KR101921346B1 - Composition for heat-curable conductive coatings, optical film and protective film - Google Patents
Composition for heat-curable conductive coatings, optical film and protective film Download PDFInfo
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- KR101921346B1 KR101921346B1 KR1020137013251A KR20137013251A KR101921346B1 KR 101921346 B1 KR101921346 B1 KR 101921346B1 KR 1020137013251 A KR1020137013251 A KR 1020137013251A KR 20137013251 A KR20137013251 A KR 20137013251A KR 101921346 B1 KR101921346 B1 KR 101921346B1
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Abstract
It is an object of the present invention to provide a thermosetting conductive coating composition capable of forming a conductive film simultaneously satisfying both scratch resistance, solvent resistance, solvent resistance and printability at a low temperature in a short time, The composition for coating is a coating composition comprising (a) a conductive polymer, (b) a melamine resin derivative, (c) a sulfonic acid curing catalyst, (d) a terminal polyether modified silicone, (e) a conductivity improver, and .
Description
The present invention relates to a composition for a thermosetting conductive coating, and to an optical film and a protective film obtained by using the composition for the thermosetting conductive coating.
In an optical film constituting a flat panel such as a liquid crystal television, a plasma television, an electroluminescence display or a solar cell, a coating layer (antistatic layer) having an antistatic function is formed in order to solve troubles such as electrostatic breakdown .
For example, in a manufacturing process or a conveying process of a flat panel display, a protective film, which is a kind of optical film, is bonded to the surface of the panel in order to prevent scratches, dirt and dust from adhering to the surface of the panel. This protective film has an adhesive layer on one side of a resin substrate such as PET and is used by bonding the adhesive layer side to the display. In order to prevent the electrical product from failing due to static electricity generated when the film is peeled off, Is formed on the side of the resin base opposite to the side of the adhesive layer.
Conventionally, the antistatic layer is required to have scratch resistance for preventing scratches, antifouling property for preventing adhesion of the pressure-sensitive adhesive at the time of cutting, and solvent resistance for wiping the adhered pressure-sensitive adhesive in addition to the antistatic function. In addition to these properties, properties such as ink adhesion of oil-based inks are required for factors such as the lot number on the protective film. Further, there is a demand for cost reduction, and it is required to form a coating that simultaneously satisfies the above-described characteristics in a single-layer coating.
As a material for forming such an antistatic layer, a conductive coating material including a conductive polymer is used.
Patent Document 1 discloses a conductive polymer composition for forming an antistatic layer. This conductive polymer composition is a composition comprising a polythiophene conductive polymer and a polyester binder and can form an antistatic layer having excellent adhesion on a resin substrate by drying at 100 DEG C for about one minute. However, since it is a solvent-drying type composition, the formed antistatic layer is insufficient in scratch resistance and solvent resistance. In order to secure these characteristics, it is necessary to laminate a top coat on the antistatic layer. Could not be satisfied.
Patent Document 3 discloses that an antistatic layer having a surface resistivity, a solvent resistance, scratch resistance, and a printability is formed as a single layer coating by a composition comprising a resin having active hydrogen, a polysiloxane-containing polyurethane resin, a polyisocyanate and an antistatic agent However, this composition is insufficient in the adhesiveness to the elements and requires aging at 40 DEG C for 48 hours in the formation of the antistatic layer, resulting in low productivity and is 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 thereof. The coating film formed using this composition has antifouling properties (contact angle against water) Of the pressure-sensitive adhesive layer. However, since the curing of this composition requires a condition of 140 占 폚 for 2 minutes, the productivity is low and it is not suitable for mass production.
Patent Document 5 discloses a composition comprising a conductive polymer, a melamine resin derivative and an acid catalyst. By using the composition, a film having antistatic function, scratch resistance, solvent resistance and antifouling property is cured at 100 占 폚 for 1 minute It can be formed at a low temperature in a short time. However, the film formed using this composition was incompatible with the printability, the factor adhesion, and the scratch resistance.
As described above, in the conventionally proposed conductive composition, when a conductive coating is formed by a one-layer coating, a conductive coating excellent in scratch resistance, solvent resistance, printability and printability is formed at a low-temperature short- I could not.
Particularly, scratch resistance and printability are generally in a trade-off relationship, and it is difficult to satisfy both of them at the same time.
The inventors of the present invention have conducted extensive studies in order to solve the above problems and found that the conductive polymer (a), the melamine resin derivative (b), the sulfonic acid curing catalyst (c), the terminal polyether modified silicone (d) And the conductive composition containing the solvent or the dispersion medium (f) can form a conductive film excellent in scratch resistance, solvent resistance, printability and printability by thermal curing at a low temperature in a short period of time. Respectively.
That is, the thermosetting conductive coating composition of the present invention,
(a) a conductive polymer,
(b) a melamine resin derivative,
(c) a sulfonic acid curing catalyst,
(d) a polyether-modified silicone of both ends,
(e) a conductivity improving agent, and
(f) a solvent or dispersion medium
. ≪ / RTI >
In the thermosetting conductive coating composition of the present invention, the conductive polymer (a) may be represented by the following formula (I):
[Chemical Formula 1]
(Wherein, R 1 and R 2 are each independently a hydrogen atom or a C 1 - represents a 4-alkyl group, or have one C 1 that may be substituted with - represents an alkylene group of 4) polyester having the repeating structure (3,4-dialkoxythiophene) or poly (3,4-alkylenedioxythiophene) and a dopant.
In the composition for a thermosetting conductive coating, 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.
In the thermosetting conductive coating composition, the sulfonic acid curing catalyst (c) is an aromatic sulfonic acid, and the content thereof is preferably 8 to 40 parts by weight per 100 parts by weight of the melamine resin derivative.
In the composition for a thermosetting conductive coating, it is preferable that the content of the polyether-modified silicone (d) is 10 to 60 parts by weight based on 100 parts by weight of the melamine resin derivative.
In the composition for a thermosetting conductive coating, the conductivity improving agent (e) is preferably a compound having at least one substituent selected from an amide group, a sulfo group and a hydroxyl group.
The thermosetting conductive coating composition preferably further contains (g) a water-soluble antioxidant, and the water-soluble antioxidant (g) is preferably ascorbic acid or erythorbic acid.
The thermosetting conductive coating composition preferably further comprises (h) a wettability improver.
The thermosetting conductive coating composition preferably further contains (i) a defoaming agent, and the defoaming agent (i) is preferably a silicone emulsion.
The optical film of the present invention is an optical film comprising a base material and a conductive film laminated on the base material,
The conductive coating is a coating formed by using the composition for a conductive coating of a thermosetting type of the present invention.
In the above optical film, it is preferable that the conductive film is formed by applying the composition for a thermosetting conductive coating onto the substrate and drying and thermosetting at a temperature of 130 ° C or lower. The calculated film thickness of the conductive film is preferably less than 45 nm.
The protective film of the present invention is characterized by comprising the optical film of the present invention.
According to the thermosetting conductive coating composition of the present invention, it is possible to form a conductive coating which simultaneously satisfies scratch resistance, solvent resistance, printability and printability by heat treatment (drying and thermosetting) at a low temperature for a short time.
By using the above-mentioned composition for a heat-curable conductive coating, it is possible to form a conductive coating that satisfies both excellent scratch resistance, good printability and good printability.
Since the optical film of the present invention is formed by coating and curing the thermosetting conductive coating composition of the present invention on a substrate, it has excellent conductivity and is excellent in resistance to scratches, solvent resistance, Film.
The optical film of the present invention is very suitable as a protective film, and a protective film comprising the optical film is also one of the present invention.
1 is a TEM observation image of the conductive film prepared in Example 28 at a magnification of 100,000 times.
First, the thermosetting conductive coating composition of the present invention will be described.
(B) a melamine resin derivative; (c) a sulfonic acid curing catalyst; (d) a terminal polyether modified silicone (hereinafter referred to as " conductive polymer " , (e) a conductivity improver, and (f) a solvent or a dispersion medium.
Hereinafter, each combination will be described in order.
1. Conductive polymer (a)
The conductive polymer (a) is a combination for imparting conductivity to the formed conductive coating (coating layer).
Examples of the conductive polymer include polythiophene, polypyrrole, polyaniline, polyacetylene, polyphenylene vinylene, polynaphthalene, derivatives thereof, and a complex of these with a dopant.
Among these, a polythiophene-based conductive polymer comprising a complex of a polythiophene and a dopant is preferable. As the polythiophene-based conductive polymer, poly (3,4-dialkoxythiophene) or poly (3,4- Alkylene dioxythiophene) and a dopant are more preferable.
Examples of the poly (3,4-dialkoxythiophene) or poly (3,4-alkylenedioxythiophene) include the following formula (I):
(2)
Is preferably a polythiophene in the form of a cation. Wherein, R 1 and R 2 are independently from each other hydrogen or C 1 - 4 alkyl group which may indicate, or be substituted is or are one C 1 - represents a group of 4 alkylene.
The C 1 - 4 as an alkyl group, for example a methyl group, may be mentioned an ethyl group, a propyl group, an isopropyl group, n- butyl group, isobutyl group, sec- butyl group, a t- butyl group.
In addition, R 1 and R 2 are defined as one, which is optionally substituted C 1 - 4 alkylene group, for example, methylene, 1,2-ethylene, 1,3-propylene group, 1 Methylene-1,2-ethylene group, 1-methyl-1,3-propylene group, 2-methyl-1,3-propylene group and the like . Preferably a methylene group, a 1,2-ethylene group or a 1,3-propylene group, and a 1,2-ethylene group is particularly preferable. As the polythiophene having an alkylene group, poly (3,4-ethylenedioxythiophene) is particularly preferable.
The composite made of poly (3,4-ethylenedioxythiophene) and the dopant has excellent chemical stability in addition to conductivity and transparency, and the conductive film formed by using the composite as the conductive polymer has very stable conductivity Very high transparency.
Further, since the conductive composition containing this complex as the conductive polymer can form a film at a low temperature in a short time, it is also very suitable for the production of an optical film such as a protective film which requires mass production.
The dopant constituting the polythiophene-based conductive polymer is an anion-type polymer capable of forming a complex by forming an ion pair with the polythiophene described above and stably dispersing the polythiophene in water.
Examples of the dopant include carboxylic acid polymers (e.g., polyacrylic acid, polymaleic acid, polymethacrylic acid, etc.), sulfonic acid polymers (e.g., polystyrenesulfonic acid, polyvinylsulfonic acid, polyisoprenesulfonic acid, etc.) . These carboxylic acid polymers and sulfonic acid polymers may also be copolymers of vinylcarboxylic acids and vinylsulfonic acids with other polymerizable monomers such as acrylates, aromatic vinyl compounds such as styrene and vinylnaphthalene. Among them, polystyrene sulfonic acid is particularly preferable.
The polystyrene sulfonic acid preferably has a weight average molecular weight of more than 20,000 and not more than 500,000. More preferably 40,000 to 200,000. When polystyrene sulfonic acid having a molecular weight outside this range is used, the dispersion stability of the polythiophene-based conductive polymer to water may be lowered. The weight average molecular weight of the polymer is a value measured by gel permeation chromatography (GPC). An ultra hydrogel 500 column manufactured by Waters Corporation was used for the measurement.
The content of the conductive polymer is preferably 0.01 to 1.2% by weight in terms of solid content with respect to the entire conductive composition. More preferably 0.03 to 0.5% by weight. When the content is less than 0.01% by weight, conductivity is difficult to be exhibited. When the content is more than 1.2% by weight, precipitation may occur due to mixing with the inert ingredient.
2. Melamine resin derivatives (b)
The melamine resin derivative (b) is a melamine resin derivative (b) which imparts a thermosetting property at a low temperature to a conductive composition and has a film appearance, conductivity (for example, surface resistivity, hereinafter referred to as SR), transparency And a haze value, hereinafter referred to as Haze), an adhesion property to a substrate, and a solvent resistance.
The above-mentioned melamine resin derivative can be obtained, for example, by the following formula (II):
(3)
Represented by - (4 represents an alkyl group of the formula, R 3 ~ R 8 denotes H or a CH 2 OR 9, R 9 is H or C 1). A melamine resin derivative in which all of the substituents R 3 to R 8 are hydrogen atoms is an imino type melamine resin derivative and all of the substituents R 3 to R 8 are CH 2 OH is a methylol type melamine resin derivative and the substituents R 3 to R is the is substituted with an alkyl group of 4 derivative is a melamine resin pool ether type melamine resin derivatives 8 are both a CH 2 OR 9, R 9 is C 1.
The melamine resin derivatives having a structure in which two of the above three substituents are mixed in one molecule are classified into iminomethyl, methylol, and iminoether types, and melamine resin derivatives in which all are mixed include iminomethylol Ether type.
When R 3 to R 8 are CH 2 OR 9 and R 9 is an alkyl group having 1 to 4 carbon atoms, examples of the C 1-4 alkyl group include a methyl group, an ethyl group, a propyl group and a butyl group. In view of low-temperature curability, a methyl group is preferable. The melamine resin derivative may be an oligomer that is self-condensed with the formula (II) as a basic skeleton.
These melamine resin derivatives may be used alone, or two or more of them may be used in combination.
Of the melamine resin derivatives having the above structure, the full ether type melamine is more preferable, and the full ether type melamine wherein R 9 is a methyl group is preferable from the viewpoints of the stability of the conductive composition and the curing property at low temperature. When the melamine resin derivative is an oligomer, in consideration of the pot life of the conductive composition, the average degree of polymerization is preferably low, more preferably 1.0 to less than 1.8.
In the present specification, the term "pot life" of the conductive composition means the appearance (presence or absence of precipitation) of the conductive composition (coating liquid), the appearance of the formed conductive film, transparency, conductivity, adhesion to substrate, scratch resistance, The solvent resistance, the solvent resistance, the solvent resistance, the solvent resistance, the solvent resistance, the printability, the printability, and the like.
The content of the melamine resin derivative (b) in the electrically conductive film cured at a low temperature is preferably 150 to 750 parts by weight based on 100 parts by weight of the solid content of the electrically conductive polymer (a) so that the electrically conductive film is excellent in film appearance, conductivity, transparency, adhesion to substrates, . More preferably 250 to 450 parts by weight.
When the content exceeds 750 parts by weight, the conductivity of the coating may be lowered, or the coating may be whitened to lower the transparency. On the other hand, when the amount is less than 150 parts by weight, sufficient solvent resistance is not imparted to the coating film.
3. The sulfonic acid curing catalyst (c)
The sulfonic acid curing catalyst (c) has a role of promoting the crosslinking of the melamine resin derivative (b) on the substrate during drying and curing. Since the sulfonic acid exhibits acidity in the conductive composition, the crosslinking of the melamine resin derivative in the conductive composition is promoted, and the pot life of the coating liquid is shortened.
The sulfonic acid curing catalyst also has a function of improving the leveling property of the conductive composition to the base material.
Therefore, it is preferable that the sulfonic acid curing catalyst is a structure capable of accelerating curing on the substrate and also capable of leveling the base material of the conductive composition and maintaining the pot life of the conductive composition.
Examples of such sulfonic acid curing catalysts include aliphatic or aromatic sulfonic acids.
Examples of the aliphatic sulfonic acid include methanesulfonic acid, trifluoromethanesulfonic acid, isoprenesulfonic acid, camphorsulfonic acid, hexanesulfonic acid, octanesulfonic acid, nonanesulfonic acid, decanesulfonic acid and hexadecanesulfonic acid. Examples of the aromatic sulfonic acid include benzenesulfonic acid, p-toluenesulfonic acid, cumenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, nonylnaphthalenesulfonic acid and the like.
Of these, aromatic sulfonic acids are preferable, and dodecylbenzenesulfonic acid is particularly preferable in view of the pot life of the coating liquid and the curing property at a low temperature.
The upper limit of the content of the sulfonic acid curing catalyst is preferably 40 parts by weight, more preferably 33 parts by weight, based on 100 parts by weight of the melamine resin derivative. The lower limit thereof is preferably 8 parts by weight based on 100 parts by weight of the melamine resin derivative. When the content is within this range, the melamine resin derivative can be cured in a short time at a low temperature, and the pot life of the coating liquid can be sufficiently maintained.
On the other hand, if the content is more than 40 parts by weight, the pot life of the coating liquid tends to be not maintained. If the content is less than 8 parts by weight, film formability of the conductive composition is deteriorated, Or the solvent resistance of the coating may be lowered.
4. Both ends polyether-modified silicone (d)
The endohedral polyether-modified silicone (d) has a role of imparting scratch resistance, solvent resistance, printability, and print adhesion to the conductive film.
Particularly, in the thermosetting conductive coating composition of the present invention, since the polyether-modified silicone at both ends is used in combination with the other components, scratch resistance and film adhesion can be simultaneously imparted to the conductive film formed.
Among the polyether-modified silicones, there are a side-chain-modified type and a hosome-modified type. Among them, the scratch-ability and the factor-attaching property are simultaneously imparted to the conductive film specifically formed only when the polyether- And even if side-chain polyether-modified silicon is used, such effect can not be obtained. These findings are newly discovered by the inventors of the present invention.
The reason why the above-mentioned effects can be attained by using polyether-modified silicon having both terminals is as follows. (1) Since the orientation of the polyether-modified silicone to the surface of the conductive film is improved and excellent slipperiness is exhibited, The scratch resistance is improved, (2) the adhesion of the ink is improved by the polyether chain at both ends, and (2) the printability and the printability can be imparted at a high level.
Also, when polyether-modified silicone of both ends is used, the solvent resistance is also maintained. This is presumably because the cross-linked polyether-modified silicone is uniformly oriented on the surface, so that the cross-linking of the melamine resin derivative is not inhibited and the cross-linking density of the film is not lowered.
Examples of the polyether-modified silicone at both ends include, for example, the following formula (III):
[Chemical Formula 4]
(Wherein R 10 is a polyether group, 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, R 11 (C 2 H 4 O) a (C 3 H 6 O) b R 12 , and R 11 and R 12 in the polyether group each independently represent an alkyl group or an alkylene group. The polyether groups R 10 at both ends of the formula (III) may be the same or different.
The degree of polymerization (n) of the polysiloxane is preferably 380 or less, more preferably 45 to 230. By blending the polysiloxane having the above degree of polymerization, excellent scratch resistance can be imparted to the formed conductive film.
The degree of polymerization (a and b) of the polyether group contained in R 10 is not particularly limited as long as the solubility of the polyether-modified silicone in both ends is maintained and the required characteristics are exhibited in the conductive composition.
The skeleton of the polyether group may be ethylene oxide, propylene oxide, or a copolymer of ethylene oxide and propylene oxide. Of these, ethylene oxide is preferable from the viewpoint of water solubility, and a copolymer of propylene oxide and ethylene oxide and propylene oxide is preferable in view of the printability and the factor adhesion.
As described above, by selecting the polyether-modified silicone having the optimum structure, it is possible to ensure compatibility between the scratch resistance and the printability of the formed conductive film.
The polyether-modified silicone of both ends contained in the conductive composition makes it possible to form a conductive film having excellent scratch resistance without deteriorating the solvent resistance and excellent in the printability and printability. Is preferably a polyether-modified silicone of both ends. One kind of polyether-modified polyether represented by the formula (III) may be used singly or two or more polyether-modified polyols having different molecular weights may be used in combination.
The upper limit of the content of the polyether-modified silicone is preferably 60 parts by weight, more preferably 33 parts by weight, based on 100 parts by weight of the melamine resin derivative. The lower limit thereof is preferably 10 parts by weight per 100 parts by weight of the melamine resin derivative.
This is because if the content is within this range, scratch resistance, printability and printability can be simultaneously imparted to the formed film.
On the other hand, when the content of the polyether-modified silicone at both ends exceeds 60 parts by weight, the solvent resistance of the formed coating may be deteriorated.
5. Conductivity improver (e)
The conductivity improving agent (e) contained in the conductive composition can improve the conductivity of the formed conductive coating.
Examples of the conductive enhancer (e) include amide compounds such as N-methylformamide, N, N-dimethylformamide,? -Butyrolactone and N-methylpyrrolidone, ethylene glycol, diethylene glycol, Propylene glycol, trimethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, catechol, cyclohexanediol, cyclohexanedimethanol, glycerin, diethylene glycol monoethyl Compounds containing a hydroxyl group such as ether and propylene glycol monomethyl ether, carbonyl group-containing compounds such as isophorone, propylene carbonate, cyclohexanone, acetylacetone, ethyl acetate, ethyl acetoacetate, methyl orthoacetate and ethyl orthoformate; And compounds having a sulfo group such as a side group.
Among these, an amide compound, a hydroxyl group-containing compound and a sulfo group-containing compound are preferable from the viewpoints of pot life of the coating liquid and curability at low temperature, transparency of the formed conductive film, scratch resistance, solvent resistance, -Methylpyrrolidone, dimethylsulfoxide, and ethylene glycol are particularly preferred.
The content of the conductive enhancer is not particularly limited, but is preferably contained in the conductive composition in an amount of 0.1 to 60% by weight.
6. Solvent or dispersion medium (f)
The solvent or 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 a mixture thereof.
In the present invention, when each component other than the solvent or dispersion medium contained in the conductive composition is dissolved, it is referred to as a solvent, and when at least one component constituting the composition is uniformly dispersed, it is referred to as a dispersion medium.
In the conductive composition, the melamine resin derivative may not dissolve in water. In this case, a mixture of water and an organic solvent may be used as a solvent or a dispersion medium. When a mixture of water and an organic solvent is used, the organic solvent preferably contains an organic solvent that is miscible with at least one kind of water. If the organic solvent contains water-miscible organic solvent, (Hydrophobic) organic solvent which does not miscible with water. The use of a mixture of an alcohol-based organic solvent having a low boiling point as a solvent or a dispersion medium improves volatility and may be advantageous in drying and thermosetting. When a resin substrate is used, the alcohol-based organic solvent can contribute to an improvement in leveling property.
Further, in the present specification, the aqueous thermosetting conductive coating composition means a composition for a thermosetting conductive coating, which is a mixture of water or an organic solvent which is miscible with water, wherein the solvent or dispersion medium is a water- The composition is a composition for a thermosetting conductive coating in which the solvent or the dispersion medium contains an organic solvent which is insoluble in water.
6-1. Organic solvent
Examples of the organic solvent include those capable of uniformly dissolving or dispersing a component such as a melamine resin derivative which is difficult to dissolve in water.
Examples of the organic solvent to be mixed with water include alcohols such as methanol, ethanol, 2-propanol and 1-propanol, ethylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol and tetraethylene glycol, Glycol ethers such as ethylene glycol monomethyl ether, glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol diethyl ether and diethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether Propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, Propylene glycol dimethyl ether Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, Propylene glycol ether acetates such as propylene glycol monoethyl ether acetate, etc .; tetrahydrofuran, acetone, acetonitrile, and mixtures thereof.
Examples of the hydrophobic organic solvent include esters such as ethyl acetate, butyl acetate and ethyl lactate; ethers such as diisopropyl ether and diisobutyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; Ketones, 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 alone or in combination of two or more.
When the conductive composition is an aqueous 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 are not uniformly dissolved or dispersed, and the film formability is deteriorated, so that the performance may not be exhibited. When 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 conductive composition of the water system include distilled water, ion-exchanged water, and ion-exchanged distilled water. The water also includes an aqueous dispersion of the conductive polymer and moisture contained in the other components.
The content of the water is preferably 1% by weight or more based on the entire conductive composition.
When the conductive composition is an aqueous conductive composition, the pH of the conductive composition is preferably in the range of 1 to 14, more preferably 1 to 7, particularly preferably 1.5 to 3 in view of the curing property at low temperature Do. 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, the amount of the pH adjuster to be added is such that the base forms an acid and a salt to lower the curing promoting effect of the melamine resin derivative. On the other hand, the higher the pH of the conductive composition, the lower the curing property at low temperature. The self-crosslinking in the solution of the solution is inhibited. Therefore, it may be suitably determined in consideration of the stability of the solution and the pot life may be improved. The pH adjusting agent is an optional component in the conductive composition.
In addition, the conductive composition containing the components (a) to (f) as described above contains 150 to 750 parts by weight of the full ether type melamine resin derivative (b) based on 100 parts by weight of the solid content of the conductive polymer, The curing catalyst (c) contains 8 to 40 parts by weight of an aromatic sulfonic acid based on 100 parts by weight of the melamine resin derivative, 10 to 60 parts by weight of the polyether-modified silicone (d) of both ends with respect to 100 parts by weight of the melamine resin derivative , And a compound having at least one of an amide group, a hydroxyl group and a sulfo group as the conductivity improver (e) is particularly preferable because the pot life of the conductive composition is remarkably improved.
The components (a) to (f) described so far are indispensable components in the thermosetting conductive coating composition of the present invention.
The thermosetting conductive coating composition of the present invention may contain a water-soluble antioxidant (g), a wettability improver (h), a defoaming agent (i) and the like, if necessary.
7. Water-soluble antioxidant (g)
The conductive composition may contain a water-soluble antioxidant (g). When the conductive coating film is formed, the water-soluble antioxidant (g) is uniformly present in the conductive polymer in the coating film, and functions to effectively suppress the increase in resistance due to air exposure.
Further, the oil-soluble antioxidant can not exist uniformly in the film, and the increase in resistance due to air exposure can not be effectively suppressed.
Examples of the water-soluble antioxidant include a reducing or non-reducing water-soluble antioxidant.
Examples of the water-soluble antioxidant having reducibility include two hydroxyl groups such as L-ascorbic acid, sodium L-ascorbate, potassium L-ascorbate, erosorbic acid, sodium erisorbate, potassium erythorbate, A compound having a substituted lactone ring, a monosaccharide or a disaccharide such as maltose, lactose, cellobiose, xylose, arabinose, glucose, fructose, galactose, mannose, etc .; catechin, rutin, myrcetin, quercetin, A compound having two or more phenolic hydroxyl groups such as curcumin, rosemarinic acid, chlorogenic acid, hydroquinone and 3,4,5-trihydroxybenzoic acid, a compound having two or more phenolic hydroxyl groups such as cysteine, glutathione, pentaerythritol tetrakis (3-mercaptobutyrate ), And the like.
Examples of the non-reducing water-soluble antioxidant include phenylimidazole sulfonic acid, phenyltriazole sulfonic acid, 2-hydroxypyrimidine, phenyl salicylate, 2-hydroxy-4-methoxybenzophenone- And compounds capable of absorbing ultraviolet rays which cause deterioration of oxidation of sodium and the like. These may be used alone or in combination of two or more.
Among these water-soluble antioxidants, ascorbic acid and erysorbic acid are preferable, and ascorbic acid is more preferable.
This is because the effect of suppressing an increase in resistance due to air exposure and the effect that the formed conductive film is excellent in transparency are remarkably exhibited.
The content of the water-soluble antioxidant is not particularly limited, but the upper limit 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.
If the content is more than 60 parts by weight, the solvent resistance of the formed conductive coating may be lowered. On the other hand, if the content is less than 9 parts by weight, the SR increase rate due to air exposure may be increased.
8. Wettability improver (h)
The conductive composition may contain a wettability improving agent (h). The wettability improver (h) improves the wettability of the conductive composition with respect to the base material, and makes it possible to improve the uniformity of the conductive film to be formed.
Examples of the wettability improver include an acrylic copolymer and a polyoxyethylene fatty acid ester compound.
Of these, an acrylic copolymer is preferred. This is because the conductive film has excellent transparency, scratch resistance and solvent resistance.
The content of the wettability improving agent as a solid content is not particularly limited, but the upper limit is preferably 70 parts by weight, more preferably 40 parts by weight, based on 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.
If the content is more than 70 parts by weight, the cross-linking density of the melamine resin derivative may be lowered and the solvent resistance may be deteriorated. When the content is less than 4 parts by weight, the film formability may not be improved and the film may be uneven.
9. Defoamer (i)
The conductive composition may contain an antifoaming agent (i). By blending the antifoaming agent (i), it is possible to effectively bubble out, thereby suppressing the generation of bubbles in the conductive composition.
Examples of the defoaming agent include glycol compounds such as polyacetylene glycol, siloxane compounds such as organic modified polysiloxane, emulsions obtained by dispersing polydimethylsiloxane in water with an emulsifier, and the like.
Of these, polydimethylsiloxane emulsions are preferred because they are excellent in bubble resistance.
The content of the defoaming agent is not particularly limited, but is preferably 1 to 30 parts by weight based on 100 parts by weight of the polyether modified silicone 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 may be deteriorated. When the amount is less than 1 part by weight, the defoaming property is not improved, and bubbles may remain for a long time.
The thermosetting conductive coating composition of the present invention may contain other components in addition to the components described above.
10. Other ingredients
10-1. Binder resin
The conductive composition may contain a binder resin for the purpose of improving the film forming property and the printing property of the conductive film formed.
In the conductive composition of the present invention, the self-crosslinking film of the melamine resin derivative has a binder function. However, by adding the binder resin, the film-forming property, the flexibility of the film and the adhesion property, .
Examples of the binder resin include polyolefins such as polyester, poly (meth) acrylate, polyurethane, polyvinyl acetate, polyvinylidene chloride, polyamide, polyimide, polyvinyl alcohol, polyacrylic polyol, And copolymers containing a compound selected from the group consisting of styrene, vinylidene chloride, vinyl chloride and alkyl (meth) acrylate as a copolymerizable 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. If the amount of the binder resin exceeds 200 parts by weight, the crosslinking density of the melamine resin derivative is lowered, and the solvent resistance of the formed conductive coating may be deteriorated.
The thermosetting 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 and solvent resistance. It is conceivable that the coating formed on the self-crosslinking of the melamine resin derivative has a high crosslinking density for reasons of excellent scratch resistance and solvent resistance.
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, the melamine resin derivative also functions as a crosslinking agent for the binder resin. The melamine resin derivative functions as a crosslinking agent for the binder resin, And the solvent resistance or solvent resistance tends to be lower than that of the self-crosslinking film of the melamine resin derivative.
10-2. Surfactants
The conductive composition may contain a surfactant for the purpose of improving the leveling property.
Examples of the surfactant include fluorinated surfactants such as perfluoroalkylcarboxylic acid and perfluoroalkylpolyoxyethylene ethanol; polyethers such as polyoxyethylene alkylphenyl ether, propylene oxide polymer and ethylene oxide polymer; Ester compounds such as castor oil sulfates, phosphoric acid esters, alkyl ether sulfates, sorbitan fatty acid esters, sulfonic acid esters, and succinic acid esters; alkylarylsulfonic acid amine salts Sulfonic acid salt compounds such as dioctyl sodium sulfosuccinate, phosphate compounds such as sodium lauryl phosphate, amide compounds such as palm oil fatty acid ethanol amide, anionic surfactants, cationic surfactants, nonionic surfactants, silicone modified acrylic compounds And 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 density of the melamine resin derivative is lowered, and the solvent resistance of the formed conductive coating may be deteriorated.
10-3. Silane coupling agent
The conductive composition may contain a silane coupling agent for the purpose of improving the solvent resistance, the printability, and the print adhesion of the conductive film.
Examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-mercapto Trimethoxysilane, and the like.
The content of the silane 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 the amount is more than 100 parts by weight, the crosslinking density of the melamine resin derivative is lowered, and the solvent resistance of the formed conductive coating may be deteriorated.
10-4. Thickener
The conductive composition may contain a thickening agent for the purpose of improving the viscosity of the conductive composition.
Examples of the thickening agent include water-soluble polymers such as salts and derivatives of alginic acid, xanthan gum derivatives, and saccharide compounds such as carrageenan and cellulose.
The content of the thickener 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 density of the melamine resin derivative is lowered, and the solvent resistance of the formed conductive coating may be deteriorated.
10-5. Particulate material
The conductive composition may contain a particulate material such as colloidal silica, hollow silica, fluorine resin fine particles, and metal fine particles such as titanium for the purpose of improving the slip property, the printing property and the print adhesion property of the conductive coating film.
The content of the particulate 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 the amount is more than 100 parts by weight, the crosslinking density of the melamine resin derivative is lowered, and the solvent resistance of the formed conductive coating may be deteriorated.
10-6. The organic carboxylic acid compound
The conductive composition may contain an organic carboxylic acid having a carboxyl group for the purpose of improving the printability of the conductive coating film and the adhesion of the ink.
The organic carboxylic acid may be an aliphatic or aromatic monovalent or polycarboxylic acid and may contain a functional group such as a hydroxyl group or a vinyl group in the molecule. Examples of the aliphatic carboxylic acid include aliphatic carboxylic acids such as acetic acid, butyric acid, hexanecarboxylic acid, octanecarboxylic acid, acetoacetic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, , And citric acid. 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 an optical film comprising a base material and a conductive film laminated on the base material,
The conductive coating is a coating formed by using the composition for a conductive coating of a thermosetting type of the present invention.
The optical film comprises a base material and a conductive film laminated on the base material.
Examples of the substrate include a resin substrate and a glass substrate.
Examples of the material resin of the resin base material include polyolefin resins such as polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, ionomer copolymer and cycloolefin resin; polyolefin resins such as polyethylene terephthalate, Polyester resins such as polybutylene terephthalate, polycarbonate, polyoxyethylene, modified polyphenylene and polyphenylene sulfide; nylon 6, nylon 6,6, nylon 9, semiaromatic polyamide 6T6, semiaromatic polyamide 6T66 , And semi-aromatic polyamide 9T; acrylic resins, polystyrene, acrylonitrile-styrene copolymers, acrylonitrile-butadiene-styrene copolymers, vinyl chloride resins and triacetylcellulose.
It is also preferable that the substrate is transparent (having a high transmittance).
Among these, in the case of an optical film used as a protective film, polyethylene terephthalate and triacetyl cellulose are preferably used from the viewpoints of workability and functionality.
The shape of the base material is not particularly limited and may be appropriately selected in accordance with the shape of the optical film, and examples thereof include film, plate, and other desired shapes. Therefore, various materials such as a film, a sheet, a plate, and a molded product may be used as the substrate.
The surface of the substrate may be subjected to physical treatment such as corona treatment, flame treatment, plasma treatment, or the like. By carrying out these treatments, the coatability of the conductive composition can be improved.
The conductive film is a film formed by using the conductive composition of the present invention. The conductive film is formed by applying the conductive composition onto a substrate, followed by drying and thermosetting.
The method of applying the conductive composition to the substrate is not particularly limited and may be appropriately selected from the general methods in the art and includes, for example, spin coating, gravure coating, bar coating, dip coating, curtain coating, Spray coating and the like.
The conductive composition may be applied by a printing method such as screen printing, spray printing, inkjet printing, relief printing, concave printing, and flat printing.
When the conductive composition is applied, a coating liquid in which the conductive composition is previously diluted with 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 according to 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.
Further, the calculated film thickness can be calculated from the following calculation formula, provided that the specific gravity of the coating liquid and the specific gravity of the film after drying can be approximated to 1.
"Film thickness = concentration (%) of coating liquid ÷ 100 × theoretical coating amount (탆) of wire bar"
Since the application amount of the wire bar is usually smaller than the theoretical value, the actual film thickness becomes thinner than the calculated value.
The conductive film has conductivity because it contains a conductive polymer, and its surface resistivity is preferably 10 4 to 10 11 Ω / □. This is because the surface resistivity in this range satisfies the required characteristics of the antistatic layer sufficiently.
The conductive film is formed by heating a conductive composition applied to a substrate to evaporate the solvent or the dispersion medium and to thermally cure (dry or thermoset) the conductive composition. Here, the heating condition is preferably a condition of heating for 1 minute (30 to 90 seconds) at a temperature of 130 占 폚 or less (80 占 폚 to 130 占 폚). In the conductive composition of the present invention, the conductive film can be sufficiently formed under the above conditions, and the above conditions are in a short time at a low temperature in the technical field of the present invention, so that the productivity is also excellent.
If the curing is insufficient under these conditions, it may be post-cured for 1 hour to several weeks in a drier or storage at 25 占 폚 to 60 占 폚 in a roll film form after roll coating.
Drying and thermal curing for evaporating a solvent or a dispersion medium may be carried out using a conventional air drier, a hot-air drier, an infrared drier, or the like. To simultaneously perform drying and heating, it is necessary to use a dryer (hot-air dryer, infrared dryer, etc.) having a heating means. As the heating means, a heating / pressing roll having a heating function, a press machine, or the like may be used in addition to the dryer.
As described above, the conductive composition of the present invention contains, as an essential component, a conductive polymer, a melamine resin derivative, a sulfonic acid curing catalyst, a polyether modified silicone of both ends and a conductive improver, and a solvent or a dispersion medium. Accordingly, it contains a water-soluble antioxidant, a wettability improver, a defoaming agent, a binder resin, a surfactant, a silane coupling agent, a thickener, and a particulate material.
The composition having such a constitution is usually supplied in a state in which the melamine resin derivative and the acidic component are separated from each other in order to prevent the self-crosslinking of the melamine resin derivative in the solution. As the component exhibiting acidity, a conductive polymer or a sulfonic acid curing Catalyst and the like).
Then, the above components are mixed at a predetermined ratio before use, and all components are used in a mixed state. When the acidic component is neutralized with a base or the like, storage stability can be maintained even when all the components are mixed and supplied.
In general, the coating liquid for preparing the conductive composition is supplied in a 2 to 3 liquid state in which the melamine resin derivative and the acidic component are separated from each other in consideration of the pot life and storage stability of the composition. The components of these coating liquids may be sufficiently concentrated in terms of cost.
The method for preparing the above conductive composition (coating liquid) is not particularly limited, but each component is mixed and stirred with a stirrer such as a mechanical stirrer or a magnetic stirrer. Here, the stirring is preferably continued for about 1 to 60 minutes.
In addition, at the time of stirring, it is preferable to first add a diluent such as alcohol in order to avoid mixing the conductive polymer or the sulfonic acid curing catalyst, and furthermore, the melamine resin derivative at a high concentration.
Particularly, when a solution containing a water-soluble electroconductive polymer is mixed with a solution containing an organic solvent such as alcohol at a high concentration, the dispersion stability is lowered and coagulation may occur to deteriorate the pot life.
Further, when the melamine resin derivative and the acidic component are directly mixed, the self-crosslinking of the melamine tends to proceed in the solution, so that the pot life of the conductive composition may be shortened.
In addition, since the pot life of the conductive composition depends on the temperature of the composition, it is preferable to maintain the pot life of the conductive composition lower than 30 캜. A more preferable liquid temperature is -5 to 10 占 폚.
The conductive composition is stable at room temperature around 25 ° C. However, when the conductive composition contains an acidic component, the self-crosslinking of the melamine resin derivative proceeds in the liquid, and the pot life may be deteriorated.
Since the pot life depends on the temperature of the coating liquid, the pot life can be improved by applying the coating with the temperature maintained at -20 캜 to 20 캜. Particularly preferably -5 ° C to 10 ° C.
The lower the temperature, the better the pot life. In the case of aqueous conductive compositions, the composition may freeze at temperatures below -20 ° C. It is preferable that the conductive composition is prepared by keeping the temperature lower than 30 占 폚 from the time of preparation, and it is more preferable that the temperature is maintained at -5 占 폚 to 10 占 폚.
The optical film having such a configuration is preferable as an optical film having an antistatic layer for use in a liquid crystal display, a polarizing plate, an electroluminescence display, a plasma display, an electrochromic display, a solar cell and the like.
The above optical film is particularly preferable as a protective film, and a protective film comprising the optical film of the present invention is also one of the present invention.
In the case of a protective film, the substrate is preferably polyethylene terephthalate in view of workability, hardness, transparency and the like.
Example
Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to these examples.
(Examples 1 to 27 and Comparative Examples 1 to 9)
Each component (raw material) shown in Table 1 was added to the solvent or dispersion medium while stirring the components. After confirming that the added components were dissolved or uniformly dispersed, the following components were added, all the components were added, and the mixture was further stirred for about 5 minutes to prepare a thermosetting conductive coating composition in a solution or dispersion state Respectively. Thereafter, the composition was diluted (1: 5, weight ratio) with 80% ethanol six times to prepare a coating liquid.
Immediately after the coating liquid was prepared, the coating liquid was coated on a substrate made of a polyethylene terephthalate film (Lumirra T-60 (trade name) manufactured by Toray Industries, Inc.). (Wet film thickness: 9 占 퐉), and dried and thermally cured at 130 占 폚 for 1 minute by a hot-air drier to form a conductive film.
As an evaluation of pot life, a conductive coating film was similarly formed even after 24 hours from the preparation of the thermosetting conductive coating composition.
(Example 28)
Each component (raw material) shown in Table 2 was added with stirring one by one in the same manner as in Examples 1 to 27 to prepare a thermosetting conductive coating composition. Thereafter, the composition was diluted (1: 3, weight ratio) with 80% ethanol four times to prepare a coating liquid.
Immediately after the coating liquid was prepared, the coating liquid was coated on a substrate made of a polyethylene terephthalate film (Lumirra T-60 (trade name) manufactured by Toray Industries, Inc.). (Wet film thickness: 9 占 퐉), and dried and thermally cured at 130 占 폚 for 1 minute by a hot-air drier to form a conductive film.
As an evaluation of pot life, a conductive coating film was similarly formed even after 24 hours from the preparation of the thermosetting conductive coating composition.
The conductive film thus formed was cut out and subjected to TEM observation. The results are shown in Fig.
1 is a TEM observation image of a conductive film produced in Example 28 at a magnification of 100,000 times. 1, reference numeral 1 denotes a conductive film, and 2 denotes a PET film. In the figure, a scale bar having a length of 115 nm is shown at the lower right.
I. Materials Used
I.1 Conductive polymer (a)
Clevios P (trade name) manufactured by HC Stark Co. (1.3 wt% poly (3,4-ethylenedioxythiophene)), which is an aqueous dispersion of a conductive polymer composed of a composite of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid, Ethylenedioxythiophene) / polystyrenesulfonic acid (weight average molecular weight = 150,000), and water (98.7 wt%) were used.
I.2 Melamine resin derivatives (b)
A melamine resin derivative, Japan Carbide Industries Co. of NIKA lock MW-390 (full-ether, formula (II) of R 9 is a methyl group, polymerization degree: 1.00), NIKA lock MS-11 (methyl-rolled, 60% by weight product, formula (R 9 in the formula (II) is a hydrogen atom, degree of polymerization: 1.80) and Cymeel 300 (full ether type, R 9 is methyl group in the formula (II), degree of polymerization: 1.35) manufactured by Japan Cytech Industries Co., Type, R 9 in formula (II) is methyl group, degree of polymerization: 1.40) (the above names are all trade names).
I.3 Sulfonic Acid Hardening Catalyst (c)
As a sulfonic acid curing catalyst, Teakatox T-500 (trade name) (molecular weight 187.2; compound name: cumene sulfonic acid; hereinafter referred to as QS) manufactured by Teika Corporation and NEOPELEX GS (trade name) , Dodecylbenzenesulfonic acid (hereinafter referred to as DBS) was used. In the comparative example, nitric acid (molecular weight 63.01; 60 wt.%) Manufactured by Wako Pure Chemical Industries, Ltd. was diluted to 2 wt% as an acid catalyst.
I.4 Polyether-modified silicone (d)
8029 additive (trade name) manufactured by Toray · Dow Corning Corporation, polyfluor KL-402 (trade name) manufactured by Kyowa Chemical Industry Co., Ltd. or BYK-378 (trade name) manufactured by BYK Co., Ltd. was used as the polyether- .
In some of the comparative examples, KF-355A (trade name) manufactured by Shin-Etsu Chemical Co., Ltd., BYK-348 (trade name) and BYK-307 (trade name) YF-3842 (trade name) was also used.
I.5 Water-soluble antioxidant (g)
As the water-soluble antioxidant, ascorbic acid or erysorbic acid manufactured by Wako Pure Chemical Industries, Ltd. was used.
Dry mix FS-20 (trade name) (main component: vitamin E) manufactured by Riken Vitamin Co., Ltd. was also used as the organic solvent-soluble antioxidant.
I.6 Conductivity improver (e)
(Hereinafter referred to as NMP), dimethylsulfoxide (hereinafter referred to as DMSO), or ethylene glycol (hereinafter referred to as EG), N-methylformamide (hereinafter referred to as NMF) Were used.
I.7 Organic solvents (f)
As the organic solvent, first grade ethanol manufactured by Wako Pure Chemical Industries, Ltd. was used.
I.8 Water (f)
Most of the water is the water contained in the conductive polymer, Clevios P, and the newly added water is pure water with ion exchange treatment.
The water described in Tables 1 and 2 is newly added water.
I.9 Wettability improver (h)
BYK-380N (trade name) (trade name: acrylic copolymer) manufactured by BYK Co., Ltd. was used as a wettability improver.
I.10 Antifoaming agent (i)
Antifoam 013A (trade name) (emulsion of polydimethylsiloxane, hereinafter referred to as 013A) manufactured by Toray Dow Corning Corporation was used as a defoaming agent.
I.11 Other additives
Other additives include SIRQUEST A-189 (trade name) (trade name: 3-mercaptopropyltriethoxysilane) manufactured by Momentive Performance Materials, Inc., a silane coupling agent, Snowtex OXS (Trade name) (compound: colloidal silica aqueous dispersion) and trimellitic acid (trade name) manufactured by Mitsubishi Gas Chemical Company, an organic carboxylic acid, were used.
II. evaluation
The outer appearance of the coating liquid prepared in Examples 1 to 28 and Comparative Examples 1 to 9 and the outer appearance of the conductive film obtained by using the same, scratch resistance, solvent resistance, printability and adhesion of the ink were evaluated in the following three stages Respectively. SR, Tt and Haze were measured. The adhesion to the substrate was evaluated according to JIS K 5400. Pot life was evaluated by using the coating liquid at the lapse of 24 hours from the liquid preparation and the coating formed using the coating liquid. The port life of the coating liquid was evaluated in the same manner as the initial value with respect to the appearance of the coating liquid, the appearance of the coating, the adhesion, the scratch resistance, the solvent resistance, the printability and the print adhesion. On the other hand, SR, Tt, and Haze of the coating film were evaluated from the initial values of the measurement values in the following three stages. In addition, the pot life was not evaluated for the examples and comparative examples in which "X" was evaluated even in one of the initial evaluations.
The evaluation results are shown in Tables 3 and 4 below.
II.1 Appearance of Composition for Conductive Coating
The appearance of the liquid after preparation of the composition was visually evaluated in three stages. Port life was evaluated in the same manner.
◎: No precipitation occurred
○: A small amount of precipitate was generated
×: gelation
II.2 Coating appearance
The appearance (uniformity) of the conductive film after application was visually evaluated in the following three steps. Port life was evaluated in the same manner.
⊚: Coating is uniformly applied, and coating unevenness is not observed
○: There is a little uneven application
X: No film was formed by cratering
II.3 Surface resistivity / SR (Ω / □)
The surface resistivity was measured using an UA probe of Hiresta UP (MCP-HT450 type, trade name) manufactured by Mitsubishi Chemical Corporation under an applied voltage of 100 V in accordance with JIS K 7194, and the measured value was evaluated. Portlife evaluated the initial magnification factor by the following three steps.
◎: 10 times or less
○: more than 10 times but less than 100 times
×: 100 times or more
II.4 Total light transmittance (Tt:%)
The total light transmittance was measured using Hayes computer HGM-2B (trade name) manufactured by Sigma-Aldrich, according to JIS K 7150, and the measured value was evaluated. Portlife evaluated the change in initial value in the following three stages.
?: Greater than -0.5, less than +0.5
?: -1.0 to -0.5 or +0.5 to +1.0
X: less than -1.0 or greater than +1.0
II.5 Haze (%)
The haze was measured by using a haze computer HGM-2B (trade name) manufactured by Sigma-Aldrich Co., Ltd. according to JIS K 7150, and the measured value was evaluated. Portlife evaluated the change in initial value in the following three stages.
?: Greater than -0.5, less than +0.5
?: -1.0 to -0.5 or +0.5 to +1.0
X: less than -1.0 or greater than +1.0
II.6 Adhesion to substrate
The adhesion of the conductive film to the substrate was evaluated according to the crosscut peel test of JIS K 5400, and the evaluation was made with the specified score. Portlife was evaluated in the following three stages.
◎: No change from initial value
&Amp; cir &: Decrease in the range of less than 2 points from the initial value
X: Decrease from the initial value in a range of 2 points or more
II.7 Scratch resistance test
The conductive film formed on the substrate was rubbed with a nail at a weight of about 200 g with a length of 10 cm, and the occurrence of scratches and generation of powder were evaluated in the following three stages. Port life was evaluated in the same manner.
◎: No scratches
○: Visible light marks but no flour
X: Scratches occur and powder is generated
II.8 Solvent resistance test
An ethanol wipe test, an ethyl acetate (hereinafter referred to as ethyl acetate) wipe test, a methyl ethyl ketone (hereinafter referred to as MEK) wipe test, and a hexane wipe test were performed on the conductive film formed on the substrate. Specifically, the length of 10 cm was rubbed 15 times with a weight of about 200 g with a spinneret impregnated with each solvent, and the appearance of the film after the test was evaluated by the following three steps. Port life was evaluated in the same manner.
◎: No change in coating
○: There is a slight crack
X: The film peeled off
II.9.
The degree of cratering when printing on the surface of the conductive film was evaluated by the following three steps using the oil-based magic (piece, thin letters) manufactured by Mitsubishi Pencil Co., Ltd.
⊚: No cratering of the factor
&Amp; cir &: The factor was slightly cratered,
X: The crater ring is too large to be used for printing
II.10 Adhesion test
The ink adhesion test was carried out by printing the oil-based magic (piece, thin letters) manufactured by Mitsubishi Pencil Co., Ltd. on the surface of the conductive film and visually observing the state of the ink when the ink was rubbed with a weight of about 500 g .
◎: No separation of factors
○: Remnant marks remain on the parameter
X: The factor is completely peeled off
II.11 Resistance to air exposures
In the air exposure test, the conductive film was stuck to the wall, and SR after one week was evaluated in the following three stages. Port life was evaluated in the same manner.
⊚: Less than 1 × 10 10 Ω / □
○: 1 × 10 10 Ω / □ or more, lower than 1 × 10 11 Ω / □
×: 1 × 10 11 Ω / □ or more
II.12 Test for vesicles
In the vesicle test, the coating liquid was shaken 5 times, and the time until the large bubbles generated were all lost was evaluated in the following four stages. Port life was evaluated in the same manner.
◎: Packets within 20 seconds
○: Within 20 minutes, exceeding 20 seconds, a parcel
DELTA: Within 20 minutes, within 1 hour,
X: Not spoiled even after 1 hour or more
It was found from Comparative Examples 1 to 4 and Examples 1 to 3 that any one of the melamine resin derivative, the sulfonic acid curing catalyst, the polyether-modified silicone of both ends and the conductivity improver is also absent and that the outer appearance of the film, conductivity, total light transmittance, Adhesion, scratch resistance, solvent resistance, printability, and print adhesion are all not satisfied at the same time. Without the conductive polymer and the conductivity enhancer, the SR is not expressed. Without the melamine resin derivative and the sulfonic acid curing catalyst, the film is not cured. The polyether-modified silicone of both ends is an essential component in order to achieve both scratch resistance and solvent adhesion.
From Examples 1 and 4 to 6, it has become clear that the stability of the coating liquid is excellent when the melamine resin derivative is in a full ether type, and the physical properties of the coating film after 24 hours are not lowered.
From Examples 1 and 7 to 10, the pot life tends to deteriorate when the content of the melamine resin derivative is increased. When the content of the melamine resin derivative is less than 150 parts by weight based on 100 parts by weight of the conductive polymer solid content, it becomes clear that the solvent resistance is low from the beginning .
From Comparative Example 5 and Example 8, it was clear that the curing catalyst was preferably a sulfonic acid. From Example 11, it was found that the QS had a slightly poor pot life of the coating liquid and deteriorated characteristics after 24 hours As a result, it has become clear that DBS is particularly preferable as a curing catalyst.
Further, it is clear from Examples 1 and 12 to 15 that the content of the melamine resin derivative is preferably 40 parts by weight or less based on 100 parts by weight of the melamine resin derivative, which is preferable in the pot life maintenance.
From Examples 1 and 16 to 18, it is essential that the polyether-modified silicone of both ends be used in order to simultaneously satisfy the scratch resistance, the printability, and the printability of the components. In Comparative Examples 6 to 9, the side chain polyether- It has become clear that the scratch resistance and the factor adhesion can not be simultaneously satisfied.
The polyether-modified silicones used in Example 1 and Comparative Example 9 all had a structure in which the molecular weight of the polydimethylsiloxane was almost the same and the modified sites were different. Example 1 is a polyether-modified silicone of both ends polyether, and it can simultaneously satisfy scratch resistance, solvent resistance, printability and printability, while it can be simultaneously satisfied with the side chain polyether-modified silicone of Comparative Example 9 There was no. From these results, it has become clear that the effect of the present invention is exerted specifically by using polyether-modified silicone of both ends as the polyether-modified silicone.
It is also clear from Examples 1 and 19 to 21 that the content of the polyether-modified silicone at both ends is preferably 60 parts by weight or less based on 100 parts by weight of the melamine resin derivative.
From Examples 1 and 22 to 24, it became clear that the conductivity of the conductive film was further improved by using a compound having an amide group, a hydroxyl group and a sulfo group as a conductivity improver.
Comparing Examples 1, 25 and Example 2, it was clarified that SR increase due to air exposure was suppressed by adding ascorbic acid or erisorbic acid as a water-soluble antioxidant. In addition, as in Example 26, such an effect was not observed in the oil-soluble antioxidant.
In Example 3, a slight cratering was confirmed. Comparing the other Examples, it is clear that the film containing the wettability improver is excellent in film-forming property, and further, by adding the defoaming agent, It was clarified from Example 27 that it is possible to dispense.
From Example 28 and Fig. 1, the film having a calculated film thickness of about 30 nm was analyzed by TEM, and as a result, it was clear that the film was about 12 nm in actual measurement. It was found that the film thickness of the composition formed by this condition was much thinner than the calculated value.
Industrial availability
The conductive composition of the present invention can form a conductive coating that simultaneously satisfies both scratch resistance, solvent resistance, solvent resistance and printability, at a low temperature in a short period of time. Therefore, for example, It can be suitably used for forming a coating (antistatic layer) or the like.
1: conductive film
2: PET film
Claims (15)
(b) a melamine resin derivative,
(c) a sulfonic acid curing catalyst,
(d) a polyether-modified silicone of both ends,
(e) a conductivity improving agent, and
(f) a solvent or dispersion medium
(E) the conductivity improving agent and (f) the solvent or dispersion medium are the same.
The conductive polymer (a) is represented by the following formula (I):
[Chemical Formula 1]
(Wherein, R 1 and R 2 are each independently a hydrogen atom or a C 1 - represents a 4-alkyl group, or have one C 1 that may be substituted with - represents an alkylene group of 4) polyester having the repeating structure (3,4-dialkoxythiophene) or poly (3,4-alkylenedioxythiophene) and a dopant.
Wherein the content of the melamine resin derivative (b) is 150 to 750 parts by weight based on 100 parts by weight of the conductive polymer.
The sulfonic acid curing catalyst (c) is an aromatic sulfonic acid,
Wherein the content is 8 to 40 parts by weight based on 100 parts by weight of the melamine resin derivative.
Wherein the content of the polyether-modified silicone (d) in the terminal polyol is 10 to 60 parts by weight based on 100 parts by weight of the melamine resin derivative.
The conductive improving agent (e) is a compound having at least one substituent selected from an amide group, a sulfo group and a hydroxyl group.
(G) a water-soluble antioxidant.
Wherein the water-soluble antioxidant (g) is ascorbic acid or erisorbic acid.
(H) a wettability-improving agent.
(I) a composition for a thermosetting conductive coating containing a defoaming agent.
Wherein the defoaming agent (i) is a silicone emulsion.
Wherein the conductive film is a film formed by using the composition for a heat curable conductive coating according to any one of claims 1 to 11.
Wherein the conductive film is formed by applying the composition for a thermosetting conductive coating to the substrate and drying and thermosetting at a temperature of 130 캜 or less.
Wherein the conductive film has a calculated film thickness of less than 45 nm.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JPJP-P-2010-243352 | 2010-10-29 | ||
| JP2010243352A JP5776957B2 (en) | 2010-10-29 | 2010-10-29 | Thermosetting conductive coating composition, optical film and protective film |
| PCT/JP2011/073701 WO2012056906A1 (en) | 2010-10-29 | 2011-10-14 | Composition for heat-curable conductive coatings, optical film and protective film |
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| Publication Number | Publication Date |
|---|---|
| KR20130132449A KR20130132449A (en) | 2013-12-04 |
| KR101921346B1 true KR101921346B1 (en) | 2018-11-22 |
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| KR1020137013251A KR101921346B1 (en) | 2010-10-29 | 2011-10-14 | Composition for heat-curable conductive coatings, optical film and protective film |
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| Country | Link |
|---|---|
| JP (1) | JP5776957B2 (en) |
| KR (1) | KR101921346B1 (en) |
| CN (1) | CN103237852B (en) |
| TW (1) | TWI518154B (en) |
| WO (1) | WO2012056906A1 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5919095B2 (en) * | 2012-05-31 | 2016-05-18 | 信越ポリマー株式会社 | Conductive polymer paint and conductive coating film |
| JP6050632B2 (en) * | 2012-08-06 | 2016-12-21 | リンテック株式会社 | Conductive composition and electrical device |
| US20140065400A1 (en) * | 2012-08-29 | 2014-03-06 | Eastman Chemical Company | Electrically conductive polymer compositions and films |
| EP2997581A4 (en) | 2013-05-17 | 2017-05-03 | Biotectix LLC | Impregnation of a non-conductive material with an intrinsically conductive polymer |
| JP6325364B2 (en) * | 2014-06-18 | 2018-05-16 | マクセルホールディングス株式会社 | Transparent conductive coating composition, transparent conductive sheet and method for producing the same, and transparent conductive pattern forming method |
| CA2994634A1 (en) | 2014-11-19 | 2016-05-26 | Biotectix, LLC | Conductive polymer coatings for three dimensional substrates |
| JP6299829B2 (en) * | 2015-10-20 | 2018-03-28 | 荒川化学工業株式会社 | Thermosetting release coating agent, release film and release polyethylene terephthalate film |
| JP7102118B2 (en) * | 2017-09-29 | 2022-07-19 | マクセル株式会社 | A transparent conductive film, a coating composition for forming a transparent conductive film, and a method for producing a transparent conductive film. |
| JP2019069541A (en) | 2017-10-06 | 2019-05-09 | 日東電工株式会社 | Film with top coat layer, surface protection film, and optical component |
| WO2019139163A1 (en) * | 2018-01-15 | 2019-07-18 | Nok株式会社 | Bioelectrode |
| CN110845933A (en) * | 2018-08-03 | 2020-02-28 | 荒川化学工业株式会社 | Aqueous antistatic release coating composition and antistatic release film |
| JP6639712B1 (en) * | 2019-02-15 | 2020-02-05 | 桜宮化学株式会社 | Thermosetting release coating and thermosetting release coating kit |
| CN109913142B (en) * | 2019-03-01 | 2021-12-10 | 苏州格睿光电科技有限公司 | Antistatic organic silicon pressure-sensitive adhesive product |
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| JP2785136B2 (en) | 1989-06-29 | 1998-08-13 | チッソ株式会社 | Conductive resin composition |
| JP2007320093A (en) | 2006-05-31 | 2007-12-13 | Dainichiseika Color & Chem Mfg Co Ltd | Antistatic film and coating for forming antistatic layer |
| JP2010106245A (en) | 2008-09-30 | 2010-05-13 | Nagase Chemtex Corp | Low temperature thermosetting electroconductive coating composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04334805A (en) * | 1991-05-11 | 1992-11-20 | Kao Corp | Conductive paste and conductive coating film |
| JP3294774B2 (en) * | 1996-11-26 | 2002-06-24 | 関西ペイント株式会社 | Paint composition and coated metal plate using the same |
| JP2004256702A (en) * | 2003-02-26 | 2004-09-16 | Toyobo Co Ltd | Conductive coating |
| JP2007324142A (en) * | 2007-08-15 | 2007-12-13 | Nissan Chem Ind Ltd | Conductive coating composition |
| JP2009107329A (en) * | 2007-10-10 | 2009-05-21 | Jsr Corp | Surface protective film |
| JP5176162B2 (en) * | 2007-12-04 | 2013-04-03 | ナガセケムテックス株式会社 | Low temperature thermosetting conductive coating composition |
| JP5460008B2 (en) * | 2008-09-24 | 2014-04-02 | 信越ポリマー株式会社 | Conductive polymer solution, conductive coating film and input device |
| JP2010083940A (en) * | 2008-09-30 | 2010-04-15 | Nagase Chemtex Corp | Method for preventing electrification of polyamide film, antistatic film and manufacturing method of the same |
| JP5509462B2 (en) * | 2009-02-27 | 2014-06-04 | ナガセケムテックス株式会社 | Composition for conductive coating |
-
2010
- 2010-10-29 JP JP2010243352A patent/JP5776957B2/en active Active
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2011
- 2011-10-14 WO PCT/JP2011/073701 patent/WO2012056906A1/en active Application Filing
- 2011-10-14 CN CN201180052196.3A patent/CN103237852B/en not_active Expired - Fee Related
- 2011-10-14 KR KR1020137013251A patent/KR101921346B1/en active IP Right Grant
- 2011-10-19 TW TW100137819A patent/TWI518154B/en active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2785136B2 (en) | 1989-06-29 | 1998-08-13 | チッソ株式会社 | Conductive resin composition |
| JP2007320093A (en) | 2006-05-31 | 2007-12-13 | Dainichiseika Color & Chem Mfg Co Ltd | Antistatic film and coating for forming antistatic layer |
| JP2010106245A (en) | 2008-09-30 | 2010-05-13 | Nagase Chemtex Corp | Low temperature thermosetting electroconductive coating composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5776957B2 (en) | 2015-09-09 |
| TW201219514A (en) | 2012-05-16 |
| CN103237852A (en) | 2013-08-07 |
| KR20130132449A (en) | 2013-12-04 |
| TWI518154B (en) | 2016-01-21 |
| WO2012056906A1 (en) | 2012-05-03 |
| JP2012097132A (en) | 2012-05-24 |
| CN103237852B (en) | 2016-04-06 |
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