JP2000071375A - Laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance workability and to prevent the thickness irregularity of the layers of a laminate by laminating a transparent conductive layer to one surface of a thin layer comprising a transparent resin and laminating a support material comprising a transparent resin to the other surface thereof. SOLUTION: A transparent conductive layer is laminated to one surface of a film base material made of a transparent resin and a support material composed of a transparent resin is laminated to the other surface thereof to obtain a laminate. In a method wherein transparent conductive layer is laminated to one surface of the film base material, it is pref. to laminate the transparent conductive layer while continuously supplying an optically transparent resin film. As a material of the transparent conductive layer laminated to the transparent film base material, a metal such as Sn, In, Ti, Pb, Au, Pt, Ag or the like or oxide thereof can be used. As necessary, an anchor coat may be formed between the film base material and the transparent conductive layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a laminate having a transparent conductive layer formed on a substrate made of a transparent resin, and more particularly to a laminate having excellent productivity.

[0002]

2. Description of the Related Art Conventionally, a transparent conductive material used for a transparent electrode, a resistance heating element, or the like has a transparent conductive layer made of a metal oxide formed on glass. Since there are many inconveniences in handling such as being heavy and fragile, in recent years, resin substrates that have excellent flexibility, workability, light weight, and productivity, and have the advantage of being able to have a large area are widely used instead of glass. Have been.

[0003]

However, conventionally, such a transparent conductive layer is laminated on a resin substrate in the same manner as in the case of glass, in which a so-called batch process is performed for each single substrate by a method such as sputtering or vacuum deposition. Since it is performed by the treatment, there is a problem in the quality between the laminates, such as a variation in the layer thickness depending on the substrate, and the work efficiency of the production is poor, and the disadvantage is large economically. SUMMARY OF THE INVENTION The present invention has been made in view of the problems of the related art, and has as its object to provide a laminate having excellent workability, uniform thickness without variation in layer thickness between laminates.

[0004]

According to the present invention, a transparent conductive layer is laminated on one surface of a transparent resin thin layer, and a transparent resin support material is laminated on the other surface of the thin layer. The present invention provides a laminate comprising:

Here, the thin layer made of a transparent resin can be formed of a film made of a transparent resin. Such a transparent film substrate can be obtained by a known film forming method such as an extrusion method or a solution casting method. In addition to the known film forming methods, a support member made of a transparent resin may be formed by a plate-shaped molding method such as injection molding or injection compression molding.

In the present invention, as a method for producing a laminate, a transparent conductive layer is laminated on one surface of a transparent resin film substrate, and the other surface of the film substrate is made of a transparent resin. It is preferable that a support is attached to form a laminate. In the above manufacturing method, as a method of laminating a transparent conductive layer on one surface of a transparent resin film substrate, the transparent conductive layer may be laminated while continuously supplying an optically transparent resin film. preferable. As an example of a method of laminating a transparent conductive layer while continuously supplying an optically transparent resin film, a plasma polymerization method while sequentially spreading the roll-shaped resin film attached to a supply roller, Sputtering, vacuum deposition, plating,
Methods such as ion plating, spraying, electrodeposition, roll coating, gravure coating, screen coating, spray coating, and bar coating can be used.

After the transparent conductive layer is laminated on one surface of the transparent resin film substrate as described above, the surface opposite to the laminated surface of the transparent conductive layer is bonded to a support made of a transparent resin. be able to. Here, the form of the support material may be a long film form or a single sheet form. In the case of a long film, a roll-shaped film support prepared separately may be sequentially spread, or a film extruded during extrusion of the support may be used as it is. .

In the present invention, the material of the transparent conductive layer laminated on the transparent film substrate is not particularly limited.
Metals such as n, Ti, Pb, Au, Pt, and Ag, or oxides thereof can generally be used. When the metal simple substance is formed into a substrate by the above-described method, it can be oxidized thereafter if necessary. There is also a method of forming an oxide layer from the beginning. Alternatively, a coating may be formed first in the form of a simple metal or a lower oxide, and then subjected to an oxidation treatment such as heat oxidation, anodic oxidation, or liquid phase oxidation to make the film transparent. The thickness of these transparent conductive layers is usually 10
10,000 to 10,000 Angstroms, preferably 50 to 50
00 angstroms, and the specific resistance of the transparent conductive film is 1
Preferably it is less than 00 ohm cm.

In the present invention, even if an anchor coat is formed between the film substrate and the transparent conductive layer for the purpose of providing adhesion between the adhesive layer and the transparent conductive film and flattening the film, if necessary. Good. Examples of the adhesive layer include heat-resistant resins such as epoxy resin, polyimide, polybutadiene, phenol resin, and polyetheretherketone. As the anchor coat layer, a layer containing a so-called acrylic prepolymer such as epoxy diacrylate, urethane diacrylate, or polyester diacrylate as a component is used. As a curing method, a known method can be used, for example, UV curing, heat curing, or the like is used.

In the laminate of the present invention, a gas barrier material such as polyvinylidene chloride or polyvinyl alcohol is used for the purpose of reducing deterioration due to permeation of oxygen or water vapor and increasing durability as required. can do. As the gas barrier material, for example, it can be laminated on a film substrate before laminating a transparent conductive layer. Further, a hard coat layer may be laminated on the gas barrier layer for the purpose of improving the scratch resistance and heat resistance of the film. As the hard coat agent, an organic hard coat material such as an organic silicon resin, a melamine resin, an epoxy resin, or an acrylic resin, or an inorganic hard coat material such as silicon dioxide can be used. Among these, a hard coat material such as an organic silicon resin or an acrylic resin is preferable. Among the organic silicon resins, those having various functional groups can be used, and those having an epoxy group are particularly preferable.

In the present invention, the thickness of the thin layer made of a transparent resin is preferably such that the film substrate used in the production thereof is in a roll form and cannot be rolled up even if it is stored for a long period of time. Is 0.005 to 0.35 mm, particularly preferably 0.01 to 0.3 mm. If the thickness of the film substrate exceeds 0.35 mm, the roll may be rolled up, and there is a possibility that trouble will occur in the processing in the subsequent step. When the thickness of the film substrate is less than 0.005 mm, the strength is inferior. If the transparent conductive layer is continuously laminated or bonded to the support material, the film may be damaged.

The support to be bonded to the film substrate may be in the form of a film or a plate. The thickness of the support material is usually 0.2 to 1 in the total thickness of the laminate of the present invention.
0 mm, preferably 0.3 to 5 mm, more preferably 0.4 to 2 mm, particularly preferably 0.4 to 1.5 m
m. The light transmittance of the laminate of the present invention is usually 80 when light of 400 to 800 nm is used.
% Or more, preferably 82% or more, particularly preferably 85%
That is all.

As the film base material and the support material used in the laminate of the present invention, celluloses such as diacetyl cellulose and triacetyl cellulose; polyesters such as polyethylene terephthalate, polyethylene isophthalate and polybutylene terephthalate; polymethyl (meth) acrylate; A film or plate made of an acrylic resin such as polyethyl (meth) acrylate; polycarbonate; polyether sulfone; polysulfone; polyimide; a thermoplastic norbornene-based resin can be used. In the present invention, the material of the film base material and the material of the support material may be the same or different from each other, but the same is more preferable. In addition, these film base materials and support materials can be freely selected according to the required properties and cost required for each application, but the film base material and the support material are particularly preferred in that the transparency of the laminate is improved. And at least one of the support material is preferably made of a thermoplastic norbornene resin, and when higher optical properties, heat resistance, and moisture resistance are required, both of them are thermoplastic norbornene resins. Is preferred.

The thermoplastic norbornene resin used in the present invention has a norbornane skeleton in its repeating unit. For example, as this thermoplastic resin,
It contains a norbornane skeleton represented by the general formulas (1) to (4).

[0015]

Embedded image

(Wherein, A, B, C and D represent a hydrogen atom or a monovalent organic group)

Examples of the thermoplastic resin having a norbornane skeleton which can be used in the present invention include, for example, JP-A-60-168708 and JP-A-62-25.
2406, JP-A-62-252407, JP-A-2-133413, JP-A-63-14532
4, JP-A-63-264626, JP-A-1
Resins described in JP-A-240517, JP-B-57-8815 and the like can be mentioned.

Specific examples of the thermoplastic resin include metathesis of at least one tetracyclododecene derivative represented by the following general formula (5) or an unsaturated cyclic compound copolymerizable with the tetracyclododecene. Examples include a hydrogenated polymer obtained by hydrogenating a polymer obtained by polymerization.

[0019]

Embedded image

(Where A to D are the same as above)

In the tetracyclododecene derivative represented by the general formula (5), a polar group is contained in A, B, C and D, from the viewpoint of adhesion to other materials and heat resistance. preferable. Further, this polar group is-(CH2
) N COOR (where R represents a hydrocarbon group having 1 to 20 carbon atoms and n represents an integer of 0 to 10), and the resulting hydrogenated polymer has a high glass transition temperature. Is preferable. In particular, this-(CH2
It is preferable that one group represented by nCOOR be contained per molecule of the tetracyclododecene derivative of the general formula (5). In the general formula, R represents 1 carbon atom.
Although it is preferable that the number of carbon atoms increases, the hygroscopicity of the obtained hydrogenated polymer decreases, but from the viewpoint of the balance with the glass transition temperature of the obtained hydrogenated polymer, It is preferably a chain alkyl group having 1 to 4 or a (poly) cyclic alkyl group having 5 or more carbon atoms,
Particularly, a methyl group, an ethyl group and a cyclohexyl group are preferred.

Further, a tetracycloalkyl group of the general formula (5) wherein a hydrocarbon group having 1 to 10 carbon atoms is simultaneously bonded as a substituent to a carbon atom to which a group represented by-(CH ₂ ) _n COOR is bonded. Dodecene derivatives are preferred because they reduce the hygroscopicity. In particular, the tetracyclododecene derivative of the general formula (5) in which this substituent is a methyl group or an ethyl group,
It is preferable in that the synthesis is easy. Specifically, 8-methyl-8-methoxycarbonyltetracyclo [4.4.
0.12,517,10] dodec-8-ene is preferred.

These tetracyclododecene derivatives or a mixture of unsaturated cyclic compounds copolymerizable therewith can be used, for example, in JP-A-4-77520, page 4, upper right column, line 12 to page 6, lower right column, column 12. The thermoplastic resin used in the present invention can be obtained by metathesis polymerization and hydrogenation by the method described in line 6.

In the present invention, the above hydrogenated polymer has an intrinsic viscosity ([η] in) measured at 30 ° C. in chloroform.
h) is preferably in the range of 0.3 to 1.5 dl / g. When [η] inh is in the above range, the resulting resin has a good balance of moldability, heat resistance, and mechanical properties. Further, the glass transition temperature (Tg) of the hydrogenated polymer is preferably in the range of 100 ° C to 250 ° C, particularly preferably in the range of 120 to 200 ° C. When the temperature is lower than 100 ° C., the heat resistance of a molded article made of the resin is inferior. When the Tg exceeds 250 ° C., the molding temperature becomes high, and it becomes difficult to obtain a high-quality molded body such as the resin being burnt and colored.

The hydrogenation rate of the hydrogenated polymer is 60 M
Hz, the value measured by 1H-NMR is 50% or more, preferably 90% or more, and more preferably 98% or more.
The higher the hydrogenation rate, the better the stability to heat and light. In the present invention, the hydrogenated polymer used as the thermoplastic resin having a norbornane skeleton has a gel content contained in the hydrogenated polymer from the viewpoint of preventing defects such as silver streaks in film forming. 5
% By weight or less, more preferably 1% by weight.

The hydrogenated polymer used in the present invention may contain a known antioxidant such as 2,6-di-tert-butyl-4-methylphenol, 2,2'-dioxy-3,
3'-di-t-butyl-5,5'-dimethylphenylmethane, tetrakis [methylene-3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionate] methane, 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl-benzene, stearyl-
β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2′-dioxy-3,3′-
Di-t-butyl-5,5′-diethylphenylmethane,
3,9-bis [1,1-dimethyl-2- [β- (3-t
-Butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl], 2,4,8,10-tetraoxyspiro [5,5] undecane, tris (2,4-di-t-butylphenyl) phospho Phyte, cyclic neopentanetetraylbis (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis (2,6-di-t-butyl-4-methylphenyl) phosphite, 2,2-methylenebis (4,6-
Di-t-butylphenyl) octyl phosphite can be added. The amount of these antioxidants to be added is generally 0.1 to 3 parts by weight, preferably 0.2 to 2 parts by weight, based on 100 parts by weight of the specific polymer. If the amount of the antioxidant is too small, the effect of improving durability is insufficient, and if it is too large, it bleeds from the molding surface,
Problems such as a decrease in transparency are not preferred.

In addition to the above-mentioned antioxidants, if necessary, ultraviolet absorbers such as pt-butylphenyl salicylate and 2,2'-dihydroxy-4 -Methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2- (2'-dihydroxy-4'-
m-octoxyphenyl) benzotriazole; a stabilizer, an antistatic agent, a flame retardant, an elastomer for improving impact resistance, and the like can be added. Further, additives such as a plasticizer and a softener can be added for the purpose of improving moldability and workability.

In order to form a film substrate or a support material from the thermoplastic norbornene-based resin by a solution casting method, for example, a method described in JP-A-5-148413 can be used. For example, a method described in JP-A-4-59218 can be used.

The laminate of the present invention is used for various displays such as a liquid crystal display for a vehicle, a liquid crystal monitor, a light control panel, a display for an office automation equipment, a display for an AV equipment, etc. In addition, it can be used for various uses such as a terraroster for an anti-fog mirror, a terraroster for a frozen showcase, and a surface emitting panel.

[0030]

The present invention will now be described in more detail with reference to Examples.
However, the present invention is limited to the following examples.
is not. In the examples, parts and% are not particularly specified.
As far as weight is concerned. Note that each measurement in the examples is as follows.
It is as follows.Plate thickness (mm) It was measured with a dial-type thickness gauge.Light transmittance (%) The light transmittance of the laminate was measured according to ASTM D1003.
Was.Uniformity of transparent conductive layer  a) Sheet resistance Using "Loresta AP" (manufactured by Mitsubishi Yuka) as a device, four terminals
Using a four-point needle method (measured applied current: 10 mA), on the laminate
Measured at 10 points selected appropriately, and
The variation was evaluated. b) "DEKTAK3030" (manufactured by sloan) as a layer thickness measurement device
The above 10 points were measured with a needle pressure of 10 mg.
Were evaluated.Stacked sled The warpage of the laminate was measured according to JIS K6911.

Example 1 As a thermoplastic resin, the intrinsic viscosity (ηinh) was 0.67,
A norbornene-based resin having a Tg of 171 ° C. (“ARTON” manufactured by JSR Corporation) was heated and melted at 300 ° C., and a film extruded from a T-die was used. One surface of the film was indium oxide / tin oxide (weight ratio). A transparent conductive layer formed by a sputtering method using a target consisting of 95: 5) was wound by a winder to obtain a roll of a transparent conductive film roll having a thickness of 0.2 mm. On the other hand, the above-mentioned thermoplastic resin was used as a support material, heated and melted at 300 ° C., and 90% by weight of n-butyl acrylate and 7% by weight of ethyl acrylate were placed on a 0.3 mm-thick sheet sequentially extruded from a T-die. Crosslinking consisting of 100 parts of an acrylic resin consisting of ethyl acrylate, 7% by weight of ethyl acrylate and 3% by weight of acrylic acid, and 2 parts of a 75% by weight ethyl acetate solution of adduct of trimethylolpropane (1 mol) with tolylene diisocyanate (3 mol). The adhesive material obtained by mixing the adhesive is applied, and then the film substrate surface opposite to the side on which the transparent conductive layer of the roll of the transparent conductive film is laminated is the adhesive material of the sheet support material. So that it is located on the surface, it is continuously fed through a take-off roll and after bonding with the sheet support,
The laminate was passed through a cutting machine to continuously obtain a laminate having a thickness of 0.5 mm. For this laminate, the light transmittance, the uniformity of the transparent conductive layer, and the warpage of the laminate were measured. Table 1 shows the evaluation results.

Example 2 The same thermoplastic resin as in Example 1 was dissolved in toluene.
A 20% by weight toluene solution is passed through a die to form a layer having a uniform thickness, which is dried at 200 ° C. to cut a film obtained, and is 295 mm in length × 210 mm in width × 0.2 m in thickness.
m of support material were obtained. The same adhesive material as in Example 1 was applied to the support material, and the material was sequentially conveyed by a conveying means. The transparent conductive material of the support material and the roll material continuously rolled and supplied as in Example 1 were used. After laminating with a film, it was cut out with a cutting machine to obtain a laminated sheet. This laminate was evaluated in the same manner as in Example 1. Table 1 shows the evaluation results.

Comparative Example 1 A roll of a transparent conductive film was prepared in the same manner as in Example 1 except that the film was extruded so that the thickness of the film substrate was 0.5 mm, and the roll was bonded to a support material. After that, the sheet was passed through a cutting machine to obtain a single-sheet laminated body. This laminate was evaluated in the same manner as in Example 1. Table 1 shows the evaluation results.

[0034]

[Table 1]

As is clear from Table 1, Examples 1 and 2 have no warp of the laminate, and are excellent in light transmittance and uniformity of the transparent conductive layer. On the other hand, in Comparative Example 1, the laminate had a large warp, and a variation in sheet resistance which was considered to be partial peeling from the support material was observed.

Comparative Example 2 The same thermoplastic resin as in Example 1 was dissolved in toluene.
A 20% by weight toluene solution was passed through a die to form a layer having a uniform thickness, which was dried at 200 ° C. to obtain a film having a thickness of 0.002 mm. Using this film as a film substrate, a transparent conductive layer was formed in the same manner as in Example 1, and the film was wound.
And affixing with a support material, but the film breakage occurred frequently in these series of steps, and the yield of the laminate was significantly reduced.

[0037]

The laminate of the present invention is obtained by laminating a transparent conductive layer and attaching the transparent conductive layer to a support material. The productivity is improved as compared with a method of directly laminating a transparent conductive layer on a single-wafer substrate. It is also excellent in quality as a transparent conductive substrate.

Claims (4)

[Claims] 1. A laminate in which a transparent conductive layer is laminated on one surface of a thin layer made of a transparent resin, and a support material made of a transparent resin is laminated on the other surface of the thin layer. 2. The method according to claim 1, wherein a transparent conductive layer is laminated on one surface of the transparent resin film substrate, and a support made of a transparent resin is bonded to the other surface of the film substrate.
The laminate according to the above. 3. The laminate according to claim 2, wherein the resin film base is made of a thermoplastic norbornene-based resin. 4. The laminate according to claim 2, wherein the support material is made of a thermoplastic norbornene-based resin.