or more, and may also be used in combination with tri- or tetraols such as trimethylolethane, trimethylolpropane, glycerin, and pentaerythritol. Further, other relatively high molecular weight diols other than those mentioned above include polyester polyols, and polyester diols such as lactone-based polyester diols obtained by ring-opening polymerization of lactones such as ε-caprolactone can also be used. .

In addition, the polyurethane used in the present invention is obtained by, for example, chain-extending polyalkylene glycol with polyisocyanate, or polyester polyol (obtained by polycondensing a carboxylic acid component and a glycol component).
produced by chain-extending with polyisocyanate.

As the polyalkylene glycol, polyethylene glycol, polybutylene glycol polybrobylene 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 glycol components listed in the section for producing the polyester can be used. In addition, as polyisocyanates, 2.4-tolylene diisocyanate, 2.6-tolylene diisocyanate, p
-Phenyl 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 +
4. 4-Diisocyanate-diphenyl ether, 1,5-naphthalene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 13-diisocyanate methylcyclohexane.

1.4-diisocyanatemethylcyclohexane, 4,
Diisocyanate compounds such as 4°-diisocyanate cyclohexane, 4.4°-diisocyanate cyclohexylmethane, and isophorone diisocyanate are used. These polyisocyanates include triisocyanate compounds such as 2,4-tolylene diisocyanate trimer and hexamethylene diisocyanate trimer,
It may be contained in a proportion of about 7 mol% or less of the total isocyanate groups.

Polyurethane is manufactured using the above-mentioned components according to conventional methods.

Next, as the ionic groups contained in polyester and polyurethane, for example, the following groups are mentioned as preferable ones, and these ionic groups can be added to the compounds exemplified corresponding to each ionic group in polyester or polyurethane. It can be introduced by using it as part of the raw material components.

(1) -COOM (M represents a hydrogen atom, an alkali metal, tetraalkylammonium or tetraalkylsulfonium) polycarboxylic acid, glyceric acid, dimethylolpropionic acid, N,N-jetanolglycine.

Oxycarboxylic acids such as hydroxyethyloxybenzoic acid; aminocarboxylic acids such as diaminopropionic acid and diaminobenzoic acid and their derivatives.

RI　　　　　Rr (2) -N or -N” R2R2R5 (R1-R3 are each independently a hydrogen atom.

(Indicates an alkyl group, aryl group, or aralkyl group having 1 to 8 carbon atoms) N-methyljetanolamine, 2-methyl-2-dimethylaminomethyl-1,3-propanol, 2-methyl-2-dimethylamino- Nitrogen-containing alcohols such as 13-brobanediol and derivatives thereof.

(3) (R1 represents the same meaning as above) picolinic acid, dipicolinic acid, aminopyridinediaminopyridine, hydroxypyridine, dihydroxypyridine,
Aminohydroxypyridine Pyridine ring-containing compounds and their derivatives, such as pyridinylmethanol, pyridinylpropanediol, and pyridinylethanol.

(4) S03M (M represents the same meaning as above) Polycarboxylic acids such as 5-sodium sulfoisophthalic acid, 5-sulfoisophthalic acid, sodium sulfosuccinic acid,
and their derivatives: sodium sulfohydroquinone and its alkylene oxide adduct; sodium sulfobisphenol A and its alkylene oxide adduct, etc.

(5) Phosphorus-containing ionic group OM.

OM.

OM.

R6- Rs-0-P = O(Ill)-5 0M.

(R4 is a trivalent hydrocarbon group having 3 to 10 carbon atoms; R5 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 may each be substituted with a halogen atom, a hydroxy group, -0M2 (M2 represents an alkali metal) or an amine group]; R6 and R2
is an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, an arylene group or a formula (CH20R8)r, respectively.
a group represented by (R11 represents an alkylene group, a cycloalkylene group, or an arylene group having 1 to 12 carbon atoms, and r is 1 to 4); and Ml is an alkali metal atom.

Hydrogen, a monovalent hydrocarbon group, or an amine group) Examples of compounds represented by formula (Ill)-1
O) I eH5 P-CH2CHCH20H(Ill)-1-2KOO)
Example of a compound represented by the formula (Ill)-2 ans O-P-CH2CHCH20H Wan OH aHs O-P-CH2CH20H20)I KG 0)l (III)-2-1 (Ill)-2-2 ( 0)I HOCH2-P-(:)+208 (Ill)-
3-1Na)101:)12-T'-C)I20H(Ill)-
3-2 Example of compound represented by formula (Ill)-4 Na HOCH2-P-CToOH(Ill)-4-11 1 P-[CH2CH20H) 2 (Ill)-4-2 Na In formula (111)-5 Examples of compounds shown H3O 0-P-CH2COOH(III)-5-1aOC)130 0-P-CH2CH2e)1. (l11)-5-
2aO These ionic groups may be introduced into the polyester and/or polyurethane after polymerization, or may be introduced into the polymer using a monomer containing these ionic groups. .

The transparent conductive resin composition of the present invention is composed of a polymer mainly composed of at least one of the above-mentioned conductive metal oxides and the above-mentioned polyester and/or polyurethane containing an ionic group, and has a conductive property. The preferred amount of mixed metal oxide is 10 to 70% by volume, more preferably 30 to 70% by volume.
The range is 60% by volume. If 10% by volume is ungrooved, the conductivity will be poor, while if it exceeds 70% by volume, not only the transparency but also the conductivity will decrease.

The transparent conductive resin composition may also contain a small amount of a curing agent such as alkoxymethylolmelamine or blocked isocyanate in order to increase the hardness of the cured product.

There are no restrictions on the type of solvent used in conjunction with the transparent conductive resin composition of the present invention as long as it can dissolve the polyester and/or polyurethane containing an ionic group. , for example, organic solvents such as Nisel-based, ketone-based, ether ester-based, chlorine-based, alcohol-based, ether-based, and hydrocarbon-based solvents. Among these, particularly preferred solvents are:
Ester solvents such as methyl acetate, ethyl acetate, isopropyl acetate, isobutyl acetate, butyl acetate, amyl acetate; methyl ethyl ketone, methyl isobutyl ketone, methyl isoamyl ketone.

Ketone solvents such as methyl amyl ketone, ethyl amyl ketone, imbutyl ketone, methoxymethyl pentanone, cyclohexanone, diacetone alcohol, isophorone; methyl cellosolve acetate.

Ethyl cellosolve acetate, butyl cellosolve acetate.

Examples include ether ester solvents such as 3-methoxybutyl acetate, methyl carpitol acetate, ethyl carpitol acetate, and butyl carpitol acetate.

In addition, when putting it into practical use as a transparent conductive resin paint,
Appropriate amounts of fluorine thread resin, silicone resin, surfactant, etc. may also be used as paintability improving agents.

The method of preparing transparent conductive resin paint itself does not require any special techniques; for example, a polymer resin solution is prepared by dissolving ionic group-containing polyester and/or polyurethane in an appropriate solvent, and this A method may be adopted in which conductive metal oxide powder is uniformly dispersed in a polymer resin solution. For dispersing the conductive metal oxide, a known dispersion method using a paint shaker, sand mill, ball mill, homogenizer, triple roll, high pressure disperser, etc. may be used.

5 6 When the transparent conductive resin composition of the present invention is used to produce a transparent conductive laminate, any transparent material may be used as the main transparent substrate, such as glass plates and various plastic sheets. and plastic films can be used. However, plastic films with high productivity and flexibility are highly versatile, and specific examples include polystyrene film, polyamide film, polycarbonate film, polyphenylene sulfide film, polyetherimide film, and polyethylene sulfide film. Ether sulfone film, polyolefin film,
Examples include PVA-based films, acrylic-based films, polyvinyl chloride-based films, etc., and these are appropriately selected and used depending on the purpose and required characteristics of the transparent conductive laminate.

However, the most common of these are polyester films such as polyethylene terephthalate and polyethylene naphthalate, and polyether sulfone films.

The transparent conductive laminate of the present invention can be coated on one or both sides of these transparent substrates by, for example, spraying, barcoding,
Doctor blade method, dipping method, roll coater
Alternatively, the transparent conductive composition described above may be formed into a sheet, film, etc., and then laminated with a transparent substrate. Alternatively, it can be manufactured by a laminating method or the like.

In addition, in the above coating or lamination, it is one of the preferred embodiments that an anchor coat layer is formed between the transparent substrate and the transparent conductive resin composition layer in order to improve the adhesion and adhesion between the two. . It is also effective to cover the transparent conductive resin composition layer with a top coat layer for the purpose of improving the abrasion resistance, abrasion resistance, surface activity, etc. of the laminate.

The transparent conductive laminate thus obtained is transparent and has excellent conductivity, and can be used as a transparent electrode for displays such as ECDLCDs and ELs, or for protecting devices such as ICs, LSIs, magnetic tapes, and magnetic cards from static electricity and electromagnetic waves. It can be widely used as a packaging material for magnetic materials or as a transparent heating element.

[Examples] Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited by the Examples below.

The evaluation method adopted in the following examples is as follows.

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

(2) Conductivity Measured using a surface resistance meter manufactured by Mitsubishi Yuka Co., Ltd., and expressed as surface resistance (Ω).

Hunao±↓ Terephthalic acid (49 mol), Isophthalic acid (48.5 mol), 5-sodium sulfoisophthalic acid (25 mol)
, ethylene glycol (50 mol), and neopentyl glycol (50 mol) (10 mol).
parts by weight), methyl ethyl ketone/toluene = 1:1 (
parts by weight) in a mixed solvent (90 parts by weight), and then a mixture of tin oxide and indium oxide (50 parts by weight) was dissolved in this solution.
was added and uniformly dispersed using a paint shaker to prepare paint A.

This coating material A was applied onto a polyethylene terephthalate film having a thickness of 100 μm to form a film having a thickness of 4.5 μm to obtain a conductive laminate 1 with excellent transparency.

The transparency and conductivity of the laminate 1 are shown in Table 1.

]U'' A copolymerized polyester consisting of sterephthalic acid (49 mol), isophthalic acid (48.5 mol), sodium ethylphosphonylethylpropionate col (50 mol), and neopentyl gelcol (50 mol). A conductive laminate 2 with excellent transparency was obtained in the same manner as in Example 1 except for using the following.

9 0 The transparency and conductivity of the laminate 2 are shown in Table 1.

A polyester diol consisting of uterephthalic acid (49 mol), isophthalic acid (48.5 mol), 5-sodium sulfoisophthalic acid (2.5 mol), ethylene glycol (50 mol), and neopentyl glycol (50 mol)
A conductive laminate with excellent transparency was obtained in the same manner as in Example 1, except that a polyurethane consisting of 100 parts by weight) and 4,4°-diphenylmethane diisocyanate (21 parts by weight) was used.

The transparency and conductivity of the laminate 3 are shown in Table 1.

11 - A compound consisting of terephthalic acid (49 mol), isophthalic acid (48.5 mol), 5-sodium sulfoisophthalic acid (2.5 mol), ethylene glycol (50 mol), and neopentyl glycol (50 mol). Polymerized polyester (1
0 parts by weight), methyl ethyl ketone/toluene; 1:1
was dissolved in a mixed solvent (90 parts by weight). Antimony-containing tin oxide (20 parts by weight) was added to this solution and uniformly dispersed using a paint shaker to prepare paint B.

This paint B was applied onto a 100 μm thick polyethylene terephthalate film to form a 1 μm thick film to obtain a conductive laminate 4 with excellent transparency.

The transparency and conductivity of the laminate 4 are shown in Table 1.

Reality 496 5 Terephthalic acid (45 mol%), isophthalic acid (50 mol%), phosphorus compound represented by the following formula (5 mol%), aHS op-co2coco2o.

KO OH Uses a polyester polyurethane with a molecular weight of 20,000 produced by the reaction of a polyester diol with a molecular weight of 2,500 consisting of ethylene glycol (70 mol%) and neopentyl glycol (30 mol%) and 4,4'-diphenylmethane diisocyanate. Then, in the same manner as in Example 1, a conductive laminate 5 with excellent transparency was obtained.

The transparency and conductivity of the laminate 5 are shown in Table 1.

Skin softener■Uterephthalic acid (50 mol), isophthalic acid (50 mol)
A laminate 6 was obtained in the same manner as in Example 1, except that a copolymerized polyester consisting of , ethylene glycol (50 mol), and neopentyl glycol (50 mol) was used.

The transparency and conductivity of the laminate 6 are shown in Table 1.

1 Soft [i Terephthalic acid (50 mol), Isophthalic acid (50 mol)
A laminate 7 was obtained in the same manner as in Example 4, except that a copolyester consisting of , ethylene glycol (50 mol), and neopentyl glycol (50 mol) was used.

The transparency and conductivity of the laminate 7 are shown in Table 1.

4 [Effects of the Invention] The present invention is configured as described above, and by using polyester and/or polyurethane having an ionic group as a matrix component and using this in combination with a conductive metal oxide, transparency can be achieved. By dissolving this in an appropriate solvent and adding other auxiliary raw materials as necessary, we can create a coating that provides a transparent coating with excellent conductivity. By forming the transparent conductive composition on one or both sides of a transparent substrate, a highly transparent conductive laminate can be obtained, and the commercial value as a conductive material can be significantly increased. Became.

Claims (3)

[Claims] (1) A transparent conductive resin composition containing a conductive metal oxide and a polymer resin as main components, characterized in that the polymer resin is made of polyester and/or polyurethane containing an ionic group. transparent conductive resin composition. (2) A transparent conductive paint containing the transparent conductive resin composition according to claim (1) and a solvent as main components. (3) The transparent conductive resin composition according to claim (1),
A transparent conductive laminate formed by laminating on at least one side of a transparent substrate.