JP2016064530A - Conductive laminate and touch panel using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive laminate which has high visibility, preferable hardness and elongation property and exhibits extremely high adhesion with a transparent polymer substrate, especially high adhesion even after damp-heat test for a long time.SOLUTION: There is provided a conductive laminate obtained by laminating a hard coat layer and a conductive layer on at least one surface of a polycarbonate substrate, where the hard coat layer is formed from a hard coating composition which comprises (A) an acrylic resin having an acrylate group on the side chain in which the acrylate group equivalent is 500 to 2000 g/mol, (B) a specific phenol novolac-type acrylate, (C) a specific bisphenol skeleton-containing diacrylate and (D) a polyfunctional acrylate having 3 or more acrylate groups.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a conductive laminate in which a hard coat layer and a conductive layer are laminated on at least one surface of a polycarbonate substrate, and particularly has high visibility and good hardness, and also has extensibility, and polycarbonate. The present invention relates to a conductive laminate having a hard coat layer that exhibits excellent adhesion to a substrate, and a touch panel using the same.

  Liquid crystal display devices (liquid crystal displays) have advantages such as thinness, light weight, and low power consumption, and are used in various fields such as computers, word processors, televisions, mobile phones, and portable information terminal devices. In these liquid crystal display devices, so-called touch panels having a mechanism for operating devices by holding down the display on the screen are rapidly spreading. Such a touch panel has, for example, a mobile phone such as a smartphone, a tablet PC, a personal digital assistant device, a bank ATM, a vending machine, a personal digital assistant (PDA), a copier, a facsimile machine, and a game machine due to its excellent operability. It is widely used in guidance display devices installed in facilities such as museums and department stores, car navigation systems, multimedia stations (multifunctional terminals installed in convenience stores), monitoring devices for railway vehicles, and the like.

  Generally in the touch panel, the transparent conductive laminated body which has the transparent conductive layer provided on the transparent base material is generally used. For the formation of the transparent conductive layer, indium-tin oxide (ITO) or the like is generally used.

  As a base film constituting a film having a transparent conductive layer, a film such as a PET film or a polycarbonate film is often used from the viewpoint of high transparency and price. These base films may be provided with a transparent hard coat layer for the purpose of improving scratch resistance and durability. On the other hand, there is a problem that interference fringes are generated by providing a transparent hard coat layer on a transparent substrate film. Generation | occurrence | production of this interference fringe brings about the fall of visibility.

  The generation of interference fringes has already been proposed by the present inventors in Japanese Patent Application Laid-Open No. 2013-209482 (Patent Document 1) and Japanese Patent Application Laid-Open No. 2013-209482 (Patent Document 2). Provided a material close to a polycarbonate base material and solved it. Further, the present inventors have made a new proposal to improve the adhesion of the hard coating composition, and have already obtained patents (Patent No. 5490954 (Patent Document 3) and Patent No. 5490955 ( Patent Document 4)).

  The two patents mentioned above were improved in adhesion as described above, and the adhesion performance sufficiently withstands use. However, the adhesion of the two patents has not been able to withstand for a long time under wet heat conditions (that is, high temperature and high humidity conditions). In reality, it has to withstand a 750 hour adhesion test at high humidity (85%) and high temperature (80 ° C.), but the above-mentioned two patent techniques lacked that.

JP 2013-209481 A JP 2013-209482 A Japanese Patent No. 5490954 Japanese Patent No. 5490955

  An object of the present invention is to solve the above problems. More specifically, the present invention improves the hard coat layer in the conductive laminates developed by the present inventors so far, and increases the adhesion with the polycarbonate substrate, which is a substrate, under wet heat conditions. It is an object to maintain the adhesion for a long time even underneath.

The present invention is a conductive laminate in which a hard coat layer and a conductive layer are laminated on at least one surface of a polycarbonate substrate,
The hard coat layer is
(A) an acrylic resin having an acrylate group in the side chain and an acrylate group equivalent of 500 to 2000 g / mol;
(B) a phenol novolak acrylate having 2 or more acrylate groups (C) a bisphenol skeleton-containing diacrylate having 2 to 4 mole equivalents of an alkylene oxide unit having 2 or 3 carbon atoms in one monomer molecule; D) formed from a hard coating composition containing a polyfunctional acrylate having 3 or more acrylate groups,
The component (A) is 10 to 30 parts by mass, the component (B) is 15 to 25 parts by mass, and the component (C) is 20 to 40 parts by mass with respect to 100 parts by mass of the total resin components contained in the hard coating composition. Part and a component (D) provide the conductive laminated body characterized by containing 5-55 mass parts, and the said subject is solved by this.

  The acrylic resin (A) preferably has an acrylate equivalent of 700 to 1500 g / mol.

（Ｉ）
［式中、Ｒ^１とＲ^２は水素原子またはメチル基であり、Ｒ^３は炭素数１〜１２の直鎖または分岐鎖アルキル基または炭素数３〜１０のシクロアルキル基であり、Ｒ^４は水素原子またはメチル基である。ｍとｎは二重結合当量で変動する値である。］ The acrylic resin (A) is preferably a copolymer represented by the following formula (a) and the following formula (b):

(I)
[Wherein, R ¹ and R ² are a hydrogen atom or a methyl group, R ³ is a linear or branched alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms, and R ⁴ is A hydrogen atom or a methyl group. m and n are values that vary depending on the double bond equivalent. ]

（ＩＩ） Preferably, the hard coating composition includes 1.1 to 1.9 parts by mass of an antioxidant with respect to 100 parts by mass of the total resin component, and the antioxidant has the following general formula (II). It is a system antioxidant.

(II)

  The hard coat layer preferably has a refractive index of 1.535 to 1.545.

The hard coat layer is substantially free of ZnO, TiO ₂ , CeO ₂ , SnO ₂ , ZrO ₂ or indium-tin oxide, and their total content is 0.0001% by mass of the solid content weight of the hard coat layer It is preferable that:

  The thickness of the conductive layer is preferably 5 to 100 nm.

In the present invention, preferably, in addition to the hard coat layer and the conductive layer, a color difference adjusting layer is present on the hard coat layer side,
The color difference adjusting layer contains one or both of the curable resin (i) and metal oxide particles (ii) having an average primary particle diameter of 100 nm or less or metal fluoride particles (iii) having an average primary particle diameter of 100 nm or less. Formed from the composition,
The total mass of the particles (ii) and (iii) is 0 to 200 parts by mass with respect to 100 parts by mass of the cured resin (i).
Reflectivity (R1) when light having a wavelength in the range of 500 to 750 nm is irradiated on the conductive laminate, and the conductive laminate is 12N hydrochloric acid, 16N nitric acid and water is 12N hydrochloric acid: 16N nitric acid: water = 3 .3: 1.0: 7.6 After mixing in a strong acid aqueous solution obtained by mixing at a mass ratio of 40.degree. C. for 3 minutes, the conductive laminate after drying has a wavelength of 500 to 750 nm. Provided is a conductive laminate in which the difference ΔR between R1 and R2 is 1 or less when the reflectance (R2) when a range of light is irradiated is used.

  It is preferable that an auxiliary electrode layer further exists on the conductive layer, and the total thickness of the conductive layer and the auxiliary electrode layer is 20 to 500 nm.

In the present invention, an anti-blocking layer is formed on the surface of the polycarbonate base that does not have a hard coat layer,
The anti-blocking layer includes a first component that is an unsaturated double bond-containing acrylic copolymer and a second component that is a polyfunctional acrylate;
A difference ΔSP between the SP value (SP1) of the first component and the SP value (SP2) of the second component is formed from the anti-blocking layer forming composition in the range of 1 to 2,
After coating the anti-blocking layer forming composition, it is preferable that the first component and the second component cause layer separation, and fine irregularities are formed on the surface.

  The present invention further provides a touch panel using the above-mentioned conductive laminate as at least one electrode substrate in a touch panel using an electrode substrate provided with a conductive layer on at least one side.

  The conductive laminate of the present invention has a hard coat layer formed by applying a hard coating composition having a specific composition to a polycarbonate substrate. The hard coat layer of the present invention is characterized by having good hardness and high visibility and extensibility. The hard coat layer of the present invention has very high smoothness. Therefore, even when the hard coat layer in the present invention is provided on a base film having a high refractive index such as a polycarbonate film, there is an advantage that no interference fringes are generated.

  The hard coat layer of the present invention is characterized by not containing a high refractive index agent such as a metal oxide. Therefore, the obtained hard coat layer is characterized by having high extensibility.

  The present invention is an improvement of the above-mentioned Patent Document 4, and the polyfunctional urethane acrylate having an ester skeleton blended in Patent Document 4 has an acrylate group in the side chain in the present invention, and the acrylate group equivalent is 500 to 500. The acrylic resin was changed to 2000 g / mol. The polyfunctional urethane acrylate of Patent Document 4 has an ester skeleton and tends to be hydrolyzed with oxygen or water. In the present invention, by changing this component to an acrylic resin having an acrylic skeleton, the influence of hydrolysis can be suppressed, and adhesion can be ensured for a long period of time even under high temperature and high humidity conditions.

  The hard coating composition for forming the hard coat layer of the present invention contains a specific acrylic resin, and as described above, even in a higher level of adhesion test, it has high adhesion (especially even under wet heat conditions). Period adhesiveness) can be ensured, and even when a hard coat layer is formed on a polycarbonate substrate, it has high smoothness, so that an effect of not generating interference fringes can be obtained. Even if the hard coating layer used in the present invention has a refractive index of 1.535 to 1.545, an effect of not generating interference fringes is seen.

It is a schematic explanatory drawing which shows the transparent conductive laminated body by which the etching process was carried out.

  The conductive laminate of the present invention is a conductive laminate in which a hard coat layer, a color difference adjusting layer and a conductive layer are laminated on at least one surface of a polycarbonate substrate. In addition, although the case where a color difference adjustment layer is not formed is also included in the present invention, a mode in which a color difference adjustment layer exists will be described for convenience. Further, the order of forming the layers is not necessarily specified in this order, but in order to simplify the description, a mode of forming in this order will be described. Furthermore, the conductive laminate of the present invention is basically used in many cases as a transparent conductive laminate, but is not necessarily limited to a transparent embodiment, and the conductive layer is opaque. Are also included within the scope of the present invention. Hereinafter, each layer which comprises the electroconductive laminated body of this invention is demonstrated.

As the polycarbonate substrate used in the conductive laminate of the present invention is generally transparent, the conductive laminate of the present invention includes non-transparent ones as described above. It is not necessarily transparent. In the case of transparency, optically low birefringence, or a phase difference controlled to 1/4 (λ / 4) of wavelength (for example, 550 nm) or 1/2 (λ / 2) of wavelength, or more Those whose refraction is not controlled at all can be appropriately selected according to the application. As mentioned here, when selecting appropriately according to the application, for example, by using polarized light such as linearly polarized light, elliptically polarized light, circularly polarized light, etc. A case where the transparent conductive laminate of the present invention is used together with a display exhibiting a function can be given.

Although the refractive index of a polycarbonate base material changes with the structural monomers, it is about 1.5 or more and less than 1.6 normally. Further, the retardation R (550) of the polycarbonate film is 0 to 160 nm, and it is desirable that the film satisfies the following formulas (1) and (2).
0.60 <R (450) / R (550) <1.20 (1)
0.80 <R (650) / R (550) <1.40 (2)
(However, R (450), R (550), and R (650) are in-plane retardations at wavelengths of 450 nm, 550 nm, and 650 nm, respectively.)
The refractive index of the polycarbonate base material is preferably a film satisfying 1.56 or more and less than 1.60. More preferably, the film has a refractive index of 1.57 or more and less than 1.59, a phase difference R (550) of 0 to 10 nm, and satisfies the following formulas (3) and (4).
1.01 <R (450) / R (550) <1.20 (3)
0.80 <R (650) / R (550) <0.99 (4)

  Although the thickness of a polycarbonate base material can be determined suitably, generally it is about 10-500 micrometers from points, such as workability | operativity, such as intensity | strength and handling property, 20-300 micrometers is especially preferable, and 30-200 micrometers is more preferable.

Hard coat layer The hard coat layer of the conductive laminate of the present invention is:
(A) an acrylic resin having an acrylate group in the side chain and an acrylate group equivalent of 500 to 2000 g / mol;
(B) a phenol novolac acrylate having two or more acrylate groups,
(C) a hard containing bisphenol skeleton-containing diacrylate having 2 or 4 molar equivalents of an alkylene oxide unit having 2 or 3 carbon atoms in a monomer molecule, and (D) a polyfunctional acrylate having 3 or more acrylate groups It is a hard coat layer obtained by applying and curing a coating composition. Here, the component (A) is 10 to 30 parts by mass, the component (B) is 15 to 25 parts by mass, and the component (C) is 20 with respect to 100 parts by mass of the total resin components contained in the hard coating composition. -40 mass parts and a component (D) are on condition that 5-55 mass parts is contained.

(A) Acrylic resin having an acrylate group in the side chain and an acrylate group equivalent of 500 to 2000 g / mol The hard coating composition of the present invention has an acrylate group in the side chain, and the acrylate group equivalent is 500. Acrylic resin (A) having ˜2000 g / mol is included. By including this specific acrylic resin (A), the obtained hard coat layer exhibits sufficient adhesion and smoothness to the polycarbonate substrate, and the refractive index of the hard coat layer to be formed is 1.535-1. .545, interference fringes can be prevented. The equivalent of an acrylate group is 500-2000 g / mol, Preferably it is 700-1500 g / mol. If the equivalent of the acrylate group is less than 500 g / mol, the adhesion due to curing shrinkage is lowered, and if the equivalent of the acrylate group is more than 2000 g / mol, there is a concern that the reactivity is lowered and the adhesion is lowered.

  The acrylic resin (A) used in the present invention preferably has a weight average molecular weight of 5,000 to 100,000, more preferably 10,000 to 20,000, but is not necessarily limited thereto. If the molecular weight is too high, the viscosity tends to increase, the smoothness is impaired and the interference fringes deteriorate, and if the molecular weight is too low, the viscosity tends to decrease, and the smoothness of the coating surface cannot be maintained and the interference fringes Gets worse.

  In this specification, the weight average molecular weight of each component can be measured by a gel permeation chromatography method. In the measurement of the weight average molecular weight, a high-speed GPC apparatus such as HLC-8220 GPC (manufactured by Tosoh Corporation) can be used. As a specific measurement condition of weight average molecular weight using HLC-8220GPC (manufactured by Tosoh Corporation), 2 g of a test sample was weighed and treated in a vacuum dryer at 40 ° C. for 2 hours to remove moisture, and then a THF solution. And a measurement is performed under the conditions of a column injection amount: 10 μl and a flow rate: 0.35 ml / min.

（Ｉ）
［式中、Ｒ^１とＲ^２は水素原子またはメチル基であり、Ｒ^３は炭素数１〜１２の直鎖または分岐鎖アルキル基または炭素数３〜１０のシクロアルキル基であり、Ｒ^４は水素原子またはメチル基である。ｍとｎは整数であるが、二重結合当量で変動する値であり、重合度により変化する値である。］ The acrylic resin (A) is not particularly limited as long as it satisfies the above acrylate group equivalent and has an acrylic skeleton. Preferably, the acrylic resin (A) is represented by the following formulas (a) and (b). Is a copolymer having repeating units

(I)
[Wherein, R ¹ and R ² are a hydrogen atom or a methyl group, R ³ is a linear or branched alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms, and R ⁴ is A hydrogen atom or a methyl group. Although m and n are integers, they are values that vary depending on the double bond equivalent, and are values that vary depending on the degree of polymerization. ]

  The repeating unit (a) of the acrylic resin (A) is a portion derived from an ester of (meth) acrylic acid and an alkyl alcohol (hereinafter referred to as “(meth) acrylic acid alkyl ester (a)”). Yes, the alkyl alcohol is a linear or branched alkyl alcohol having 1 to 12 carbon atoms or a cycloalkyl alcohol having 3 to 10 carbon atoms. Examples of the (meth) acrylic acid alkyl ester (a) include, for example, (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid n-butyl ester, (meth) acrylic acid i-butyl. Ester, (meth) acrylic acid t-butyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid benzyl ester, (meth) acrylic acid cyclohexyl ester, (meth) acrylic acid isobornyl ester, (meth) Examples include acrylic acid hydroxyethyl ester, (meth) acrylic acid hydroxypropyl ester, (meth) acrylic acid dimethylaminoethyl ester, and (meth) acrylic acid diethylaminoethyl ester. The (meth) acrylic acid alkyl ester (a) may be used alone or in combination of two or more.

  The repeating unit (b) of the acrylic resin (A) is obtained by reacting (meth) acrylic acid with glycidyl alcohol to obtain a (meth) glycidyl glycidyl ester, and the (meth) acrylic acid alkyl ester (a). After obtaining a copolymer by reacting with glycidyl, it is formed by reacting a glycidyl group present in the copolymer with (meth) acrylic acid.

  In this invention, the acrylic resin of a component (A) is contained on the condition that 10-30 mass parts is contained with respect to 100 mass parts of all the resin components contained in a hard-coating composition. When the amount of the component (A) is less than 10 parts by mass or exceeds 30 parts by mass, the adhesion is impaired.

(B) A phenol novolac type acrylic having two or more acrylate groups
Rate The hard coating composition comprises a phenol novolac acrylate having component (B) 2 or more acrylate groups. When the hard coating composition contains the phenol novolac acrylate (B), the resulting hard coat layer is transparent and has a high refractive index layer having high hardness.

（ＩＩＩ）
［式（ＩＩＩ）中、Ｒ_５は、ＨまたはＣＨ_２ＯＨであり、Ｒ_６は、ＨまたはＯＨであり、ｋは２〜５であり、ｐは０〜５である。］
で示される、フェノールノボラック型アクリレートであるのが好ましい。上記式（ＩＩＩ）中、ｍは２〜４でありｐは０〜３であるであるのがより好ましく、ｍは２〜４でありｐは０〜１であるのがさらに好ましい。 The phenol novolac acrylate (B) has the following formula (III)

(III)
[In Formula (III), R ₅ is H or CH ₂ OH, R ₆ is H or OH, k is 2 to 5, and p is 0 to 5. ]
It is preferable that it is a phenol novolak-type acrylate shown by these. In said formula (III), it is more preferable that m is 2-4 and p is 0-3, m is 2-4, and it is still more preferable that p is 0-1.

  The weight average molecular weight of the phenol novolak acrylate (B) is preferably 400 to 2500, and more preferably 450 to 2000. Further, the hydroxyl value of the phenol novolac acrylate (B) is preferably 100 to 180 mgKOH / g, and more preferably 120 to 160 mgKOH / g.

  The said phenol novolak-type acrylate (B) is on condition that 15-25 mass parts is contained with respect to 100 mass parts of resin components contained in a hard-coating composition. When the amount of the phenol novolac acrylate (B) is less than 15 parts by mass, the refractive index of the resulting hard coat layer is lowered so that the visibility is deteriorated, and the amount of the phenol novolac acrylate (A) is 25 parts by mass. When exceeding, there exists a malfunction which adhesiveness with a polycarbonate film falls.

(C) A diacrylate having a bisphenol skeleton having 2 or 4 mol of an alkylene oxide structure having 2 or 3 carbon atoms in the molecule. The hard coating composition of the present invention has (C) 2 to 4 mol of an alkylene oxide structure in the molecule. And diacrylate containing a bisphenol skeleton. This diacrylate (C) has the advantage of improving wettability with a polycarbonate base material such as a polycarbonate film by containing a bisphenol skeleton, and increasing adhesion with the hard coat layer. Specific examples of the diacrylate (C) include those obtained by extending the chain of bisphenol A with ethylene oxide and reacting it with (meth) acrylic acid.

  In this invention, it is on condition that 20-40 mass parts of components (C) are contained with respect to 100 mass parts of resin components contained in a hard-coating composition. When the amount of the component (C) is less than 20 parts by mass, there is a problem that the adhesiveness is lowered and the refractive index of the obtained hard coat layer is lowered, and the visibility is impaired, and the amount of (C) is 40 parts by mass. When exceeding, there exists a malfunction which the adhesive force by the fall of reactivity impairs.

(D) Polyfunctional acrylate having 3 or more acrylate groups The hard coating composition of the present invention comprises a polyfunctional acrylate having 3 or more acrylate groups. The polyfunctional acrylate has a molecular weight generally referred to as a monomer, but may be an oligomer in which two or more molecules are bonded. These polyfunctional acrylate monomers have the advantage that a hard reaction layer based on the reaction of (meth) acryloyl groups occurs by irradiation with active energy rays after applying the hard coating composition, and a hard coat layer having high hardness can be obtained. There is.

  Examples of polyfunctional acrylates having 3 or more acrylate groups include, for example, hydroxypropylated trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, trimethylolpropane triacrylate, tris (acryloxyethyl) ) Isocyanurate, ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and oligomers thereof. These polyfunctional acrylates may be used alone or in combination of two or more.

  In the present invention, the component (D) is included in an amount of 5 to 55 parts by mass with respect to 100 parts by mass of the resin component contained in the hard coating composition. When the amount of the component (D) is less than 5 parts by mass, there is a problem that the adhesive force with a transparent polymer substrate such as a polycarbonate film is reduced, and when the amount of the component (D) exceeds 55 parts by mass, The refractive index of the resulting hard coat layer is lowered, and visibility is impaired.

The hard coating composition of the present invention such as a photopolymerization initiator preferably contains a photopolymerization initiator. Due to the presence of the photopolymerization initiator, the resin component is favorably polymerized by irradiation with active energy rays such as ultraviolet rays. Examples of photopolymerization initiators include alkylphenone photopolymerization initiators, acylphosphine oxide photopolymerization initiators, titanocene photopolymerization initiators, and oxime ester polymerization initiators. Examples of alkylphenone photopolymerization initiators include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, and 2-hydroxy-2-methyl-1-phenyl-propane. -1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2 -Hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl 1- [4- (4-morpholinyl) phenyl] -1-butanone and the like. Examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like. Examples of titanocene-based photopolymerization initiators include bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium. Is mentioned. Examples of oxime ester polymerization initiators include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2 -Methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime), oxyphenylacetic acid, 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester, 2- (2-hydroxy And ethoxy) ethyl ester. These photoinitiators may be used individually by 1 type, and may use 2 or more types together.

  Among the photopolymerization initiators, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1- (4-methylthiophenyl) -2 -Morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2,2-dimethoxy-1,2-diphenylethane-1-one and the like More preferably used.

  A preferable amount of the photopolymerization initiator is 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the components (A), (B), (C) and (D). Part.

  The hard coating composition used in the present invention may contain a solvent. The solvent is not particularly limited, and can be appropriately selected in consideration of the components contained in the composition, the type of base material to be coated, the coating method of the composition, and the like. Specific examples of the solvent that can be used include aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, and ethylene glycol. Ether solvents such as dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, and phenetol; ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate, and ethylene glycol diacetate; dimethylformamide, Amide solvents such as diethylformamide and N-methylpyrrolidone; methyl Cellosolve, ethyl cellosolve, cellosolve solvents such as butyl cellosolve; methanol, ethanol, alcohol solvents such as propanol; and the like; dichloromethane, halogenated solvents such as chloroform. These solvents may be used alone or in combination of two or more. Of these solvents, ester solvents, ether solvents, alcohol solvents and ketone solvents are preferably used.

  Various additives can be added to the hard coating composition of the present invention as necessary. Examples of such additives include conventional additives such as antistatic agents, plasticizers, surfactants, and antioxidants.

  Among the above-mentioned additives, various known antioxidants can be used. For example, various antioxidants such as phenol-based antioxidants, sulfur-based antioxidants or phosphorus-based antioxidants can be used. Of these, hindered phenolic antioxidants are preferred, and hindered phenolic antioxidants having the following chemical formula (II) are most preferred.

（ＩＩ）

(II)

  The hindered phenolic antioxidant of the above chemical formula (II) is blended in the hard coating composition in an amount of 1.1 to 1.9 parts by mass with respect to 100 parts by mass of the total resin components, thereby allowing wet heat adhesion. The adhesion can be maintained even after 1500 hours in the test over 750 hours.

The hard coating composition is high even if it does not contain a high refractive index agent composed of a metal oxide such as ZnO, TiO ₂ , CeO ₂ , SnO ₂ , ZrO _2, or indium-tin oxide due to the above configuration. It is characterized in that a hard coat layer having a refractive index can be formed. Therefore, the hard coating composition preferably does not contain a high refractive index agent such as a metal oxide selected from the group consisting of ZnO, TiO ₂ , CeO ₂ , SnO ₂ , ZrO ₂ and indium-tin oxide. . More specifically, the total content of ZnO, TiO ₂ , CeO ₂ , SnO ₂ , ZrO ₂ and indium-tin oxide contained in the hard coat layer formed using the hard coating composition is a hard coat layer. The content is preferably 0.0001% by mass or less. This is because when a high refractive index agent such as a metal oxide is present in the hard coat layer, the stretchability and the bending resistance are generally inferior as compared with the layer containing only the resin component.

  The hard coat layer provided by using the hard coating composition is characterized by having high extensibility and high adhesion to a polycarbonate substrate in addition to the performance required in the hard coat layer such as high visibility and good hardness. And And this high extensibility has the advantage that the visibility of the transparent conductive laminate is dramatically improved. In the production of a transparent conductive laminate, a partial load tends to be generated on a base film having a hard coat layer during processing for providing a transparent conductive layer. For example, in a base film having a hard coat layer, when a partial load is applied, the film swells or twists based on the difference in thermal shrinkage / thermal expansion between the hard coat layer and the base film. There is. The waviness / twisting of these films brings about a decrease in visibility in which a portion where a transparent conductive layer such as ITO is present and a portion where it is not present are visually distinguished. This greatly reduces visibility in a touch panel or the like.

  The hard coat layer provided using the hard coating composition used in the present invention is characterized by having high extensibility in addition to the performance required for the hard coat layer such as high visibility and good hardness. Since the hard coat layer in the present invention has high extensibility, the hard coat layer follows well even when the base film is locally thermally expanded by heating in the stage of providing the transparent conductive layer. As a result, there is an advantage that the problem of reduced visibility in which the portion where the transparent conductive layer such as ITO is present and the portion where the transparent conductive layer is not present is visually distinguished is eliminated. In addition, the conductive laminate of the present invention has high adhesion to the polycarbonate substrate, and ensures a good state even in an advanced adhesion test (advanced adhesion exceeding 750 hours in the wet heat adhesion test).

  A hard-coat layer is formed by apply | coating said hard-coating composition on a polycarbonate base material. The coating method of the hard coating composition can be selected as appropriate according to the situation of the hard coating composition and the painting process. For example, dip coating method, air knife coating method, curtain coating method, roller coating method, wire bar coating method It can be applied by a gravure coating method or an extrusion coating method (US Pat. No. 2,681,294).

  The thickness of the hard coat layer is not particularly limited, and can be set as appropriate in consideration of various factors. For example, the hard coating composition can be applied so that a hard coat layer of 0.01 to 20 μm is obtained.

A hard coat layer is formed by curing the coating film obtained by applying the hard coating composition. This curing can be performed by irradiation using a light source that emits an active energy ray having a wavelength as required. As the active energy ray to be irradiated, for example, light having an exposure amount of 0.1 to 1.5 J / cm ² , preferably 0.3 to 1.5 J / cm ² can be used. The wavelength of the irradiation light is not particularly limited, and for example, irradiation light having a wavelength of 360 nm or less can be used. Such light can be obtained using a high-pressure mercury lamp, an ultra-high pressure mercury lamp, or the like.

  The hard coat layer of the present invention preferably has a glass transition temperature of 60 to 80 ° C. Within this range, there is an advantage that high extensibility is exhibited in the process of manufacturing the touch panel electrode, and the pattern of the transparent conductive layer is difficult to see. If the glass transition temperature of the hard coat layer is lower than 60 ° C., sufficient hardness cannot be obtained in the hard coat film, and whitening occurs during the formation of the transparent conductive layer. On the other hand, if the glass transition temperature of the hard coat layer is higher than 80 ° C., the extensibility is impaired, and the effect of making the transparent conductive layer pattern difficult to see cannot be obtained.

Color Difference Adjustment Layer The conductive laminate of the present invention may form a color difference adjustment layer on the hard coat layer. The color difference adjusting layer is preferably present between the hard coat layer and the transparent conductive layer. The color difference adjusting layer may be a single layer or a layer composed of two layers or more. The color difference adjusting layer is a layer that improves adhesion between layers and optical properties (such as transmittance and color tone) of the transparent conductive laminate.

In the present invention, this color difference adjusting layer is
Cured resin component (i) and metal oxide particles (ii) having an average primary particle size of 100 nm or less and / or metal fluoride particles (iii) having an average primary particle size of 100 nm or less
It is a layer containing. Here, the total mass of the particles (ii) and (iii) in the color difference adjusting layer is conditional on being in the range of 0 to 200 parts by mass with respect to 100 parts by mass of the cured resin component (i).

  As the curable resin component (i), an ultraviolet curable resin or a thermosetting resin can be used. In the color difference adjusting layer of the present invention, it is more preferable to use an ultraviolet curable resin as the cured resin component (i).

  The ultraviolet curable resin can be obtained by a composition containing a monomer having ultraviolet curing performance. Examples of the monomer having ultraviolet curing performance include monofunctional and polyfunctional acrylates such as polyol acrylate, polyester acrylate, urethane acrylate, epoxy acrylate, modified styrene acrylate, melamine acrylate, and silicon-containing acrylate.

  Specific monomers include, for example, trimethylolpropane trimethacrylate, trimethylolpropane ethylene oxide modified acrylate, trimethylolpropane propylene oxide modified acrylate, isocyanuric acid alkylene oxide modified acrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, diester Multifunctional monomers such as methylol tricyclodecane diacrylate, tripropylene glycol triacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, epoxy-modified acrylate, urethane-modified acrylate such as urethane (meth) acrylate, and epoxy-modified acrylate Can be mentioned. These monomers may be used independently and may use 2 or more types together.

  Among these monomers having ultraviolet curing performance, urethane-modified acrylate is preferable. A commercially available product can be used as the urethane-modified acrylate. For example, a purple light series manufactured by Nippon Synthetic Chemical Industry Co., Ltd., for example, UV1700B, UV6300B, UV765B, UV7640B, UV7600B, etc .; Art Resin HDP, Art Resin UN 9000H, Art Resin UN 3320HA, Art Resin UN 3320HB, Art Resin UN 3320HC, Art Resin UN 3320HS, Art Resin UN 901M, Art Resin UN 902MS, Art Resin UN 903; UA manufactured by Shin-Nakamura Chemical Co., Ltd. H , U4H, U6H, U15HA, UA32P, U6LPA, U324A, U9HAMI, etc .; Ebecryl series made by Daicel UCB Co., Ltd., For example, 1290, 5129, 254, 264, 265, 1259, 1264, 4866, 9260, 8210, 204, 205, 6602, 220, 4450, etc .; Beam set series manufactured by Arakawa Chemical Industries, Ltd., for example, 371, 371MLV 371S, 577, 577BV, 577AK, etc .; RQ series, manufactured by Mitsubishi Rayon Co., Ltd .; Unidic series, manufactured by DIC Corporation, etc .; ) Etc. can be used.

  When the curable resin component (i) is an ultraviolet curable resin, the composition forming the color difference adjusting layer preferably contains a photopolymerization initiator. As the photopolymerization initiator, commonly used photopolymerization initiators such as acetophenone, benzophenone, benzoin, benzoylbenzoate, and thioxanthone can be used.

  The composition forming the color difference adjusting layer may further contain a photosensitizer. As the photosensitizer, for example, commonly used photosensitizers such as triethylamine and tri-n-butylphosphine can be used.

  The composition forming the color difference adjusting layer may further contain hydrolysates of various alkoxysilanes.

  When the curable resin component (i) is a thermosetting resin, the composition for forming the color difference adjusting layer is an organosilane thermosetting monomer having a silane compound such as methyltriethoxysilane or phenyltriethoxysilane as a monomer. A thermosetting monomer such as a melamine thermosetting monomer, an isocyanate thermosetting monomer, a phenol thermosetting monomer, or an epoxy thermosetting monomer using a monomer or etherified methylol melamine as a monomer may be included. These thermosetting monomers may be used alone or in combination of two or more. In addition to the said thermosetting monomer, you may contain the thermoplastic resin component as needed.

  When the cured resin component (i) is a thermosetting resin, the composition forming the color difference adjusting layer preferably contains a reaction accelerator or a curing agent. Examples of the reaction accelerator include triethylenediamine, dibutyltin dilaurate, benzylmethylamine, pyridine and the like. Examples of the curing agent include methylhexahydrophthalic anhydride, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, diaminodiphenylsulfone, and the like.

  In the present invention, in addition to the cured resin component (i), the color difference adjusting layer includes metal oxide particles (ii) having an average primary particle diameter of 100 nm or less and / or metal fluoride particles having an average primary particle diameter of 100 nm or less. (Iii) is included. And the total mass of these particle | grains (ii) and (iii) is on condition that it exists in the range of 0-200 mass parts with respect to 100 mass parts of cured resin components (i). The total mass of the particles (ii) and (iii) can be adjusted as appropriate according to the refractive index of each of (i), (ii), and (iii) in order to obtain desired optical properties, but from the viewpoint of film strength after curing Is preferably in the range of 0 to 150 parts by mass, more preferably in the range of 0 to 100 parts by mass with respect to 100 parts by mass of the cured resin component (i).

  When the total mass of the particles (ii) and (iii) in the color difference adjusting layer exceeds 200 parts by mass, there is a problem that interlayer adhesion is inferior.

Specific examples of the metal oxide particles (ii) include ZnO, TiO ₂ , CeO ₂ , SnO ₂ , ZrO ₂ and indium-tin oxide. These metal oxide particles (ii) are all characterized by having a high refractive index. Therefore, the color difference adjusting layer containing the metal oxide particles (ii) is basically a high refractive index layer. As the metal oxide particles (ii), ZnO, TiO ₂ and ZrO ₂ are more preferably used. As the metal oxide particles (ii), one type may be used alone, or two or more types may be used in combination.

  In addition, as above-mentioned, all of these metal oxide particles (ii) are on condition that an average primary particle diameter is 100 nm or less. When the average primary particle diameter exceeds 100 nm, the size is easily visible due to aggregation of particles during the formation of the color difference adjusting layer, so that there are problems such as an increase in haze value or a foreign appearance defect. In this specification, the average primary particle diameter represents a 50% volume particle diameter when a liquid in which particles are dispersed in a solvent such as n-BuOH is measured with a particle size distribution meter.

Specific examples of the metal constituting the metal fluoride particles (iii) include calcium, barium, magnesium, strontium and the like. Among these metals, magnesium is more preferable. These metal fluoride particles (iii) may be used alone or in combination of two or more. If necessary, it may be used in combination the metal fluoride particles (iii) and SiO _2.

  These metal fluoride particles (iii) are all characterized by having a low refractive index. Therefore, the color difference adjusting layer containing the metal fluoride particles (iii) is basically a low refractive index layer. In addition, as above-mentioned, as for these metal fluoride particles (iii), all are on condition that an average primary particle diameter is 100 nm or less. When the average primary particle diameter exceeds 100 nm, the size is easily visible due to aggregation of particles during the formation of the color difference adjusting layer, so that there are problems such as an increase in haze value or a foreign appearance defect.

  The color difference adjusting layer in the present invention may be composed of one layer or may be composed of two or more layers. For example, when the color difference adjusting layer is a single layer, it is preferably a high refractive index layer containing the metal oxide particles (ii). As another aspect, the aspect containing both the said metal oxide particle (ii) and metal fluoride particle (iii) is mentioned, for example. When the color difference adjusting layer is one layer, the thickness of the color difference adjusting layer is preferably 30 to 300 nm, and more preferably 50 nm to 200 nm.

  For example, when the color difference adjusting layer is a two-layer structure, it has a two-layer structure including a high refractive index layer containing the metal oxide particles (ii) and a low refractive index layer containing the metal fluoride particles (iii). Is preferred. In this case, it is more preferable that the hard coat layer and the high refractive index layer are in contact with each other. When the color difference adjusting layer is composed of two layers consisting of one high refractive index layer and one low refractive index layer, the total thickness of the color difference adjusting layer is preferably 30 to 300 nm, preferably 50 nm to 200 nm. More preferably.

  The color difference adjusting layer is formed by, for example, converting a composition containing a monomer having ultraviolet curing performance and the metal oxide particles (ii) and / or metal fluoride particles (iii) into a transparent polymer group having a hard coat layer. It can be formed by coating on a hard coat layer of the material and then irradiating and curing with an active energy ray such as ultraviolet rays. Alternatively, a composition containing a thermosetting monomer and the metal oxide particles (ii) and / or metal fluoride particles (iii) is applied onto the hard coat layer of a transparent polymer substrate having a hard coat layer. Then, it can be formed by heat curing.

  As an example of the case where the color difference adjusting layer has two layers, first, a composition containing metal oxide particles (ii) is coated on a hard coat layer and cured, and then a composition containing metal fluoride particles (iii). By coating and curing the object, a color difference adjusting layer composed of two layers can be formed.

  As another example when the color difference adjusting layer has two layers, first, a composition containing metal fluoride particles (iii) is coated and cured, and then a composition containing metal oxide particles (ii) is hardened. By coating and curing on the coat layer, a color difference adjusting layer comprising two layers can be formed.

  As a method for coating the above composition, a coating method using a coating machine usually used by those skilled in the art such as a doctor knife, bar coater, gravure roll coater, curtain coater, knife coater, spin coater, a coating method using a spray, Examples of the coating method include immersion.

  Moreover, the said composition may also contain the organic solvent as needed. Examples of the organic solvent include alcohol solvents such as ethanol, isopropyl alcohol, butanol, and 1-methoxy-2-propanol, hydrocarbon solvents such as hexane, cyclohexane, ligroin, and cyclohexanone, and ketone solvents such as methyl isobutyl ketone and isobutyl acetate. Examples of the solvent include aromatic solvents such as xylene and toluene. These organic solvents may be used individually by 1 type, and may use 2 or more types together.

In the case of curing a composition containing a monomer having ultraviolet curing performance, this curing can be performed by irradiating with a light source that emits an active energy ray having a wavelength as required. As the active energy ray to be irradiated, for example, light having an exposure amount of 0.1 to 1.5 J / cm ² , preferably 0.3 to 1.5 J / cm ² can be used. The wavelength of the irradiation light is not particularly limited, and for example, irradiation light having a wavelength of 360 nm or less can be used. Such light can be obtained using a high-pressure mercury lamp, an ultra-high pressure mercury lamp, or the like.

  Moreover, when hardening the composition containing a thermosetting monomer, it can be hardened by heating at 60-140 degreeC for 1 to 60 minutes, for example. Here, the heating temperature and the heating time can be selected according to the type of the thermosetting monomer contained in the composition.

Conductive layer and conductive laminate In the conductive laminate of the present invention, a conductive layer is usually formed on a hard coat layer or a color difference adjusting layer. The conductive layer may be a transparent conductive layer when the entire conductive laminate is transparent, and may be a normal metal conductive layer when not transparent. The constituent material of the transparent conductive layer is not particularly limited, and examples thereof include a metal layer or a metal compound layer. Examples of the component constituting the transparent conductive layer include metal oxide layers such as silicon oxide, aluminum oxide, titanium oxide, magnesium oxide, zinc oxide, indium oxide, and tin oxide. Of these, a crystalline layer mainly composed of indium oxide is preferable, and a layer made of crystalline ITO (Indium Tin Oxide) is particularly preferably used.

  In the case where the transparent conductive layer is crystalline ITO, the crystal grain size need not be particularly limited, but is preferably 500 nm or less. If the crystal grain size exceeds 500 nm, the bending durability deteriorates, which is not preferable. Here, the crystal grain size is defined as the largest diagonal line or diameter in each polygonal or oval region observed under a transmission electron microscope (TEM). When the transparent conductive layer is amorphous ITO, environmental reliability may be lowered.

  The conductive layer can be formed by a known method. For example, a physical formation method such as a DC magnetron sputtering method, an RF magnetron sputtering method, an ion plating method, a vacuum deposition method, a pulse laser deposition method, or the like can be used. Can be used. Focusing on industrial productivity of forming a metal compound layer having a uniform film thickness over a large area, the DC magnetron sputtering method is desirable. In addition to the physical formation method (PVD), a chemical formation method such as a chemical vapor deposition method or a sol-gel method can be used, but the sputtering method is desirable from the viewpoint of film thickness control.

  The film thickness of the conductive layer is preferably 5 to 50 nm from the viewpoint of conductivity. More preferably, it is 5-30 nm. If the thickness of the conductive layer is less than 5 nm, the resistance value tends to be inferior in stability over time, and if it exceeds 50 nm, the bending durability is lowered, which is not preferable as a touch panel.

  When the conductive laminate of the present invention is used for a touch panel, the surface resistance value of the transparent conductive layer is more preferably 10 to 2000Ω / □ at a film thickness of 10 to 40 nm because of reduction in power consumption of the touch panel and circuit processing. Is preferably a transparent conductive layer showing a range of 30 to 1000Ω / □.

  In addition, when the conductive layer is transparent, a wet dispersion method (for example, spin coating method, gravure, slot die, printing, etc.) on a polymer substrate with a dispersion of metal nanowires, carbon nanotubes, conductive oxide fine particles, etc. It is also possible to use a layer formed by (1).

  The conductive layer thus formed is patterned by an etching process. This etching process is generally performed by covering the conductive layer with a pattern formation mask and then etching the conductive layer using an etching solution such as an acidic aqueous solution. Examples of the etchant include inorganic acids such as hydrogen chloride, hydrogen bromide, sulfuric acid, nitric acid, and phosphoric acid, organic acids such as acetic acid, and mixtures thereof, and aqueous solutions thereof. As a more specific etching solution, a strong acid aqueous solution obtained by mixing 12N hydrochloric acid, 16N nitric acid and water in a mass ratio of 12N hydrochloric acid: 16N nitric acid: water = 3.3: 1.0: 7.6 can be mentioned.

  In addition, you may heat-process as needed before or after patterning a conductive layer. In the case of ITO in which the conductive layer is crystallized by heat treatment, there is an advantage that transparency and conductivity can be improved by performing the heat treatment. The heat treatment can be performed, for example, by heating at 100 to 150 ° C. for 15 to 180 minutes.

  The conductive laminate of the present invention has a reflectance (R1) when the conductive laminate is irradiated with a light source having a wavelength in the range of 500 to 750 nm, and the conductive laminate comprises 12N hydrochloric acid, 16N nitric acid and water. After being immersed in a strong acid aqueous solution obtained by mixing 12N hydrochloric acid: 16N nitric acid: water at a mass ratio of 3.3: 1.0: 7.6 at 40 ° C. for 3 minutes, and then dried. A difference ΔR between R1 and R2 is 1 or less in reflectance (R2) when the laminate is irradiated with a light source having a wavelength of 500 to 750 nm.

  The strong acid aqueous solution is a so-called aqua regia strong acid aqueous solution that is generally used in an etching process. By conducting an etching process using the strong acid aqueous solution, the conductive layer is etched. FIG. 1 is a schematic explanatory view showing a conductive laminate subjected to etching. The conductive laminate (10) has a structure in which a hard coat layer (3), a color difference adjusting layer (5), and a transparent conductive layer (7) are sequentially laminated on one surface of a polycarbonate substrate (1). . Here, the portion indicated by (11) is a portion where the conductive layer (7) has been removed by patterning by the etching process, and the portion indicated by (13) is a portion masked in the etching process. There is a portion where the conductive layer is left as it is. Here, the reflectance R1 means the reflectance at the portion (13) in FIG. 1, and the reflectance R2 means the reflectance at the portion (11) in FIG. And in the electroconductive laminated body of this invention, the difference (DELTA) R of R1 and R2 is 1 or less in the reflectance at the time of irradiating the light source of the wavelength range of 500-750 nm, It is characterized by the above-mentioned. That is, in the conductive laminate of the present invention, there is almost no difference in reflectance between the portion where the conductive layer (7) is present and the portion where it is not present. Thereby, extremely high visibility was achieved.

  The reflectance of the conductive laminate can be measured using a spectrophotometer such as Hitachi U-3000, for example, and the spectral reflectance at an incident angle of 10 degrees can be measured according to JIS K5600-4-5. .

Anti-blocking layer The conductive laminate of the present invention has a structure in which a hard coat layer, a color difference adjusting layer, and a conductive layer are sequentially laminated on one surface of a polycarbonate substrate. In this conductive laminate, an anti-blocking layer may be formed on the other surface of the polycarbonate substrate as necessary. By forming the anti-blocking layer on the other surface, it is possible to suppress the occurrence of the blocking phenomenon in the production process of the conductive laminate, and there is an advantage that the storage stability during production is improved.

  As a composition which forms an antiblocking layer, the antiblocking layer forming composition containing a 1st component and a 2nd component is mentioned, for example. The difference ΔSP between the SP value (SP1) of the first component and the SP value (SP2) of the second component is in the range of 1 to 2, and after coating the anti-blocking layer forming composition, the first component and the second component More preferably, the composition is an anti-blocking layer-forming composition in which the component causes phase separation and an anti-blocking layer having fine irregularities on the surface is formed.

  As the first component, an unsaturated double bond-containing acrylic copolymer is used. An unsaturated double bond-containing acrylic copolymer is, for example, a resin obtained by copolymerizing a (meth) acrylic monomer and another monomer having an ethylenically unsaturated double bond, a (meth) acrylic monomer and another ethylenically unsaturated Acrylic acid or glycidyl acrylate for resins reacted with monomers having double bonds and epoxy groups, resins made by reacting (meth) acrylic monomers with other monomers having ethylenically unsaturated double bonds and isocyanate groups, etc. And those having an unsaturated double bond and other functional groups added thereto. One of these unsaturated double bond-containing acrylic copolymers may be used alone, or two or more thereof may be mixed and used. The unsaturated double bond-containing acrylic copolymer preferably has a weight average molecular weight of 2,000 to 100,000, more preferably 5,000 to 50,000.

  The monomer or oligomer of the second component is more preferably a polyfunctional unsaturated double bond-containing monomer or an oligomer thereof. The “oligomer” in the present specification refers to a polymer having a repeating unit and having 3 to 10 repeating units. As the polyfunctional unsaturated double bond-containing monomer, for example, a polyfunctional acrylate which is a dealcoholization reaction product of a polyhydric alcohol and (meth) acrylate, specifically, dipentaerythritol hexa (meth) acrylate, dipenta Erythritol penta (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, neopentyl glycol di (meth) acrylate, and the like can be used. In addition, an acrylate monomer having a polyethylene glycol skeleton such as polyethylene glycol # 200 diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) can also be used. One of these polyfunctional unsaturated double bond-containing monomers may be used alone, or two or more thereof may be mixed and used. The second component is more preferably a polyfunctional acrylate.

  Preferred organic solvents when the first component and the second component are the above combinations include, for example, ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; alcohol solvents such as methanol, ethanol, propanol, isopropanol, and butanol An ether solvent such as anisole, phenetol propylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether; One of these solvents may be used alone, or two or more organic solvents may be mixed and used.

  The anti-blocking layer forming composition preferably contains a photopolymerization initiator. Examples of the photopolymerization initiator include 2-hydroxy-2methyl-1phenyl-propan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1- [4- (methylthio) phenyl] -2. -Morpholinopropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, etc. Can be mentioned.

  In the anti-blocking layer forming composition, phase separation is caused by the difference in SP value between the first component and the second component. By this phase separation, an anti-blocking layer having fine irregularities on the surface is formed. The difference between the SP value of the first component and the SP value of the second component is preferably 1 or more, and more preferably in the range of 1 to 2. When the difference between the SP value of the first component and the SP value of the second component is 1 or more, the compatibility of the resins with each other is low, whereby the first component and the second component are applied after application of the anti-blocking layer forming composition. It is thought that phase separation is brought about.

  The SP value is an abbreviation for solubility parameter (solubility parameter) and is a measure of solubility. The SP value indicates that the polarity is higher as the numerical value is larger, and the polarity is lower as the numerical value is smaller.

  For example, the SP value can be measured by the following method [references: SUH, CLARKE, J. et al. P. S. A-1, 5, 1671-1681 (1967)].

Measurement temperature: 20 ° C
Sample: Weigh 0.5 g of resin in a 100 ml beaker, add 10 ml of good solvent using a whole pipette, and dissolve with a magnetic stirrer.
solvent:
Good solvent: Dioxane, acetone, etc. Poor solvent: n-hexane, ion-exchanged water, etc. Muddy point measurement: The poor solvent is added dropwise using a 50 ml burette, and the point at which turbidity occurs is defined as the amount added.

  The SP value δ of the resin is given by the following equation.

Vi: Molecular volume of solvent (ml / mol)
φi: Volume fraction of each solvent at cloud point δi: SP value of solvent ml: Low SP poor solvent mixed system mh: High SP poor solvent mixed system

  The anti-blocking layer forming composition may contain conventional additives such as an antistatic agent, a plasticizer, a surfactant, an antioxidant, and an ultraviolet absorber, if necessary.

  In addition to the first component and the second component, the anti-blocking layer forming composition may contain a resin that is usually used. The anti-blocking layer forming composition is characterized in that, by using the first component and the second component as described above, a resin layer having irregularities can be formed without including resin particles or the like. . Therefore, it is preferable that the anti-blocking layer forming composition does not contain resin particles. However, the anti-blocking layer forming composition may contain at least one or more inorganic particles, organic particles, or a composite thereof, if necessary. These particles are not particularly added for the purpose of forming irregularities on the surface, but are added to form more uniform and fine irregularities by controlling phase separation and precipitation. These particles have an average particle size of 0.5 μm or less, preferably 0.01 to 0.3 μm. When it exceeds 0.5 μm, the transparency slightly decreases.

  Examples of inorganic particles include silica, alumina, titania, zeolite, mica, synthetic mica, calcium oxide, zirconium oxide, zinc oxide, magnesium fluoride, smectite, synthetic smectite, vermiculite, ITO (indium oxide / tin oxide), ATO There may be mentioned at least one selected from the group consisting of (antimony oxide / tin oxide), tin oxide, indium oxide and antimony oxide.

  Examples of the organic particles include at least one selected from the group consisting of acrylic, olefin, polyether, polyester, urethane, polyester, silicone, polysilane, polyimide, and fluorine particles.

  The anti-blocking layer forming composition is prepared by mixing the first component and the second component, and additives such as a solvent, a photopolymerization initiator, a catalyst, and a photosensitizer as necessary. The ratio of the first component and the second component in the anti-blocking layer forming composition is preferably 0.1: 99.9 to 50:50, more preferably 0.3: 99.7 to 20:80, and 0 5: 99.5-10: 90 is more preferable. When a polymerization initiator, a catalyst, and a photosensitizer are used, the first component, the second component, and other resin as necessary (referred to collectively as “resin component”) are 100 parts by mass. 0.01 to 20 parts by mass, preferably 1 to 10 parts by mass can be added. When using a solvent, it is 1-9900 mass parts with respect to 100 mass parts of said resin components, Preferably 10-900 mass parts can be added.

  By coating the anti-blocking layer forming composition and then curing, an anti-blocking layer having fine irregularities on the surface can be formed. Examples of the coating method of the anti-blocking layer forming composition include dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, and extrusion coating. Examples of the thickness of the anti-blocking layer include an embodiment having a thickness of 0.01 to 20 μm.

After coating the anti-blocking layer forming composition, it can be phase-separated and cured by irradiating light. As light to irradiate, for example, light having an exposure amount of 0.1 to 3.5 J / cm ² , preferably 0.5 to 1.5 J / cm ² can be used. Further, the wavelength of the irradiation light is not particularly limited, and for example, irradiation light having a wavelength of 360 nm or less can be used. Such light can be obtained using a high-pressure mercury lamp, an ultra-high pressure mercury lamp, or the like. By irradiating light in this way, phase separation and curing will occur.

Touch panel The touch panel of the present invention has a transparent conductive laminate. Examples of the touch panel of the present invention include a capacitive touch panel. Moreover, you may use the transparent conductive laminated body of this invention for a resistive film type touch panel.
Touch panel The touch panel of the present invention has a transparent conductive laminate. Examples of the touch panel of the present invention include a capacitive touch panel. Moreover, you may use the transparent conductive laminated body of this invention for a resistive film type touch panel.

Specific examples of the layer structure in the case where the transparent conductive laminate of the present invention is used as a touch panel substrate include the following layer structures:
Transparent conductive layer / color difference adjusting layer / hard coat layer / polycarbonate substrate,
Transparent conductive layer / hard coat layer / polycarbonate substrate,
Transparent conductive layer / color difference adjusting layer / hard coat layer / polycarbonate substrate / anti-blocking layer,
Transparent conductive layer / hard coat layer / polycarbonate substrate / anti-blocking layer,
Transparent conductive layer / color difference adjusting layer / hard coat layer / polycarbonate substrate / hard coat layer / color difference adjusting layer / transparent conductive layer,
Transparent conductive layer / hard coat layer / polycarbonate substrate / hard coat layer / color difference adjusting layer / transparent conductive layer,
Auxiliary electrode layer / transparent conductive layer / color difference adjusting layer / hard coat layer / polycarbonate substrate,
Auxiliary electrode layer / transparent conductive layer / hard coat layer / polycarbonate substrate,
Auxiliary electrode layer / transparent conductive layer / color difference adjusting layer / hard coat layer / polycarbonate substrate / anti-blocking layer, auxiliary electrode layer / transparent conductive layer / color difference adjusting layer / hard coat layer / transparent polymer substrate / anti-blocking layer,
Auxiliary electrode layer / transparent conductive layer / color difference adjusting layer / hard coat layer / polycarbonate substrate / hard coat layer / color difference adjusting layer / transparent conductive layer / auxiliary electrode layer,
Auxiliary electrode layer / transparent conductive layer / hard coat layer / polycarbonate substrate / hard coat layer / transparent conductive layer / auxiliary electrode layer. In the above layer configuration, layers are described in order from the uppermost layer to the lowermost layer. A metal oxide layer (specifically, a layer made of a metal oxide such as silicon dioxide, niobium oxide, molybdenum oxide) is formed immediately below the transparent conductive layer in order to adjust color difference or improve adhesion. May be. A hard coat layer for the purpose of surface protection may be provided on the upper layer of the uppermost transparent conductive layer. In this case, the hard coat layer may be the hard coat layer of the present invention, but may be a normal hard coat layer other than the present invention.

The auxiliary electrode layer mentioned here means a layer that can be used as an electrode material for wiring. As a material for the auxiliary electrode layer, a material having a specific resistance of 1 × 10 ⁻⁶ Ωcm or more and 1 × 10 ⁻⁴ Ωcm or less is desirable. When a metal material having a specific resistance of less than 1 × 10 ⁻⁶ Ωcm is used, it is unstable in terms of application functions, and it becomes difficult to form a thin film. On the other hand, when a metal material having a specific resistance larger than 1 × 10 ⁻⁴ Ωcm is used, the resistance value is too high, and thus the resistance value is increased when thin wire processing is performed. For the above reasons, a metal suitable for practical use is recommended to be a single metal selected from the group consisting of Cu, Ag, Al, Au, Ni, Ni / Cr, and Ti, or an alloy composed of a plurality of types. In particular, it is a metal with high electrical conductivity and excellent workability such as pattern etching and electroplating, and has good electrical and mechanical connectivity (solder, anisotropic conductive connector, etc.) between the electrode and the lead portion of the circuit, Cu, Al, and the like are preferable in terms of bending resistance, high thermal conductivity, and low cost, and Cu is particularly preferable.

  The thickness of the auxiliary electrode layer is not particularly limited, but a normal design specification of 0.001 to 100 μm, preferably 0.01 to 25 μm is recommended. A known treatment method can be used for forming the auxiliary electrode, but it is preferable to form the auxiliary electrode by a sputtering method. Further, if necessary, the electroconductivity may be increased by further increasing the film thickness by electrolysis / electroless wet metal plating.

  In addition, for the purpose of protecting (mainly preventing oxidation) the auxiliary electrode layer, if necessary, a refractory metal layer made of Ni, Ni / Cr, Cr, Ti, Mo or the like on the upper and lower layers of the auxiliary electrode layer, and these An oxide layer may be provided.

  The following examples further illustrate the present invention, but the present invention is not limited thereto. In the examples, “parts” and “%” are based on mass unless otherwise specified.

Production Example 1 Production of Acrylic Resin (1) While stirring 70 parts of butyl acetate into a reactor equipped with a stirring blade, thermometer, dropping device, temperature control device, gas inlet and cooling pipe, and introducing nitrogen gas, The temperature was raised to 110 ° C. with stirring. Next, a mixture consisting of 15.3 parts of glycidyl methacrylate, 76.8 parts of methyl methacrylate and 7.9 parts of n-butyl acrylate, and 2.0 parts of perbutyl O (manufactured by NOF Corporation) into 25.0 parts of butyl acetate. The dissolved solution was dropped into the reactor over 3 hours. After completion of the dropwise addition, the mixture was aged for 1 hour, and a solution obtained by dissolving 1.0 part of perbutyl O (manufactured by NOF Corporation) in 25.0 parts of butyl acetate was dropped into the reactor over 1 hour. After maintaining the temperature at 110 ° C. for 1 hour after the completion of the dropping, the temperature was raised to 120 ° C., and the reaction was completed by aging for 2 hours. Next, the gas was changed from nitrogen gas to air and cooled to 90 ° C. with stirring, and 7.8 parts of acrylic acid and 0.3 part of P-methoxyphenol were charged. Further, a solution in which 0.6 part of tetrabutylammonium bromide was dissolved in 3.0 parts of butyl acetate was added, and the temperature was raised to 105 ° C. for reaction. The reaction was monitored by the acid value, and the reaction was continued until the acid value of the solid content was 5 or less. The acid value was determined according to JIS-5601-2-1, and the reaction solution was titrated with a 0.1N potassium hydroxide solution and calculated according to the following formula.

  Acid value = {(Drop amount of KOH solution [mL]) × (Molar concentration of KOH solution [mol / L])} / (Weight of solid content [g])

  After completion of the reaction, 12.0 parts of butyl acetate was added and cooled to obtain an acrylic resin (1) having an acrylic equivalent of 1000. The nonvolatile content after 3 hours at 105 ° C. was 45.1%.

Production Examples 2 to 5 Production of Acrylic Resins (2) to (5) Acrylic resins (2) to (5) were produced in the same manner as in Production Example 1 with the formulation shown in Table 1.

Production Example 6 Production of phenol novolac acrylate 150 g of phenol novolac resin (weight average molecular weight 700 to 900, epoxy equivalent 150 to 200) and epichlorohydrin 550 g were mixed in a reactor equipped with a stirrer, thermometer, dropping funnel and refluxing device. Then, 110 g of 48.5% aqueous sodium hydroxide solution was added dropwise over 2 hours under reduced pressure conditions of 100 ° C. and 100 to 200 mg. After completion of the reaction, the temperature is cooled to room temperature, an excess aqueous sodium hydroxide solution is neutralized with an acid, heated under reduced pressure to remove excess epichlorohydrin, the product is dissolved in methyl isobutyl ketone, washed with water and filtered. By-product salts were removed to obtain a phenol novolac type epoxy resin solution.
Metoquinone 1000 ppm and triphenylphosphine 2000 ppm are added to 100 parts by weight of the solid content of the obtained phenol novolac type epoxy resin, and acrylic acid is added dropwise at 100 ° C. until the acid value becomes 1 mgKOH / g or less. A phenol novolac type epoxy acrylate (1) was obtained.

  The obtained phenol novolac epoxy acrylate had a weight average molecular weight of 950, a hydroxyl value of 140 mgKOH / g, and a refractive index of 1.572.

Production Example 7 Production of Polyfunctional Urethane Acrylate Polycarbonate diol (PCDL T manufactured by Asahi Kasei Chemicals Co., Ltd.) of 1,5-pentanediol and 1,6-hexanediol was added to a 1 L four-necked flask equipped with a thermometer, a condenser, and a stirring device. -5652, number average molecular weight: 2000) 341 g, acrylic acid adduct of 1,6-hexanediol diglycidyl ether (Lipoxy SP-16LDA manufactured by Showa Polymer Co., Ltd.), 43 g of isophorone diisocyanate, dibutyltin dilaurate (reaction catalyst) ) 0.2 g and methyl ethyl ketone (organic solvent) 400 g were added and stirred at 70 ° C. for about 24 hours to be reacted. After the reaction, it was confirmed by the infrared absorption spectrum that no isocyanate residue was observed. In this way, an unsaturated group-containing urethane resin having a number average molecular weight of 30000 and an unsaturation degree of 0.23 mol / kg was obtained.

Example 1
As the preparation component (A) of the hard coating composition, the acrylic resin (1) obtained in Production Example 1 and the component (B) as the component (B) are the phenol novolac epoxy acrylate (1) obtained in Production Example 6 and the component ( A hard coating composition was prepared using bisphenol A ethylene oxide 2 mol modified diacrylate as C) and pentaerythritol triacrylate as component (D). The raw materials shown in Table 1 were sequentially mixed at the solid content mass shown in Table 1 and stirred to obtain a hard coating composition.

Preparation of Hard Coat Film The obtained hard coating composition was dropped onto a 100 μm optical PC film (Pure Ace) manufactured by Teijin Chemicals and coated using a bar coater # 9. After coating, it was dried at 70 ° C. for 1 minute, and irradiated with 350 mJ of ultraviolet rays with an ultraviolet irradiator (manufactured by Fusion) to obtain a hard coat film having a polycarbonate film and a hard coat layer having a thickness of 3.0 μm. The refractive index of the hard coat layer was 1.542 as measured using an Abbe refractometer by a method based on JIS K0062.

Production of transparent conductive laminate On the hard coat layer of the obtained hard coat film, a sputtering method using an indium oxide-tin oxide target having a weight ratio of 95: 5 and a packing density of 98% is used. Then, an ITO layer was formed to produce a transparent conductive laminate that would be a movable electrode substrate. The thickness of the formed ITO layer was about 30 nm, and the surface resistance value after film formation was about 150Ω / □.

Examples 2-20
The type and amount of the component (A) were changed to those described in Table 2, and the amounts of the components (B) to (D) were changed to those described in Table 2, and the same as in Example 1. A hard coating composition was prepared. A hard coat film was obtained in the same manner as in Example 1 using the obtained hard coating composition. The thickness of the hard coat layer was 3.0 μm, and the refractive index was 1.542 as measured with an Abbe refractometer in accordance with JIS K0062. On the hard coat layer of the obtained hard coat film, an ITO layer is formed by a sputtering method using an indium oxide-tin oxide target having an indium oxide and tin oxide composition of 95: 5 by weight and a filling density of 98%, A transparent conductive laminate to be a movable electrode substrate was produced. The thickness of the formed ITO layer was about 30 nm, and the surface resistance value after film formation was about 150Ω / □.

Comparative Example 1
In this example, an example is shown in which the polyester urethane acrylate obtained in Production Example 7 is used instead of the acrylic resin of the present application with a composition corresponding to the invention of Patent Document 4. The composition prepared the hard coating composition by the mixing | blending of the comparative example 1 of Table 3, and it carried out similarly to Example 1, and obtained the hard coat film. The thickness of the hard coat layer was 3.0 μm, and the refractive index was 1.542 as measured with an Abbe refractometer in accordance with JIS K0062. On the hard coat layer of the obtained hard coat film, an ITO layer is formed by a sputtering method using an indium oxide-tin oxide target having an indium oxide and tin oxide composition of 95: 5 by weight and a filling density of 98%, A transparent conductive laminate to be a movable electrode substrate was produced. The thickness of the formed ITO layer was about 30 nm, and the surface resistance value after film formation was about 150Ω / □.

Comparative Examples 2-10
A hard coating composition was prepared in the same manner as in Example 1 with the formulation shown in Comparative Examples 2 to 10 in Table 3. A hard coat film was obtained in the same manner as in Example 1 using the obtained hard coating composition. The thickness of the hard coat layer was 3.0 μm, and the refractive index was 1.542 as measured with an Abbe refractometer in accordance with JIS K0062. On the hard coat layer of the obtained hard coat film, an ITO layer is formed by a sputtering method using an indium oxide-tin oxide target having an indium oxide and tin oxide composition of 95: 5 by weight and a filling density of 98%, A transparent conductive laminate to be a movable electrode substrate was produced. The thickness of the formed ITO layer was about 30 nm, and the surface resistance value after film formation was about 150Ω / □.

  The following evaluation was performed about the hard-coating composition, hard-coat film, and transparent conductive laminated body which were obtained in the said Examples 1-20 and Comparative Examples 1-10. The evaluation results are shown in Tables 2 and 3.

Measurement of Reflectance Difference ΔR The reflectance of the transparent conductive laminates obtained in Examples 1 to 20 and Comparative Examples 1 to 10 was measured using a spectrophotometer (Hitachi U-3000). The reflectance R1 was measured at 10 degrees in accordance with JIS K5600-4-5. The wavelength of the light source used in the reflectance measurement was 500 to 750 nm.

  Next, the obtained transparent conductive laminate was mixed with 12N hydrochloric acid, 16N nitric acid and water in a mass ratio of 12N hydrochloric acid: 16N nitric acid: water = 3.3: 1.0: 7.6. It was immersed in an aqueous solution at 40 ° C. for 3 minutes and dried. The transparent conductive laminate was irradiated with light having a wavelength of 500 to 750 nm, and the reflectance R2 was measured. The reflectance R1 means the reflectance of the portion where the transparent conductive layer is present as shown in the portion (13) in FIG. 1, and the reflectance R2 is the portion (11) in FIG. The reflectance of the part where a transparent conductive layer does not exist as shown in FIG.

  The difference between R1 and R2 thus obtained was taken as ΔR. Tables 1 and 2 show the values of ΔR at which ΔR became the maximum between wavelengths of 500 to 750 nm.

Interference fringe evaluation After coating the hard coating compositions of Examples 1 to 20 or Comparative Examples 1 to 10 on a polycarbonate substrate with a bar coater, they were left in a drying oven at 70 ° C. for 1 minute, and then a Fusion-H light source. The test piece corresponding to each Example or Comparative Example was obtained. The obtained test piece was bonded to a 100 × 100 mm black acrylic plate using an optical film pressure-sensitive adhesive so that the hard coat coated surface was on the surface. A sample is placed at a distance of 10 cm vertically from the fluorescent tube of a stand-type three-wavelength fluorescent lamp (SLH-399, manufactured by TWINBARD) and visually observed. Visual observation was performed and judged based on the following evaluation criteria.

A: Interference fringes (interference patterns) are not visually recognized under a three-wavelength fluorescent lamp or in sunlight.
○: Interference fringes (interference patterns) are not visually recognized under a three-wavelength fluorescent lamp, but slightly visible under sunlight.
Δ: Interference fringes (interference patterns) are slightly visible.
X: Interference fringes (interference patterns) are clearly visible.

Etching mark (visual evaluation)
The transparent conductive laminates obtained in Examples 1 to 20 and Comparative Examples 1 to 10 were mixed with hydrochloric acid (12 N): nitric acid (16 N): pure water in a mass ratio of 3.3: 1.0: 7. From a fluorescent tube of a stand-type three-wavelength fluorescent lamp (SLH-399, manufactured by TWINBARD) using a sample that was immersed in strong acid mixed at a ratio of 6 at 40 ° C. for 3 minutes, etched, and patterned. A sample was placed at a distance of 10 cm vertically and visually observed. Samples with an evaluation result of ◯ or more were further visually observed under sunlight and evaluated according to the following criteria.

◎: Difficult to distinguish between pattern part and non-pattern part under sunlight and under 3-wavelength fluorescent lamp ○: Pattern part and non-pattern part are slightly distinguishable under sunlight, but pattern part under 3-wavelength fluorescent lamp Difficult to distinguish between non-patterned part and Δ: Slightly distinguishable between pattern part and non-patterned part under three-wavelength fluorescent lamp x: Easy to distinguish between pattern part and non-patterned part under three-wavelength fluorescent lamp

Adhesion test 1 (Adhesion [initial])
An adhesion test was performed in accordance with JIS K5400. The transparent conductive laminates obtained in Examples 1 to 20 and Comparative Examples 1 to 10 were cross-cut using a cutter knife so that 100 1 mm ² cuts (cross cuts) could be made. Next, the cellophane adhesive tape was completely adhered on the created grid, and one end of the tape was lifted and peeled upward. This peeling operation was performed three times at the same location. Thereafter, the number of peeled grids was determined according to the criteria described below. The following evaluation criteria are passed 8 or more.

10: No peeling 8: Peeling is within 5 eyes 6: Peeling is over 5 eyes and within 15 eyes 4: Peeling is over 15 eyes and within 35 eyes 2: Peeling is over 35 eyes It is within 65 eyes 0: Peeling exceeds 65 eyes and is within 100 eyes

Wet heat adhesion test (after 85 ° C x 85% x 500H)
The hard coat films obtained in Examples 1 to 20 and Comparative Examples 1 to 10 were treated for 500 hours in a wet heat test at 85 ° C. × 85% RH. One hour after the wet heat treatment, a cross-cut was performed using a cutter knife so that 100 1 mm ² cuts (cross cuts) could be made. Next, the cellophane adhesive tape was completely adhered on the created grid, and one end of the tape was lifted and peeled upward. This peeling operation was performed three times at the same location. Thereafter, the number of grids that were peeled off was determined by 6-step evaluation based on the same criteria as in the adhesion test 1.

Wet heat adhesion test (after 85 ° C x 85% x 750H)
The hard coat films obtained in Examples 1 to 20 and Comparative Examples 1 to 10 were treated for 750 hours in a wet heat test of 85 ° C. × 85% RH. One hour after the wet heat treatment, a cross-cut was performed using a cutter knife so that 100 1 mm ² cuts (cross cuts) could be made. Next, the cellophane adhesive tape was completely adhered on the created grid, and one end of the tape was lifted and peeled upward. This peeling operation was performed three times at the same location. Thereafter, the number of grids that were peeled off was determined by 6-step evaluation based on the same criteria as in the adhesion test 1.

Wet heat adhesion test (after 85 ° C x 85% x 1500H)
The hard coat films obtained in Examples 1 to 20 and Comparative Examples 1 to 10 were treated for 1500 hours in a wet heat test at 85 ° C. × 85% RH. One hour after the wet heat treatment, a cross-cut was performed using a cutter knife so that 100 1 mm ² cuts (cross cuts) could be made. Next, the cellophane adhesive tape was completely adhered on the created grid, and one end of the tape was lifted and peeled upward. This peeling operation was performed three times at the same location. Thereafter, the number of grids that were peeled off was determined by 6-step evaluation based on the same criteria as in the adhesion test 1.

（ＩＩ）

・ヒンダードフェノール系酸化防止剤（２）イルガノックス１０１０を示す。 In Tables 2 and 3 above: Bisphenol A EO-modified (2 mol) diacrylate: manufactured by Toagosei Co., Ltd., Aronix M-211B, bisphenol A EO (2 mol) -modified diacrylate Irgacure 184: 1-hydroxycyclohexyl phenyl ketone, Photopolymerization initiator Hindered phenolic antioxidant (1) Irganox 1726
This hindered phenolic antioxidant (1) has the following chemical formula (I):

(II)

-Hindered phenolic antioxidant (2) Irganox 1010 is shown.

  Any hard coating film having a hard coat layer formed using the hard coating composition of the example had no interference fringes and had good hardness. Further, the obtained hard coating film has high extensibility and bending resistance, and there is no problem in the adhesion even if it exceeds 750 hours in the adhesion as a hard coat film and the wet heat adhesion test in addition to the initial adhesion. It was a thing. Examples 14-20 contain hindered phenolic antioxidant especially, but when the quantity of hindered phenolic antioxidant which has said Chemical formula (II) is a suitable quantity (Examples 15-17), wet heat It can be seen that the state where the adhesiveness may exceed 1500 hours continues.

  Comparative Example 1 shows an example of Patent Document 4 which is a prior application of the present invention. Although the performance is good after 500 hours in the wet heat adhesion test, the result is bad in the wet heat adhesion test exceeding 750 hours. Is out. In Comparative Example 2, the acrylic resin (4) having an acrylate group equivalent of 2200 g / mol of Production Example 4 was used, and the adhesion was poor when the wet heat adhesion test exceeded 750 hours. In Comparative Example 3, the acrylic resin (5) in which the acrylate group equivalent of the acrylate resin of Production Example 5 is 400 g / mol is used, and the adhesion is poor when the wet adhesion test exceeds 750 actual feeling. The comparative example 4 is a case where the amount of the phenol novolak acrylate of the component (B) is as small as 10 parts by weight, and when the wet adhesion test exceeds 750 hours, the adhesion is inferior. Comparative Example 5 is an example in which the amount of the acrylic resin of component (A) and the amount of the bisphenol skeleton-containing diacrylate of component (C) is less than the range of the present invention, and when the wet heat adhesion test again exceeds 750 hours, Adhesion is poor. Comparative Examples 6 and 7 are examples showing the case where the acrylic resin of the component (A) is less than the range of the present invention (Comparative Example 6) and the case where the acrylic resin is large (Comparative Example 7), and both are 750 hours in the wet heat adhesion test. When it exceeds, adhesiveness will worsen. The comparative example 8 is an aspect which does not contain the polyfunctional acrylate of a component (D), and adhesiveness is bad from the beginning. In Comparative Examples 9 and 10, both the component (A) is less than the range of the present invention and the amount of the component (B) is large (Comparative Example 9) and the amount of the component (C) is large (Comparative Example 10). ), And when both exceed 750 hours in the wet heat adhesion test, the adhesion deteriorates.

  Also, from the results of these Examples and Comparative Examples, the hard coat layer obtained by the present invention has an excellent interference fringe suppressing effect and high adhesion effect (particularly adhesion exceeding 750 hours in the wet heat adhesion test). You can see that it has been achieved.

  The present invention provides a hard coat layer that has high visibility and good hardness, has extensibility, and exhibits excellent adhesion to a polycarbonate substrate. The transparent hard coat layer formed by the hard coating composition of the present invention is characterized by extremely high smoothness. Therefore, even when the transparent hard coat layer in the present invention is provided on a substrate film having a high refractive index such as a polycarbonate film, interference fringes are not generated and high extensibility is achieved. Since it has advantages and exhibits high adhesion, it can withstand more than 750 hours even in a wet heat adhesion test, and the use application is greatly expanded.

DESCRIPTION OF SYMBOLS 1 ... Polycarbonate base material 3 ... Hard-coat layer 5 ... Color difference adjustment layer 7 ... Conductive layer 10 ... Conductive laminated body 11 ... Part which shows reflectance R2 13 ... Part which shows reflectance R1

Claims (11)

A conductive laminate in which a hard coat layer and a conductive layer are laminated on at least one surface of a polycarbonate substrate,
The hard coat layer is
(A) an acrylic resin having an acrylate group in the side chain and an acrylate group equivalent of 500 to 2000 g / mol;
(B) a phenol novolac acrylate having two or more acrylate groups,
(C) a bisphenol skeleton-containing diacrylate having 2 to 4 mole equivalents of an alkylene oxide unit having 2 or 3 carbon atoms in a monomer molecule, and (D) a polyfunctional acrylate having 3 or more acrylate groups Formed from a hard coating composition;
The component (A) is 10 to 30 parts by mass, the component (B) is 15 to 25 parts by mass, and the component (C) is 20 to 40 parts by mass with respect to 100 parts by mass of the total resin components contained in the hard coating composition. 5 to 55 parts by mass of the component and the component (D) are contained.   The conductive laminate according to claim 1, wherein the acrylic resin (A) has an acrylate equivalent of 700 to 1500 g / mol. The conductive laminate according to claim 1 or 2, wherein the acrylic resin (A) is a copolymer represented by the following formula (a) and the following formula (b):

(I)
[Wherein, R ¹ and R ² are a hydrogen atom or a methyl group, R ³ is a linear or branched alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms, and R ⁴ is A hydrogen atom or a methyl group. m and n are values that vary depending on the double bond equivalent. ] The hard coating composition contains 1.1 to 1.9 parts by mass of an antioxidant with respect to 100 parts by mass of the total resin component, and the antioxidant has the following general formula (II). The conductive laminate according to claim 1, wherein

(II)   The conductive laminate according to claim 1, wherein the hard coat layer has a refractive index of 1.535 to 1.545. The hard coat layer is substantially free of ZnO, TiO ₂ , CeO ₂ , SnO ₂ , ZrO ₂ or indium-tin oxide, and the total content thereof is 0.0001% by mass or less of the solid content weight of the hard coat layer The conductive laminate according to any one of claims 1 to 5, wherein   The conductive laminate according to claim 1, wherein the conductive layer has a thickness of 5 to 100 nm. In addition to the hard coat layer and the conductive layer, a color difference adjusting layer exists on the hard coat layer side,
The color difference adjusting layer contains one or both of the curable resin (i) and metal oxide particles (ii) having an average primary particle diameter of 100 nm or less or metal fluoride particles (iii) having an average primary particle diameter of 100 nm or less. Formed from the composition,
The total mass of the particles (ii) and (iii) is 0 to 200 parts by mass with respect to 100 parts by mass of the cured resin (i).
Reflectivity (R1) when light having a wavelength in the range of 500 to 750 nm is irradiated on the conductive laminate, and the conductive laminate is 12N hydrochloric acid, 16N nitric acid and water is 12N hydrochloric acid: 16N nitric acid: water = 3 .3: 1.0: 7.6 After mixing in a strong acid aqueous solution obtained by mixing at a mass ratio of 40.degree. C. for 3 minutes, the conductive laminate after drying has a wavelength of 500 to 750 nm. The conductive laminate according to any one of claims 1 to 7, wherein a difference ΔR between R1 and R2 is 1 or less when the reflectance (R2) when a range of light is irradiated is used.   The conductive laminate according to any one of claims 1 to 8, wherein an auxiliary electrode layer is present on the conductive layer, and a total film thickness of the conductive layer and the auxiliary electrode layer is 20 to 500 nm. An anti-blocking layer is formed on the surface of the polycarbonate base that does not have a hard coat layer,
The anti-blocking layer includes a first component that is an unsaturated double bond-containing acrylic copolymer and a second component that is a polyfunctional acrylate;
A difference ΔSP between the SP value (SP1) of the first component and the SP value (SP2) of the second component is formed from the anti-blocking layer forming composition in the range of 1 to 2,
The conductive material according to any one of claims 1 to 9, wherein the first component and the second component cause layer separation after the anti-blocking layer forming composition is applied, and fine irregularities are formed on the surface. Laminate.   In the touch panel using the electrode base | substrate with which the conductive layer was provided in the at least single side | surface, the conductive laminated body in any one of Claims 1-10 is used as an at least 1 electrode board | substrate.

Images