JP2009270047A - Conductive composition, antistatic paint, and protective film using the conductive composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a conductive composition superior in adhesion, antistaticity and antifouling properties to PET film, and capable of forming a coating film with high transparency. <P>SOLUTION: The conductive composition includes a polymer (A) having a polyester skeleton, polysiloxane skeleton and/or fluororesin skeleton, and a conductive polymer (B), wherein the mass ratio of the polymer (A) to the polymer (B) is in the range of 85/15-20/80. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a conductive composition, an antistatic paint and a protective film using the same.

  In the manufacturing process of polarizing plates and retardation plates, after attaching a surface protective film to prevent dirt and scratches on the surface, the opposite surface is adhesively processed to form a laminate, and further to the desired size Cut. The cut products are handled in a stacked state until they are used in a later process. Cut products are prone to static electricity and have the problem of attracting dust and sticking together. Also, when the surface protection film is peeled off, static electricity is generated and dust adheres to the surface of the optical film, the liquid crystal of the liquid crystal member using the optical film is abnormal, or the semiconductor used in the panel of the flat panel display It may be damaged. For this reason, it is necessary to quickly discharge the generated static electricity.

As the surface protective film, one having an antistatic layer and an antifouling layer provided thereon on one surface of a substrate and an adhesive layer on the other surface of the substrate is generally used ( For example, see Patent Document 1).
Patent Document 2 includes a “base material, an adhesive layer provided on one side surface of the base material, and a polymer layer provided on the other side surface of the base material, wherein the polymer layer has an average molecular weight. 10,000 or more polyester resins and acrylic resins, one or two or more polymer compounds composed of urethane resin having a tensile strength of 100 kgf / cm ² or more as a coating film with an average molecular weight of 5000 or more, silicone-based, fluorine-based, etc. 1 type or 2 or more types of mold release agents consisting of, ITO (indium oxide compound doped with tin), ATO (tin oxide doped with antimony), AZO (zinc oxide doped with aluminum), tin oxide or the like "A surface protective film characterized by being a layer mainly composed of two or more kinds of metal oxide-based conductive agents."

Japanese Patent Laid-Open No. 2003-320631 JP 2006-326961 A

  The protective film described in Patent Document 2 is produced at a lower cost than a method in which an antistatic layer as described in Patent Document 1 is formed on a substrate and an antifouling layer is formed in two steps. However, there is a problem in that a polymer such as a polyester resin and a polymer such as a silicone-based resin or a fluorine-based polymer are hardly compatible with each other and the haze increases (that is, the transparency decreases).

Therefore, an object of the present invention is to provide a conductive composition and an antistatic coating material that are excellent in adhesion to PET film, antistatic property and antifouling property and can form a highly transparent film.
In addition, the present invention can be easily and inexpensively produced as compared with a commonly used protective film, and can provide adhesion, antistatic property and anti-static property to a layer obtained by laminating a substrate and a conductive composition. An object is to provide a protective film having excellent soiling and high transparency.

  As a result of intensive studies, the inventor contains a polymer (A) having a polyester skeleton, a polysiloxane skeleton and / or a fluororesin skeleton, and a conductive polymer (B). A conductive composition having a mass ratio with the conductive polymer (B) of 85/15 to 20/80 is excellent in adhesion to PET film, antistatic property and antifouling property, and forms a highly transparent film. I found that I can do it. Furthermore, a protective film having at least a base material and a layer obtained by laminating the conductive composition on one surface of the base material is produced more easily and inexpensively than a commonly used protective film. It has been found that it is excellent in adhesiveness, antistatic property and antifouling property with a layer obtained by laminating a base material and a conductive composition, and has high transparency. The present inventor has completed the present invention based on these findings.

That is, the present invention provides the following (1) to (7).
(1) A polymer (A) having a polyester skeleton, a polysiloxane skeleton and / or a fluororesin skeleton, and a conductive polymer (B), and the polymer (A) and the conductive polymer (B ) And a conductive composition having a mass ratio of 85/15 to 20/80.

  (2) The polymer (A) contains 10 mol% or more of a repeating unit represented by the following formula (1), and the conductive polymer (B) is doped by a dopant containing sulfosuccinic acid, The electrically conductive composition as described in said (1).

  (3) The polymer (A) is obtained by reacting at least a polyester polyol, a siloxane-containing polyol compound and / or a fluorine-containing polyol compound, and a compound having two or more functional groups that react with a hydroxy group. The conductive composition according to the above (1) or (2), which is a polymer.

  (4) The electrically conductive composition as described in said (3) whose mass ratio of the said polyester polyol, the said siloxane containing polyol compound, and / or the said fluorine containing polyol compound is 30 / 70-80 / 20.

  (5) The conductive composition according to (3) or (4), wherein the siloxane-containing polyol compound is a siloxane-containing diol compound having two hydroxy groups at one end.

  (6) An antistatic coating comprising the conductive composition according to any one of (1) to (5) above.

  (7) A protective film having at least a substrate and a layer obtained by laminating the conductive composition according to any one of (1) to (5) on one surface of the substrate.

The conductive composition and antistatic paint of the present invention are excellent in adhesion to PET film, antistatic property and antifouling property, and can form a film with high transparency.
In addition, the protective film of the present invention can be easily and inexpensively produced as compared with a commonly used protective film, and adhesion between a substrate and a layer obtained by laminating a conductive composition and antistatic properties. Excellent in soil resistance and antifouling properties, and has high transparency.

Hereinafter, the present invention will be described in more detail.
The conductive composition of the present invention (hereinafter also referred to as “the composition of the present invention”) includes a polymer (A) having a polyester skeleton, a polysiloxane skeleton and / or a fluororesin skeleton, and a conductive polymer (B ) And the mass ratio [polymer (A) / conductive polymer (B)] of the polymer (A) and the conductive polymer (B) is 85/15 to 20/80.

The polymer (A) will be described below.
The polymer (A) is a polymer having a polyester skeleton, a polysiloxane skeleton, and / or a fluororesin skeleton.
The polyester skeleton has a structure having an ester bond in the main chain, and the polysiloxane skeleton has a structure having a siloxane bond in the main chain. The fluororesin skeleton has a structure having a repeating unit represented by the following formula.

  In the above formula, R is a fluorine atom, a hydrogen atom or an alkyl group, and at least one of the plurality of R is a fluorine atom.

  The polymer (A) preferably contains a repeating unit represented by the following formula (1), and more preferably contains 10 mol% or more of a repeating unit represented by the following formula (1). These polymers (A) are excellent in mixing properties, can be dispersed uniformly, and have high adhesion and transparency when used in combination with a conductive polymer (B) that is doped with a dopant containing sulfosuccinic acid. Become. Furthermore, the thing containing 20 mol% or more of repeating units represented by following formula (1) from the point which can reduce the surface resistance after drying is more preferable.

  Although the manufacturing method of a polymer (A) is not specifically limited, For example, it reacts the polyester polyol, the siloxane containing polyol compound and / or the fluorine containing polyol compound, and the compound which has two or more functional groups which react with a hydroxyl group. The method of making it preferable is.

The polyester polyol used for production of the polymer (A) will be described below.
As said polyester polyol, the polyester polyol obtained by making the polyol component containing neopentyl glycol and the carboxylic acid component react is mentioned suitably from the point which is excellent in the adhesiveness with respect to PET film, for example.
In addition, the repeating unit represented by the said Formula (1) can be introduce | transduced into a polymer (A) by using the polyol component containing neopentyl glycol.

The polyol component is a compound having two or more hydroxy groups, and may contain glycols such as ethylene glycol and propylene glycol in addition to neopentyl glycol.
The amount of neopentyl glycol in the polyol component is preferably 30 mol% or more. Within this range, it is excellent in miscibility with the conductive polymer (B) and can be uniformly dispersed. Furthermore, it is more preferably 50 mol% or more from the viewpoint that the surface resistance after drying can be lowered.

  The carboxylic acid component is not particularly limited as long as it is a compound having two or more carboxy groups. For general polyester, for example, terephthalic acid, isophthalic acid, phthalic anhydride, succinic acid, adipic acid, azelaic acid, sebacic acid, etc. are used, but it is particularly clear that terephthalic acid and isophthalic acid are used in combination. It is preferable from the viewpoints of excellent properties, water resistance, chemical resistance and low cost.

  The manufacturing method of the said polyester polyol is not specifically limited, It can manufacture by a well-known method.

  The number average molecular weight of the polyester polyol is preferably 10,000 to 500,000, more preferably 20,000 to 200,000, from the viewpoint of easy mixing with the conductive polymer (B) and physical properties of the conductive composition. preferable.

The siloxane-containing polyol compound used for the production of the polymer (A) will be described below.
The siloxane-containing polyol compound is not particularly limited as long as it is a compound having two or more hydroxy groups and dimethylsiloxane [—Si (—CH ₃ ) ₂ —O—].

One molecule of the siloxane-containing polyol compound has two or more hydroxy groups, preferably two to three, and more preferably two.
The number of dimethylsiloxanes contained in one molecule of the siloxane-containing polyol compound is preferably 10 to 132, and more preferably 63 to 132.

  In the siloxane-containing polyol compound, the structure other than two or more hydroxy groups and dimethylsiloxane is not particularly limited. Examples of the structure other than two or more hydroxy groups and dimethylsiloxane include a hydrocarbon group having at least one selected from the group consisting of an oxygen atom, a nitrogen atom, a silicon atom, and a sulfur atom. The hydrocarbon group can be branched.

Suitable examples of the siloxane-containing polyol compound include a compound represented by the following formula (2) and a compound represented by the following formula (3).
When a siloxane-containing diol compound having two hydroxy groups at one end, such as a compound represented by the following formula (3), is used as the siloxane-containing polyol compound, it is preferable because the contact angle increases and the antifouling property is excellent. .

In said formula (2), n is an integer of 9-250.
In said formula (3), R < ¹ > represents a hydrocarbon group and m is an integer of 9-131. Examples of the hydrocarbon group include a methyl group and an ethyl group.

  The number average molecular weight of the siloxane-containing polyol compound is preferably 1,000 to 15,000, more preferably 5,000 to 10,000, in view of the necessity of film strength of the conductive composition.

Commercially available products can be used as the siloxane-containing polyol compound. Examples of commercially available siloxane-containing polyol compounds include Silaplane FM-DA11, Silaplane FM-DA21, and Silaplane FM-DA26 (all manufactured by Chisso Corporation).
A siloxane containing polyol compound can be used individually or in combination of 2 types or more, respectively.

The fluorine-containing polyol compound used for production of the polymer (A) will be described below.
The fluorine-containing polyol compound is not particularly limited as long as it has two or more hydroxy groups and fluoroethylene.
In the present invention, two carbon atoms in fluoroethylene constitute the main chain of the fluorine-containing polyol compound.
The _{fluoroethylene, -CFH-CH 2 -, -} CF 2 -CH 2 -, - CF 2 -CFH -, - CF 2 -CF 2 - is.
Fluorine fluoroethylene-containing polyol compound in one _{molecule, -CFH-CH 2 -, -} CF 2 -CH 2 -, - CF 2 -CFH- and -CF ₂ -CF ₂ -, at least one selected from the group consisting of Is selected.
The number of hydroxy groups contained in one molecule of the fluorine-containing polyol compound is preferably 2 or more, and preferably 2 to 4 from the viewpoint that the product is difficult to gel when the polymer (A) is produced. More preferably, the number is ~ 3.
The number of fluoroethylenes contained in one molecule of the fluorine-containing polyol compound is preferably 230 to 270, more preferably 270.

  In the fluorine-containing polyol compound, the structure other than having two or more hydroxy groups and having fluoroethylene is not particularly limited. Examples of the structure other than having two or more hydroxy groups and having fluoroethylene include, for example, at least one selected from the group consisting of a urethane bond, an ether bond, an ester bond, a carboxy group, a chlorine atom, a bromine atom, and a fluorine atom. The hydrocarbon group which has is mentioned.

  As a fluorine-containing polyol compound, the compound represented by following formula (4) is mentioned, for example.

In the formula, A represents a hydroxy group or R ⁶ —NH—COO—, R ⁶ represents a hydrocarbon group, X represents a fluorine atom or a chlorine atom, and R ² and R ³ each independently represents an alkyl group. , R ⁴ and R ⁵ each independently represents an alkylene group, and p is an integer of 40 to 52.
The alkyl group as R ² and R ³ , the alkylene group as R ⁴ and R ⁵ , and the hydrocarbon group as R ⁶ are not particularly limited.

  The number average molecular weight of the fluorine-containing polyol compound is preferably 25,000 to 32,000, and more preferably 28,000 to 30,000 in view of the necessity of the film strength of the conductive composition.

The method for producing the fluorine-containing polyol compound is not particularly limited.
When the fluorine-containing polyol compound has two hydroxy groups, for example, a method of reacting a fluorine-containing polyol compound having three or more hydroxy groups as a raw material with a monoisocyanate compound under conditions of 80 ° C. and 12 hours can be mentioned. It is done.
The fluorine-containing polyol compound having 3 or more hydroxy groups used in the preparation of the fluorine-containing polyol compound is not particularly limited.
As a commercial item of the fluorine-containing polyol compound which has 3 or more of hydroxyl groups, Lumiflon (made by Asahi Glass Co., Ltd.) is mentioned, for example.
The monoisocyanate compound used in the preparation of the fluorine-containing polyol compound is not particularly limited as long as it is a compound having one isocyanate group. For example, it consists of at least one diisocyanate selected from the group consisting of tolylene diisocyanate (TDI) and isophorone diisocyanate (IPDI), isopropyl alcohol (IPA), 2-ethylhexanol (2-EH) and butyl alcohol (BA). Examples thereof include those obtained by reacting at least one alcohol selected from the group using equimolar amounts at about 80 ° C. for about 12 hours.
The alcohol used in preparing the monoisocyanate compound is one of the preferred embodiments having a boiling point of 80 ° C. or higher.
A fluorine-containing polyol compound can be used individually or in combination of 2 types or more, respectively.

The compound having two or more functional groups that react with the hydroxy group used in the production of the polymer (A) will be described below.
Examples of the compound having two or more functional groups that react with a hydroxy group include polyisocyanate compounds and polycarboxylic acids. These may be used alone or in combination of two or more. Among these, a polyisocyanate compound is preferable because the reaction for preparing the polymer is fast and simple, and the strength of the polymer (A) is increased. The compound having two or more functional groups that react with the hydroxy group may have a total of two or more functional groups that react with different types of hydroxy groups in one molecule.

  As said polyisocyanate compound, the various thing used for manufacture of a normal polyurethane can be used. Specifically, for example, TDI such as 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate; MDI such as diphenylmethane-4,4′-diisocyanate; tetramethylxylylene diisocyanate (TMXDI), trimethylhexamethylene Diisocyanate (TMHMDI), 1,5-naphthalene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI), triphenylmethane triisocyanate, norbornane skeleton And diisocyanate (NBDI) having a modified form thereof, and modified products thereof. These may be used alone or in combination of two or more.

  The polycarboxylic acid is not particularly limited as long as it is a compound having two or more carboxy groups, and examples thereof include terephthalic acid, isophthalic acid, phthalic anhydride, succinic acid, adipic acid, azelaic acid, and sebacic acid.

  The ratio of mixing the polyol and the compound having two or more functional groups that react with the hydroxy group in the production of the polymer (A) is 2 functional groups that react with the hydroxy group with respect to the number of hydroxy groups of the polyol. The ratio of the number of functional groups that react with the hydroxy group of the compound having at least one (functional group that reacts with hydroxy group / hydroxy group) is preferably 0.5 / 1 to 1.2 / 1, 0.8 More preferably, the ratio is / 1 to 2/1.

  The production of the polymer (A) can be performed, for example, in the same manner as a normal urethane prepolymer, and the above-described polyols and polyisocyanate compounds in a predetermined amount ratio are mixed and at normal temperature to 100 ° C. under normal pressure. This can be done by heating and stirring.

  The mass ratio of the polyester polyol to the siloxane-containing polyol compound and / or the fluorine-containing polyol compound in producing the polymer (A) is 30 because it is excellent in adhesion to a PET film and antifouling property. / 70 to 80/20 is preferable, and 40/60 to 70/30 is more preferable.

  The weight average molecular weight of the polymer (A) is preferably 10,000 to 200,000 from the viewpoint of the miscibility with the conductive polymer (B) and the film strength of the conductive composition, and preferably 30,000 to 100 More preferably, it is 1,000.

Next, the conductive polymer (B) will be described.
The conductive polymer (B) is not particularly limited. Specific examples include polyaniline, polypyrrole, polythiophene, poly (p-phenylene), poly (p-phenylene vinylene), and derivatives thereof. These may be used alone or in combination of two or more. Among these conductive polymers, polyanilines are preferable from the viewpoint of versatility and economy.

  The polyaniline is a polyaniline, a polyaniline derivative, or a mixture thereof, and specifically, a polymer of a compound represented by the following formula (5) is preferably exemplified.

In said formula (5), q represents the integer of 0-5.
R ⁷ is a hydrogen atom, alkyl group, alkenyl group, alkoxy group, alkanoyl group, alkylthio group, aryloxy group, alkylsulfinyl group, alkylthioalkyl group, aryl group, alkylaryl group, arylalkyl group, alkoxyalkyl group, alkyl A sulfonyl group, a carboxy group, a halogen group, a cyano group, a haloalkyl group, a nitroalkyl group or a cyanoalkyl group, preferably a hydrogen atom or an alkyl group. A plurality of R ⁷ may be the same or different.

Specific examples of the compound represented by the formula (5) include aniline, o-toluidine, m-toluidine, o-ethylaniline, m-ethylaniline, o-ethoxyaniline, m-butylaniline, m-hexylaniline, m-octylaniline, 2,3-dimethylaniline, 2,5-dimethylaniline, 2,5-dimethoxyaniline, o-cyanoaniline, 2,5-dichloroaniline, 2-bromoaniline, 5- Examples include chloro-2-methoxyaniline and 3-phenoxyaniline.
The polyaniline may be a polymer using one of these monomers, or may be a copolymer using two or more. In addition to the above monomers, other monomers may be used in the polyanilines as long as the object of the present invention is not impaired.

  Specific examples of the polyanilines include polyaniline, poly (methylaniline), poly (dimethylaniline), poly (ethylaniline), and poly (aniline sulfonic acid). These may be used alone or in combination of two or more.

  The polyaniline is preferably a polyaniline that is doped with a dopant during synthesis. Such polyanilines are excellent in the mixing property with the polymer (A) as compared with those doped after the synthesis.

The weight average molecular weight when the conductive polymer (B) is not dope-bonded is preferably more than 10,000 from the viewpoint of reducing the electric resistance.
The weight average molecular weight when the conductive polymer (B) is not doped is 10,000 to 1,000,000 because the electric resistance can be lowered and the mixing property with the polymer (A) is excellent. 000 is preferable, and 50,000 to 300,000 is more preferable from the viewpoint of excellent balance between conductivity and mixing property.

  The manufacturing method of the said conductive polymer (B) is not specifically limited, A well-known manufacturing method can be used. In the case of producing polyanilines, it is generally considered that polymerization is preferably carried out for a long time (about 48 hours) at a very low temperature (−10 ° C. or lower). In addition, aniline is polymerized when polymerized in a system containing an anionic surfactant even at a relatively high temperature of 0 ° C. to room temperature, and polyaniline having a molecular weight of 20,000 to 1,000,000 can be synthesized. Furthermore, you may use the method of synthesize | combining by combining low temperature and long-time superposition | polymerization, and an anionic surfactant.

  Moreover, it is preferable that the said conductive polymer (B) superposes | polymerizes the said monomer in presence of a dopant from the point which can improve the electroconductivity of the conductive polymer obtained. It is also possible to dope by adding a dopant to an undoped conductive polymer.

  In the present invention, it is preferable to use a material containing sulfosuccinic acid as the dopant because the compatibility with the polymer (A) is increased and the adhesion to the PET film and the transparency are increased. The sulfosuccinic acid is a compound represented by the following formula (6).

In said formula (6), R < ⁸ > and R < ⁹ > are respectively an alkyl group, and a C4-C20 alkyl group is preferable and a C6-C12 alkyl group is more preferable from availability.

  As said sulfosuccinic acid, what is marketed in the form of sulfosuccinate (for example, sodium salt) can also be used.

Examples of dopants other than sulfosuccinic acid include halogen compounds such as iodine, bromine, chlorine, and iodine; proton acids such as sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, and borohydrofluoric acid; various salts of these protonic acids; Lewis acids such as aluminum, iron trichloride, molybdenum chloride, antimony chloride, arsenic pentafluoride, antimony pentafluoride; organic carboxylic acids such as acetic acid, trifluoroacetic acid, polyethylene carboxylic acid, formic acid, benzoic acid; these organic carboxylic acids Phenols such as phenol, nitrophenol and cyanophenol; various salts of these phenols; benzenesulfonic acid, p-toluenesulfonic acid, polyethylenesulfonic acid, p-dodecylbenzenesulfonic acid, alkylnaphthalenesulfonic acid, anthraquinone Sulfonic acid, alkylsulfonic acid Organic sulfonic acids such as dodecyl sulfonic acid, camphor sulfonic acid, copper phthalocyanine tetrasulfonic acid, porphyrin tetrasulfonic acid, polystyrene sulfonic acid, polyvinyl sulfonic acid, naphthalene sulfonic acid condensate; various salts of these organic sulfonic acids; polyacrylic acid, etc. High molecular acid; propyl phosphate ester, butyl phosphate ester, hexyl phosphate ester, phosphate ester such as polyethylene oxide dodecyl ether phosphate ester, polyethylene oxide alkyl ether phosphate ester; various salts of these phosphate esters; lauryl sulfate ester Sulfates such as cetyl sulfate, stearyl sulfate, and lauryl ether sulfate; and various salts of these sulfates. These may be used alone or in combination of two or more.
From the viewpoint of excellent mixing of the conductive polymer (B) and the polymer (A), the dopant preferably contains 100 mol% of sulfosuccinic acid.

  In addition, the above-mentioned dopant includes sulfosuccinic acid, alkylbenzenesulfonic acid and / or alkylnaphthalenesulfonic acid from the viewpoint of excellent mixing of the conductive polymer (B) and the polymer (A) and lowering electric resistance. One of the preferred embodiments is included. The molar ratio of sulfosuccinic acid to alkylbenzene sulfonic acid and / or alkyl naphthalene sulfonic acid (total of sulfo succinic acid / alkyl benzene sulfonic acid and alkyl naphthalene sulfonic acid) at the time of addition of the dopant is determined between the conductive polymer (B) and the polymer (A 10/90 to 90/10, more preferably 20/80 to 80/20, and more preferably 30/70 to 50/50. More preferably.

  The alkylbenzenesulfonic acid is a compound represented by the following formula (7), and the alkylnaphthalenesulfonic acid is a compound represented by the following formula (8).

In the above formula (7), R ¹⁰ is an alkyl group having 1 to 20 carbon atoms, in general are commercially available alkyl benzene sulfonic acids and their salts having an alkyl group of 10 to 14 carbon atoms. The most common dodecyl group is more preferable from the viewpoint of price. Although dodecylbenzenesulfonic acid has a linear type and a branched type, both can be used in the same manner.
In the formula (8), R ¹¹ is an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 2 to 12 carbon atoms, more alkyl groups having 4 to 12 carbon atoms because it is easily available preferable. Usually, it is handled in the form of a salt on the market and can be used in the same manner.

  The content of the dopant is such that the molar ratio of the structural unit of the conductive polymer (B) to the dopant (the structural unit of the conductive polymer (B) / dopant) is 100/20 to 100/200. It is preferable that the amount is 100/40 to 100/100, and more preferable. When the content of the dopant is within this range, the conductivity is excellent (resistance value is small) and the mixing property with the polymer (A) is excellent.

  The mass ratio of the polymer (A) and the conductive polymer (B) in the composition of the present invention is 85/15 to 20/80. Within this range, antistatic properties and adhesion to PET film, antifouling properties and transparency can be satisfied in a well-balanced manner. From the point which is excellent by these characteristics, it is preferable that mass ratio of a polymer (A) and a conductive polymer (B) is 80 / 20-50 / 50, and it is 75 / 25-60 / 40. More preferred.

  The composition of the present invention preferably further contains a solvent from the viewpoint that viscosity can be lowered and workability can be improved. Solvents include toluene, methyl ethyl ketone (MEK), acetone, methanol, ethanol, isopropanol, toluene, xylene, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP) Etc. These may be used alone or in combination of two or more. Among these, toluene is preferable from the viewpoint of excellent mixing and volatility with other components.

The amount of the solvent can be freely set in order to obtain an optimum film thickness depending on the workability at the time of applying the paint and the performance (resistance value, strength, etc.) of the coating film.
It is preferable that content of a solvent is 100-100,000 mass parts with respect to 100 mass parts of polymers (A).

  The composition of the present invention is, as necessary, a filler, a reaction retardant, an anti-aging agent, an antioxidant, a pigment (dye), a plasticizer, a thixotropic agent, as long as the object of the present invention is not impaired. Various additives such as an ultraviolet absorber, a flame retardant, a surfactant, a dispersant, a dehydrating agent, and an adhesion-imparting agent can be contained.

  Examples of the filler include organic or inorganic fillers having various shapes. Specifically, for example, fumed silica, calcined silica, precipitated silica, ground silica, fused silica; diatomaceous earth; iron oxide, zinc oxide, titanium oxide, barium oxide, magnesium oxide; calcium carbonate, magnesium carbonate, zinc carbonate; Waxite clay, kaolin clay, calcined clay; carbon black; these fatty acid treated products, resin acid treated products, urethane compound treated products, and fatty acid ester treated products.

Specific examples of the anti-aging agent include hindered phenol compounds.
Specific examples of the antioxidant include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA).

  Specific examples of the pigment include inorganic pigments such as titanium oxide, zinc oxide, ultramarine, bengara, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride, sulfate, etc .; azo pigment, phthalocyanine pigment, quinacridone Pigment, quinacridone quinone pigment, dioxazine pigment, anthrapyrimidine pigment, anthanthrone pigment, indanthrone pigment, flavanthrone pigment, perylene pigment, perinone pigment, diketopyrrolopyrrole pigment, quinonaphthalone pigment, anthraquinone pigment, thioindigo pigment, benzimidazolone Examples thereof include organic pigments such as pigments, isoindoline pigments, and carbon black.

  Specific examples of the plasticizer include dioctyl phthalate (DOP) and dibutyl phthalate (DBP); dioctyl adipate, isodecyl succinate; diethylene glycol dibenzoate, pentaerythritol ester; butyl oleate, methyl acetylricinoleate; phosphorus Examples include tricresyl acid, trioctyl phosphate; propylene glycol polyester adipate, butylene glycol polyester adipate, and the like.

Specific examples of the thixotropic agent include Aerosil (manufactured by Nippon Aerosil Co., Ltd.), Dispalon (manufactured by Enomoto Kasei Co., Ltd.), and the like.
Specific examples of the adhesion-imparting agent include terpene resins, phenol resins, terpene-phenol resins, rosin resins, xylene resins, and the like.

  Specific examples of the flame retardant include chloroalkyl phosphate, dimethyl / methyl phosphonate, bromine / phosphorus compound, ammonium polyphosphate, neopentyl bromide-polyether, brominated polyether, and the like.

Although the manufacturing method of the composition of this invention is not specifically limited, For example, it can carry out as follows.
First, an aniline monomer, the above-mentioned dopant, water and hydrochloric acid are added to a reaction vessel, and after cooling to about 0 ° C., an appropriate chemical oxidation polymerization catalyst is added and held for several hours, and polyaniline doped with a dopant (dope-doped) Polyaniline). Methanol is added thereto, and the filtered residue is sufficiently mixed with the polymer (A) and the solvent in a suitable mixing mixer to obtain the composition of the present invention.

The surface resistance of the coating film obtained from the composition of the present invention is not particularly limited, but is preferably 1 × 10 ^{4 to} 9.9 × 10 ¹¹ Ω / □, and 1 × 10 ^{7 to} 9 × 10 ⁹ Ω. More preferably, it is / □.
The said surface resistance means the surface resistance measured using the resistance measuring device (Dia Instruments company make, Hiresta IP and HR probe).

Since the composition of the present invention described above has a polyester skeleton, a polysiloxane skeleton and / or a fluororesin skeleton in the polymer (A), the polyester and the polysiloxane and / or the fluororesin are not phase separated. The haze of the resulting coating can be reduced. Further, the coating is excellent in adhesion to PET film, antistatic property and antifouling property.
The conductive composition of the present invention can be used for various applications such as adhesives and coding agents, but is particularly useful as an antistatic coating.

Hereinafter, a suitable example of the protective film of the present invention will be described in detail.
The protective film of the present invention is a protective film having a base material, a layer obtained by laminating the composition of the present invention on one surface of the base material, and an adhesive layer formed on the other surface of the base material. is there.

  Although the said base material is not specifically limited, A transparent film is more preferable. Specific examples include films of polyester, nylon, polyolefin, and the like. Among these, a polyester film is preferable from the viewpoint of excellent adhesion to the antistatic layer, and a polyethylene terephthalate film (PET film) is more preferable.

  Although the thickness of a base material is not specifically limited, 1-100 micrometers is preferable and 10-50 micrometers is more preferable.

  The method for laminating the composition of the present invention is not particularly limited. For example, after applying by gravure printing, screen printing, brush coating method, spray coating method, wire bar method, blade method, roll coating method, dipping method, etc. The method of drying and laminating | stacking is mentioned. Also, a two-layer extrusion method with a base material, a sandwich method by injection molding, heat fusion of two films, and the like can be employed.

  The thickness of the layer obtained by laminating the composition of the present invention on one surface of the substrate (hereinafter referred to as “antifouling / antistatic layer”) is not particularly limited, but is 0.01 μm to 2 mm. The thickness is preferably 0.05 μm to 0.5 μm from the viewpoint of price and production speed.

The antifouling / antistatic layer preferably has a contact angle of 80 ° or more from the viewpoint of antifouling properties. In addition, from the viewpoint of antistatic properties, the surface resistance is preferably 10 ¹¹ Ω / □ or less. From the viewpoint of transparency, the total light transmittance is preferably 80% or more, and the haze is preferably 5 or less. However, the measurement conditions and methods of each characteristic are the same as the evaluation methods of the examples described later.

The pressure-sensitive adhesive layer is the same as the pressure-sensitive adhesive layer of a known protective film, and is provided on the surface opposite to the surface of the base material on which the antifouling / antistatic layer is formed, that is, on the surface side in contact with the protected member. .
For the adhesive layer, an acrylic adhesive, a rubber adhesive, a silicone adhesive, or the like can be used, but an acrylic adhesive is preferred from the viewpoint of heat resistance and economy.
The pressure-sensitive adhesive layer can be formed by, for example, the coating method described above after dissolving the pressure-sensitive adhesive as described above in an organic solvent.

The protective film of the present invention described above has a layer having both antifouling properties and antistatic properties on the base material, so that the protective film has an antistatic layer and an antifouling layer on the base material. The number of layers can be reduced. Therefore, it can be manufactured easily and inexpensively.
In addition, since the protective film of the present invention uses the conductive composition of the present invention, the protective film has excellent adhesion, antistatic properties and antifouling properties between the substrate and the antifouling / antistatic layer, and has high transparency.

  The protective film of this invention is not limited to embodiment mentioned above, A various improvement can be added. For example, it is preferable that a release film is attached to the surface of the pressure-sensitive adhesive layer to prevent dust and dirt from adhering to the protective film and facilitate storage.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
<Synthesis of polymer (A)>
(Synthesis Examples 1-8)
Each component shown in the following Table 1 is put in a proportion (part by mass) shown in Table 1 in a reaction vessel equipped with a stirrer, a condenser, and a thermometer, and each polymer is reacted at 80 ° C. for 6 hours. Produced.

Each component in Table 1 is as follows.
Polyester diol 1: Adeka New Ace Y9-10, manufactured by Adeka Corporation, polyol component neopentyl glycol, acid component adipic acid, number average molecular weight 1000
Polyester diol 2: Adeka New Ace F9-30, manufactured by Adeka, polyol component 1,4-butanediol, acid component adipic acid, number average molecular weight 2000
Siloxane-containing polyol compound 1: Silaplane FM4411, manufactured by Chisso Corporation, compound represented by the above formula (2), number average molecular weight 1000
Siloxane-containing polyol compound 2: Silaplane DA21, manufactured by Chisso Corporation, compound represented by the above formula (3), number average molecular weight 5000
Fluorine-containing polyol compound: Lumiflon LF200, manufactured by Asahi Glass Co., Ltd., number average molecular weight 10,000
-Tolylene diisocyanate: TDI80, manufactured by Mitsui Takeda Chemical Co., Ltd.-Bismuth octylate: Pucat 25, manufactured by Nippon Chemical Industry Co., Ltd., solid content 25% by mass

<Synthesis of polyaniline>
(Synthesis Example 9)
1 part by mass of aniline, sodium di-2-ethylhexylsulfosuccinate (Ripal 870P, manufactured by Lion Akzo, solid content of 70% by mass), 2.4 parts by mass, 1.7 mass of dodecylbenzenesulfonic acid (reagent, manufactured by Kanto Chemical Co., Inc.) And 50 parts by weight of distilled water were mixed. Next, 1.8 parts by mass of 6N hydrochloric acid was added to the mixture.
After cooling this mixed liquid to 0 ° C., 2.7 parts by mass of ammonium persulfate was added as an oxidizing agent, and oxidative polymerization was performed for 10 hours.
Thereafter, methanol was added to precipitate polyaniline, and the solid obtained by filtration was washed with a large amount of distilled water to remove excess sulfosuccinic acid, dodecylbenzenesulfonic acid, and ammonium persulfate residue, And dried in vacuo to obtain polyaniline. The obtained polyaniline was dispersed in toluene to obtain a toluene dispersion containing 5% by mass of polyaniline doped with sulfosuccinic acid and dodecylbenzenesulfonic acid. This is designated as polyaniline dispersion of Synthesis Example 9. The solid content in this polyaniline dispersion is 5% by mass, and the mass ratio of sulfosuccinic acid to dodecylbenzenesulfonic acid is 1/1.
At the end of filtration, a part of polyaniline was taken, dedoped with ammonia water, dissolved in NMP, and the weight average molecular weight was measured by GPC. The weight average molecular weight of the obtained polyaniline was 70,000. .

(Synthesis Example 10)
Polyaniline was synthesized in the same manner as in Synthesis Example 9 except that only 3.3 parts by mass of dodecylbenzenesulfonic acid (reagent, manufactured by Kanto Chemical Co., Inc.) was used as a dopant.
When the weight average molecular weight of polyaniline was measured in the same manner as in Synthesis Example 9, the weight average molecular weight of the obtained polyaniline was 180,000.

<Preparation and Evaluation of Conductive Composition>
(Examples 1-11 and Comparative Examples 1-2)
Each component shown in the following Table 2 was mixed at a ratio (parts by mass) shown in Table 2 for 5 minutes using a homogenizer to obtain each composition shown in Table 2.

Next, the obtained composition was applied onto a PET film (thickness 25 μm) using a spin coater, and then dried in an oven at 100 ° C. for 1 minute to give an antifouling / antistatic material having a thickness of 0.5 μm. A protective film was obtained by forming a layer.
About each obtained protective film, the following method evaluated surface resistance, the adhesiveness with respect to PET film, a contact angle, total light transmittance, and Haze. The results are shown in Table 2.

(Surface resistance)
About the obtained protective film, the surface resistance of the antifouling / antistatic layer at 100 V was determined under the conditions of 25 ° C. and 50% RH using a resistance measuring instrument (Dia Instruments, Hiresta IP and HR probe).

(Adhesiveness)
Make 100 mm (10 × 10) of 1 mm substrate on the antifouling / antistatic layer of the protective film, and attach cellophane adhesive tape (width 18 mm) completely on the substrate, and immediately keep one end of the tape at right angle. Then, the number of base eyes that were left apart without being completely peeled off was examined.

(Contact angle)
On the obtained protective film, a 1 μm ³ water droplet was dropped with a contact angle meter (manufactured by Excimer), and the contact angle of water was measured.

(Total light transmittance / haze)
About the obtained protective film, the total light transmittance and haze were calculated | required with the haze meter (the Murakami Color Research Laboratory company make, HM-150).

(Comparative Example 3)
100 g of siloxane-containing polyol having a methacryloxy group (Silaplane FM-0711, manufactured by Chisso, number average molecular weight 1000) and 100 g of methyl methacrylate (reagent, manufactured by Aldrich) are mixed so that the solid content becomes 10% by mass. Diluted with toluene. To this mixture, 0.1 g of ammonium persulfate was added and reacted at 80 ° C. for 4 hours to obtain a polymer in which silicone was grafted onto the acrylic skeleton. Further, 50 g of the polymer solution obtained and 50 g of a polyester resin (Byron 200, manufactured by Toyobo Co., Ltd.) dissolved in MEK at a solid content of 10% were mixed. To 100 g of this mixture, 85.7 g of the polyaniline dispersion of Synthesis Example 9 was added to produce an antistatic coating.
The obtained antistatic coating was applied onto a PET film (thickness 25 μm) using a spin coater and then dried in an oven at 100 ° C. for 1 minute to form a 0.5 μm thick protective film. Got.
When the physical properties of the obtained protective film were measured by the above method, the surface resistance was 2.5E + 08Ω / □, the adhesion to the PET film was 100/100, the contact angle was 89 degrees, the total light transmittance was 75%, Haze was 10.5.

  As is apparent from the results shown in Table 2 above, Comparative Example 1 having a large proportion of the polymer (A) had a low surface charge resistance due to a large surface resistance. Moreover, the comparative example 2 with a small ratio of a polymer (A) had low adhesiveness with respect to a PET film. Further, in Comparative Example 3, the compatibility between the silicone-containing acrylic resin and the polyester resin was not good, so that the transparency of the paint was lowered and the haze was increased. On the other hand, in Examples 1 to 11, the surface resistance was low, the adhesiveness to the PET film was excellent, the contact angle was high, the total light transmittance was high, and the haze was small.

Claims (7)

A polymer (A) having a polyester skeleton, a polysiloxane skeleton and / or a fluororesin skeleton, and a conductive polymer (B),
The conductive composition whose mass ratio of the said polymer (A) and the said conductive polymer (B) is 85/15-20/80. The polymer (A) contains 10 mol% or more of a repeating unit represented by the following formula (1), and the conductive polymer (B) is doped by a dopant containing sulfosuccinic acid. The electroconductive composition as described in.

  The polymer (A) is a polymer obtained by reacting at least a polyester polyol, a siloxane-containing polyol compound and / or a fluorine-containing polyol compound, and a compound having two or more functional groups that react with a hydroxy group. The conductive composition according to claim 1 or 2.   The electrically conductive composition according to claim 3, wherein a mass ratio of the polyester polyol to the siloxane-containing polyol compound and / or the fluorine-containing polyol compound is 30/70 to 80/20.   The conductive composition according to claim 3 or 4, wherein the siloxane-containing polyol compound is a siloxane-containing diol compound having two hydroxy groups at one end.   An antistatic paint comprising the conductive composition according to claim 1.   The protective film which has a base material and the layer obtained by laminating | stacking the electroconductive composition in any one of Claims 1-5 on one surface of the said base material at least.