JP2016120650A - Laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate that improves the application properties of an antistatic layer and has excellent alkali resistance.SOLUTION: A laminate has an antistatic layer that comprises a polythiophene polymer, and polyoxyethylene alkyl ether phosphate and/or polyoxyethylene alkyl phenyl ether sulfuric acid salt on a base material.SELECTED DRAWING: None

Description

  The present invention relates to a laminate having an antistatic layer on a substrate.

  Conventionally, resin films such as polyethylene terephthalate and polyethylene naphthalate have excellent optical properties, heat resistance, chemical resistance, mechanical strength, dimensional stability, smoothness, etc. Therefore, it is used for a wide range of applications such as a film for plate making and a film for optical parts.

  However, since these resin films are insulative, they are easily charged by friction or peeling, and are charged with static electricity. For this reason, the plate-making film has problems such as pinholes and missing images due to dust adhering to the film. In addition, in film applications for optical components, there are problems that dust is attached to the film, resulting in a decrease in the commercial value of the product, and in electronic devices and the like, malfunction due to electric discharge is caused.

  Therefore, it is known to impart conductivity to the surface of the insulating base material by applying a conductive material to the surface of the resin film and providing an antistatic layer. Conductive materials used for such purposes include low molecular weight antistatic agents such as surfactants, high molecular weight polymer antistatic agents, or metal oxides such as fine metal particles, titanium oxide, zinc oxide, and tin oxide. And fine particles, conductive carbon black, and various other conductive fillers.

  An antistatic layer containing a low molecular weight antistatic agent is difficult to impart sufficient water resistance. For example, in applications such as a plate-making film, the antistatic layer is used in a development processing step for forming an image. It becomes difficult to impart sufficient conductivity to the plate-making film after being washed away. Further, when the antistatic layer contains metal fine particles, metal oxide fine particles such as titanium oxide, zinc oxide and tin oxide, and conductive fillers such as conductive carbon black, the light transmittance of the substrate is reduced. In the use of a panel member of a thin flat display typified by a liquid crystal display or an organic EL display, the sharpness of the image may be impaired.

  The polymer type antistatic agent has a relatively high water resistance. In addition, although the polymer type antistatic agent itself is generally slightly colored, even a very thin antistatic layer exhibits sufficient conductivity, and thus excellent light transmission can be obtained. Among them, it is known that an antistatic layer containing a polythiophene polymer is excellent in optical properties, heat resistance, moist heat resistance, and the like, and has a small change in resistance value over time. For example, JP 2012-172024 A Gazette (patent document 1), JP 2010-196022 (patent document 2), JP 2000-052522 (patent document 3), JP 2010-024457 (patent document 4), JP 2003. -246874 (Patent Document 5) and the like. However, when an antistatic layer containing the polythiophene polymer is applied on a substrate, application defects may occur in the antistatic layer, and improvement has been demanded.

  It is common to use a surfactant or a leveling agent for improving coating properties. For example, the above Patent Documents 3 to 5 describe specific examples using polyoxyethylene nonylphenyl ether together with a polythiophene polymer. Has been. However, in this case, the alkali resistance of the antistatic layer is lowered, and in the film-making film application, the antistatic layer is washed away during the developing process, and sufficient conductivity cannot be maintained after image formation. That is, it has been extremely difficult to achieve both coating properties and alkali resistance of the antistatic layer.

  In recent years, in the use of a light-transmitting conductive material used for a light-transmitting electrode of a touch panel, a conductive layer having a mesh-shaped metal pattern is used in place of a conventional light-transmitting conductive layer using ITO. It is known. As a method for producing a light-transmitting conductive layer having a metal pattern, for example, a method of forming a metal pattern on a conductive material precursor having a silver halide emulsion layer by a direct development method is disclosed in Japanese Patent Application Laid-Open No. 2004-221564. Japanese Patent Laid-Open Nos. 2003-077735 and 2007-188655 disclose a method of forming a metal pattern on a conductive material precursor having a silver halide emulsion layer by using a silver salt diffusion transfer method. Has been. In JP 2007-287994 A and JP 2007-287953 A, a thin catalyst layer is formed on a substrate, a resist pattern is formed thereon, and then a metal layer is formed in the resist opening by plating. A semi-additive method is described in which a metal pattern is formed by laminating and finally removing the resist layer and the underlying metal protected by the resist layer.

  In these methods, development processing with an alkali developer is performed to form a metal pattern on a substrate or to form a resist pattern. Therefore, the antistatic layer needs to have sufficient alkali resistance, and when the alkali resistance is not sufficient, physical electrode destruction caused by ESD (Electro-Static Discharge) may occur and is exposed to an alkaline environment. It is extremely important to maintain sufficient electrical conductivity (antistatic properties) even after the operation.

JP 2012-172024 A JP 2010-196022 A JP 2000-052222 A JP 2010-024457 A JP 2003-246874 A

  An object of the present invention is to provide a laminate in which the coating property of the antistatic layer is improved and the alkali resistance is excellent.

The object of the present invention has been achieved by the following means.
1. A laminate having an antistatic layer containing a polythiophene polymer and polyoxyethylene alkyl ether phosphate and / or polyoxyethylene alkyl phenyl ether sulfate on a substrate.

  According to the present invention, it is possible to provide a laminate having improved antistatic layer coating properties and excellent alkali resistance.

  Hereinafter, the present invention will be described in detail.

  The antistatic layer of the laminate of the present invention contains a polythiophene polymer from the viewpoint of obtaining excellent optical properties, antistatic properties, heat resistance, and the like. The polythiophene-based polymer can be used as a water-soluble conductive polymer or a water-dispersible conductive polymer. Examples of the polythiophene polymer include polythiophene, polyethylenedioxythiophene, polypropylenedioxythiophene, polyhexylthiophene, polycyclohexylenedioxythiophene, and the like.

  When a water-soluble conductive polymer or water-dispersible conductive polymer is used as the polythiophene polymer, the coating liquid (polymer composition) for forming the antistatic layer can be prepared as an aqueous solution or aqueous dispersion. There is no need to use organic solvents. Therefore, since it becomes possible to suppress the quality change and deterioration of the base film base material by an organic solvent, it is preferable. The aqueous solution or aqueous dispersion is preferably water only from the viewpoint of adhesion, but may be contained because stability in coating increases when a small amount of a hydrophilic solvent is used. Examples of the hydrophilic solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol, and tert-amyl alcohol. , 1-ethyl-1-propanol, 2-methyl-1-butanol, n-hexanol, and cyclohexanol. The weight average molecular weight of the water-soluble or water-dispersible polythiophene in terms of polystyrene is preferably 400,000 or less, more preferably 300,000 or less.

  The above-mentioned water-soluble conductive polymer means that the solubility in 100 g of water is 5 g or more, and a more preferable solubility is 20 to 30 g. A water-dispersible conductive polymer is a polythiophene-based resin that is dispersed in water in the form of fine particles. The aqueous dispersion has a small liquid viscosity and is easy to apply to a thin film. Are better. Here, the size of the fine particles is preferably 1 μm or less from the viewpoint of the uniformity of the antistatic layer.

  Moreover, it is preferable that the polythiophene polymer which is the above-described water-soluble or water-dispersible conductive polymer has a hydrophilic functional group in the molecule. Examples of hydrophilic functional groups include sulfo groups, amino groups, amide groups, imino groups, quaternary ammonium bases, hydroxyl groups, mercapto groups, hydrazino groups, carboxyl groups, sulfate ester groups, phosphate ester groups, or salts thereof. Etc. Since the solubility in water is improved by having a hydrophilic functional group in the molecule, or the dispersion stability in water is improved, a coating solution containing a polythiophene polymer can be easily prepared.

  The polythiophene-based polymer described above is commercially available, for example, as the Denatron series from Nagase ChemteX, and can be obtained and used.

In the present invention, the solid content of the polythiophene polymer contained in the antistatic layer is preferably in the range of 1 to 60 mg / m ² . Especially, it is especially preferable that it is 15-45 mg / m < ² >.

In the present invention, the polyoxyethylene alkyl ether phosphate contained in the antistatic layer is represented by polyoxyethylene monoalkyl ether phosphate (RO (CH ₂ CH ₂ O) _m PO (OH) OM ⁺ , R Is an alkyl group, m is a positive number, and M ⁺ represents a cation), but is polyoxyethylene dialkyl ether phosphate (R ¹ O (CH ₂ CH ₂ O) _m PO (O (CH ₂ CH ₂ O) _n R ² ) OM ⁺ , R ¹ and R ² are each an alkyl group, m and n are each a positive number, and M ⁺ is a cation). R, R ¹ and R ² are preferably those having 12 to 18 carbon atoms, more preferably those having 12 carbon atoms. Moreover, what m and n are respectively 4-10 is preferable. There is no restriction | limiting in particular about a cation, Alkali metal ions, such as sodium and potassium, are mentioned.

  Specific examples of the polyoxyethylene alkyl ether phosphate include, for example, sodium polyoxyethylene lauryl ether phosphate, sodium polyoxyethylene mystyryl ether phosphate, sodium polyoxyethylene cetyl ether phosphate, polyoxyethylene oleyl Examples include sodium ether phosphate, potassium polyoxyethylene lauryl ether, potassium polyoxyethylene mystyryl ether phosphate, potassium polyoxyethylene cetyl ether phosphate, potassium polyoxyethylene oleyl ether phosphate, and the like.

In the present invention, the polyoxyethylene alkylphenyl ether sulfate contained in the antistatic layer is represented by R ⁴ —O— (C ₂ H ₄ O) ^m2 SO ₃ —M ₁ , wherein R ⁴ is an alkylphenyl group, M ₁ Represents any selected from alkali metal ions, quaternary ammonium, quaternary phosphonium, and alkanolamine. m2 represents an integer. Among them, the “alkyl” of the alkylphenyl group of R ⁴ is preferably a linear or partially substituted alkyl having 6 to 20 carbon atoms, more preferably a linear alkyl having 8 to 17 carbon atoms, particularly carbon. A linear alkyl having 9 is preferred. The thing M ₁ is an alkali metal ion.

  Specific examples of the polyoxyethylene alkyl phenyl ether sulfate described above include, for example, polyoxyethylene octyl phenyl ether sodium sulfate, polyoxyethylene octyl phenyl ether ammonium sulfate, polyoxyethylene nonyl phenyl ether sodium sulfate, polyoxyethylene nonyl phenyl ether Examples thereof include ammonium sulfate, sodium polyoxyethylene lauryl phenyl ether sulfate, ammonium polyoxyethylene lauryl phenyl ether sulfate, sodium polyoxyethylene stearyl phenyl ether sulfate, and ammonium polyoxyethylene stearyl phenyl ether sulfate.

In the present invention, when the antistatic layer contains the above-mentioned polyoxyethylene alkyl ether phosphate alone, or when it contains polyoxyethylene alkyl phenyl ether sulfate alone, these preferable solid contents are 1 to 20 mg. / ^m is in the range of ^2, and more preferably 5 to 15 mg / ^{m 2.} Moreover, also when it contains both polyoxyethylene alkyl ether phosphate and polyoxyethylene alkyl phenyl ether sulfate, preferable content is the same. In addition, the ratio of polyoxyethylene alkyl ether phosphate and polyoxyethylene alkyl phenyl ether sulfate when used together is arbitrary.

  In the present invention, the total amount of the polythiophene polymer and the polyoxyethylene alkyl ether phosphate and / or polyoxyethylene alkyl phenyl ether sulfate is 95% by mass or more based on the total solid content of the antistatic layer. Preferably, it is 98 mass% or more more preferably.

  As a base material which the laminated body of this invention has, the resin film which has glass and flexibility is mentioned, The resin film which has flexibility is preferable at the point which is easy to handle. Specific examples of the resin film used in the present invention include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylic resins, epoxy resins, fluororesins, silicone resins, polycarbonate resins, diacetate resins, Examples include triacetate resin, polyarylate resin, polyvinyl chloride, polysulfone resin, polyether sulfone resin, polyimide resin, polyamide resin, polyolefin resin, and cyclic polyolefin resin. The thickness of these resin films is preferably 20 to 300 μm. In applications where light transmittance is required, the total light transmittance of the substrate of the laminate of the present invention is preferably 80% or more, more preferably 88% or more.

  The above-mentioned base material may have an easily bonding layer. This easy-adhesion layer can improve the applicability of the layer mainly applied on the substrate and the adhesion between the substrate and the coating film. As an easily bonding layer, the easily bonding layer etc. which contain a hydrophilic binder or various polymer latex are mentioned. The polymer latex is preferably formed using an aqueous dispersion, and the easy-adhesion layer is preferably formed by aqueous coating. Further, the easy-adhesion layer may contain a matting agent such as silica, a lubricant, a pigment, a dye, a surfactant, an ultraviolet absorber and the like. Further, the base material may have a known layer such as a hard coat layer (HC layer) for the purpose of scratch resistance and an anti-reflection layer (AR layer) for the purpose of reducing the reflectance.

  In the present invention, as a method of providing an antistatic layer on a substrate, a coating solution containing a polythiophene polymer and polyoxyethylene alkyl ether phosphate and / or polyoxyethylene alkyl phenyl ether sulfate is prepared, What is necessary is just to apply | coat this on a base material using coating means, such as a blade coater, an air knife coater, a roll coater, a bar coater, a gravure coater, a reverse coater. Examples of the drying method after coating include those using a hot air dryer such as a straight tunnel dryer, arch dryer, air loop dryer, sine curve air float dryer, etc., and can be selected and used as appropriate. .

  The antistatic layer obtained by the present invention has excellent alkali resistance. As described above, the light-transmitting conductive material used for the light-transmitting electrode of the touch panel uses a conductive layer having a mesh-like metal pattern instead of the conventional light-transmitting conductive layer using ITO. It is known. As a method for producing a conductive layer having a metal pattern on a substrate, for example, a thin catalyst layer is formed on the substrate, a resist pattern is formed thereon, and then a metal layer is formed on the resist opening by plating. And a semi-additive method for forming a metal pattern by removing the resist layer and the base metal protected by the resist layer at the end, for example, Japanese Patent Application Laid-Open No. 2007-287994 and Japanese Patent Application Laid-Open No. 2007-28753. It is disclosed in gazettes. In these techniques, an alkaline solution is applied to strip the resist layer, so that the present invention works particularly effectively in such a system.

  In addition, as another method for producing a conductive layer having a metal pattern on a base material, there is a method in which a silver halide photographic light-sensitive material is used as a conductive material precursor and a development process is performed following an exposure step. . The method using such a conductive material precursor includes: (1) a development process according to the silver salt diffusion transfer method, (2) a development process for fixing directly after development, and (3) a development process according to curing development. Can be classified into three types. For example, the silver salt diffusion transfer method (1) is described in JP-A No. 2003-077735, JP-A No. 2007-188655, and the like. The method (2) for fixing after direct development is described in, for example, International Publication No. 2001/512276 pamphlet and Japanese Patent Application Laid-Open No. 2004-221564. The curing and developing (3) is described in, for example, JP-A-2007-059270, JP-A-2007-095408, and the like. In any of these methods, since an alkaline developer is used, the present invention works particularly effectively in such a system.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in more detail, this invention is not limited to this Example.

  In order to obtain the laminate of the present invention, a polyethylene terephthalate film having a thickness of 100 μm (Lumirror U34 manufactured by Toray Industries, Inc., the same easy-adhesion layer on both sides, and a total light transmittance of 92%) was used as a substrate. By using a gravure roll having a gravure pattern with a line number of 110 / inch and a depth of 70 μm on one surface of this polyethylene terephthalate film, the coating liquid is applied at a substrate conveyance speed of 50 m / min. Then, antistatic layers (AS-1 to AS-14) having the following composition were formed to obtain laminates 1 to 14.

<Antistatic layer composition><AS-1> per 1 m ²
Denatron P-502RG (as solids) 28mg
(Polythiophene polymer manufactured by Nagase ChemteX Corporation)
Polyoxyethylene nonylphenyl ether sodium sulfate 10mg

<AS-2>
Denatron P-502RG (as solids) 28mg
(Polythiophene polymer manufactured by Nagase ChemteX Corporation)
Polyoxyethylene lauryl ether potassium phosphate 10mg

<AS-3>
Denatron P-502RG (as solids) 28mg
(Polythiophene polymer manufactured by Nagase ChemteX Corporation)
Polyoxyethylene nonylphenyl ether sodium sulfate 5mg
Polyoxyethylene lauryl ether potassium phosphate 5mg

<AS-4>
Denatron P-502RG (as solids) 28mg
(Polythiophene polymer manufactured by Nagase ChemteX Corporation)

<AS-5>
Denatron P-502RG (as solids) 28mg
(Polythiophene polymer manufactured by Nagase ChemteX Corporation)
Polyoxyethylene tridecyl ether 10mg

<AS-6>
Denatron P-502RG (as solids) 28mg
(Polythiophene polymer manufactured by Nagase ChemteX Corporation)
Polyoxyethylene nonylphenyl ether 10mg

<AS-7>
Denatron P-502RG (as solids) 28mg
(Polythiophene polymer manufactured by Nagase ChemteX Corporation)
Polyoxyethylene lauryl ether 10mg

<AS-8>
Denatron P-502RG (as solids) 28mg
(Polythiophene polymer manufactured by Nagase ChemteX Corporation)
Polyoxyethylene tridecyl ether phosphate
・ Monoethanolamine salt 10mg

<AS-9>
Denatron P-502RG (as solids) 28mg
(Polythiophene polymer manufactured by Nagase ChemteX Corporation)
Polyoxyethylene phenyl ether 10mg

<AS-10>
Denatron P-502RG (as solids) 28mg
(Polythiophene polymer manufactured by Nagase ChemteX Corporation)
Polyoxyethylene naphthyl ether 10mg

<AS-11>
Denatron P-502RG (as solids) 28mg
(Polythiophene polymer manufactured by Nagase ChemteX Corporation)
Polyoxyethylene lauryl ether ammonium sulfate solution 10mg

<AS-12>
Denatron P-502RG (as solids) 28mg
(Polythiophene polymer manufactured by Nagase ChemteX Corporation)
Polyoxyethylene lauryl ether sulfate triethanolamine 10mg

<AS-13>
Denatron P-502RG (as solids) 28mg
(Polythiophene polymer manufactured by Nagase ChemteX Corporation)
Sodium polyoxyethylene lauryl ether sulfate 10mg

<AS-14>
Denatron P-502RG (as solids) 28mg
(Polythiophene polymer manufactured by Nagase ChemteX Corporation)
Polyoxyethylene sulfosuccinic acid disodium 10mg

  For the antistatic layer coating solution, water and ethyl alcohol were also used as solvents. The amount of solvent was added so that the concentration of the used polythiophene polymer was about 0.25 wt%, and ethyl alcohol was adjusted to 5 wt% in the coating solution.

About the laminated bodies 1-14 obtained above, the surface resistance value of the surface which has an antistatic layer was measured. For the measurement of the surface resistance value, Diainstrument Co., Ltd. Hiresta UP MCP-HT450 type was used, the applied voltage was set to 100 V, and measured at five locations in an environment of 20 ° C. and 10% RH, and the average value was obtained. Evaluation was performed according to the following criteria, and the results are shown in Table 1 (antistatic properties).
○: A surface resistance value of less than 1 × 10 ¹⁰ Ω / □ can be maintained.
×: The surface resistance value is 1 × 10 ¹⁰ Ω / □ or more, or measurement is impossible.

For each of the obtained laminates 1 to 14, 10 points were randomly sampled in 30 × 30 cm squares, the coating defects in the antistatic layer were counted, and the determination was made according to the following three-stage criteria. (Coating defect of antistatic layer). Note that almost all types of coating defects were repellency.
○: No coating defects △: Total coating defects = 1 to 2 ×: Total coating defects = 3 or more

  Next, a light transmissive conductive material was produced using the laminates 1 to 14 obtained above. First, in order to obtain a light-transmitting conductive material precursor, an antihalation layer having the following composition was applied on the antistatic layer of the laminates 1 to 14.

<Anti-halation layer composition> ² g of gelatin per 1 m ²
Longis K-25 0.1g
(Disproportionated rosin potassium salt manufactured by Arakawa Chemical Industries, Ltd.)
Amorphous silica matting agent (average particle size 5μm) 20mg
Polyoxyethylene nonylphenyl ether sodium sulfate 400mg
Dye 1 200mg

  Next, a physical development nucleus layer having the following composition using a palladium sulfide sol prepared as follows was applied on the substrate opposite to the surface having the antihalation layer.

<Preparation of palladium sulfide sol>
Liquid A Palladium chloride 5g
Hydrochloric acid 40ml
1000ml distilled water
B liquid sodium sulfide 8.6g
1000ml distilled water
Liquid A and liquid B were mixed with stirring, and 30 minutes later, the solution was passed through a column filled with an ion exchange resin to obtain palladium sulfide sol.

<Physical development nucleus layer composition> The palladium sulfide sol 0.4 mg per 1 m ²
Grioquizal 0.004mg
Polyoxyethylene sorbitan monooleate 3mg
Denacol EX-830 10mg
(Polyethylene glycol diglycidyl ether manufactured by Nagase ChemteX Corporation)
Epomin SP-200 0.02g
(Nippon Shokubai Co., Ltd. polyethyleneimine; average molecular weight 10,000)

  Next, following the coating of the physical development nucleus layer, the intermediate layer, silver halide emulsion layer, and protective layer having the following composition are simultaneously formed using a slide coater so that the intermediate layer is the bottom layer and the protective layer is the top layer. By applying the layers, light-transmitting conductive material precursors 1 to 14 were obtained. The silver halide emulsion was prepared using a double jet mixing method, which is a general method for producing a photographic silver halide emulsion. This silver halide emulsion was prepared with 95 mol% of silver chloride and 5 mol% of silver bromide, and an average grain size of 0.15 μm. The silver halide emulsion thus obtained was subjected to gold sulfur sensitization using sodium thiosulfate and chloroauric acid according to a conventional method. The silver halide emulsion thus obtained contains 0.3 g of gelatin per gram of silver.

<Intermediate layer composition> per 1 m ² CPG gum FA (Dainippon Pharmaceutical Co., Ltd.) 0.03 g
Polyoxyethylene nonylphenyl ether sodium sulfate 10mg

<Silver halide emulsion layer composition> 0.2 g of gelatin per 1 m ²
Silver halide emulsion 3.8 g equivalent to silver 1-phenyl-5-mercaptotetrazole 10 mg
Polyoxyethylene nonylphenyl ether sodium sulfate 20mg

<Protective layer composition> 1 g of gelatin per 1 m ²
Amorphous silica matting agent (average particle size 3.5μm) 15mg
Polyoxyethylene nonylphenyl ether sodium sulfate 10mg

  The light transmissive conductive material precursors 1 to 14 thus obtained were exposed and developed by the following methods to obtain light transmissive conductive materials.

<Exposure>
Through a close contact printer using a mercury lamp as a light source, a transparent original having a mesh pattern with a fine line width of 7 μm and a lattice interval of 300 μm was brought into close contact via a resin filter that cuts light of 400 nm or less.

<Development>
After an immersion treatment at 20 ° C. for 90 seconds with an alkali treatment liquid having the following composition, it was washed with water and dried in a 35 ° C. hot water shower. In addition, the metal pattern (silver pattern) was exposed on one surface of the base material by this immersion and washing treatment, and the antihalation layer on the antistatic layer was removed.

<Alkaline treatment liquid composition>
Potassium hydroxide 25g
Hydroquinone 18g
1-phenyl-3-pyrazolidone 2g
Potassium sulfite 100g
N-methylethanolamine 15g
Potassium bromide 0.2g
Total volume 1000ml with water
Adjust to pH = 12.2

The surface resistance value of the surface opposite to the surface having the metal pattern of the light-transmitting conductive material thus obtained was measured in the same manner as the previous surface resistance value 1, and the following criteria were used. evaluated. The results are shown in Table 1 (alkali resistance).
○: A surface resistance value of less than 1 × 10 ¹⁰ Ω / □ can be maintained.
Δ: 1 × 10 ¹⁰ Ω / □ or more, but surface resistance can be measured.
X: The surface resistance value could not be measured.

  As is apparent from the results in Table 1, it can be seen that the present invention provides a laminate having improved antistatic layer coating properties and excellent alkali resistance.

Claims (1)

  A laminate having an antistatic layer containing a polythiophene polymer and polyoxyethylene alkyl ether phosphate and / or polyoxyethylene alkyl phenyl ether sulfate on a substrate.