TWI518154B - A thermosetting type conductive coating composition, an optical film, and a protective film - Google Patents

Description

Thermosetting conductive coating composition, optical film and protective film

The present invention relates to a thermosetting conductive coating composition and an optical film and a protective film obtained by using the thermosetting conductive coating composition.

In an optical film constituting a flat panel of a liquid crystal television, a plasma television, an electroluminescence display, or a solar cell, a coating (antistatic layer) having an antistatic function may be provided in order to eliminate malfunction such as electrostatic damage.

For example, in the manufacturing step or the transporting step of the flat panel display, in order to prevent damage to the surface of the panel, adhesion of dirt or dust, the surface is bonded to form a protective film of an optical film. The protective film has an adhesive layer on one side of a resin substrate such as PET, and the user adheres the adhesive layer side to the display, and the user protects the resin from damage due to static electricity caused by peeling off the film. An antistatic layer is formed on the surface on the opposite side of the layer side.

In the past, in addition to the antistatic function, the antistatic layer is required to prevent scratch resistance due to damage, antifouling property for preventing adhesion of the adhesive at the time of cutting, and wiping off the adhered adhesive. In recent years, in addition to these characteristics, in order to print a lot number or the like on a protective film, characteristics such as printing adhesion of an oil-based ink are also required. Further, the demand for cost reduction is also increased, and it is required to form a film which satisfies the above characteristics with one coat layer.

As the material for forming such an antistatic layer, a conductive coating material containing a conductive polymer is used.

Patent Document 1 discloses a conductive polymer composition for forming an antistatic layer. The conductive polymer composition contains a composition of a polythiophene-based conductive polymer and a polyester binder, and can form an antistatic layer excellent in adhesion on a resin substrate by drying at 100 ° C for about 1 minute. . However, since it is a solvent-drying type composition, the formed antistatic layer is insufficient in scratch resistance and solvent resistance, and in order to secure these characteristics, it is necessary to laminate an overcoat layer on the antistatic layer to One layer of coating does not meet all of the above properties.

Patent Document 2 discloses a composition comprising a conductive polymer and a water-soluble polyether modified polyfluorene oxide, and discloses that a film having excellent lubricity can be formed by adding a polyfluorene modified by a polyether having a side chain. However, there is no mention of scratch resistance and printability, and a conductive composition containing a polyether modified by a polyether having a side chain cannot satisfy scratch resistance and printability at the same time.

Patent Document 3 discloses that a composition composed of a resin having active hydrogen and a polyurethane resin, a polyisocyanate, and an antistatic agent containing polyoxyalkylene can be used to form a surface resistivity and a resistance by one coating layer. Solvent-based, scratch-resistant, and printable antistatic layer, but this composition is insufficient in terms of printing adhesion, and when it is formed into an antistatic layer, it needs to be aged at 40 ° C for 48 hours, so productivity is better. Low, not suitable for mass production.

Patent Document 4 discloses a composition containing an organosiloxane having a reactive functional group such as a hydroxyl group at the terminal, and discloses a film formed using the composition while achieving antifouling property (higher contact angle with water) and Printing adhesion of specific inks. However, the hardening of the composition requires a condition of 140 ° C for 2 minutes, so that the productivity is low and it is not suitable for mass production.

Patent Document 5 discloses a composition containing a conductive polymer, a melamine resin derivative, and an acid catalyst, and discloses that by using the composition, an antistatic function can be formed at a low temperature of about 1 minute at 100 ° C. A film that is resistant to scratches, solvents, and stains. However, the film formed using the composition cannot simultaneously achieve printability, print adhesion, and scratch resistance.

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2002-060736

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2007-308549

[Patent Document 3] Japanese Laid-Open Patent Publication No. 2006-178424

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2009-107329

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2009-138042

As described above, in the case where the conductive coating is formed of a single layer coating on the conductive composition previously proposed, scratch resistance, solvent resistance, printability, and printing cannot be formed under low-temperature curing conditions for a short period of time. A conductive film excellent in adhesion.

In particular, scratch resistance, printability, and print adhesion generally have a trade-off relationship, and it is difficult to satisfy both of them at the same time.

The present inventors have diligently studied to solve the above problems, and as a result, found that the conductive polymer (a), the melamine resin derivative (b), the sulfonic acid hardening catalyst (c), and the two-end polyether modified polyoxyl (d) The conductive enhancer (e), and the conductive composition of the solvent or dispersion medium (f) can form scratch resistance, solvent resistance, printability, and print density by thermal hardening at a low temperature for a short period of time. The conductive film excellent in compatibility is completed to complete the present invention.

That is, the thermosetting conductive coating composition of the present invention contains:

(a) a conductive polymer,

(b) a melamine resin derivative,

(c) sulfonic acid hardening catalyst,

(d) Two-end polyether modified polyfluorene,

(e) a conductivity enhancer, and

(f) solvent or dispersion medium.

Further, in the thermosetting conductive coating composition of the present invention, it is preferred that the conductive polymer (a) is a poly(3,4-dialkoxy group) having a repeating structure of the following formula (I). a complex of a thiophene) or a poly(3,4-alkylenedioxythiophene) with a dopant,

(Wherein, R ¹ is and R ² each independently represents a hydrogen atom or a C _1-4 alkyl group, or together represent may be substituted with the C _1-4 alkylene group).

Moreover, in the thermosetting conductive coating composition, the content of the melamine resin derivative (b) is preferably 150 to 750 parts by weight based on 100 parts by weight of the conductive polymer.

Further, in the thermosetting conductive coating composition, the sulfonic acid curing catalyst (c) is preferably an aromatic sulfonic acid, and the content thereof is 8 to 40 by weight based on 100 parts by weight of the melamine resin derivative. Share.

Further, in the thermosetting conductive coating composition, the content of the both-end polyether modified polyfluorene (d) is preferably 10 to 60 parts by weight based on 100 parts by weight of the melamine resin derivative.

Moreover, in the thermosetting conductive coating composition, the conductive enhancer (e) preferably has at least one substituent selected from the group consisting of a mercapto group, a sulfo group and a hydroxyl group.

It is preferable that the thermosetting conductive coating composition further contains (g) a water-soluble antioxidant, and the water-soluble antioxidant (g) is preferably ascorbic acid or isoascorbic acid.

It is preferable that the thermosetting conductive coating composition further contains (h) a wetness improving agent.

It is preferable that the thermosetting conductive coating composition further contains (i) an antifoaming agent, and the antifoaming agent (i) is preferably a polyoxymethylene emulsion.

The optical film of the present invention is composed of a substrate and a conductive film laminated on the substrate, and the conductive film is formed using the thermosetting conductive coating composition of the present invention.

In the above-mentioned optical film, it is preferable that the conductive film is applied to the substrate by applying the thermosetting conductive coating composition, and dried and thermally cured at a temperature of 130 ° C or lower. . Further, it is preferable that the calculated film thickness of the conductive film is less than 45 nm.

The protective film of the present invention is composed of the optical film of the present invention.

According to the thermosetting conductive coating composition of the present invention, it can be formed by heat treatment (drying or thermal curing) at a low temperature for a short period of time while satisfying scratch resistance, solvent resistance, printability, and printing adhesion. Conductive film.

Moreover, by using the above-mentioned thermosetting conductive coating composition, it is possible to form a conductive film which satisfies both excellent scratch resistance and excellent printability and printing adhesion.

Moreover, the optical film of the present invention is provided with a conductive film which is obtained by applying the thermosetting conductive coating composition of the present invention to a substrate and curing it, thereby having excellent conductivity. Moreover, it is excellent in scratch resistance, solvent resistance, printability, and printing adhesiveness.

Further, the optical film of the present invention is extremely suitable as a protective film, and the protective film composed of the above optical film is also one of the inventions.

First, the thermosetting conductive coating composition of the present invention will be described.

The thermosetting conductive coating composition of the present invention (hereinafter also referred to simply as "conductive composition") contains (a) a conductive polymer, (b) a melamine resin derivative, and (c) a sulfonic acid hardening catalyst. And (d) a polyether modified polyfluorene at both ends, (e) a conductivity enhancer, and (f) a solvent or a dispersion medium.

Hereinafter, each formulation will be described in order.

1. Conductive polymer (a)

The conductive polymer (a) is a formulation for imparting conductivity to the formed conductive film (coating).

Examples of the conductive polymer include polythiophene, polypyrrole, polyaniline, polyacetylene, polyphenylacetylene, polynaphthalene, derivatives thereof, and the like, and a composite thereof.

Among these, a polythiophene-based conductive polymer composed of a composite of polythiophene and a dopant is preferable, and a polythiophene-based conductive polymer is more preferably a poly(3,4-dialkoxy group). A complex of thiophene) or poly(3,4-alkylenedioxythiophene) with a dopant.

The above poly(3,4-dialkoxythiophene) or poly(3,4-alkylenedioxythiophene) is preferably a cationic form composed of repeating structural units represented by the following formula (I). Thiophene,

Here, R ¹ and R ² each independently represents a hydrogen atom or a C _1-4 alkyl group, or together represent may be substituted with the C _1-4 alkylene group.

Examples of the alkyl group of the above C _1-4 include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a second butyl group, and a third butyl group.

Further, R ¹ and R ² may be substituted by a C _1-4 alkylene group which may be substituted, and examples thereof include a methylene group, a 1,2-extended ethyl group, a 1,3-propanyl group, and 1, 4-tert-butyl, 1-methyl-1,2-extended ethyl, 1-ethyl-1,2-extended ethyl, 1-methyl-1,3-propanyl, 2-methyl- 1,3-propyl group and the like. Preferably, a methylene group, a 1,2-extended ethyl group, a 1,3-propanyl group, and more preferably a 1,2-extended ethyl group. The polythiophene having an alkylene group as described above is particularly preferably poly(3,4-ethylenedioxythiophene).

The composite composed of poly(3,4-ethylenedioxythiophene) and a dopant is extremely excellent in electrical conductivity and transparency, and is also excellent in chemical stability, and is formed using the composite as a conductive polymer. The conductive film has extremely stable conductivity independent of humidity and extremely high transparency.

Further, since the conductive composition containing the composite as a conductive polymer can form a film at a low temperature for a short period of time, it is also highly productive for producing an optical film such as a protective film which is mass-produced.

The dopant constituting the polythiophene-based conductive polymer is a polymer having an anionic form by forming an ion pair with the polythiophene to form a complex and stably dispersing the polythiophene in water.

Examples of such a dopant include carboxylic acid polymers (for example, polyacrylic acid, polymaleic acid, polymethacrylic acid, etc.), and sulfonic acid polymers (for example, polystyrenesulfonic acid, polyethylene). Sulfonic acid, polyisoprene sulfonic acid, etc.). The carboxylic acid polymers and sulfonic acid polymers may also be ethylene carboxylic acids and vinyl sulfonic acids and other polymerizable monomers, such as aromatic vinyl compounds such as acrylates, styrenes, and vinyl naphthalenes. Copolymer. Among them, polystyrenesulfonic acid is particularly preferred.

The polystyrenesulfonic acid preferably has a weight average molecular weight of more than 20,000 and not more than 500,000. More preferably, it is 40,000 to 200,000. When polystyrenesulfonic acid having a molecular weight outside this range is used, there is a case where the dispersion stability of the polythiophene-based conductive polymer with respect to water is lowered. Further, the weight average molecular weight of the above polymer is a value measured by gel permeation chromatography (GPC). An ultrahydroge 1500 column manufactured by Waters Corporation was used for the measurement.

The content of the conductive polymer is preferably from 0.01 to 1.2% by weight based on the total of the conductive composition. More preferably, it is 0.03 to 0.5% by weight. If it is less than 0.01% by weight, it is difficult to express conductivity, and if it is more than 1.2% by weight, precipitation may occur by mixing with other components.

2. Melamine resin derivative (b)

The melamine resin derivative (b) can impart a low-temperature thermosetting property to the conductive composition, and can form a film appearance, conductivity (for example, surface resistivity, hereinafter referred to as SR), and transparency (for example, total permeability). The light transmittance is hereinafter referred to as Tt and haze value, and is referred to as Haze), a conductive film excellent in adhesion to a substrate, and solvent resistance.

The above melamine resin derivative is represented, for example, by the following formula (II).

(wherein R ³ to R ⁸ represent H or CH ₂ OR ⁹ , and R ⁹ represents H or a C _1-4 alkyl group). The melamine resin derivative in which the substituents R ³ to R ⁸ are each a hydrogen atom is an imide-based melamine resin derivative; the melamine resin derivative in which the substituents R ³ to R ⁸ are both CH ₂ OH is a hydroxymethyl type melamine resin The derivative; the melamine resin derivative in which the substituents R ³ to R ⁸ are both CH ₂ OR ⁹ and R ⁹ is a C _1-4 alkyl group is a perether type melamine resin derivative.

Further, a melamine resin derivative in which two of the above three substituents are mixed in one molecule is classified into an imidomethylol type, a methylol ether type, and an imino ether type, all of which are mixed with a melamine resin. The substance is an imidohydroxymethyl ether type.

In the case where R ³ to R ⁸ represent CH ₂ OR ⁹ and R ⁹ is a C _1-4 alkyl group, a C _1-4 alkyl group may have a methyl group, an ethyl group, a propyl group, a butyl group or the like. A methyl group is preferred in view of low temperature hardenability. The above melamine resin derivative may also be an oligomer having a basic skeleton of the formula (II) and self-condensing.

These melamine resin derivatives may be used singly or in combination of two or more.

Among the melamine resin derivatives having the above-described structure, from the viewpoint of stability of the conductive composition and curability at low temperature, it is more preferably a perether type melamine, and particularly preferably a total ether type melamine in which R ⁹ is a methyl group. Further, when the melamine resin derivative is an oligomer, considering the pot life of the conductive composition, the average degree of polymerization is preferably low, and more preferably more than 1.0 is less than 1.8.

In the present specification, the application period of the conductive composition means the appearance of the conductive composition (coating liquid) (presence of precipitation), the appearance of the formed conductive film, transparency, conductivity, and Many properties such as adhesion to the substrate, scratch resistance, solvent resistance, printability, and printing adhesion can be sufficiently maintained after the preparation of the conductive composition (coating liquid).

The content of the melamine resin derivative (b) having a film appearance, conductivity, transparency, adhesion to a substrate, and solvent resistance in the conductive film which is cured at a low temperature is preferably relative to the conductive polymer ( The solid content of a) is 150 to 750 parts by weight in 100 parts by weight. More preferably, it is 250 to 450 parts by weight.

When the content exceeds 750 parts by weight, the conductivity of the film may be lowered, or the film may be whitened to lower the transparency. On the contrary, in the case of less than 150 parts by weight, it is difficult to impart sufficient solvent resistance to the film.

3. Sulfonic acid hardening catalyst (c)

The sulfonic acid hardening catalyst (c) has a function of promoting crosslinking of the melamine resin derivative (b) on the substrate during drying and hardening. Since the sulfonic acid exhibits acidity in the conductive composition, crosslinking of the melamine resin derivative in the conductive composition is promoted, and the pot life of the coating liquid is shortened.

Further, the sulfonic acid hardening catalyst also has an effect of improving the leveling property of the conductive composition on the substrate.

Therefore, the sulfonic acid hardening catalyst is preferably a structure which promotes hardening on a substrate and maintains the leveling property of the conductive composition on the substrate and the pot life of the conductive composition.

As such a sulfonic acid hardening catalyst, an aliphatic or aromatic sulfonic acid can be mentioned.

Examples of the aliphatic sulfonic acid include methanesulfonic acid, trifluoromethanesulfonic acid, isoprenesulfonic acid, camphorsulfonic acid, hexanesulfonic acid, octanesulfonic acid, sulfonic acid, sulfonic acid, and hexadecane. Sulfonic acid and the like. Further, examples of the aromatic sulfonic acid include benzenesulfonic acid, p-toluenesulfonic acid, cumenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, and decylnaphthalenesulfonic acid.

Among these, from the viewpoint of the pot life of the coating liquid and the curability at low temperature, an aromatic sulfonic acid is preferred, and a dodecyl benzene sulfonic acid is preferred.

The content of the sulfonic acid hardening catalyst is preferably 40 parts by weight, more preferably 33 parts by weight, based on 100 parts by weight of the melamine resin derivative. Further, the lower limit thereof is preferably 8 parts by weight based on 100 parts by weight of the melamine resin derivative. The reason for this is that if it is in this range, the melamine resin derivative can be hardened at a low temperature for a short period of time, and the pot life of the coating liquid can be sufficiently maintained.

On the other hand, when the content is more than 40 parts by weight, the application period of the coating liquid may not be maintained. On the other hand, if it is less than 8 parts by weight, the film formation property of the conductive composition may be deteriorated. The case of cissing is visible, or there is a case where the solvent resistance of the film is lowered.

4. Two-end polyether modified polyoxane (d)

The both-end polyether modified polyfluorene (d) has an effect of imparting scratch resistance, solvent resistance, printability, and printing adhesion to the conductive film.

In particular, in the thermosetting conductive coating composition of the present invention, the both-end polyether modified polyfluorene oxide and other components are used in combination, so that the formed conductive film can be simultaneously provided with scratch resistance and printability. And printing adhesion.

The polyether modified polyfluorene has a side chain modification type and a two-end modification type. However, in the case where only the two-end polyether is modified to form a polyfluorene oxide, the conductive film formed can be specifically formed simultaneously. Scratch resistance, printability, and printing adhesion are imparted, and this effect cannot be obtained even if a side chain polyether is used to modify polyfluorene. Moreover, this kind of insight is the newly discovered insight of the inventor of the present case.

Further, the reason why the above effects can be obtained by using the polyether modified polyether at the both ends is considered to be: (1) the directionality of the polyether modified polyfluorene on the surface of the conductive film is improved, and the performance is excellent. The result is that the scratch resistance is improved, and (2) the adhesion of the ink is improved by the polyether chains at both ends, and the printability and the printing adhesion can be imparted to a high degree.

Further, the solvent resistance is also maintained in the case where the polyether is modified by the two-end polyether. The reason for this is considered to be that since the two-end polyether modified polyfluorene is uniformly oriented on the surface, the crosslinking of the melamine resin derivative is not inhibited, so that the crosslinking density of the film does not decrease.

Examples of the above-mentioned two-terminal polyether-modified polyfluorene oxide include those represented by the following formula (III).

(wherein R ¹⁰ is a polyether group, and R ¹¹ (C ₂ H ₄ O) _a R ¹² composed of ethylene oxide, R ¹¹ (C ₃ H ₆ O) _b R ¹² composed of propylene oxide, or the like R ¹¹ (C ₂ H ₄ O) _a (C ₃ H ₆ O) _b R ^{12 is} mixed, and R ¹¹ and R ¹² in the polyether group each independently represent an alkyl group or an alkylene group). Further, the polyether groups R ¹⁰ at both ends of the above formula (III) may be the same or different.

Further, the degree of polymerization (n) of the polyoxyalkylene is preferably 380 or less, preferably 45 to 230. By forming the polyoxyalkylene having the above polymerization degree, it is possible to impart more excellent scratch resistance to the formed conductive film.

Further, in the above-mentioned conductive composition, the degree of polymerization (a and b) of the polyether group contained in R ¹⁰ is maintained as long as the solubility of the both-end polyether-modified polyfluorene is maintained and the properties required are exhibited. There are no special restrictions.

The skeleton of the above polyether group is represented by ethylene oxide, propylene oxide, or a copolymer of ethylene oxide and propylene oxide. Among these, from the viewpoint of water solubility, ethylene oxide is preferred, and in view of printability and printing adhesion, propylene oxide or a copolymer of ethylene oxide and propylene oxide is preferred.

As described above, by selecting a polyether-modified polyfluorene having an optimum structure, scratch resistance can be surely made to coexist with printability and print adhesion in the formed conductive film.

The both-end polyether modified polyfluorene-based oxygen contained in the conductive composition can be formed into a conductive film which is excellent in printability and print adhesion without imparting solvent resistance and imparting scratch resistance. The polyether at the two ends of the structure represented by the above formula (III) is modified to form polyfluorene. The two-end polyether modified polyfluorene represented by the above formula (III) may be used singly or in combination of two or more kinds of terminal polyethers having different molecular weights.

The content of the above-mentioned two-end polyether modified polyfluorene is preferably such that the upper limit thereof is 60 parts by weight, more preferably 33 parts by weight, per 100 parts by weight of the melamine resin derivative. Further, the lower limit thereof is preferably 10 parts by weight based on 100 parts by weight of the melamine resin derivative.

The reason for this is that when it is in this range, scratch resistance, printability, and printing adhesion can be simultaneously provided to the formed film.

On the other hand, when the content of the polyether modified polyfluorene at both ends is more than 60 parts by weight, the solvent resistance of the formed film may be deteriorated.

5. Conductivity enhancer (e)

The conductivity enhancer (e) contained in the conductive composition can improve the conductivity of the formed conductive film.

Examples of the conductive enhancer (e) include decylamine compounds such as N-methylformamide, N,N-dimethylformamide, γ-butyrolactone, and N-methylpyrrolidone; Ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, Hydroxy-containing compounds such as catechol, cyclohexanediol, cyclohexanedimethanol, glycerin, diethylene glycol monoethyl ether, propylene glycol monomethyl ether; isophorone, propylene carbonate, cyclohexanone, A carbonyl group-containing compound such as acetone, ethyl acetate, ethyl acetate, methylorthoacetate or ethyl orthoformate; a compound having a sulfo group such as dimethylhydrazine.

Among these, a guanamine compound and a hydroxyl group are preferable from the viewpoints of the pot life of the coating liquid, the curability at low temperature, the transparency of the formed conductive film, the scratch resistance, the solvent resistance, and the like. A compound or a sulfo group-containing compound, particularly preferably N-methylpyrrolidone, dimethyl azine or ethylene glycol.

Further, the content of the conductive enhancer is not particularly limited, but it is usually preferably contained in an amount of 0.1 to 60% by weight based on the conductive composition.

6. Solvent or dispersion medium (f)

The solvent or the dispersion medium (f) is not particularly limited as long as it dissolves or disperses each component contained in the conductive composition, and examples thereof include water, an organic solvent, and the like.

In the present invention, when a solvent or a component other than the solvent contained in the conductive composition is dissolved, it is called a solvent, and when at least one component constituting the composition is uniformly dispersed, it is called a dispersion medium. .

In the above conductive composition, the above melamine resin derivative is insoluble in water. In this case, a solvent or a dispersion medium may be a mixture of water and an organic solvent. Further, when a mixture of water and an organic solvent is used, the organic solvent preferably contains at least one organic solvent mixed with water, and may further contain no water mixed with water as long as it contains an organic solvent mixed with water ( Hydrophobic) organic solvent. By using a mixture of an alcohol-based organic solvent having a relatively low boiling point and water as a solvent or a dispersion medium, there is a case where the volatility is improved and it is advantageous in drying and heat curing. Further, in the case of using a resin substrate, an alcohol-based organic solvent can contribute to an improvement in leveling property.

In the present specification, the water-based thermosetting conductive coating composition is a thermosetting conductive coating for a solvent or a dispersion medium which is only water or a mixture of water and an organic solvent mixed with water. Composition: The solvent-based thermosetting conductive coating composition is a thermosetting conductive coating composition containing a solvent or a dispersion medium containing a water-insoluble organic solvent.

6-1. Organic solvents

Examples of the organic solvent include those in which a component such as a melamine resin derivative which is not easily dissolved in water is uniformly dissolved or dispersed.

Examples of the organic solvent to be mixed with water include alcohols such as methanol, ethanol, 2-propanol and 1-propanol; and ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol. Alcohols; glycol ethers such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether; ethylene glycol monoethyl ether Glycol ether acetates such as acid esters, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate; propylene glycols such as propylene glycol, dipropylene glycol, and tripropylene glycol; propylene glycol monomethyl ether , propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol diethyl ether and other propylene glycol ethers Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, etc.; propylene glycol ether acetate; tetrahydrofuran, acetone, acetonitrile And mixtures of such and the like.

Further, examples of the hydrophobic organic solvent include esters such as ethyl acetate, butyl acetate, and ethyl lactate; and ethers such as diisopropyl ether and diisobutyl ether; methyl ethyl ketone and methyl group; Ketones such as diisobutyl ketone; aliphatic hydrocarbons such as hexane, octane and petroleum ether; aromatic hydrocarbons such as toluene and xylene; and mixtures thereof.

These organic solvents may be used singly or in combination of two or more.

In the case where the conductive composition is a water-based conductive composition, the content of the organic solvent is preferably 20 parts by weight or more based on 100 parts by weight of water. When the amount is less than 20 parts by weight, the components such as the melamine resin derivative may be dissolved or dispersed unevenly, and the film forming property may be deteriorated, and the performance may not be exhibited. In the case where the conductive composition is a solvent-based conductive composition, the content of the solvent is not limited.

6-2. Water

Examples of the water used in the water-based conductive composition include distilled water, ion-exchanged water, and ion-exchange distilled water. Further, the water also contains water in an aqueous dispersion of a conductive polymer and other components.

The content of the water is preferably 1% by weight or more based on the total of the conductive composition.

In the case where the conductive composition is a water-based conductive composition, the pH of the conductive composition is preferably in the range of 1 to 14, and more preferably 1 to 7 in consideration of low-temperature hardenability, and particularly preferably 1.5 to 3. The pH of the conductive composition may be adjusted by a pH adjuster such as a base.

Examples of the pH adjuster include alkanolamines such as ammonia, ethanolamine, and isopropanolamine.

Here, it is considered that the alkali forms an acid and a salt to lower the hardening promoting effect of the melamine resin derivative. On the other hand, the higher the pH of the conductive composition, the lower the hardenability of the low temperature, but the melamine is inhibited by the melamine. In the case of self-crosslinking in the solution of the resin derivative, the stability or the pot life of the solution may be improved, and the amount of the pH adjusting agent may be appropriately determined. Further, the pH adjuster is an optional component of the conductive composition.

Further, the conductive composition containing the components (a) to (f) as described above is particularly preferable in that the pot life of the conductive composition is remarkably improved as follows: 100 parts by weight relative to the solid content of the conductive polymer 150 to 750 parts by weight of the perether type melamine resin derivative (b), which contains 8 to 40 parts by weight of aromatic sulfonic acid as a sulfonic acid hardening catalyst (c) relative to 100 parts by weight of the melamine resin derivative, relative to melamine 100 parts by weight of the resin derivative contains 10 to 60 parts by weight of the terminal polyether modified polyfluorene oxide (d), and contains one or more compounds having a mercapto group, a hydroxyl group or a sulfo group as the conductivity enhancer (e).

The components (a) to (f) described above are essential components in the thermosetting conductive coating composition of the present invention.

Further, the thermosetting conductive coating composition of the present invention may contain a water-soluble antioxidant (g), a wettability enhancer (h), an antifoaming agent (i), or the like as needed.

7. Water-soluble antioxidants (g)

The above conductive composition may also contain a water-soluble antioxidant (g). The water-soluble antioxidant (g) has a function of uniformly forming a conductive polymer in the film when the conductive film is formed, and effectively suppressing an increase in electric resistance caused by exposure to air.

Further, the fat-soluble antioxidant cannot be uniformly present in the film, and the increase in electric resistance caused by exposure to air cannot be effectively suppressed.

The water-soluble antioxidant may be a reducing or non-reducing water-soluble antioxidant.

Examples of the water-soluble antioxidant having a reducing property include L-ascorbic acid, sodium L-ascorbate, potassium L-ascorbate, erythorbic acid, sodium erythorbate, and potassium erythorbate having a lactone ring substituted by two hydroxyl groups. a compound; a monosaccharide or a disaccharide such as maltose, lactose, cellobiose, xylose, arabinose, glucose, fructose, galactose, mannose; catechin, rutin, myricetin, quercetin, non-flavonol Flavonoids such as (kaempferol); compounds having more than two phenolic hydroxyl groups such as curcumin, rosmarinic acid, drifting acid, hydroquinone, 3,4,5-trihydroxybenzoic acid; cysteine, A compound having a thiol group such as glutathione or neopentyltetrakis(3-mercaptobutyrate).

Examples of the non-reducing water-soluble antioxidant include phenylimidazoliumsulfonic acid, phenyltriazolesulfonic acid, 2-hydroxypyrimidine, phenyl salicylate, and 2-hydroxy-4-methoxybenzophenone. A compound such as sodium 5-sulfonate which absorbs ultraviolet rays which is a cause of oxidative degradation. These may be used alone or in combination of two or more.

Among these water-soluble antioxidants, ascorbic acid and isoascorbic acid are preferred, and ascorbic acid is more preferred.

This is because the effect of suppressing the increase in electric resistance caused by exposure to air and the effect of making the formed conductive film transparent are excellent.

The content of the water-soluble antioxidant is not particularly limited, but the upper limit thereof is preferably 60 parts by weight, more preferably 40 parts by weight, per 100 parts by weight of the melamine resin derivative. On the other hand, the lower limit thereof is preferably 9 parts by weight, more preferably 20 parts by weight.

When the content is more than 60 parts by weight, the solvent resistance of the formed conductive film may be lowered. Conversely, if it is less than 9 parts by weight, the SR increase rate may be increased by exposure to air.

8. Hygroscopic enhancer (h)

The above conductive composition may also contain a wetting enhancer (h). The moisture-reducing agent (h) can improve the wettability of the substrate of the conductive composition and can improve the uniformity of the formed conductive film.

Examples of the above-mentioned wetness improving agent include an acrylic copolymer or a polyoxyethylene fatty acid ester compound.

Among these, an acrylic copolymer is preferred. The reason for this is that the conductive film is excellent in transparency, scratch resistance, and solvent resistance.

The content of the solid content of the above-mentioned moisture-reducing agent is not particularly limited, but the upper limit thereof is preferably 70 parts by weight, more preferably 40 parts by weight, per 100 parts by weight of the melamine resin derivative. On the other hand, the lower limit thereof is preferably 4 parts by weight based on 100 parts by weight of the melamine resin derivative.

When the content is more than 70 parts by weight, the crosslinking density of the melamine resin derivative is lowered and the solvent resistance is deteriorated. When the amount is less than 4 parts by weight, the film formability is not improved and the film is not uniform.

9. Defoamer (i)

The above conductive composition may also contain an antifoaming agent (i). By disposing the above antifoaming agent (i), it is possible to effectively defoam and suppress foaming of the conductive composition.

Examples of the antifoaming agent include a diol-based compound such as polyacetylene glycol, a siloxane-based compound such as an organically modified polyoxyalkylene oxide, and a polydimethyl methoxy olefin by an emulsifier. An emulsion or the like dispersed in water.

Among these, an emulsion of polydimethyl methoxyoxane is preferred in terms of excellent defoaming property.

The content of the antifoaming agent is not particularly limited, but is preferably from 1 to 30 parts by weight based on 100 parts by weight of the polyether modified polyfluorene at both ends. When the amount is more than 30 parts by weight, the crosslinking density of the melamine resin derivative is lowered and the solvent resistance is deteriorated. When the amount is less than 1 part by weight, the defoaming property is not improved and the foam remains for a long period of time.

The thermosetting conductive coating composition of the present invention may contain other components as needed in addition to the above components.

10. Other ingredients

10-1. Adhesive resin

In order to improve the film formability or printability of the formed conductive film, the conductive composition may contain a binder resin.

In the conductive composition of the present invention, the self-crosslinking film of the melamine resin derivative has a binder function, but by adding a binder resin, the film formability, the flexibility and adhesion of the film are further improved, and further The situation of printability and print adhesion.

Examples of the binder resin include polyester, poly(meth)acrylate, polyurethane, polyvinyl acetate, polyvinylidene chloride, polyamine, polyimine, polyvinyl alcohol, and polyacryl polyol. a homopolymer such as a polyester polyol; a copolymer selected from the group consisting of styrene, vinylidene chloride, vinyl chloride, and alkyl (meth)acrylate as a copolymerization component.

The content of the binder resin is not particularly limited, but is preferably 200 parts by weight or less, more preferably 40 parts by weight or less based on 100 parts by weight of the melamine resin derivative. When the amount of the binder resin exceeds 200 parts by weight, the crosslinking property of the melamine resin derivative may decrease, and the solvent resistance of the conductive film formed may be deteriorated.

The thermal hardening of the melamine resin derivative in the conductive composition of the present invention is preferably a self-crosslinking reaction of the melamine resin derivative. This is because the formed conductive film is excellent in scratch resistance or solvent resistance. The reason why the film formed by self-crosslinking of the melamine resin derivative is excellent in scratch resistance or solvent resistance is that the crosslinking density is high.

On the other hand, since the melamine resin derivative can react with a functional group such as a carbonyl group or a hydroxyl group contained in the binder resin, it also functions as a crosslinking agent of the binder resin, but the melamine resin derivative is used as a binder resin. The film formed by the function of the crosslinking agent tends to have lower scratch resistance or solvent resistance than the self-crosslinking film of the melamine resin derivative.

10-2. Surfactant

In order to improve the leveling property, the above conductive composition may also contain a surfactant.

Examples of the surfactant include fluorine-based surfactants such as perfluoroalkylcarboxylic acid and perfluoroalkylpolyoxyethyleneethanol; and polyoxyethylene alkylphenyl ether, propylene oxide polymer, and ethylene oxide polymer. An ether compound; a carboxylic acid such as a coconut oil fatty acid amine salt or a rosin gum; an ester compound such as a castor oil sulfate, a phosphate ester, an alkyl ether sulfate, a sorbitan fatty acid ester, a sulfonate or a succinic acid ester; a sulfonate compound such as an alkylarylsulfonate amine salt or a sodium dioctyl sulfosuccinate; a phosphate compound such as sodium lauryl phosphate; a guanamine compound such as coconut oil fatty acid ethanolamine; an anionic surfactant; A surfactant, a nonionic surfactant, a hydrazine-modified acrylic compound, or the like.

The content of the surfactant is not particularly limited, but is preferably 100 parts by weight or less based on 100 parts by weight of the melamine resin derivative. When the amount is more than 100 parts by weight, the crosslinking property of the melamine resin derivative may be deteriorated, and the solvent resistance of the conductive film formed may be deteriorated.

10-3. Decane coupling agent

The conductive composition may contain a decane coupling agent in order to improve solvent resistance, printability, and printing adhesion of the conductive film.

The above decane coupling agent may, for example, be 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane or 2-(3,4-epoxy ring). Hexyl)ethyltrimethoxydecane, 3-mercaptotrimethoxydecane, and the like.

The content of the decane coupling agent is not particularly limited, but is preferably 100 parts by weight or less based on 100 parts by weight of the melamine resin derivative. When it is more than 100 parts by weight, the solvent resistance of the conductive film formed by the decrease in the crosslinking density of the melamine resin derivative may be deteriorated.

10-4. Tackifier

In order to increase the viscosity of the above conductive composition, the conductive composition may further contain a tackifier.

Examples of the tackifier include water-soluble polymers such as salts and derivatives of alginic acid, santillac derivatives, carrageenan or cellulose, and the like.

The content of the tackifier is not particularly limited, but is preferably 100 parts by weight or less based on 100 parts by weight of the melamine resin derivative. When it is more than 100 parts by weight, the solvent resistance of the conductive film formed by the decrease in the crosslinking density of the melamine resin derivative may be deteriorated.

10-5. Microparticle material

In order to improve the smoothness, printability, and printing adhesion of the conductive film, the conductive composition may contain fine particles such as colloidal cerium oxide, hollow cerium oxide, fluororesin fine particles, or metal fine particles such as titanium dioxide.

The content of the fine particle material is not particularly limited, but is preferably 100 parts by weight or less based on 100 parts by weight of the melamine resin derivative. When it is more than 100 parts by weight, the solvent resistance of the conductive film formed by the decrease in the crosslinking density of the melamine resin derivative may be deteriorated.

10-6. Organic carboxylic acid compounds

In order to improve the printability and print adhesion of the conductive film, the conductive composition may contain an organic carboxylic acid having a carboxyl group.

The organic carboxylic acid may be an aliphatic or aromatic monovalent or polyvalent carboxylic acid, and may have a functional group such as a hydroxyl group or a vinyl group in the molecule. Examples of the aliphatic carboxylic acid include acetic acid, butyric acid, hexanecarboxylic acid, octanecarboxylic acid, acetoacetic acid, malonic acid, succinic acid, glutaric acid, adipic acid, and fumaric acid. Maleic acid, malic acid, tartaric acid, citric acid, and the like. Further, examples of the aromatic carboxylic acid include benzoic acid, salicylic acid, gallic acid, cinnamic acid, phthalic acid, trimellitic acid, and pyromellitic acid.

Next, the optical film of the present invention will be described.

The optical film of the present invention is composed of a substrate and a conductive film laminated on the substrate, and the conductive film is formed by using the thermosetting conductive coating composition of the present invention. .

The optical film is composed of a substrate and a conductive film laminated on the substrate.

Examples of the substrate include a resin substrate and a glass substrate.

Examples of the material resin of the resin substrate include polyolefin resins such as polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer, ionic polymer copolymer, and cycloolefin resin; Polyethylene phthalate, polybutylene terephthalate, polycarbonate, polyoxyethylene, modified polyphenylene, polyphenylene sulfide and other polyester resins; nylon 6, nylon 6,6, nylon 9, half Aramid resin such as aromatic polyamine 6T6, semi-aromatic polyamide 6T66, semi-aromatic polyamine 9T; acrylic resin, polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene- Styrene copolymer, vinyl chloride resin, triacetyl cellulose, and the like.

Further, the above substrate is preferably transparent (having a high light transmittance).

Moreover, in the case of using as an optical film of a protective film, it is preferable to use polyethylene terephthalate or triacetium cellulose from a viewpoint of processability and functionality.

The shape of the substrate is not particularly limited, and may be appropriately selected depending on the shape of the optical film, and examples thereof include a film shape, a plate shape, and other desired shapes. Therefore, various substrates such as a film, a sheet, a sheet, and a molded article can be used as the substrate.

Further, physical treatment such as corona treatment, flame treatment, or plasma treatment may be applied to the surface of the substrate. The coating property of the conductive composition can be improved by applying such treatment.

The conductive film is formed by using the conductive composition of the present invention, and is formed by applying the conductive composition to a substrate, drying it, and thermally curing the conductive composition.

The method of applying the conductive composition to the substrate is not particularly limited, and may be appropriately selected from methods common in the field, and examples thereof include spin coating, gravure coating, bar coating, and dip coating. Coating methods such as curtain coating, die coating, and spray coating.

Further, the conductive composition may be applied by a printing method such as screen printing, jet printing, inkjet printing, letterpress printing, gravure printing, or lithography.

Further, when the conductive composition is applied, a coating liquid in which the conductive composition is previously diluted with an alcohol or the like may be prepared, and the coating liquid may be applied.

The thickness of the conductive film is not particularly limited and may be appropriately selected depending on the purpose.

From the viewpoint of coating cost, the calculated film thickness after heat drying is preferably 45 nm or less, more preferably 10 to 20 nm.

In addition, when the specific gravity of the coating liquid and the specific gravity of the film after drying can be approximated to 1, the calculated film thickness can be calculated according to the following calculation formula.

"Thickness = concentration of coating solution (%) ÷ 100 × theoretical coating amount of wire rod (μm)"

Usually, since the coating amount of the wire bar is less than the theoretical value, the actual film thickness is thinner than the calculated value.

The conductive film has conductivity because it contains a conductive polymer, and its surface resistivity is preferably from 10 ⁴ to 10 ¹¹ Ω/□. The reason for this is that if the surface resistivity in this range is present, the required characteristics as an antistatic layer are sufficiently satisfied.

The conductive film is formed by heating a conductive composition applied to a substrate, and evaporating the solvent or the dispersion medium while thermally hardening (drying, heat curing).

Here, the heating condition is preferably a condition of heating at a temperature of 130 ° C or lower (80 ° C to 130 ° C) for about 1 minute (30 to 90 seconds). The reason for this is that the conductive composition of the present invention can sufficiently form a conductive film under the above-described conditions, and the above conditions are in a low-temperature condition for a short period of time in the technical field of the present invention, and therefore, productivity is also excellent.

Further, in the case where the curing is insufficient under the above conditions, the film is cured in a state of a roll film at 25 ° C to 60 ° C in a state of a roll film and post-cured for 1 hour to several weeks.

A drying machine such as a general air dryer, a hot air dryer, or an infrared dryer is used for drying and heat curing of the solvent or the dispersion medium. In order to perform drying and heating at the same time, it is necessary to use a dryer (hot air dryer, infrared dryer, etc.) having a heating means. Further, as the heating means, in addition to the above-described dryer, a heating and pressing roller having a heating function, a pressurizing machine, or the like may be used.

As described above, the conductive composition of the present invention contains a conductive polymer, a melamine resin derivative, a sulfonic acid hardening catalyst, a two-terminal polyether modified polyfluorene oxide, a conductivity improving agent, and a solvent or a dispersion medium as essential The component further contains a water-soluble antioxidant, a moisturizing enhancer, an antifoaming agent, a binder resin, a surfactant, a decane coupling agent, a tackifier, a microparticle material, and the like as needed.

In order to prevent self-crosslinking in the solution of the melamine resin derivative, the composition of the composition of the melamine resin derivative is usually supplied in a state in which the melamine resin derivative is separated from the acidic component (here, as a component showing acidity) Conductive polymer or sulfonic acid hardening catalyst, etc.).

Further, each of the above components is mixed in a predetermined ratio before use, and used in a state in which all the components are mixed. Further, when the acidic component is neutralized with an alkali or the like, the storage stability can be maintained even if all the components are supplied in a mixed state.

In general, in consideration of the pot life and storage stability of the composition, the coating liquid for preparing the above-mentioned conductive composition is supplied in a state in which two or three liquids of the melamine resin derivative and the acidic component are separated. The components of the coating liquids may also be sufficiently concentrated from the viewpoint of cost.

The method for preparing the conductive composition (coating liquid) is not particularly limited, and each component is prepared by mixing with a stirrer such as a mechanical stirrer or a magnetic stirrer while stirring. Here, the agitation is preferably continued for about 1 to 60 minutes.

Further, in the case of stirring, in order to avoid the conductive polymer or the sulfonic acid hardening catalyst, and further the melamine resin derivative is mixed at a high concentration, it is desirable to previously add a diluent such as an alcohol.

In particular, when a solution containing a water-soluble conductive polymer and a solution containing an organic solvent such as an alcohol are mixed at a high concentration, the dispersion stability is lowered to cause aggregation, and the pot life is reduced.

Further, in the case where the melamine resin derivative and the acidic component are directly mixed, since the self-crosslinking of melamine is easily carried out in the solution, the application period of the conductive composition is shortened.

Further, since the pot life of the conductive composition is also dependent on the temperature of the composition, it is preferably prepared by keeping the liquid temperature below 30 °C. A more preferable liquid temperature is -5 ° C to 10 ° C.

The conductive composition is stable at a normal temperature of about 25 ° C. However, when an acidic component is contained, the melamine resin derivative may be self-crosslinked in a solution and the pot life may be deteriorated.

Since the pot life depends on the temperature of the coating liquid, the application period can be improved by coating the temperature at -20 ° C to 20 ° C. It can be preferably applied to the substrate at a temperature of from -5 ° C to 10 ° C.

The lower the temperature is, the higher the pot life is. In the case of the water-based conductive composition, the temperature of the composition below -20 ° C may freeze. The above conductive composition is preferably prepared by keeping the temperature below 30 ° C from the time of preparation, and more preferably at a temperature of -5 ° C to 10 ° C.

The optical film composed of such a composition is preferably used as an optical film having an antistatic layer for a liquid crystal display, a polarizing plate, an electroluminescence display, a plasma display, an electronic color display, a solar cell or the like.

Further, the above optical film is particularly preferable as a protective film, and the protective film composed of the optical film of the present invention is also one of the inventions.

Further, in the case of a protective film, the substrate is preferably polyethylene terephthalate in terms of workability, hardness, transparency, and the like.

[Examples]

Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to the examples.

(Examples 1 to 27 and Comparative Examples 1 to 9)

Each component (the raw material used) shown in Table 1 was added to the solvent or dispersion medium one by one while stirring. After confirming that the added components were dissolved or uniformly dispersed, the next component was added, and after all the components were added, the mixture was further stirred for 5 minutes to prepare a thermosetting conductive coating composition in a solution or dispersion state. Thereafter, the composition was diluted to 80 times (1:5, by weight) with 80% ethanol to prepare a coating liquid.

Immediately after the preparation of the coating liquid, a wire rod (wet film thickness: 9 μm) of No. 4 was applied to a polyethylene terephthalate film (Lumirror T-60 (trade name) manufactured by Toray Co., Ltd.). The substrate was dried by a hot air dryer at 130 ° C and thermally cured for 1 minute to form a conductive film.

Further, in the evaluation of the pot life, a conductive film was produced in the same manner after 24 hours from the preparation of the thermosetting conductive coating composition.

(Embodiment 28)

In the same manner as in the examples 1 to 27, each component (the raw material used) shown in Table 2 was added while stirring, and a thermosetting conductive coating composition was prepared. Thereafter, the composition was diluted to 80 times (1:3, by weight) with 80% ethanol to prepare a coating liquid.

Immediately after the preparation of the coating liquid, a wire rod (wet film thickness: 9 μm) of No. 4 was applied to a polyethylene terephthalate film (Lumirror T-60 (trade name) manufactured by Toray Co., Ltd.). The substrate was dried by a hot air dryer at 130 ° C and thermally cured for 1 minute to form a conductive film.

Further, in the evaluation of the pot life, a conductive film was produced in the same manner after 24 hours from the preparation of the thermosetting conductive coating composition.

Further, the produced conductive film was cut and subjected to TEM observation. The results are shown in Fig. 1.

Fig. 1 is a TEM observation image obtained by taking the conductive film produced in Example 28 at a magnification of 100,000 times. In Fig. 1, 1 is a conductive film, 2 is a PET film, and a scale of 115 nm in length is shown in the lower right corner of the figure.

I. Use of raw materials

I.1 Conductive polymer (a)

An aqueous dispersion containing a conductive material, which is an aqueous dispersion of a conductive polymer composed of a composite of poly(3,4-ethylenedioxythiophene) and polystyrenesulfonic acid, Clevios P manufactured by HC Starck Co., Ltd. Trade name) (1.3% by weight of a poly(3,4-ethylenedioxythiophene)/polystyrenesulfonic acid (weight average molecular weight = 1,500,000) composite dispersion aqueous solution, water 98.7% by weight).

I.2 melamine resin derivative (b)

A melamine resin derivative using NIKALAC MW-390 manufactured by NIPPON CARBIDE Industrial Co., Ltd. (per ether type, R ⁹ in the formula (II) is a methyl group, a polymerization degree: 1.00), NIKALAC MS-11 (hydroxymethyl type, 60 % by weight of the product, R ⁹ in the formula (II) is a hydrogen atom, degree of polymerization: 1.80) and Cymel 300 manufactured by Nippon Sytecs Industry Nihon Cytec Industries, Inc. (all ether type, R ⁹ in the formula (II) is a methyl group, Degree of polymerization: 1.35), Cymel 301 (per ether type, R ⁹ in the formula (II) is a methyl group, degree of polymerization: 1.40) (the above names are all trade names).

I.3 sulfonic acid hardening catalyst (c)

Sulfonic acid hardening catalyst, Taycatox T-500 (trade name) manufactured by Tayca Co., Ltd. (molecular weight: 187.2; compound name: cumenesulfonic acid; hereinafter referred to as QS), NEOPELEX GS (trade name) manufactured by Kao Corporation (molecular weight) 326.8; Compound name: dodecylbenzenesulfonic acid; hereinafter referred to as DBS). Further, in one of the comparative examples, nitric acid (molecular weight 63.01; 60% by weight of a product) manufactured by Wako Pure Chemical Industries, Ltd. was diluted to 2% by weight as an acid catalyst.

I.4 polyether modified polyoxane (d)

The two-end polyether modified polyfluorene oxygen, using 8029 additive (trade name) manufactured by Toray‧Dow Corning Co., Ltd., Polyflow KL-402 (trade name) manufactured by Kyoeisha Chemical Industry Co., Ltd., or BYK-378 manufactured by BYK Corporation (Product name).

In one part of the comparative example, KF-355A (trade name) manufactured by Shin-Etsu Chemical Co., Ltd., BYK-348 (trade name) manufactured by BYK Corporation, and BYK-307 (trade name) are also used as the side chain polyether modified polyfluorene oxygen. ), or YF-3842 (trade name) manufactured by Momentive Performance Materials.

I.5 Water Soluble Antioxidant (g)

As the water-soluble antioxidant, ascorbic acid or erythorbic acid manufactured by Wako Pure Chemical Industries, Ltd. is used.

As an organic solvent-soluble antioxidant, DRY MIX FS-20 (trade name) (main component: vitamin E) manufactured by Riken Vitamin Co., Ltd. was also used.

I.6 conductivity enhancer (e)

For the conductivity-increasing agent, N-methylpyrrolidone (hereinafter referred to as NMP), dimethyl hydrazine (hereinafter referred to as DMSO), or ethylene glycol (hereinafter referred to as EG) manufactured by Wako Pure Chemical Industries, Ltd., N-methylformamide (hereinafter referred to as NMF).

I.7 organic solvent (f)

For the organic solvent, the first grade ethanol manufactured by Wako Pure Chemical Industries, Ltd. was used.

I.8 water (f)

Most of the water is water contained in the aqueous dispersion of conductive polymer Clevios P, and the newly added water is pure water treated by ion exchange.

The newly added water in the water system described in Tables 1 and 2.

I.9 wetness enhancer (h)

For the wetness improving agent, BYK-380N (trade name) (Compound name: acrylic copolymer) manufactured by BYK Corporation was used.

I.10 defoamer (i)

As the antifoaming agent, ANTIFOAM 013A (trade name) manufactured by Toray‧Dow Corning Co., Ltd. (compound name: emulsion of polydimethyl methoxy oxane, hereinafter referred to as 013A) was used.

I.11 other additives

Other additives, SIRQUEST A-189 (trade name) (Compound name: 3-mercaptopropyl triethoxy decane) manufactured by Momentive ‧ Performance Productions, a decane coupling agent, and Snowtex manufactured by Nissan Chemical Co., Ltd. OXS (trade name) (compound name: aqueous dispersion of colloidal cerium oxide), Trimellitic Acid (trade name) manufactured by Mitsubishi Gas Chemical Co., Ltd. of organic carboxylic acid.

II. Evaluation

The appearance of the liquid of the coating liquid prepared in Examples 1 to 28 and Comparative Examples 1 to 9, the appearance of the coating film of the conductive film obtained using the film, the scratch resistance, the solvent resistance, the printability, and the printing adhesion The evaluation was performed in the following three grades. Further, the values of SR, Tt, and Haze were measured. The adhesion to the substrate was evaluated in accordance with JIS K 5400. The pot life is a coating liquid which is subjected to 24 hours from the preparation of the solution and a film formed using the coating liquid. The application period of the coating liquid was evaluated in the same manner as the initial value in consideration of the appearance of the coating liquid, the appearance of the coating film, the adhesion, the scratch resistance, the solvent resistance, the printability, and the printing adhesion. On the other hand, the fluctuations of the measured values of SR, Tt, and Haze of the film from the initial values were evaluated in the following three levels. In addition, in the initial evaluation, even if there is one "X" evaluation example and comparative example, the evaluation period is not evaluated.

The evaluation results are shown in Tables 3 and 4 below.

II.1 Appearance of Conductive Coating Composition

The appearance of the solution after the preparation of the composition was evaluated by visual evaluation on a grade of 3. The applicability period is also evaluated in the same manner.

◎: no sediment production

○: a small amount of precipitate is produced

×: gelation

II.2 Appearance of the film

The appearance (uniformity) of the coated conductive film was evaluated by visual observation in the following three grades. The applicability period is also evaluated in the same manner.

◎: The film was uniformly coated, and no uneven coating was observed.

○: There is a little uneven coating

×: no film was formed due to shrinkage

II.3 Surface resistivity / SR (Ω / □)

The surface resistivity was measured in accordance with JIS K 7194 using a UA probe of Hiresta UP (MCP-HT450 type, trade name) manufactured by Mitsubishi Chemical Corporation, and a voltage was measured at 100 V, and the measured value was evaluated. The increase rate of the pot life relative to the initial value was evaluated in the following three grades.

◎: 10 times or less

○: more than 10 times less than 100 times

×: 100 times or more

II.4 total light transmittance (Tt:%)

The total light transmittance was measured in accordance with JIS K 7150 using Haze Computer HGM-2B (trade name) manufactured by Suga Test Instruments, Inc., and the measured values were evaluated. The amount of change in the pot life relative to the initial value was evaluated in the following three grades.

◎: greater than -0.5, not up to +0.5

○: -1.0 to -0.5 or +0.5 to +1.0

×: not up to -1.0 or greater than +1.0

II.5 Haze (%)

Haze was measured in accordance with JIS K 7150 using Haze Computer HGM-2B (trade name) manufactured by Suga Test Instruments, Inc., and the measured values were evaluated. The amount of change in the pot life relative to the initial value was evaluated in the following three grades.

◎: greater than -0.5, not up to +0.5

○: -1.0 to -0.5 or +0.5 to +1.0

×: not up to -1.0 or greater than +1.0

II.6 Adhesion to the substrate

The adhesion of the conductive film to the substrate was evaluated in accordance with the grid peeling test of JIS K 5400, and evaluated by a certain score. The pot life is evaluated at the following 3 levels.

◎: No change since the initial value

○: Decrease from the initial value by less than 2 points

×: Decrease from the initial value by 2 or more

II.7 scratch resistance test

The conductive film formed on the substrate was rubbed with a claw by a load of about 200 g for a length of 10 cm, and the formation of the flaw and the generation of the powder were evaluated in the following three grades. The applicability period is also evaluated in the same manner.

◎: no scars were formed

○: Lighter friction marks are visible, but no powder is produced.

×: scar formation, powder production

II.8 Solvent resistance test

The conductive film formed on the substrate was subjected to an ethanol wiping test, an ethyl acetate wiping test, a methyl ethyl ketone (hereinafter referred to as MEK) wiping test, and a hexane wiping test. Specifically, the appearance of the film after the test was evaluated by the following three grades using a dust-free paper (BEMCOT) infiltrated with each solvent with a load of about 200 g for 15 times. The applicability period is also evaluated in the same manner.

◎: no change in the film

○: visible traces of friction

×: peeling off the film

II.9 printability test

In the printing test, the oily marking ink (Pi: S, fine type) manufactured by Mitsubishi Pencil Co., Ltd. was used, and the shrinkage at the time of printing on the surface of the conductive film was evaluated in the following three grades.

◎: The printed words are not shrinking at all.

○: The printed words are slightly shrunk and uneven

×: The shrinkage is large and cannot be printed.

II.10 Printing adhesion test

The printing adhesion test was performed by printing an oil-based marking ink (Pi:S, fine type) manufactured by Mitsubishi Pencil Co., Ltd. on the surface of a conductive film, and rubbing with a kimwipe at a load of about 500 g after 1 minute, by visual observation as follows. The rating evaluates the printing status at this time.

◎: no peeling of printing

○: There is trace of friction in printing

×: Printing is completely peeled off

II.11 Air resistance test

In the air exposure test, the conductive film was attached to the wall, and the SR after one week was evaluated in the following three levels. The applicability period is also evaluated in the same manner.

◎: less than 1 × 10 ¹⁰ Ω / □

○: 1 × 10 ¹⁰ Ω / □ or more, less than 1 × 10 ¹¹ Ω / □

×: 1 × 10 ¹¹ Ω / □ or more

II.12 defoaming test

In the defoaming test, the coating liquid was shaken 5 times, and evaluated in the following four grades until the time when the larger foam produced disappeared. The applicability period is also evaluated in the same manner.

◎: Defoaming within 20 seconds

○: Defoaming within 20 minutes in less than 20 seconds

△: Defoaming within 1 hour for more than 20 minutes

×: No defoaming even after more than 1 hour

According to Comparative Examples 1 to 4 and Examples 1 to 3, it is apparent that even if one of the melamine resin derivative, the sulfonic acid hardening catalyst, the two-end polyether modified polyoxane, and the conductivity improving agent is absent, The film appearance, conductivity, total light transmittance, Haze, adhesion to the substrate, scratch resistance, solvent resistance, printability, and printing adhesion cannot all be satisfied at the same time. If there is no conductive polymer or conductivity enhancer, SR is not exhibited, and the film is not cured without the melamine resin derivative and the sulfonic acid hardening catalyst. The two-end polyether modified polyfluorene is an essential component for imparting scratch resistance, printability, and printing adhesion.

According to Examples 1 and 4 to 6, it is apparent that the melamine resin derivative is excellent in the stability of the coating liquid of the all-ether type, and the physical properties of the coating film after 24 hours are not lowered.

According to Examples 1 and 7 to 10, it is apparent that if the content of the melamine resin derivative is increased, the pot life tends to be deteriorated, and if it is less than 150 parts by weight based on 100 parts by weight of the conductive polymer solid content, from the beginning Low solvent resistance.

According to Comparative Example 5 and Example 8, it is apparent that the hardening catalyst is preferably a sulfonic acid, and further, according to Example 11, it is apparent that the application period of the coating liquid is slightly deteriorated due to the use of QS, and there is a characteristic deterioration after 24 hours. Therefore, as a hardening catalyst, it is especially good for DBS.

Further, according to Examples 1 and 12 to 15, it is apparent that the content is preferably 40 parts by weight or less based on 100 parts by weight of the melamine resin derivative, which is preferable in terms of maintenance of the pot life.

According to Examples 1 and 16 to 18, it is apparent that in order to simultaneously satisfy the scratch resistance, the printability, and the printing adhesion, it is necessary to use a two-end polyether modified polyfluorene, even if the side chains are used as in Comparative Examples 6 to 9. Polyether modified polyfluorene, also can not meet the scratch resistance and printability and printing adhesion.

Further, in the first embodiment and the comparative example 9, the polyether modified polyfluorene oxygen system is substantially the same as the molecular weight of the polydimethyl siloxane, and the modified portion has a different structure. Further, Example 1 is a polyether modified polyfluorene at both ends, which satisfies both scratch resistance, solvent resistance, printability, and printing adhesion. On the other hand, the side chain polyether of Comparative Example 9 is modified. Polyoxyl cannot be satisfied at the same time. From the results, it is apparent that the effects of the present invention are specifically achieved by using a two-terminal polyether modified polyfluorene as a polyether modified polyfluorene oxygen.

Further, according to Examples 1 and 19 to 21, it is apparent that the content of the polyether modified polyfluorene at both ends is preferably 60 parts by weight or less based on 100 parts by weight of the melamine resin derivative.

According to Examples 1 and 22 to 24, it is apparent that the conductivity of the conductive film is further improved by using a compound having a mercapto group, a hydroxyl group or a sulfo group as a conductivity improving agent.

Comparing Examples 1 and 25 with Example 2, it is apparent that the addition of ascorbic acid or isoascorbic acid of a water-soluble antioxidant can suppress the SR rise of exposure to air. Further, such an effect was not observed in the oil-soluble antioxidant as in Example 26.

Further, in Example 3, a slight shrinkage was confirmed, and when compared with other examples, it was apparent that the film forming property of the moisture-containing enhancer was excellent, and further, according to Example 27, it was apparent that defoaming was added by adding The agent can effectively defoam the foam produced.

Further, according to Example 28 and Fig. 1, it is apparent that the film having a film thickness of about 30 nm was analyzed by TEM, and as a result, the actual measurement was about 12 nm. It is known that the film thickness of the film formed under the present conditions is much thinner than the calculated value.

The conductive composition of the present invention can be preferably used for forming, for example, a protective film because it can form a conductive coating which satisfies scratch resistance, solvent resistance, printability, and printing adhesion at a low temperature for a short period of time. A conductive film (antistatic layer) or the like of various optical films.

1. . . Conductive film

2. . . PET film

Fig. 1 is a TEM observation image of the conductive film produced in Example 28 taken at a magnification of 100,000 times.

Claims (14)

A thermosetting conductive coating composition comprising: (a) a conductive polymer, (b) a melamine resin derivative, (c) a sulfonic acid hardening catalyst, and (d) a two-end polyether modified polyfluorene Oxygen, (e) a conductivity enhancer, and (f) a solvent or a dispersion medium; and the content of the polyether modified polyoxane (d) at both ends is 10 to 60 parts by weight based on 100 parts by weight of the melamine resin derivative. The thermosetting conductive coating composition according to the first aspect of the invention, wherein the conductive polymer (a) is a poly(3,4-dialkoxy group) having a repeating structure of the following formula (I). a complex of thiophene) or poly(3,4-alkylenedioxythiophene) with a dopant, (Wherein, R ¹ is and R ² each independently represents a hydrogen atom or a C _1-4 alkyl group, or together represent may be substituted with the C _1-4 alkylene group). The thermosetting conductive coating composition according to the first or second aspect of the invention, wherein the content of the melamine resin derivative (b) is from 150 to 750 parts by weight based on 100 parts by weight of the conductive polymer. For example, the thermosetting conductive coating of claim 1 or 2 A composition for a cloth, wherein the sulfonic acid hardening catalyst (c) is an aromatic sulfonic acid, and the content thereof is 8 to 40 parts by weight based on 100 parts by weight of the melamine resin derivative. The thermosetting conductive coating composition according to the first or second aspect of the invention, wherein the conductivity improving agent (e) has at least one substituent selected from the group consisting of a mercapto group, a sulfo group and a hydroxyl group. Compound. The composition for thermosetting conductive coating of the first or second aspect of the patent application further contains (g) a water-soluble antioxidant. The thermosetting conductive coating composition according to claim 6, wherein the water-soluble antioxidant (g) is ascorbic acid or isoascorbic acid. The composition for thermosetting conductive coating of the first or second aspect of the patent application further contains (h) a wetness improving agent. The thermosetting conductive coating composition according to the first or second aspect of the patent application, further comprising (i) an antifoaming agent. The thermosetting conductive coating composition according to claim 9, wherein the antifoaming agent (i) is a polyoxymethylene emulsion. An optical film comprising a substrate and a conductive film laminated on the substrate, wherein the conductive film is made of a thermosetting conductive material according to any one of claims 1 to 10. It is formed by the composition for coating. The optical film according to claim 11, wherein the conductive film is applied to the substrate by applying the composition for thermosetting conductive coating, and dried at a temperature of 130 ° C or lower. Formed by heat hardening. The optical film of claim 11 or 12, wherein the conductive film has a calculated film thickness of less than 45 nm. A protective film comprising the optical film of any one of the items 11 to 13.