JPS6316264B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to plastic laminates, and more particularly to transparent conductive films with good scratch resistance. With the development of the information society, electrochromic displays, liquid crystal displays, electroluminescent displays, etc. have been developed.
Related advances have been made in transparent conductive materials. Other applications of such materials include electrophotographic supports, antistatic films, and automobile window glass films. For such applications, a transparent conductive film in the form of a film is more effective than the long-known Nesa glass, and its application is being studied; The conductive film must have excellent scratch resistance, chemical resistance, etc. For such purposes, for example, on the surface of Nesa glass
It is known to form a vapor deposited film of SiO ₂ . On the other hand, transparent conductive film is different from Nesa glass in that it has flexibility, and has the advantage of not only being easy to produce continuously and increasing its area, but also having good processability. In order to fully exploit the advantages of such processability, the layer provided to impart scratch resistance and chemical resistance must also have appropriate elongation. The present inventors have arrived at the present invention as a result of extensive research into a transparent conductive film that can be industrially mass-produced, is inexpensive, and has scratch resistance. That is, the present invention provides a flexible film (A), a transparent conductive layer (B) laminated thereon, and an organic scratch-resistant layer provided on the film (A) on or opposite to the layer (B). The scratch-resistant layer (C) has a thickness of 0.01 to 100 μm that does not cause cracks when stretched by 5%.
It is a scratch resistant transparent conductive film that is a thick organic scratch resistant layer. Examples of the flexible film (A) in the present invention include polyester films such as polyethylene terephthalate and polyethylene naphthalate; polyamide films such as poly·ε-caproamide, polyhexamethylene adipamide, and polymetaphenylene isophthalamide; Examples include polycarbonate films; polyolefin films such as polypropylene; cellulose films such as triacetate; and fluorine-containing polymer films; however, polyester films such as polyethylene terephthalate and polyethylene naphthalate have poor mechanical strength and dimensional stability. It is particularly preferred as the flexible film of the present invention in terms of properties, heat resistance, etc. The above-mentioned film may contain additives such as colorants such as pigments and dyes, light stabilizers, and antistatic agents to the extent that the transparency thereof is not impaired. Further, the thickness of the film is not particularly limited as long as it has flexibility, but it is usually 2 μm to 200 μm, preferably 6 μm to 130 μm. The transparent conductive layer (B) provided on the film is generally a thin layer of a metal oxide such as indium oxide or tin oxide, or a metal such as gold, silver, or palladium. In particular, a transparent conductive layer made of a metal oxide is effective from the viewpoint of transparency. The thickness of the transparent conductive layer made of metal oxide such as indium oxide or tin oxide is approximately
It is 10 to 5000 Å, preferably 50 to 1000 Å, its surface resistance is approximately 10 ¹ to 10 ⁶ Ω/mouth, preferably 10 ² to ^{10 5} Ω/mouth, and its visible light transmittance is Has 80-87% (visible light transmittance 87
% polyester film). Lamination methods for transparent conductive layers of metal oxides include, for example, the method described in Japanese Patent Publication No. 51-37667, in which a metal oxide is vacuum-deposited and then thermally oxidized, a high-frequency sputtering method, and a direct current reactivity method. Known methods such as sputtering, ion beam sputtering, and high frequency ion plating can be used. In particular, a method combining vacuum deposition and thermal oxidation is preferred from the viewpoint of production efficiency. a scratch-resistant layer (C) coated on the film (A) on or opposite to the transparent conductive layer (B);
shows strong resistance to abrasion caused by dirt and dust, or damage formation caused by scratches, etc.
Moreover, its elongation is high. The scratch-resistant layer (C) of the present invention
The haze value is 30 when measured under the conditions of 10F wheels 50 times.
Below, preferably 0.5 to 20, particularly preferably 1 to
10, and its elongation is 5% or more, preferably 10% to 50%, particularly preferably 20% to 40%, when measured using an Instron tensile tester at a head speed of 2 cm/min. It is. An organic polymer layer is suitable as a layer having elongation, scratch resistance, and abrasion resistance.
A three-dimensionally crosslinked polymer layer is particularly suitable. Such organic scratching agents include melamine-formaldehyde resins, urea-formaldehyde resins, unsaturated polyester resins, alkyd resins, epoxy resins, and partially metal salt crosslinked ethylene-acrylic acid copolymers (for example, "Surlyn A").
du pont), poly(meth)acrylonitrile, fluorine-containing hydrocarbon polymers, mixtures of fluorine-containing polymers and melamine resins, melamine cured products of hydroxyl group-containing polymers, and cured products of trimethylolpropane triacrylate. Functional (meth)acrylate cured products and cured products of mixtures thereof with bifunctional (meth)acrylates, linear or cyclic hydrocarbon groups that may have different atoms such as O, N, S, etc. Examples include cured products of poly(meth)acryloyl compounds to which the above (meth)acryloyl groups are bonded. In this specification, the term "(meth)acrylic ester" means "methacrylic ester and/or acrylic ester." Similarly, the description "(meth)acryloyl group" means "methacryloyl group and/or acryloyl group." Among these, melamine or silicate crosslinked products of fluorine-containing polymers, melamine crosslinked products of water oxygen-containing polymers such as poval and ethylene poval, O,
Cured product of a compound in which two (meth)acryloyl groups are bonded to an aliphatic group with a molecular weight of 100 or less which may have a different atom such as N, a molecular weight of 100 which may have a different atom such as O or N Compounds in which three or more (meth)acryloyl groups are bonded to the above aliphatic groups ((meth)
(preferably those with a molecular weight of 30 to 500 per acroyl group); aromatic and alicyclic compounds with a molecular weight of 250 to 3000, which may have different atoms such as O, N, and S;
Examples include cured products of compounds in which two or more (meth)acryloyl groups are bonded to a heterocyclic group (preferably those with a molecular weight of 30 to 500 per (meth)acryloyl group), and in particular, compounds containing cyclic groups ( Examples of the meth)acryloyl compound include those represented by the following general formula (). [However, in the formula, R ₁₀ is a hydrogen atom or a methyl group; R ₂₀
is an alkylene group or oxydialkylene group having 1 to 10 carbon atoms; R ₃ is an N-substituted or unsubstituted melamine residue, cyanuric acid residue, isocyanuric acid residue, or 3 or 4 having 9 to 18 carbon atoms aromatic polycarboxylic acid residue; n represents an integer of 3 to 6;
R ₁ and R ₂ in the same molecule may all be the same, or may be radically different. ] A (meth)acrylic acid ester represented by More specific examples of these compounds include those represented by the following general formulas () to (). [However, in the formula, R ₁₁ is a hydrogen atom or a methyl group; R ₂₁
is ethylene or propylene group; R ₄ is

【formula】

[Formula] or

[Formula] and n is 3 or 4. In R ₁ and R ₂ , all n atoms in the same molecule may be the same or different. ] [However, in the formula, R ¹² is a hydrogen atom or a methyl group, R ²² is an alkylene group having 2 to 4 carbon atoms, and R ⁵⁰ is a divalent to tetravalent alkylene group having 2 to 4 carbon atoms, respectively.
6 saturated hydrocarbon group. This saturated hydrocarbon group can have an ether bond in which some of the carbon atoms are replaced with oxygen atoms. m is an integer of 1 to 3, l is an integer of 0, 1, or 2, and (l+m+1) is an integer of 2 to 4. n is 0 or an integer of 1 to 3, preferably 0 or 1. q is an integer from 1 to 3, p is 0, 1, 2
is an integer of , and (p+q+1) is an integer of 2 to 4. r is 0 or an integer of 1 to 3, preferably 0 or 1. [However, R ₁₃ is as defined in the above formula (), and R ₂₃ is the same or different and is ethylene, propylene or

[Formula] (However, bond (a) is bonded to an acid atom and bond (b) is bonded to a nitrogen atom.), and R ₆₁ , R ₆₂ and R ₆₃ are the same or different, and are hydrogen atoms, carbon an alkyl group having 1 to 4 atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group having 2 to 6 carbon atoms, or

[Formula] (wherein R ₁ and R ₂ are as defined in the above formula ()). However, when R ₆₁ , R ₆₂ and R ₆₃ have a (meth)acryloyl group, it is preferable that they do not contain a (meth)acrylic group at the same time, and especially if any one of them contains a (meth)acrylic group. It is preferable that it contains ] Among these compounds represented by the general formulas () to (), the compounds represented by the formula () are particularly preferred, and among these, the compound represented by the following formula (-a) is preferred. [However, in the formula, R ¹² is a hydrogen atom or a methyl group, R ²² is an alkylene group having 2 to 4 carbon atoms, and R ⁵⁰ is a divalent to tetravalent alkylene group having 2 to 4 carbon atoms, respectively.
6 saturated hydrocarbon group. This saturated hydrocarbon group can have an ether bond in which some of the carbon atoms are replaced with oxygen atoms. m is an integer of 1 or 2, and l is 0 or 1. n is 0 or 1. q is 1 and p is 0. r is 0. However, in the formula, all R ¹² , R ²² and R ⁵⁰ may be the same or different. ] Some specific examples of such compounds are shown below. [Here, in each of the above formulas (-b) to (-k),
R ¹² , R ²² and R ⁵⁰ have the same meanings as defined in the formula () above. ] The above-mentioned scratch-resistant agents may be in a single composition or in mixtures with each other. Furthermore, materials other than those described above may be contained within a range that does not impair the object of the present invention. In this case, said compound is at least 70% by weight, preferably 85% by weight.
Contained above. Especially the general formula () and even ()
～() In particular, the cured product of the compound represented by () has excellent scratch resistance, so it is used by mixing it with other compounds, curing resins, and resins for performance adjustment such as improving adhesion. It is possible to do so. The applied thickness of these scratch-resistant agents is
The physical properties of the scratch resistant agent can vary depending on its haze value and elongation, but it is usually 0.01μ~
100μ, preferably 0.1μ to 30μ, more preferably
It is 0.5μ to 10μ, particularly preferably 2μ to 5μ. As a method for providing such a scratch-resistant layer, a conventional coating method is suitably used. For example, it can be obtained by applying a coating liquid mainly composed of a curable composition containing a scratch-resistant agent to the surface to be coated, and drying and curing the coating liquid if it contains a solvent. When at least one compound selected from (meth)acrylic esters represented by the general formula () is used as the coating liquid,
If necessary, a radical polymerization initiator, for example, benzoin ethers such as benzophenone, benzoin, benzoin methyl ether, and benzoin ethyl ether; benzyl ketals such as benzyl, benzyl dimethyl ketal, and benzyl diethyl ketal; 2-alkylanthraquinones, diacetyl, etc. Azo compounds such as azobisisobutyronitrile; 0.01 to 10% by weight of peroxides such as benzoyl peroxide, lauryl peroxide, di-tert-butyl peroxide, dicumyl peroxide, cumene hydroperoxide, and polymerization As inhibitors, for example hydroquinone, hydroquinone monomethyl ether, catechol, 2,6-di-tert
A coating solution containing -butylphenol, N-nitrosodiphenylamine, phenothiazine, etc., usually in an amount of 10 to 1000 ppm relative to the (meth)acrylic ester, may be cured by the above method. Various other additives include, for example, ultraviolet absorbers, stabilizers such as antioxidants, pigments, fluorescent brighteners,
A filler such as glass fiber or the like may be added. Further, the coating liquid can be diluted as desired with a common solvent. The curing reaction is generally carried out by heating or irradiation with radiation such as actinic light (ultraviolet rays, etc.), electron beams, gamma rays, etc. Anti-wear agents obtained using (meth)acrylic compounds by curing by UV irradiation are advantageous. Methods for applying the coating liquid include dipping the film in the coating liquid, spraying the film with the coating liquid, coating with a brush, doctor knife, bar coater, roll, etc., and roll transfer. The method is also preferably used. Furthermore, the film may be surface-treated to further improve adhesion. Examples of such surface treatment methods include a method of coating with an adhesive layer. The transparent conductive film thus obtained has excellent abrasion resistance and is highly flexible, so it does not crack even under bending conditions and can be attached to curved objects. It is easy to handle in any case. Therefore, the structure of the present invention can be suitably used in antistatic applications that come in contact with the outside air, such as as an antistatic film for indoor walls and windows, as a protective film for electronic components that dislike static electricity, and as a front panel for televisions. . Furthermore, it is useful for protecting the transparent conductivity of a device that utilizes the conductivity of a transparent conductive film, that is, for protection against chemicals during post-processing. Moreover, such a structure effectively acts against corrosion of the transparent conductive layer and increases durability. Although the above uses are listed, the present invention is not limited thereto. The present invention will be further explained below with reference to Examples. In addition, parts in the examples mean parts by weight. Example 1 A coating liquid consisting of 10 parts of trisacryloyloxyethyl cyanurate obtained by reacting 1 mole of cyanuric chloride with 3 moles of 2-hydroxyethyl acrylate, 0.15 parts of benzyl dimethyl ketal, and 10 parts of methyl isobutyl ketone was mixed into 1.0 μ
Surface resistance value 2 provided on a 25μ thick biaxially stretched polyethylene terephthalate film with an adhesive layer of
×10 ⁴ Ω/mouth, visible light transmittance 87% (550 mμ) on an indium oxide layer using a gravure coater, and after removing the solvent at 120°C, irradiated with a 2kw high pressure mercury lamp 25cm below for 2 minutes. A scratch-resistant transparent conductive film having a scratch-resistant layer with a thickness of 3.0 μm was obtained. This film is ASTM-D1044
As a result of the Taber abrasion test (CS-10F abrasion wheel, load 500g x 2, 50 rotations) based on -56, the haze value of the coated surface was 5.0%. In addition, the film was tested at a tensile speed of 2 using an Instron tensile tester.
When the elongation was measured at cm/mm until cracking occurred, the elongation was 30%. Example 2 As a curing agent, a compound was used that binds on average 2 acryloyloxyethyl groups and 0.33 cyanuric acid ester residues derived from trimethylolprobone, a trihydric alcohol, per cyanurate ring. A scratch-resistant transparent conductive film having a 3.0 μm scratch-resistant layer was prepared in the same manner as in Example 1, except that trisacryloyloxyethyl cyanurate was used instead. The Taber abrasion haze value (according to the measurement method of Example 1) of this product was 4%, and the elongation was 32%. As a comparison, an abrasion resistant film was made using dipentaerythritol hexaacrylate as a hardening agent. This material had an elongation of 3%. When each of the above films was attached to a cathode ray tube of a television for the purpose of preventing static electricity, the film of the present invention could be processed well and withstood long-term use. On the other hand, the comparison product had cracks at the tapered end of the cathode ray tube when it was pasted. Example 3 Hexakisacryloyloxyethylmelamine
10 parts, benzoin ethyl ether 0.2 parts, benzoyl peroxide 0.1 parts and methyl isobutyl ketone 10 parts
A coating solution consisting of 3.0 μm was applied onto a 25 μm thick polyethylene terephthalate film having a transparent conductive layer of indium oxide, and passed through a 140° C. drying zone to obtain a 3.0 μm thick coating layer. this
Photocuring was carried out at a film speed of 3 m/mm using two high-pressure mercury lamps of 80 W/cm. The physical properties of this film were as follows: Taber abrasion (measurement method in Example 1) haze value of 3.0 and elongation of 10%. When this film was used as a protective film for a cathode ray tube in the same manner as in Example 2, it showed good performance. However, when a transparent conductive film without a scratch-resistant layer was used alone, scratches were caused by dusting once a day, and the image became difficult to see after three months.

Claims (1)

[Scope of Claims] 1. A flexible film (A), a transparent conductive layer (B) laminated on the film (A), and a flexible film on or opposite the transparent conductive layer (B). The organic scratch-resistant layer (C) is laminated on a flexible film (A), and the organic scratch-resistant layer (C) has a thickness of 0.01 to 100 μm that does not cause cracks when stretched by 5%. formula [However, in the formula, R ₁₀ is a hydrogen atom or a methyl group; R ₂₀
is an alkylene group or oxydialkylene group having 1 to 10 carbon atoms; R ₃ is an N-substituted or unsubstituted melamine residue, cyanuric acid residue, isocyanuric acid residue, or 3 or 4 having 9 to 18 carbon atoms a group having a valent aromatic polycarboxylic acid residue; n represents an integer of 3 to 6; Regarding R ₁₀ and R ₂₀ , all n digits in the molecule may be the same or different. ] A scratch-resistant transparent conductive film which is an organic scratch-resistant layer obtained by subjecting a (meth)acrylic acid ester represented by the following formula to a crosslinking reaction. 2 The above (meth)acrylic acid ester has the following formula; [However, in the formula, R ₁₁ is a hydrogen atom or a methyl group; R ₂₁
is an ethylene or propylene group; R ₄ is [Formula] [Formula] or [Formula], and n is 3 or 4. In R ₁₁ and R ₂₁ , all n's in the same molecule may be the same or different. ] The following formula; [However, in the formula, R ¹² is a hydrogen atom or a methyl group, R ²² is an alkylene group having 2 to 4 carbon atoms, and R ⁵⁰ is a divalent to tetravalent alkylene group having 2 to 4 carbon atoms, respectively.
6 saturated hydrocarbon group. This saturated hydrocarbon group can have an ether bond in which some of the carbon atoms are replaced with oxygen atoms. m is an integer of 1 to 3, l is an integer of 0, 1, or 2, and (l+m+1) is an integer of 2 to 4. n is 0 or an integer of 1-3. q is an integer of 1 to 3, p is an integer of 0 or 1, 2, and (p+
q+1) is an integer from 2 to 4. r is 0 or 1~
It is an integer of 3. ] and the following formula; [However, R ₁₃ is as defined in R ₁₂ above, and R ₂₃
are the same or different, and are ethylene, propylene, or [Formula] (however, bond (a) is bonded to an oxygen atom and bond (b) is bonded to a nitrogen atom), and R ₆₁ , R ₆₂ and R ₆₃ are The same or different, hydrogen atom, alkyl group having 1 to 4 carbon atoms, hydroxyalkyl group having 1 to 4 carbon atoms,
It is an alkoxyalkyl group having 2 to 6 carbon atoms or a group represented by the formula (where R ₁ and R ₂ are as defined for R ₁₁ and R ₁₂ in the above formula). However, when R ₆₁ , R ₆₂ and R ₆₃ have a (meth)acryloyl group, it is preferable that they do not simultaneously contain a (meth)acryloyl group,
In particular, it is preferable that one of them contains a (meth)acryloyl group. ] The scratch-resistant transparent conductive film according to claim 1, which is selected from the group of compounds represented by the following.