JPH11300903A - Conductive laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve antistatic performance under low humidity and enable maintaining of transparency without clouding even when a film is thick by laminating a conductive layer mainly composed of a π-conjugated conductive polymer and an acrylic denatured resin on at least one side of an inorganic and/or organic base. SOLUTION: A conductive laminate is formed by laminating a conductive layer mainly composed of a π-conjugated conductive polymer and an acrylic denatured resin on at least one side of an inorganic and/or organic base. A polyaniline and/or its derivative, a polypyrrole and/or its derivative, a polyacetylene and/or its derivative, a polythiophene and/or its derivative or the like is used for the π-conjugated conductive polymer. A graft body, which is modified by introducing an acrylic side chain by a resin B with respect to a resin A composing a main chain by graft coplymerization, is used for the acrylic denatured resin. Thereby, antistatic performance under low humidity can be improved.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive laminate, and more particularly, to a thermoplastic resin film having excellent antistatic properties and conductivity even under low humidity, especially a polyester film, Specific examples include industrial films such as magnetic tapes, OHPs, shielding materials, and conductive layers of LCDs; and carrier tapes, trays, magazines, and packaging films and sheets such as IC / LSI packages.

[0002]

2. Description of the Related Art Conventionally, thermoplastic films such as polyester and nylon have been used in a large amount and in a wide range as packaging films and industrial films because of their excellent heat resistance, dimensional stability and mechanical strength. . Polyethylene, polypropylene, polyvinyl chloride and the like are generally used as packaging materials because of their low heat resistance but good moldability and low cost. Since the synthetic resin is generally hydrophobic, static electricity is easily generated on the surface of the structure forming body made of the synthetic resin, and dust and the like easily adhere to the surface, causing various troubles.

In general, a surfactant is used as an antistatic agent for a film, a packaging material, or the like. However, the surfactant has a surface resistance (1) sufficient to suppress adhesion of dust and dirt.
0 ¹⁰ Ω / port or less), and the antistatic ability is liable to change due to the influence of ambient moisture and moisture. In particular, there is a disadvantage that the surface resistance of the film lowered by the surfactant is greatly increased under low humidity, and a desired antistatic ability cannot be obtained.

As a result, dust adheres to the surface of the film or the packaging material, which causes various troubles. In today's high-tech environment, films that are free from static electricity in low-humidity environments are being demanded.
There is a demand for an antistatic agent that provides a surface resistance value of 0 ¹⁰ Ω / mouth or less. Conductive polymers such as polyaniline and polypyrrole are known as materials giving such a low surface resistance value. All of them are soluble in a specific organic solvent, but water or a water / alcohol mixed solvent system is used. Has been insoluble or cannot be dispersed, and a method of bonding a sulfonic acid group to an aromatic ring has been used. Furthermore, since sufficient film properties cannot be obtained by itself, a method of mixing a water-soluble or water-dispersible resin has been used. However, when the film thickness is small, the film is transparent and has sufficient antistatic properties.However, when the film thickness is increased to increase the conductivity by the in-line coating method or the conductivity, the coat layer becomes cloudy and the original transparency of the film is reduced. Damage
There has been a problem that the conductivity is reduced depending on the resin.

Conventionally, coating resins include polyester resins, polyurethane resins, epoxy resins,
A phenoxy resin, a phenol resin, a polyolefin resin, an acrylic resin, and the like are used, and these are used for various applications, taking advantage of their respective features. However, in each case, there are many problems that each resin alone cannot solve in terms of high functionality such as transparency, adhesion to the base, strength, heat resistance, water resistance, solvent resistance, antistatic property, conductivity, etc. Exists. For example, in the case of a polyester resin or a polyurethane resin, when high workability is required, when a resin having a high molecular weight is used, the amount of terminal hydroxyl groups decreases, and effective curing is difficult. Also, polyolefin resins used for coating applications generally do not have a sufficient amount of reactive functional groups, and it is difficult to achieve high functionality. It tends to be inferior to the above resins in terms of acrylic resins and the like.

[0006] From these facts, a method of modifying the above resin with an acrylic resin is known at present from the viewpoint of maintaining basic characteristics and enhancing functions. This is because, for example, an unsaturated monomer containing a hydroxyl group, an amino group, a carboxyl group, or the like is chemically bonded to a resin having a low reactive functional group by a method such as grafting / blocking. And make up for the reactivity. However, there are problems with these methods as well. For example, in order to improve curability and adhesion, it is common to introduce a functional group such as a hydroxyl group or a carboxyl group into a resin, but only an unsaturated monomer containing those functional groups is used. When grafting is performed, curability and adhesion are not improved with a small amount of acrylic resin, and curability and adhesion are improved with a large amount of acrylic resin, but basic characteristics such as mechanical characteristics are reduced.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made as a result of earnest research focusing on the above problems, and its purpose is to make use of the excellent points of the original substrate (structure forming body). In addition, it has sufficient antistatic ability to overcome static electricity damage even under low humidity, and the conductive layer maintains transparency without becoming cloudy even when the film thickness is thick, and it has good adhesion to the substrate. Excellent, strength,
An object of the present invention is to provide a conductive laminate excellent in heat resistance, water resistance, solvent resistance and the like.

Therefore, the mechanical properties of a graft of a polyester resin or a polyester polyurethane resin as a main chain and an acrylic / vinyl resin as a side chain are examined. The reason for this is that even when the grafting efficiency is greatly increased, We found that a combination with low compatibility with chains and side chains made the coating film brittle, but with a combination with high compatibility, it was possible to functionalize by introducing various functional groups while maintaining the mechanical properties of the base resin. (Japanese Patent Laid-Open No. 7-330841). In order to further improve the properties such as curing efficiency, the effects of the side chain composition were further investigated.Partially, an ionic unsaturated monomer neutralized with an acid or base was added to the acrylic resin composition. By improving the association properties of the acrylic resin while maintaining compatibility and miniaturizing the domains formed, it is possible to achieve both the properties such as curability and adhesion and the mechanical properties. Heading, the present invention has been completed.

[0009]

SUMMARY OF THE INVENTION The present invention provides an inorganic and / or inorganic material.
Another object is to provide a conductive laminate in which a conductive layer mainly composed of a π-conjugated conductive polymer and an acrylic modified resin is laminated on at least one surface of an organic base material.

[0010] In this specification, "film" means
The thickness is not limited, and includes a so-called “sheet”.

The inorganic and / or organic substrate in the present invention is not particularly limited, but when the substrate is a thermoplastic film, the effect of the present invention is particularly effectively exhibited, and in particular, the substrate is made of polyethylene terephthalate. Polyester, nylon, polypropylene, polyethylene, etc.
It is preferable to use a single polymer such as polystyrene, a mixture of two or more polymers obtained by mixing them, or a film obtained by laminating a plurality of films of the same type or different types of the above polymers. Particularly when the substrate is a polyester film, the remarkable effects of the present invention can be obtained.

In the case of a laminated film, it is sufficient that at least the surface on which the conductive layer is formed is made of the above-mentioned material, and other layers are made of materials other than the above-mentioned material as long as they do not affect the operation of the present invention. It may be formed of a material.

Further, the inorganic and / or organic base material may include:
Instead of a continuous film, it may be formed of fibers. As the material forming the fiber, when it is the same as the material forming the thermoplastic film described above,
The effect of the present invention is effectively exhibited.

Examples of the π-conjugated conductive polymer in the present invention include polyaniline and / or a derivative thereof, polypyrrole and / or a derivative thereof, polyacetylene and / or a derivative thereof, and polythiophene and / or a derivative thereof. Above all, as the polyaniline and / or its derivative, a sulfonated polyaniline, especially a sulfonated polyaniline containing an alkoxy group-substituted aminobenzenesulfonic acid as a main component is preferable, and aminoanisolesulfonic acid is particularly preferable.

Here, specific examples of aminoanisolesulfonic acids include 2-aminoanisole-3-sulfonic acid, 2-aminoanisole-4-sulfonic acid, 2-aminoanisole-5-sulfonic acid, and 2-aminoanisole-sulfonic acid. 6-sulfonic acid, 3-aminoanisole-2-sulfonic acid, 3-aminoanisole-4-sulfonic acid, 3-aminoanisole-5-sulfonic acid, 3-aminoanisole-6-sulfonic acid, 4-aminoanisole- Examples thereof include 2-sulfonic acid and 4-aminoanisole-3-sulfonic acid.

Among them, 2-aminoanisole-3-sulfonic acid, 2-aminoanisole-4-sulfonic acid, 2-aminoanisole-4-sulfonic acid,
Aminoanisole-5-sulfonic acid, 2-aminoanisole-6-sulfonic acid, 3-aminoanisole-2-sulfonic acid, 3-aminoanisole-4-sulfonic acid, 3
-Aminoanisole-6-sulfonic acid is preferably used.

It is also possible to use a compound in which the methoxy group of anisole is substituted by another alkoxy group such as an ethoxy group or an isopropoxy group.

The acrylic modified resin in the present invention is, specifically, a resin B constituting a main chain and a resin B
A graft body modified by introducing an acrylic side chain by graft polymerization is preferred. Preferred configurations of the resin A and the resin B are described below.

[Resin A] The resin A forms the main chain of the graft, and is preferably a resin having an unsaturated bond in the molecule. Examples of the resin A include a polyester resin, a polyurethane resin, an epoxy resin, a phenoxy resin, a phenol resin, and a polyolefin resin.

The amount of unsaturated bonds contained in the molecule of the resin A is 5 mol / 106 g or more and 1000 mol / 106 g.
The following is preferred. If the amount is less than 5 mol / 106 g, it is difficult to perform sufficient grafting, and it is difficult to obtain the effect of acrylic modification. Also, 1000mol / 1
If the amount exceeds 06 g, gelation or the like is observed during grafting, which is not preferable.

The resin A has a weight average molecular weight of 1,000 to 10
It is preferably in the range of 0000.

The polyester resin as the resin A is mainly composed of one or more dicarboxylic acid components and glycol components. Preferably, among the dicarboxylic acid components, aromatic dicarboxylic acids and aliphatic and / or fatty acids are used. The ratio of the aromatic dicarboxylic acid to the aromatic dicarboxylic acid is 1
The molar ratio is preferably not less than 00 mol% or 50/50 (aromatic dicarboxylic acid / [aliphatic and / or alicyclic dicarboxylic acid]) or more.

Regarding the introduction of an unsaturated bond into the polyester resin, a dicarboxylic acid having an unsaturated double bond copolymerizable in the polyester and a glycol having an unsaturated bond can be used as described below. In addition, it is also possible to introduce by reacting an unsaturated compound having a functional group reactive with a carboxyl group and a hydroxyl group at the polyester terminal. Examples of such unsaturated compounds include epoxy group-containing unsaturated monomers such as glycidyl methacrylate, isocyanate group-containing unsaturated monomers such as methacryloyl isocyanate, and unsaturated acid anhydrides such as maleic anhydride. Can be used.

Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, and sodium sulfoisophthalic acid. Examples of the aliphatic dicarboxylic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecandionic acid, and dimer acid. Examples of the alicyclic dicarboxylic acid include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, and acid anhydrides thereof.

Examples of the dicarboxylic acid having an unsaturated double bond include fumaric acid and α, β-unsaturated dicarboxylic acids.
Maleic acid, maleic anhydride, itaconic acid, citraconic acid, and alicyclic dicarboxylic acids having an unsaturated double bond include 2,5-norbornene dicarboxylic anhydride, tetrahydrophthalic anhydride and the like. Most preferred among these are fumaric, maleic, itaconic and 2,5-norbornene dicarboxylic anhydrides.

Further, p-hydroxybenzoic acid and p- (2
-Hydroxyethoxy) benzoic acid, or hydroxycarboxylic acids such as hydroxypivalic acid, γ-butyrolactone, and ε-caprolactone can also be used as needed.

On the other hand, the glycol component has 2 carbon atoms.
Aliphatic glycols having 6 to 10 carbon atoms, alicyclic glycols having 6 to 12 carbon atoms, and ether bond-containing glycols.

Examples of the aliphatic glycol having 2 to 10 carbon atoms include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-
Pentanediol, 1,9-nonanediol, 2-ethyl-2-butylpropanediol, neopentyl glycol hydroxypivalate, dimethylol heptane and the like.

Examples of the alicyclic glycol having 6 to 12 carbon atoms include 1,4-cyclohexanedimethanol and tricyclodecanedimethylol.

Examples of the glycol containing an ether bond include glycols obtained by adding one to several moles of ethylene oxide or propylene oxide to two phenolic hydroxyl groups of diethylene glycol, triethylene glycol, dipropylene glycol, and bisphenol, respectively. 2,2-bis (4-hydroxyethoxyphenyl) propane and the like.

Further, polyethylene glycol, polypropylene glycol and polytetramethylene glycol can be used if necessary.

Examples of the glycol containing an unsaturated bond include glycerin monoallyl ether, trimethylolpropane monoallyl ether, and pentaerythritol monoallyl ether.

In the polyester resin used in the present invention, a polycarboxylic acid and / or polyol having three or more functional groups may be copolymerized. Examples of trifunctional or higher polycarboxylic acids include (anhydrous) trimellitic acid, (anhydrous) pyromellitic acid, (anhydrous) benzophenonetetracarboxylic acid, trimesic acid, ethylene glycol bis (anhydrotrimellitate), and glycerol tris (anhydro). Trimellitate) is used. On the other hand, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and the like are used as the trifunctional or higher functional polyol. The above trifunctional or higher polycarboxylic acid and / or polyol is preferably at most 5 mol%, more preferably at most 3 mol%, based on the total acid component or the total glycol component. If it exceeds 5 mol%, the processability will be reduced.

The polyester resin used in the present invention may be one obtained by adding an acid anhydride such as maleic anhydride or trimellitic anhydride to the molecular terminal.

The polyurethane resin as the resin A is mainly composed of (a) a polyol, (b) an organic diisocyanate compound, and, if necessary, (c) a chain extender having an active hydrogen group.

As the polyol (a), various polyols can be used. For example, in addition to polyester polyols, polyether polyols, polycarbonate polyols, polyolefin polyols and the like, epoxy resins, phenoxy resins, phenol resins, and cellulosic resins described later. And butyral resins, and one or more of these can be used. As the polyester polyol, a polyester polyol containing an aromatic dicarboxylic acid as a dicarboxylic acid component is preferable, and more preferably, an aromatic dicarboxylic acid 30 to
It is preferably 100 mol%, 0 to 40 mol% of aliphatic and / or alicyclic dicarboxylic acid. The polyol used in the present invention desirably contains the polyester polyol as described above in an amount of 50 to 100% by weight based on the total polyol.

(B) As the organic diisocyanate compound, hexamethylene diisocyanate, tetramethylene diisocyanate, 3,3'-dimethoxy-4,4'-
Biphenylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 1,3
-Diisocyanatemethylcyclohexane, 4,4'-
Diisocyanate dicyclohexane, 4,4′-diisocyanate cyclohexylmethane, isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6
-Tolylene diisocyanate, p-phenylene diisocyanate, diphenylmethane diisocyanate, m-phenylene diisocyanate, 2,4-naphthalene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 4,4'-diisocyanate diphenyl ether, 1, 5-naphthalenediisocyanate and the like.

(C) Examples of the chain extender having an active hydrogen group include ethylene glycol, propylene glycol, neopentyl glycol, 2,2-diethyl-1,2
3-propanediol, diethylene glycol, spiro glycol, glycols such as polyethylene glycol, hexamethylene diamine, propylene diamine, amines such as hexamethylene diamine, and the like,
In addition, active hydrogen groups such as dimethylolpropionic acid
Compounds having two or more and other functional groups are also included.

The polyurethane resin used in the present invention is:
(A) a polyol, (b) an organic diisocyanate,
(C) a chain extender having an active hydrogen group,
A polyurethane resin obtained by reacting the active hydrogen groups (c) / isocyanate groups (b) in a ratio of 0.4 to 1.3 (equivalent ratio) is preferred.

The unsaturated bond in the polyurethane resin can be contained in any of the above (a), (b) and (c). For example, the unsaturated bond is contained in (c). In this case, glycols such as glycerin monoallyl ether and glycerol monomethacrylate can be used.

The polyurethane resin is produced in a known manner, for example, in a solvent at a reaction temperature of 20 to 150 ° C. in the presence or absence of a catalyst. As the solvent used at this time, for example, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, toluene,
Aromatic hydrocarbons such as xylene and esters such as ethyl acetate and butyl acetate can be used. As a catalyst for accelerating the reaction, amines, organotin compounds and the like are used.

Examples of the epoxy resin as the resin A include dihydric alcohols and phenols, hydrogenated and halogenated products of these phenols, and novolaks (acid catalysts of polyhydric phenols and aldehydes such as formaldehyde). One or a mixture of two or more types of acid-modified products such as an epoxy resin obtained from the reaction product in the presence of a fatty acid and the like can be used. Among them, a bisphenol A type epoxy resin is preferable. And hydrogenated bisphenol A type epoxy resins, bisphenol F type epoxy resins and modified products thereof.

The unsaturated bond is introduced into the epoxy resin by reacting an unsaturated compound having a functional group highly reactive with an epoxy group or a hydroxyl group in the epoxy resin, such as an unsaturated acid compound or an unsaturated amine compound. This is possible. Such unsaturated acid compounds include acrylic acid,
Methacrylic acid, fumaric acid, maleic acid and its anhydride, itaconic acid and its anhydride, acid phosphooxyethyl (meth) acrylate (trade name Phosmer
M, etc., manufactured by Unichemical). In addition, as the unsaturated amine compound, aminoethyl acrylate, aminoethyl methacrylate and the like can be used. In that case,
It is also possible to carry out the reaction under various catalysts such as pyridine.

The phenoxy resin as the resin A is obtained by further increasing the molecular weight of the above-mentioned epoxy resin, and various resins can be used. The introduction of unsaturated bonds is the same as in epoxy resins.

Examples of the phenolic resin as the resin A include formaldehyde condensates of alkylated phenols and cresols. Specifically, alkylated (methyl, ethyl, propyl, isopropyl, butyl) phenol, p-tert-amylphenol,
4,4'-sec-butylidenephenol, p-ter
t-butylphenol, o-, m-, p-cresol,
Formaldehyde condensates such as p-cyclohexylphenol, 4,4′-isopropylidenephenol, p-nonylphenol, p-octylphenol, 3-pentadecylphenol, phenol, phenyl-o-cresol, p-phenylphenol, and xylenol are exemplified. .

The polyolefin resin as the resin A is preferably a solvent-soluble resin, for example, chlorinated polyolefin, chlorinated polyethylene, and the like. Further, the polyolefin resin has a reactivity for introducing an unsaturated bond such as a maleic acid-modified product thereof. Those having a functional group are preferred. Introduction of an unsaturated bond into a maleic acid-modified chlorinated polyolefin resin is possible by reacting an unsaturated compound having an epoxy group or an amino group, which is reactive with maleic acid.

[Resin B] The resin B is for introducing a side chain into the resin A constituting the main chain, and is preferably a polymer obtained from an unsaturated monomer mixture. −
1) An unsaturated monomer capable of dissolving the resin A at a temperature of 150 ° C. or lower, (B-2) a water-soluble unsaturated monomer containing a functional group such as a hydroxyl group, a carboxyl group, or an amino group. And (B-3) those containing an ionic unsaturated monomer neutralized with an acid or a base.

(B-1) The unsaturated monomer capable of dissolving the resin A at a temperature of 150 ° C. or lower is compatible with the main chain (resin A) and the side chain (resin B) in the conductive layer. Work as an improvement. At a temperature of 150 ° C. or less, resin A
And the unsaturated monomer capable of dissolving the resin A10
0 parts by weight and 200 parts by weight of unsaturated monomer are added,
It refers to an unsaturated monomer that can dissolve Resin A at a temperature of 150 ° C. or less. When considering solvents as a rough guide for solubility, polyester resins, polyurethane resins,
Epoxy resins, phenoxy resins, etc. can be dissolved in solvents such as aromatic solvents, ester solvents, ketone solvents, ether solvents and their mixed solvents, and polyolefin resins can be dissolved in aromatic solvents. It can be selected from unsaturated monomers having a similar structure.

Examples of the above unsaturated monomers are shown below. Unsaturated monomers similar in structure to common aromatic solvents: styrene, styrene derivatives Unsaturated monomers similar in structure to common ester solvents: lower alkyl esters of (meth) acrylic acid, vinyl esters Unsaturated monomers similar in structure to common ether solvents:
Vinyl ethers, glycol ether (meth) acrylate ethers Unsaturated monomers similar in structure to other solvents: N, N-
Dimethylacrylamide, vinylpyridine, vinylpyrrolidone, acryloylmorpholine, etc.

As the component (B-1), one or more of the above unsaturated monomers can be used. Among these, preferably, the resin A is a polyester resin,
In the case of a polyurethane resin, an epoxy resin, or a phenoxy resin, styrene or a derivative thereof or an alkyl ester of (meth) acrylic acid having 1 to 6 carbon atoms is preferable, and more preferably styrene or a derivative thereof and a carbon number of (meth) acrylic acid. Mixtures of 1 to 6 alkyl esters are preferred. When the resin A is a polyolefin resin, styrene and its derivatives are preferred.

(B-2) A water-soluble unsaturated monomer containing a functional group such as a hydroxyl group, a carboxyl group, or an amino group is used to improve the curability and adhesion to the conductive layer due to the hydroxyl group and the like. To contribute. The water-soluble unsaturated monomer containing a functional group such as a hydroxyl group is not particularly limited, and a known unsaturated monomer can be used. Here, the term "water-soluble" means that it is completely miscible with water at any temperature at a temperature of 100 ° C or lower.

Examples of the unsaturated monomer as described above are shown below. Hydroxyl group-containing unsaturated monomer: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, diethylene glycol mono (meth) acrylate,
Dipropylene glycol mono (meth) acrylate, glycerin mono (meth) acrylate, allyl alcohol, glycerin monoallyl ether, N-methylol (meth) acrylamide, etc. Carboxyl group-containing unsaturated monomer: acrylic acid, methacrylic acid, etc. Amino group containing Unsaturated monomer: N, N-dimethyl (meth)
Acrylamide, etc.

As the component (B-2), one or more of the above unsaturated monomers can be used. Of these, preferably, one or more hydroxyl group-containing unsaturated monomers, a mixture of one or more hydroxyl group-containing unsaturated monomers and one or more carboxyl group-containing unsaturated monomers, Mixtures of one or more hydroxyl-containing unsaturated monomers and one or more amino-containing unsaturated monomers are preferred.
More preferably, the content of the hydroxyl group-containing unsaturated monomer in the component (B-2) is 30% or more.

(B-3) The ionic unsaturated monomer neutralized with an acid or a base has an effect of easily causing association of a polymer of the unsaturated monomer mixture in the conductive layer. ,
Although it is effective in improving the curing efficiency and suppressing the decrease in adhesion, it is desirable to keep the amount to a minimum because an excessive amount may cause a decrease in water resistance.

Examples of the ionic unsaturated monomer neutralized with an acid or a base include unsaturated carboxylic acid compounds, unsaturated phosphoric acid compounds, unsaturated sulfonic acid compounds, and quaternary compounds neutralized with a base. Examples thereof include an ammonium group-containing unsaturated monomer. Specifically, alkali metal salts, ammonium salts, organic amine salts, sodium styrenesulfonate, acid phosphooxyethyl (meth) acrylate (trade name: Phosmer M) of (meth) acrylic acid
Alkali metal salts, ammonium salts, organic amine salts, acrylamidomethylpropanesulfonic acid alkali metal salts, ammonium salts, organic amine salts, (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxy Ethyltriethylammonium chloride, (meth) acryloyloxyethyltrimethylammonium sulfate, (meth) acryloyloxyethyltriethylammonium sulfate, (meth) acryloyloxyethyltrimethylammonium phosphate, (meth) acryloyloxyethyltriethylammonium phosphate, (meth) acrylic acid N, N-dimethylaminoethyl acetate, hydrochloride, phosphate, sulfate, (meth) acrylate N, N- Acetate ethyl aminoethyl, hydrochlorides, phosphates, sulfates, etc. may be mentioned.

As the component (B-3), one or more of the above unsaturated monomers can be used. Of these, unsaturated monomers in the form of a combination of a strong acid and a strong base are preferred, and examples thereof include sodium styrenesulfonate. Further, the component (B-3) can be converted into an alkali metal salt, an ammonium salt, or an organic amine salt after the polymerization of the resin A and the resin B.

The resin (B) includes (B-1), (B
-2) In addition to the components of (B-3), other known various unsaturated monomers including a polyfunctional unsaturated monomer may be contained as necessary. Examples of various unsaturated monomers include various vinyl compounds, vinyl ester compounds, vinyl ether compounds, (meth) acrylic acid esters, and the like. Can be adjusted or provided. Preferably, examples of the polyfunctional unsaturated monomer include ethylene glycol di (meth) acrylate and diethylene glycol di (meth) acrylate.

The resin B in the present invention is in the range of Y / X = 1/99 to 90/10, where X is the weight ratio of the resin A and Y is the weight ratio of the resin B in the acrylic-modified resin. Is preferable, and Y / X = 10 / 90-80 is more preferable.
/ 20 is preferred. When the ratio of the resin A is lower than this ratio, the characteristics of the resin A are hardly exhibited, and when the ratio is higher than this ratio, the effect such as improvement in curability is small.

For each unsaturated monomer in the resin B, the weight ratio of the resin A in the acrylic-modified resin is X, the weight ratio of the resin B is Y, and the weight ratio of the component (B-1) is Y1. , (B
When the weight ratio of the component -2) is Y2 and the weight ratio of the component (B-3) is Y3, 0.6 ≦ (Y1 + Y2 + Y3) / Y ≦
It is necessary to be 1.0, and when it is smaller than this range, effects such as improvement of curability are small. For the component (B-1), 0.005 ≦ Y1 / X and 0.3 ≦ Y1 /
It is necessary that Y ≦ 0.7, and if it is smaller than this range, it becomes difficult to impart compatibility. (B-2) For the component, 0.005 ≦ Y2 / X and 0.3 ≦ Y2 / Y
It is necessary that ≦ 0.7, and if it is smaller than this range, the curability of the resin B is reduced. Regarding the component (B-3), Y3 / X ≦ 0.05 and 0.0001 ≦ Y3 / Y
It is necessary that ≦ 0.1, and if it is larger than this range, the water resistance and the like are undesirably reduced.

In the present invention, the acrylic-modified resin used for the conductive layer is preferably 5 to 1000 mol / 106 g.
Weight average molecular weight having an unsaturated bond of 1,000 to 100
000 resin (resin A) and a polymer (resin B) obtained from an unsaturated monomer mixture are chemically integrated, and (resin B) is (B-1) at a temperature of 150 ° C. or lower. An unsaturated monomer capable of dissolving (Resin A)
(B-2) a water-soluble unsaturated monomer containing a functional group such as a hydroxyl group, a carboxyl group, or an amino group;
3) Acrylic modified resin characterized by containing an ionic unsaturated monomer neutralized with an acid or a base is preferable, and an acrylic graft copolymerized polyester having such a configuration is particularly preferable. Is preferred.

[Production Method of Acrylic-Modified Resin] As described above, the acryl-modified resin was modified by introducing an acrylic side chain by graft polymerization with resin B to resin A constituting the main chain. In the case of a graft, the polymerization method can be modified by polymerizing the unsaturated monomer mixture constituting the resin B in the presence of the resin A by using a polymerization initiator or radiating active energy rays. A known polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization can be used.

In the case of carrying out acrylic modification using solution polymerization, general-purpose solvents such as aromatic hydrocarbons, ketones, esters, ethers (cyclic ethers, glycol ethers, etc.), N-substituted amides , Alcohols, carboxylic acids, amines, and other organic solvents, water, and mixtures of two or more thereof. When performing suspension polymerization, emulsion polymerization, etc., various additives such as known surfactants and buffers can be added.However, since these may cause a decrease in adhesion, the amount used is It is desirable to keep it to a minimum.

As a polymerization initiation method at this time, a method suitable for various polymerization methods can be used. For example, polymerization initiation of known azo compounds, peroxides, persulfate compounds, redox initiators, etc. In addition to using an agent, polymerization using an active energy ray or the like is also possible. The amount of the polymerization initiator used is at least 0.1% by weight based on the monomer.
The above is necessary. In addition, known additives such as a chain transfer agent such as octyl mercaptan, dodecyl mercaptan, mercaptoethanol, and α-methylstyrene dimer can also be used. The addition amount of these is desirably such that the various characteristics are not deteriorated.

Further, in the present invention, an acrylic modified resin can be produced by the following method.
That is, even when the resin A does not disperse in water and contains only a very small amount of a hydrophilic group, the resin A is first converted into an unsaturated monomer (B-3) other than the unsaturated monomer (B-3) component.
1) Dissolved in an unsaturated monomer mixture containing the component (B-2) and then dissolved the component (B-3) in water or a mixed solution of water and a trace amount of a completely water-soluble solvent. Is added, it is possible to disperse the resin A in water with a fine particle diameter, and by directly starting / completion of polymerization by using a polymerization initiator or the like, acrylic modification in a process without using a solvent can be achieved. It is possible. In this case, the unsaturated monomer (B-1) component desirably contains at least 20% of a poorly water-soluble unsaturated monomer such as styrene in the component (B-1). When the resin A is dissolved in the unsaturated monomer mixture, it is preferable to add a trace amount of a polymerization inhibitor such as hydroquinone to suppress polymerization by heating during the dissolution. By using this method, the amount of the hydrophilic group that affects the water resistance can be minimized, and problems such as use / reuse / disposal of a solvent can be avoided.

The acrylic-modified resin used in the conductive layer of the present invention can use the above-mentioned graft as it is, but by blending a cross-linking agent (curing resin) and performing bake-hardening, a high solvent resistance can be obtained. Properties, water resistance, and hardness. Examples of the crosslinking agent include a phenol formaldehyde resin, an amino resin, a polyfunctional epoxy compound, a polyfunctional isocyanate compound and various blocked isocyanate compounds thereof, and a polyfunctional aziridine compound.

Examples of the phenol formaldehyde resin include formaldehyde condensates of alkylated phenols and cresols. Specifically, alkylated (methyl, ethyl, propyl, isopropyl, butyl) phenol, p-tert-amylphenol, 4,4'-sec-butylidenephenol, p
-Tert-butylphenol, o-, m-, p-cresol, p-cyclohexylphenol, 4,4'-isopropylidenephenol, p-nonylphenol, p
-Octylphenol, 3-pentadecylphenol,
Examples include formaldehyde condensates such as phenol, phenyl-o-cresol, p-phenylphenol, and xylenol.

Examples of the amino resin include formaldehyde adducts such as urea, melamine, and benzoguanamine, and alkyl ether compounds of these alcohols having 1 to 6 carbon atoms. Specific examples include methoxylated methylol urea, methoxylated methylol N, N-ethylene urea, methoxylated methylol dicyandiamide, methoxylated methylol melamine, methoxylated methylol benzoguanamine, butoxylated methylol melamine, butoxylated methylol benzoguanamine, and the like. They are methoxylated methylolmelamine, butoxylated methylolmelamine, and methylolated benzoguanamine, which can be used alone or in combination.

Examples of the polyfunctional epoxy compound include diglycidyl ethers of bisphenol A and oligomers thereof, diglycidyl ethers of hydrogenated bisphenol A and oligomers thereof, diglycidyl orthophthalate, diglycidyl isophthalate, and diglycidyl terephthalate. Diglycidyl p-oxybenzoate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, diglycidyl succinate, diglycidyl adipate, diglycidyl sebacate, ethylene glycol diglycidyl ether, Propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether And polyalkylene glycol diglycidyl ethers, trimellitic acid triglycidyl ester, triglycidyl isocyanurate, 1,4
Examples thereof include diglycidyloxybenzene, diglycidylpropylene urea, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol triglycidyl ether, and triglycidyl ether of a glycerol alkylene oxide adduct.

Examples of the polyfunctional isocyanate compound include aromatic and aliphatic diisocyanates and tri- or higher polyisocyanates, and may be either low molecular weight compounds or high molecular weight compounds. For example, tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate or trimers of these isocyanate compounds, and excess of these isocyanate compounds Amount and, for example, ethylene glycol, propylene glycol, trimethylolpropane,
Glycerin, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, low molecular weight active hydrogen compounds such as triethanolamine or various polyester polyols, polyether polyols, terminal obtained by reacting with high molecular weight active compounds such as polyamides and the like. An isocyanate group-containing compound is exemplified.

The isocyanate compound may be a blocked isocyanate. The blocked isocyanate can be obtained by subjecting the above isocyanate compound and an isocyanate blocking agent to an addition reaction by a conventionally known method or the like. As the isocyanate blocking agent, for example, phenols such as phenol, thiophenol, methylthiophenol, cresol, xylenol, resorcinol, nitrophenol, chlorophenol, oximes such as acetoxime, methylethylketoxime, cyclohexanone oxime, methanol, ethanol, propanol, Alcohols such as butanol; halogen-substituted alcohols such as ethylene chlorohydrin and 1,3-dichloro-2-propanol; t-butanol;
Tertiary alcohols such as pentanol, ε-caprolactam, δ-valerolactam, γ-butyrolactam, β
-Lactams such as propyl lactam, and other aromatic amines, imides, acetylacetone,
Active methylene compounds such as acetoacetate and malonic acid ethyl ester, mercaptans, imines, ureas, diaryl compounds and sodium bisulfite are also included.

In addition to these crosslinking agents, a curing agent or an accelerator can be used in combination.

The curing reaction of the graft is performed by using 5 to 40 parts of the curing resin with respect to 100 parts by weight (solid content) of the graft.
Part by weight (solid content), 60 depending on the type of curing agent
It is performed by heating in a temperature range of ２５０250 ° C. for about 10 seconds to 60 minutes. A reaction catalyst and a promoter are also used if necessary.

In the present invention, the acrylic-modified resin can be used by mixing with other resins within a range not to impair the function of the present invention, and the processability thereof can be improved.

The acrylic-modified resin of the present invention may contain various additives such as inorganic powders such as colloidal silica, pigments, dyes and inorganic compounds as long as the effects of the present invention are not impaired.

The ratio of the constituent components of the conductive layer in the present invention may be appropriately set according to the desired properties of the conductive layer and the adhesion to the base material. The ratio with the acrylic modified resin is 3/97 by weight.
It is preferably in the range of 40/60 (π-conjugated conductive polymer / acrylic modified resin).

As a method for forming the conductive layer in the present invention, a conventionally known method can be used. For example, after dissolving or dispersing the components constituting the conductive layer in a solvent or the like, developing the solution on a base material by coating or the like, and then developing the solvent. For example, by drying the film.

It is particularly preferable to prepare a solution in which a solution in which a π-conjugated conductive polymer is dissolved in a solvent and a solution in which an acrylic-modified resin is dissolved or dispersed, and develop the mixture on a substrate. To form a conductive layer.

In the method for forming a conductive layer as described above, π
When polyaniline and / or a derivative thereof is used as the conjugated conductive polymer, the mixing ratio of the solution is preferably set to 100 parts by weight of the solvent with respect to polyaniline and / or a derivative thereof.
Alternatively, the amount of the derivative is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 4 parts by weight. When the ratio of the polyaniline and / or its derivative to the solvent is less than 0.01 part by weight, the long-term storage property of the solution is deteriorated, pinholes are easily generated in the surface coat layer, and the conductivity of the coated surface is significantly deteriorated. On the other hand, if the proportion exceeds 10 parts by weight, the solubility and dispersibility of polyaniline and / or its derivative in a solvent and the applicability of the coat layer tend to deteriorate, which is not preferable.

In the method of forming the conductive layer as described above, the mixing ratio of the solution in which the acrylic-modified resin is dissolved or dispersed is preferably 1 to 45 parts by weight of the acrylic-modified resin per 100 parts by weight of the solvent. And more preferably 5 to 40 parts by weight. If the ratio of the acrylic-modified resin to the solvent is less than 1 part by weight, it is difficult to form a mixed solution with the conjugated polymer, and if the ratio exceeds 45 parts by weight, the storage stability deteriorates.

As the solvent, any organic solvent can be used as long as it does not dissolve or swell the base material such as a thermoplastic film. A method using water or a mixed solvent with an organic solvent such as water / alcohol is used. Not only is it preferable from the viewpoint of the use environment, but also the coatability to the substrate and the conductivity are sometimes improved. Organic solvents include methanol, ethanol, propanol, alcohols such as isopropyl alcohol, ketones such as acetone methyl ethyl ketone and methyl isobutyl ketone, cellosolves such as methyl cellosolve and ethyl cellosolve, propylene glycols such as methyl propylene glycol and ethyl propylene glycol, Amides such as dimethylformamide and dimethylacetamide, and pyrrolidones such as N-methylpyrrolidone and N-ethylpyrrolidone are preferably used. They are,
It can be used by mixing with water at any ratio. Specific examples of this include water / methanol, water / ethanol, water / propanol, water / isopropanol, water / methyl propylene glycol, water / ethyl propylene glycol, and the like. The ratio used is preferably water / organic solvent = 1/10 to 10/1.

The conductive layer according to the present invention has excellent coatability and spreadability even when its constituent components are only the conjugated conductive polymer and acrylic modified resin, and the obtained conductive layer has good surface hardness. By additionally using a surfactant and / or a polymer compound soluble in the above-mentioned solvent, application to a substrate having poor wettability becomes possible.

Examples of the above surfactant include nonionic surfactants such as polyoxyethylene octyl phenyl ether, polyoxyethylene alkyl ether and polyoxyethylene sorbitan fatty acid ester, and fluoroalkyl carboxylic acids and perfluoroalkyl carboxylic acids. Fluorinated surfactants such as perfluoroalkylbenzenesulfonic acid, perfluoroalkylquaternary ammonium, and perfluoroalkylpolyoxyethyleneethanol are used.

The amount of the surfactant used in the present invention is preferably polyaniline and / or a derivative thereof.
It is preferable that the amount is not less than 0.001 part by weight and not more than 1000 parts by weight based on part by weight. If the amount of the surfactant exceeds 1,000 parts by weight, the surfactant in the coat layer is set off on the uncoated surface, and problems are likely to occur in secondary processing or the like.

The conductive layer of the conductive laminate of the present invention may contain various additives in addition to the above. Such additives include TiO ₂ , SiO ₂ , kaolin, CaCO ₃ ,
Inorganic particles such as Al ₂ O ₃ , BaSO ₄ , ZnO, talc, mica, and composite particles; and organic particles composed of polystyrene, polyacrylate, or a crosslinked product thereof. In order to further improve the conductivity, Sn
Adding powders of O ₂ , (tin oxide), ZnO (zinc oxide), inorganic particles (TiO ₂ , BaSO _4, etc.) coated with them, and carbon-based conductive fillers such as carbon black, graphite, and carbon fibers. Is also possible. It is preferable that the content of the additive is 4000 parts by weight or less based on 100 parts by weight of the polyaniline and / or the derivative. If it exceeds 4000 parts by weight,
An increase in the viscosity of the conductive layer may cause uneven coating.

As a method of forming a conductive layer on a base material,
There are a gravure roll coating method, a reverse roll coating method, a knife coater method, a dip coating method, and a spin coating method, but there is no particular limitation. When the substrate is a film, there are an in-line coating method in which application to the film is performed simultaneously in the film-forming process and an offline method in which coating is independently performed after the film-forming roll is manufactured. Yes, without any restrictions.

The surface resistance of the conductive layer in the present invention is 10 ⁶ to 10 at 25 ° C. and 15% RH from the viewpoint of antistatic properties.
^It is preferably in the range of ¹² Ω / port.

In the conductive laminate of the present invention, the thickness of the entire conductive laminate, the base material, and the thickness of the conductive layer are not particularly limited, and are appropriately set according to the intended degree of antistatic property and the like and the intended use. do it.

Next, the effects of the present invention will be described in more detail with reference to Test Examples and Examples, but the present invention is not limited to these. Test example Test Method (1) Presence or Absence of Whitening of Conductive Layer The surface of the conductive layer was irradiated with light using bromite, and the presence or absence of whitening was evaluated based on the following criteria. No whitened part on the surface of conductive layer: ○ Part of the surface of conductive layer is whitened: ×

(2) Surface resistance value A surface resistance measurement device manufactured by Mitsubishi Yuka Co., Ltd.
It was measured under the conditions of 25 ° C. and 15% RH.

(3) Substrate of conductive layer (thermoplastic film)
Evaluation of Adhesiveness to Adhesive Tape After sticking the adhesive tape on the conductive layer surface, the adhesive tape was peeled off, and whether or not the conductive layer was peeled from the substrate (thermoplastic film) was evaluated based on the following criteria. The conductive layer does not peel off and does not adhere to the adhesive tape at all. : ○ The conductive layer slightly peeled off and adhered to the adhesive tape. : △ The conductive layer completely peels off and adheres to the adhesive tape. : ×

(4) Using a scratch resistance fastness tester,
The surface of the conductive layer was rubbed 10 times with a gauze under a load of 00 g, and the degree of scratches on the surface of the conductive layer was evaluated based on the following criteria. No scratches on the conductive layer surface. : There are several fine scratches on the conductive layer surface. : △ The surface of the conductive layer has a clearly visible scratch. : ×

(5) Water Resistance The surface of the conductive layer was wiped 10 times at a constant pressure using a commercially available tissue paper impregnated with water, and evaluated based on the following criteria. The conductive layer is not wiped off at all. : ○ Slightly wiped off. : △ Completely wiped off. : ×

2. Test results The above results are shown in Table 1. As shown in Table 1, all of the examples were transparent without whitening, were excellent in adhesion, scratch resistance, and water resistance, and were excellent in antistatic properties (antistatic properties) under low humidity. On the other hand, Comparative Example 1 had a whitened portion and was insufficient in transparency. Comparative Examples 2 and 3 had insufficient antistatic properties under low humidity and did not have water resistance.

[0094]

[Table 1]

[0095]

EXAMPLES (Synthesis Example 1) In a stainless steel autoclave equipped with a stirrer, a thermometer and a partial reflux condenser, 466 parts of dimethyl terephthalate, 456 parts of dimethyl isophthalate, 340 parts of ethylene glycol and 340 parts of 3-methyl-1 were added. 650 parts of 1,5-pentanediol and 0.5 part of tetra-n-butyl titanate were charged at 160 ° C.
The transesterification reaction was performed over 4 hours to 220 ° C.
Next, 29 parts of fumaric acid was added, and the temperature was raised from 200 ° C. to 220 ° C. over 1 hour to carry out an esterification reaction. Next, the temperature was raised to 255 ° C., and the reaction system was gradually depressurized, and then reacted under a reduced pressure of 0.2 mmHg for 1 hour and 30 minutes to obtain a polyester. The obtained polyester was pale yellow and transparent. The weight average molecular weight of the obtained polyester is 20.
000 (in terms of polystyrene), the unsaturated bond content is 21
It was 6 mol / 106 g (calculated value).

Next, 75 parts of a polyester resin and 80 parts of methyl ethyl ketone were placed in a reactor equipped with a stirrer, a thermometer, a reflux device and a fixed-rate dropping device, heated, stirred and maintained at 70 ° C. to dissolve the resin. After the resin is completely dissolved, 5 parts of styrene,
12.5 parts of methyl methacrylate, 7.5 parts of 2-hydroxyethyl acrylate, 0.07 part of acrylamidomethylpropanesulfonic acid, azobisisobutylnitrile
5 parts, a solution of 5 parts of α-methylstyrene dimer in a mixed solvent of 30 parts of methyl ethyl ketone and 5 parts of dimethylformamide were dropped into the polyester solution over 1.5 hours while maintaining the system at 70 ° C. The reaction was further performed for 3 hours. After cooling to room temperature, sodium hydroxide 0.01
5 parts and methyl ethyl ketone are added and the solid content concentration is 30%
To obtain a graft body solution.

(Synthesis Example 2) In a stainless steel autoclave equipped with a stirrer, a thermometer and a partial reflux condenser, 466 parts of dimethyl terephthalate, 456 parts of dimethyl isophthalate, 341 parts of ethylene glycol, 341 parts of 3-methyl-1, Charge 649 parts of 5-pentanediol and 0.5 parts of tetra-n-butyl titanate,
The transesterification reaction was carried out over 4 hours to 220 ° C. Next, 29 parts of fumaric acid was added, and the temperature was 200 to 220 ° C
The temperature was raised over 1 hour until the esterification reaction was performed. Next, the temperature was raised to 255 ° C., and the reaction system was gradually depressurized, and then reacted under a reduced pressure of 0.2 mmHg for 1 hour and 30 minutes to obtain a polyester. The obtained polyester was pale yellow and transparent. The weight average molecular weight of the obtained polyester is 2
000 (in terms of polystyrene), the unsaturated bond content is 21
It was 0 mol / 106 g (calculated value). 30 parts of this polyester polyol and 20 parts of Kurapol L2010 (manufactured by Kuraray, molecular weight: 2,000) were charged with methyl ethyl ketone 5
After charging and dissolving together with 0 parts, 5.5 parts of isophorone diisocyanate and 0.01 part of dibutyltin laurate were charged,
The reaction was performed at 60 to 70 ° C. for 6 hours. The weight average molecular weight of the obtained polyurethane resin was 18,000, and the unsaturated bond content was 114 mol / 106 g (calculated value). Thereafter, 35 parts of methyl methacrylate, 11 parts of 2-hydroxyethyl methacrylate, 4 parts of dimethylacrylamide,
0.25 parts of acrylic acid, azobisisobutylnitrile 3
And a solution prepared by dissolving 5 parts of α-methylstyrene dimer in 50 parts of methyl ethyl ketone was dropped into the polyester solution over 1.5 hours while maintaining the inside of the system at 70 ° C., and further reacted for 3 hours. After cooling to room temperature, 0.13 parts of sodium hydroxide and methyl ethyl ketone were added to adjust the solid content to 30% to obtain a graft solution.

(Synthesis Example 3) 70 parts of bisphenol F type epoxy resin (YDF2004, manufactured by Toto Kasei) and 80 parts of methyl ethyl ketone were charged into a reactor equipped with a stirrer, a thermometer and a reflux device, and the resin was dissolved under heating. Thereafter, 10 parts of maleic anhydride and 0.1 part of pyridine were added and reacted under reflux for 3 hours. Next, styrene 10
2 parts of 2-hydroxyethyl methacrylate, 2 parts of methacrylic acid, 0.5 part of acrylamidomethylpropanesulfonic acid, 3 parts of azobisisobutyronitrile, 30 parts of methyl ethyl ketone, and 1 part of triethylamine were reacted in 2 hours. It was dropped into the system. Thereafter, the reaction was continued for 2 hours, and then 10 parts of triethylamine, 30 parts of isopropyl alcohol and 250 parts of water were added. After dispersing in water, the solvent was removed by azeotropic distillation. A dispersion was obtained. The average particle size of the obtained aqueous dispersion was 450 nm.

(Synthesis Example 4) In a stainless steel autoclave equipped with a stirrer, a thermometer and a partial reflux condenser, 374 parts of dimethyl terephthalate, 374 parts of dimethyl isophthalate, 29 parts of dimethyl 5-sodium sulfoisophthalate, ethylene Glycol 273 parts, 3-methyl-1,5-pentanediol 519 parts, and tetra-n-butyl titanate 0.52 part were charged, and 160 ° C.
The transesterification reaction was carried out over 4 hours to 220 ° C. Next, 4.6 parts of fumaric acid was added and the temperature was lowered from
The temperature was raised to 0 ° C. over 1 hour to carry out an esterification reaction. Next, the temperature was raised to 255 ° C., and the reaction system was gradually depressurized, and then reacted under a reduced pressure of 0.2 mmHg for 1 hour and 30 minutes to obtain a polyester. The obtained polyester was pale yellow and transparent. The obtained polyester has a weight average molecular weight of 23,000 and an unsaturated bond content of 41 mol / 10.
6 g. Next, in a reactor equipped with a stirrer, a thermometer and a reflux device, 66 parts of the obtained polyester, 10 parts of methyl methacrylate, 10 parts of glycerin monomethacrylate, 4 parts of methacrylic acid, 10 parts of butyl acrylate,
16 parts of isopropyl alcohol, hydroquinone 0.0
One part was added and dissolved by heating to 90 ° C. After the resin was dissolved, 10 parts of styrene was added.
, And stirring was continued for 10 minutes. Next, after adding an aqueous solution obtained by dissolving 0.6 part of sodium styrenesulfonate in 40 parts of water, 0.9 part of potassium persulfate and 10 parts of water were added to initiate polymerization. Reaction 7
After continuing at 0 ° C. for 4 hours, the mixture was cooled to room temperature to obtain an aqueous dispersion of a graft having a solid content of 30%. The average particle diameter of the obtained aqueous dispersion was 120 nm.

Synthesis Example 5 In a stainless steel autoclave equipped with a stirrer, a thermometer and a partial reflux condenser, 456 parts of dimethyl terephthalate, 456 parts of dimethyl isophthalate, 59 parts of dimethyl 5-sodium sulfoisophthalate, ethylene Glycol 465 parts, bisphenol A ethylene oxide adduct (manufactured by Sanyo Chemical Industries, B
1120 parts of PE20F) and 0.52 part of tetra-n-butyl titanate were charged, and transesterification was performed at 160 ° C. to 220 ° C. for 4 hours. Next, 12 parts of fumaric acid was added, and the temperature was raised from 200 ° C. to 220 ° C. over 1 hour to carry out an esterification reaction. Then 255 ° C
The temperature of the reaction system was gradually reduced to 0.2 mmH
The reaction was carried out for 1 hour and 30 minutes under a reduced pressure of g to obtain a polyester. The obtained polyester was pale yellow and transparent. The weight average molecular weight of the obtained polyester was 19000, and the unsaturated bond content was 46 mol / 106 g. Next, 66 parts of the obtained polyester, 18 parts of methyl ethacrylate, 10 parts of glycerin monomethacrylate, 8 parts of methacrylic acid, 16 parts of isopropyl alcohol and 0.1 part of hydroquinone were placed in a reactor equipped with a stirrer, a thermometer and a reflux device. 01 parts was added and dissolved by heating to 90 ° C. After the resin is dissolved, add 8 parts of styrene and then
While maintaining the liquid temperature at 70 ° C., 180 parts of water was added, and 10 parts of water was added.
Stirring was continued for minutes. Next, after adding an aqueous solution obtained by dissolving 0.6 part of sodium styrenesulfonate in 40 parts of water, 0.9 part of potassium persulfate and 10 parts of water were added to initiate polymerization. After continuing the reaction at 70 ° C. for 4 hours, the reaction mixture was cooled to room temperature to obtain an aqueous dispersion of a graft having a solid content of 30%.
The average particle diameter of the obtained aqueous dispersion was 250 nm.

Synthesis Example 6 46 mol% of dimethyl terephthalate, 47 mol% of dimethyl isophthalate and 7 mol% of sodium 5-sulfoisophthalate were used as dicarboxylic acid components, and 50 mol% of ethylene glycol and neopentyl glycol were used as glycol components. Using 50 mol%, a transesterification reaction and a polycondensation reaction were carried out in a conventional manner. The glass transition temperature of the obtained sulfonic acid group-containing polyester was 68 ° C. 300 parts of this sulfonic acid group-containing polyester and n-butyl cellosolve 1
The mixture was heated and stirred with 50 parts to form a viscous solution, and 540 parts of water was gradually added with further stirring to obtain a solid content of 28% by weight.
Was obtained as a homogeneous pale white aqueous dispersion.

(Synthesis Example 7) 2-aminoanisole-4-
100 mmol of sulfonic acid was dissolved by stirring in a 4 mol / liter aqueous ammonia solution at 24 ° C., and a 100 mmol aqueous solution of ammonium peroxodisulfate was added dropwise. After the dropwise addition, the mixture was further stirred at 24 ° C. for 10 hours, and the reaction product was separated by filtration, washed and dried to obtain 14 g of a powdery copolymer. The volume resistivity of this copolymer was 12.7 Ω · cm.
3 parts by weight of the above polymer was dissolved in 100 parts by weight of a 0.3 mol / l sulfuric acid aqueous solution with stirring at room temperature to prepare a conductive composition.

(Preparation of base film) Average particle size 0.5 μm
m is extruded at 290 ° C. and cooled with a cooling roll at 30 ° C. to give a thickness of about 180 μm.
m of unstretched film was obtained. 85 of this unstretched film
A base film was stretched 3.5 times in the longitudinal direction between a pair of rolls heated at different temperatures and having different peripheral speeds.

(Preparation of Conductive Laminate) Obtained thickness of about 5
A coating solution having a solid content of 4% was applied to a thickness of about 10 μm on a 0 μm base material (PET film), and then 3 × in the horizontal direction.
The film was stretched 5 times to produce conductive laminates of Examples 1 to 5 described below.

Example 1 The aqueous solution of the sulfonated polyaniline prepared in Synthesis Example 7 and the aqueous dispersion prepared in Synthesis Example 1 were mixed at a solid content of 10/90.
(Weight ratio), and the surfactant Emulgen 810 (manufactured by Kao) was mixed with the sulfonated polyaniline at a ratio of 8
/ 100, and a solvent having a water / IPA ratio of 50/50 (weight ratio) and a solid concentration of 4%.
It was adjusted to be. Using this liquid, a conductive laminate was prepared by the above-mentioned method, and Example 1 was performed.

Example 2 A conductive laminate was prepared in the same manner as in Example 1 except that the aqueous dispersion prepared in Synthesis Example 2 was used instead of the aqueous dispersion prepared in Synthesis Example 1. And 2.

Example 3 A conductive laminate was prepared in the same manner as in Example 1 except that the aqueous dispersion prepared in Synthesis Example 3 was used instead of the aqueous dispersion prepared in Synthesis Example 1. It was set to 3.

Example 4 A conductive laminate was prepared in the same manner as in Example 1 except that the aqueous dispersion prepared in Synthesis Example 4 was used instead of the aqueous dispersion prepared in Synthesis Example 1. And 4.

Example 5 A conductive laminate was prepared in the same manner as in Example 1 except that the aqueous dispersion prepared in Synthesis Example 5 was used instead of the aqueous dispersion prepared in Synthesis Example 1. It was set to 5.

Comparative Example 1 A laminate was prepared in the same manner as in Example 1 except that the aqueous dispersion prepared in Synthesis Example 6 was used instead of the aqueous dispersion prepared in Synthesis Example 1. did.

Comparative Example 2 An anionic coating liquid Chemistat SA-9 was used as a coating liquid.
A laminate was prepared in the same manner as in Example 1 except that (manufactured by Sanyo Chemical Industries) was used, and Comparative Example 2 was obtained.

Comparative Example 3 Cationic Coating Solution Chemistat 6300 as Coating Solution
A laminate was prepared in the same manner as in Example 1 except that -H (manufactured by Sanyo Chemical Industries, Ltd.) was used.

[0113]

As is apparent from the above description, the conductive laminate of the present invention does not whiten even when the thickness of the conductive layer is large, has excellent transparency, and has excellent antistatic properties even under low humidity. In addition to the advantages of surface strength, water resistance, solvent resistance and heat resistance peculiar to the substrate. Therefore, the conductive laminate of the present invention,
It is suitable for various industrial films such as magnetic tapes, OHP films, shielding materials, and conductive diagrams of LCDs; and various packaging films such as carrier tapes, tray magazines, and IC / LSI packages.

Claims (12)

[Claims] 1. A conductive laminate comprising a conductive layer mainly composed of a π-conjugated conductive polymer and an acrylic modified resin laminated on at least one surface of an inorganic and / or organic substrate. 2. The conductive laminate according to claim 1, wherein the inorganic and / or organic substrate is a thermoplastic film. 3. The conductive laminate according to claim 2, wherein the thermoplastic film is a polyester. 4. The conductive laminate according to claim 1, wherein the inorganic and / or organic substrate is formed of fibers. 5. The conductive laminate according to claim 1, wherein the π-conjugated conductive polymer is polyaniline and / or a derivative thereof. 6. The conductive laminate according to claim 5, wherein the polyaniline and / or a derivative thereof is a sulfonated polyaniline. 7. The conductive laminate according to claim 6, wherein the sulfonated polyaniline has an alkoxy group-substituted aminobenzenesulfonic acid as a main component. 8. The conductive laminate according to claim 7, wherein the alkoxy-substituted aminobenzenesulfonic acid is aminoanisolesulfonic acid. 9. The conductive laminate according to claim 1, wherein the acrylic modified resin is an acrylic graft copolymerized polyester. 10. A resin (A) in which the acrylic graft copolymerized polyester has an unsaturated bond of 5 to 1000 mol / 106 g and a weight average molecular weight of 1,000 to 100,000.
And a resin obtained by chemically bonding a polymer (B) obtained from an unsaturated monomer mixture, wherein (B) is an unsaturated monomer capable of dissolving (A) at a temperature of 150 ° C. or lower. (B-1), a water-soluble unsaturated monomer (B-2) containing a functional group selected from a hydroxyl group, a carboxyl group, and an amino group, an ionic neutralized with an acid or a base. The conductive laminate according to claim 9, comprising an unsaturated monomer (B-3). 11. The conductive laminate according to claim 1, wherein the conductive layer contains a surfactant. 12. The conductive layer has a surface resistance of 25 ° C., 15 ° C.
The conductive laminate according to claim 1, wherein the% RH is 10 ⁶ to 10 ¹² Ω / port.