JP4894079B2 - Optical plastic substrate - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an optical plastic substrate having a multilayer structure suitable for various optical applications including an electrode substrate of a liquid crystal cell of a liquid crystal display element.
[0002]
[Prior art]
With the spread of personal computers and portable information terminals, the use of liquid crystal display elements is increasing year by year. In particular, a glass substrate has been used as an electrode substrate for a liquid crystal cell, but an optical plastic substrate is used for portable information terminals and the like from the viewpoints of lighter elements, resistance to impact, and flexibility. It is often done. As an optical plastic substrate, Japanese Patent Application Laid-Open No. 9-29881 discloses two kinds of air-resistant layers comprising an organic air-resistant layer X and an inorganic air-resistant layer Y on at least one surface of a base film. One of the air-resistant layers is provided, and the other air-resistant layer is provided on the one air-resistant layer, and an anchor coating layer is provided between adjacent layers. A good optical laminated sheet is shown. The specific layer structure is “heat resistant solvent resistant resin layer / inorganic air resistant layer / organic air resistant layer / base film / organic air resistant layer / inorganic air resistant layer / heat resistant solvent” Resin layer ”,“ Heat resistant solvent resistant resin layer / Curing cured resin layer / Inorganic air resistant layer / Organic air resistant layer / Base film / Organic air resistant layer / Inorganic air resistant property ” Layer / cured resin cured product layer / heat resistant solvent resistant resin layer ".
[0003]
Japanese Patent Application Laid-Open No. 9-96803 discloses “external heat-resistant solvent-resistant layer / air-permeable resin layer / inner side curable resin cured layer / active energy ray curable resin cured layer / internal side curable resin cured”. An optical laminated sheet having a layer structure such as “physical layer / air-permeable resin layer / external heat-resistant solvent-resistant layer” is shown.
[0004]
In JP-A-9-254332, JP-A-9-254333, and JP-A-9-254334, both outer layers are composed of a curable resin cured material layer, and at least on the inner side sandwiched between these two outer layers. A plastic substrate is shown having a structure in which a single air-permeable layer is present. On the inner side, a base film or a further curable resin cured material layer may be present in addition to the air-resistant layer.
[0005]
Japanese Patent Application Laid-Open No. 10-67064 discloses “moisture-proof and alkali-resistant layer / inorganic thin layer / cured resin cured layer / core resin layer / curable resin cured layer / inorganic thin layer / moisture-proof and alkali-resistant layer”. An optical laminated sheet having a layer structure, in which the core resin layer is “air-permeable-resistant resin layer / base film layer / air-resistant resin layer” in particular, is shown.
[0006]
Japanese Patent Application Laid-Open No. 10-82983 discloses “cured resin cured product layer / organic moisture-proof layer / organic moisture-proof layer / light isotropic substrate sheet layer / organic moisture-proof layer / organic moisture-proof layer / curable resin cured product layer”. An optical laminated sheet having a layer structure such as the above, wherein the organic moisture-proof layer is composed of a polymer layer containing a water-repellent unit is shown.
[0007]
[Problems to be solved by the invention]
In the electrode substrate of a liquid crystal cell of a liquid crystal display element, the importance of a plastic substrate replacing a glass substrate is increasing. Plastics substrates are required to have various properties such as air resistance, solvent resistance, and liquid crystal resistance, but plastics substrates inevitably lack properties such as heat resistance and surface hardness compared to glass substrates. Will not be spared.
[0008]
However, when the heat resistance and surface hardness are insufficient, when a transparent electrode is provided on the substrate and used as an electrode substrate, the collective connection between the pattern electrode and the outer lead of the control IC (TCP or FPC) is between the two. When performing thermocompression bonding with an anisotropic conductive sheet (ACF) interposed between the film and sheet, the film and sheet constituting the substrate are not deformed or warped, and there are problems such as wire breakage caused by cracks in the electrode pattern. Get up. TCP stands for Tape Carrier Package, and FPC stands for Flexible Printed Circuit.
[0009]
Among the publications listed above, there are some that aim to improve the ACF crimping connectivity, and some results have been obtained. The number of terminals is reduced from 2 mm to 0.1 mm and the number of terminals exceeds 20 / inch. Especially in the case of color, the three terminals R, G and B play a role, making the terminals extremely fine. In addition, the thermocompression bonding conditions for connection are also (120 to 150) ° C. × (15 to 60) seconds × (10 to 50) kg / cm in the conventional heat sealing method.²From, for example, 160 ° C. or higher × (10-60) seconds × 20 kg / cm²There is a circumstance that the above-described crimp connection by ACF is required. Prior to such a demand for higher sophistication, there is a strong demand to further improve ACF pressure bonding connectivity by further increasing heat resistance and surface hardness.
[0010]
According to the study by the present inventors, it has been found that the ACF crimping connectivity is limited only by increasing the heat resistance and surface hardness of the layer on the surface side of the electrode substrate. According to the study by the present inventors, this seems to be due to the lack of heat resistance and hardness of the organic air-resistant layer (air barrier layer) which is the inner layer (in other words, the scaffold is soft). In the inventions of the above-listed publications (JP-A-8-248400, JP-A-9-29881, etc.), as an organic air barrier layer, for example, a polyvinyl alcohol graft copolymer is blended with a crosslinking agent. Although a film-formed layer is used, it is necessary to further improve the organic air barrier layer in order to cope with the advancement of the ACF pressure bonding connectivity.
[0011]
An object of the present invention is to provide an optical plastic substrate capable of performing ACF crimping connection under severe conditions under such circumstances.
[0012]
[Means for Solving the Problems]
The optical plastic substrate of the present invention is a multilayer plastic substrate, wherein the substrate (1) includes at least one layer (A) containing a layered compound. It is.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
<Layer (A) comprising layered compound>
The layer (A) comprising the layered compound comprises the layered compound (a), may consist of the layered compound (a), and in addition to the layered compound (a), the resin (b) and It may contain other component (c).
[0014]
The layered compound (a) is a compound having a layered structure in which unit crystal layers are stacked on each other. Among them, the inorganic layered compound (hereinafter referred to as “inorganic layered compound”) is preferably cleaved. In the cleaved state, the particle size is 10 μm or less and the aspect ratio is 10 to 10. Those within the range of 10,000 are preferred.
Further, as will be described later, if the particle size of the inorganic layered compound is 3 μm or less, it is preferable because the transparency of the layer (layer (A) comprising the layered compound) becomes better, and further the particle size is 1 μm or less. Is more preferable. The aspect ratio can be obtained by the method described in JP-A-6-93133.
The larger the aspect ratio, the higher the heat resistance and air permeability of the layer (A), and it is often preferable. From this viewpoint, the aspect ratio is preferably 30 to 5000, and more preferably 200 to 3000.
[0015]
Specific examples of the inorganic layered compound include, for example, graphite, phosphate derivative compounds (such as zirconium phosphate compounds), chalcogenides, clay minerals, hydrotalcite compounds and the like. . The chalcogenide is a dichalcogenide of group IV (Ti, Zr, Hf), group V (V, Nb, Ta) and group VI (Mo, W) in the periodic table, and has the chemical formula MX.₂(Wherein, M represents a group IV or VI element and X represents chalcogen (S, Se, Te)).
[0016]
Only one type of inorganic layered compound may be used, or two or more types may be appropriately mixed and used. Among the inorganic layered compounds, when the coating liquid containing the inorganic layered compound as described below is applied to the surface of the substrate to form the layer (A), I is swollen in the dispersion medium used for the coating liquid. An inorganic layered compound having a property of cleaving, that is, a swellable inorganic layered compound is preferable, and a compound having a property of cleaving in a dispersion medium (a property of swelling and cleaving with a solvent) is more preferable.
[0017]
Among the inorganic layered compounds, as the inorganic layered compound that swells or cleaves in the dispersion medium, clay minerals and hydrotalcite compounds having a swellability and / or cleaving property and similar compounds are particularly preferably used.
Generally, clay minerals having swellability and cleavage (hereinafter sometimes referred to as swelling / cleavage clay minerals) are generally (1) an eight metal centered on aluminum, magnesium, or the like above the tetrahedral layer of silica. A type having a two-layer structure having a plane layer and a type having a three-layer structure in which the tetrahedral layer of silica is narrowed from both sides of an octahedral layer centered on aluminum, magnesium, or the like. . The former (1) two-layer structure type includes clay minerals such as kaolinite group and antigolite group. The latter (2) three-layer structure type includes clay minerals such as smectite group, vermiculite group, and mica group depending on the number of interlayer cations.
[0018]
More specifically, these clay minerals include kaolinite, dickite, nacrite, halloysite, antigolite, chrysotile, pyrophyllite, montmorillonite, beidellite, nontronite, saponite, sauconite, stevensite hectorite, tetrasilic Examples include mica, sodium teniolite, muscovite, margarite, talc, vermiculite, phlogopite, xanthophyllite, chlorite. In addition, those obtained by treating these clay minerals with an organic substance (see Asakura Shoten, “Encyclopedia of Clay”; hereinafter also referred to as “organic modified clay mineral”) can be used.
[0019]
Among the swellable / cleavable clay minerals, smectite group, vermiculite group, and mica group clay minerals are preferable, and the smectite group is more preferable, from the viewpoint of easier swelling or cleavage. Specific examples of the smectite clay mineral include montmorillonite, beidellite, nontronite, saponite, soconite, stevensite, and hectorite.
[0020]
The hydrotalcite compound and its similar compounds are characterized in that the interlayer ion of the clay mineral is a cation whereas the anion is a cation, and specifically, for example, those represented by the following formula: It can be illustrated.
First, as hydrotalcite compounds, the following formula (I):
M²⁺ _1-xAl³⁺ _x(OH^-)₂(A₁ ^n-)_{x / n}・ MH₂O (I)
(Where M²⁺Is a divalent metal ion, A₁ ^n-Is an n-valent anion, and x, m, and n satisfy the conditions of 0 <x <0.5, 0 ≦ m ≦ 2, and 1 ≦ n. ). M²⁺As Mg²⁺, Ca²⁺, Zn²⁺Etc. are exemplified. The n-valent anion is not particularly limited. For example, Cl^-, Br^-, I^-, NO_Three ^-, ClO_Four ^-, SO_Four ^2-, CO_Three ^2-, SiO_Three ^2-, HPO_Four ^3-, HBO_Four ^3-, PO_Four ^3-, Fe (CN)₆ ^3-, Fe (CN)₆ ^Four-, CH_ThreeCOO^-, C₆H_Four(OH) COO^-, (COO)₂ ^2-And anions such as terephthalate ions and naphthalene sulfonate ions, and polysilicate ions and polyphosphate ions described in JP-A-8-217912. Specific examples include synthetic hydrotalcite such as natural hydrotalcite and Alkamizer DHT-4A (trade name, manufactured by Kyowa Chemical Industry Co., Ltd.).
[0021]
As the hydrotalcite-like compound, for example, the following formula (II) disclosed in JP-A-5-179052:
Li⁺(Al³⁺)₂(OH^-)₆・ (A₂ ^n-)_{1 / n}・ MH₂O (II)
(Where A₂ ^n-Is an n-valent anion, and m and n satisfy the condition of 0 ≦ m ≦ 3, 1 ≦ n). The n-valent anion is not particularly limited. For example, A in the compound of the above formula (I)₁ ^n-And the same anion.
[0022]
Further, the following formula (III) disclosed in WO97 / 00828:
[(Li⁺ _(1-x)M²⁺ _x) (Al³⁺)₂(OH^-)₆]₂(Si_yO_{(2y + 1)} ^2-)_{(1 + x)}・ MH₂O (III)
(Where M²⁺Is a divalent metal ion, and m, x and y satisfy the following conditions: 0 ≦ m <5, 0 ≦ x <1, 2 ≦ y ≦ 4, and Japanese Patent Application Laid-Open No. 8-217912 The following formula (IV) disclosed in the publication No .:
[(Li⁺ _(1-x)M²⁺ _x) (Al³⁺)₂(OH^-)₆]₂(A_Three ^n-)_{2 (1 + x) / n}・ MH₂O (IV)
(Where M²⁺Is a divalent metal ion, A_Three ^n-Is an n-valent anion, and m, x and n can be exemplified by compounds represented by the following conditions: 0 ≦ m <5, 0.01 ≦ x <1, 1 ≦ n. In the formulas (III) and (IV), M²⁺As Mg²⁺, Ca²⁺, Zn²⁺Etc. are exemplified. The compounds represented by the above formulas (III) and (IV) are more preferable among the hydrotalcite-like compounds.
[0023]
Examples of the resin (b) include polyolefin resins, polyester resins, amide resins, acrylic resins, styrene resins, acrylonitrile resins, cellulose resins, halogen-containing resins, hydrogen bonding resins, liquid crystal resins, and polyphenylenes. Examples thereof include oxide resins, polymethylene oxide resins, polycarbonate resins, polysulfone resins, polyether sulfone resins, polyether ether ketone resins, and thermosetting resins such as unsaturated polyester resins, epoxy resins, and phenol resins.
[0024]
Among the above resins, from the viewpoint of heat resistance, hardness, and gas permeability, a high hydrogen bonding resin (described later) having a hydrogen bonding group or an ionic group as a crosslinkable functional group is preferable. The content of hydrogen bonding groups or ionic groups in the high hydrogen bonding resin (the total amount of both when both are included) is usually in the range of 20 mol% to 60 mol%, preferably It exists in the range of 30 mol%-50 mol%. The content of these hydrogen bonding group and ionic group is, for example, nuclear magnetic resonance (for example,¹H-NMR,¹³C-NMR etc.).
[0025]
Specific examples of the hydrogen bonding group possessed by the high hydrogen bonding resin include a hydroxyl group, an amino group, a thiol group, a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Examples of the ionic group include ionic groups such as a carboxylate group, a sulfonate ion group, a phosphate ion group, an ammonium group, and a phosphonium group. Among these hydrogen bonding groups and ionic groups, particularly preferred functional groups include a hydroxyl group, an amino group, a carboxyl group, a sulfonic acid group, a carboxylate group, a sulfonic acid ion group, and an ammonium group.
[0026]
Specific examples of such a high hydrogen bonding resin include, for example, polyvinyl alcohol, polysaccharides, ethylene-vinyl alcohol copolymers, polyacrylic acid and esters thereof, sodium polyacrylate, polystyrene sulfonic acid, sodium polystyrene sulfonate, Examples include polyethyleneimine, polyallylamine and its quaternary ammonium salt, polyvinyl thiol, polyglycerin and the like.
[0027]
The above polyvinyl alcohol (PVA) is usually a saponified product obtained by hydrolysis or transesterification of an ester moiety such as a vinyl ester polymer or hydrolysis of an ether moiety of a vinyl ether polymer. Polymer obtained by saponifying acetate ester part; polymer obtained by saponifying vinyl trifluoroacetate polymer, vinyl formate polymer, vinyl pivalate polymer, t-butyl vinyl ether polymer, trimethylsilyl vinyl ether polymer, etc. Can be mentioned. (For details on PVA, see, for example, “The World of PVA” edited by the Poval Society (1992, Kobunshi Publishing Co., Ltd.); “Poval” (1981, Kobunshi Publishing Co., Ltd., Nagano et al.) Etc.)
[0028]
The saponification rate of the PVA is preferably 70 mol% or more, more preferably 85 mol% or more, particularly preferably 98 mol% or more, and most preferably a complete saponified product. The degree of polymerization of the PVA is preferably in the range of 100 to 20000, more preferably in the range of 200 to 5000, and more preferably in the range of 200 to 3000. The PVA may be a modified product modified with a small amount of a copolymerization monomer as described later as long as the effects of the present invention are not inhibited.
[0029]
The polysaccharide is a polymer synthesized by polycondensation of various monosaccharides, and the polymer may be chemically modified. Specific examples of the polysaccharide include cellulose; cellulose derivatives such as hydroxymethylcellulose, hydroxyethylcellulose, and carboxymethylcellulose; amylose; amylopectin; pullulan; curdlan; xanthan;
[0030]
The ethylene-vinyl alcohol copolymer (EVOH) preferably has a vinyl alcohol fraction in the range of 40 mol% to 80 mol%, and the vinyl alcohol fraction in the range of 45 mol% to 75 mol%. Are particularly preferred. The melt index (MI) of the EVOH is not particularly limited, but is preferably 0.1 g / 10 min to 50 g / 10 min under conditions of a temperature of 190 ° C. and a load of 2160 g. The EVOH may be a modified product modified with a small amount of a copolymerization monomer as described later as long as the effects of the present invention are not inhibited.
[0031]
Of the high hydrogen bonding resins, PVA and its modified products, EVOH and its modified products, and polysaccharides are particularly suitable.
[0032]
The modified product of PVA and the modified product of EVOH are, for example, when vinyl acetate monomer is used as a vinyl ester in the production process of PVA and EVOH, respectively, and vinyl acetate monomer and other copolymerizable with this. Unsaturated monomers such as olefins such as ethylene, propylene, α-hexene, α-octene, unsaturated acids such as (meth) acrylic acid, crotonic acid, (anhydrous) maleic acid, fumaric acid, itaconic acid, And alkyl esters and alkali salts thereof, sulfonic acid-containing monomers such as vinyl sulfonic acid, styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, and alkali salts thereof, dimethylaminoethyl (meth) acrylate, diethylaminoethyl ( Meth) acrylate and trimethyl-2- (1- (meth) acrylamide -1,1-dimethylethyl) ammonium chloride, trimethyl-3- (1- (meth) acrylamidopropyl) ammonium chloride, 1-vinyl-2-ethylimidazole, other quaternizable cationic monomers, styrene, Examples thereof include copolymers with monomers such as alkyl vinyl ether and (meth) acrylamide.
[0033]
The ratio of these copolymerization components is not particularly limited, but is preferably 50 mol% or less, more preferably 30 mol% or less, and more preferably 30 mol% or less based on the vinyl alcohol unit in the PVA or EVOH modified product. Arbitrary forms such as random copolymerization, block copolymerization, and graft copolymerization are possible.
[0034]
Among these modified products, a so-called block copolymer containing a polycarboxylic acid component in which carboxylic acid units are continuously polymerized during the copolymerization is particularly preferably used, and the carboxylic acid component is particularly preferably methacrylic acid. . Further, the block copolymer is particularly preferably an AB type block copolymer in which a polyacrylic acid chain is extended to one end of a polyvinyl alcohol chain in the modified body. The case where the weight ratio (a) / (b) of a) to the polyacrylic acid block component (b) is 50/50 to 95/5 is preferred, and particularly preferred is the case where it is 60/40 to 90/10. A saponified vinyl ester polymer modified with at least one compound having a silyl group in the molecule is also preferred.
[0035]
As a method for obtaining a silyl group modified product of a vinyl alcohol polymer such as PVA or EVOH, a compound having a silyl group in the molecule is reacted with a vinyl alcohol polymer (or a modified product thereof) obtained by a conventional method. A method for introducing a silyl group into a polymer, a method for activating the end of a vinyl alcohol polymer (or a modified product thereof), and introducing an unsaturated monomer having a silyl group in the molecule into the polymer end, a molecule A method of modifying a vinyl alcohol polymer (or a modified product thereof), such as a method of graft copolymerizing an unsaturated monomer having a silyl group on a vinyl alcohol polymer (or a modified product thereof); A method of obtaining a copolymer from a monomer and an unsaturated monomer having a silyl group in the molecule and saponifying the copolymer; in the presence of mercaptan having a silyl group, etc. Polymerizing glycol ester, such as this method of introducing a silyl group at the end by saponifying are effectively used.
[0036]
As a result, the modified silyl group obtained by these methods may have any silyl group in the molecule. However, the silyl group contained in the molecule may have an alkoxyl group or an acyloxyl group and a hydrolysis thereof. Those having a reactive substituent such as a silanol group or a salt thereof are preferable, and among them, a silanol group is particularly preferable.
[0037]
Examples of the compound having a silyl group in the molecule used for obtaining these modified silyl groups include, for example, trimethylchlorosilane, dimethylchlorosilane, methyltrichlorosilane, vinyltrichlorosilane, diphenyldichlorosilane, triethylfluorosilane and the like. Organohalosilanes, trimethylacetoxysilane, dimethyldiacetoxysilane and other organosilicon esters, trimethylmethoxysilane, dimethyldimethoxysilane and other organoalkoxysilanes, trimethylsilanol, diethylsilanediol and other organosilanols, N-amiethyltrimethoxysilane And the like, and organosilicon isocyanates such as aminoalkylsilane and trimethylsilicon isocyanate. The degree of modification by the compound having a silyl group can be arbitrarily adjusted depending on the type and amount of the compound having a silyl group used, other reaction conditions, and the like.
[0038]
Examples of the unsaturated monomer used in a method for saponifying a copolymer of a vinyl ester monomer and an unsaturated monomer having a silyl group in the molecule include vinyl trimethoxysilane and vinyl. Vinyl silane compounds such as vinyl alkoxy silanes such as triethoxy silane, vinyl methyl dimethoxy silane, vinyl alkoxy silanes typified by vinyl triisopropoxy silane, etc. And a polyalkylene glycolated vinyl silane in which a part or all of the above is substituted with a polyalkylene glycol such as polyethylene glycol. Furthermore, (meth) acrylamide-alkylsilanes such as 3- (meth) acrylamino-propyltrimethoxysilane, 3- (meth) acrylamide-propyltriethoxysilane, and the like can also be preferably used.
[0039]
On the other hand, in a method in which a vinyl ester is polymerized in the presence of a mercaptan having a silyl group and then saponified to introduce a silyl group at the terminal, the mercaptan having a silyl group may be 3- (trimethoxysilyl) -propyl mercaptan or the like The alkoxysilylalkyl mercaptan is preferably used.
[0040]
When the silyl group-modified product is used in the present invention, the degree of modification of the silyl group-modified product, that is, the silyl group content, the saponification degree, and the like are different in the appropriate range. The ratio is usually 30 mol% or less, preferably 10 mol% or less, more preferably 5 mol% or less, more preferably 2 mol as a monomer containing a silyl group with respect to the vinyl alcohol unit in the polymer. % Or less is particularly preferably used. Although a minimum is not specifically limited, Usually, it is 0.1 mol% or more from a heat resistant and air-permeable viewpoint.
[0041]
The silylation rate indicates the ratio of the introduced silyl group after silylation to the amount of hydroxyl group contained in the polyvinyl alcohol resin before silylation.
[0042]
The modified silyl group is dissolved in an alcohol solvent such as alcohol or a mixed solvent of alcohol / water by the presence of the introduced silyl group. Therefore, the coating liquid used for forming the layer (A) is preferably an alcohol solvent as a dispersion medium from the viewpoint of handling the coating liquid. Further, when the silyl group-modified product is dissolved in a solvent, a part of the introduced silyl group reacts and crosslinks by dealcoholization reaction or dehydration reaction, so that the strength of the layer (A) can be further increased. When the layer (A) is formed by coating using a modified silyl group, it is more preferable to use a mixed solvent of alcohol / water as a dispersion medium of the coating liquid.
[0043]
The PVA or a modified product thereof, EVOH or a modified product thereof may be used alone, but may be a copolymer with another copolymerizable monomer as long as the effects of the present invention are not impaired. However, you may use as a mixture which used other resin together. Examples of other resins include resins such as polyacrylic acid or esters thereof, polyester resins, polyurethane resins, polyamide resins, epoxy resins, and melamine resins.
[0044]
The mixing ratio of the layered compound (a) and the resin (b) in the resin composition used for the layer (A) of the present invention is preferably 1/100 to 100/1 by weight ratio of (layered compound / resin), 5/100 to 100/5 is more preferable. Furthermore, from the viewpoint of heat resistance, hardness, and air resistance, the weight ratio is more preferably 10/100 to 100/20. When it is smaller than 1/100, the improvement of heat resistance, hardness and air permeability is insufficient, and when it exceeds 100/1, the layer (A) tends to become brittle or the transparency tends to decrease. There is.
[0045]
In the layer (A), various additives may be used as the other component (c). In particular, when the resin to be included is a high hydrogen bond resin, a cross-linking structure capable of undergoing a cross-linking reaction with the high hydrogen bond resin is used for the purpose of further improving heat resistance and hardness, and the layer (A) has a cross-linked structure. It is more preferable to introduce.
[0046]
Examples of such cross-linking agents include compounds that can undergo a cross-linking reaction with a highly hydrogen bonding resin by coordination bond, hydrogen bond, ionic bond, etc., for example, aldehyde-based cross-linking agents such as formaldehyde and gliogisar, isocyanate-based cross-linking agents, melamine Examples thereof include a system cross-linking agent and a metal organic compound. From the viewpoint of high cross-linking reactivity with the high hydrogen bonding resin and improved cross-linking efficiency as compared with, for example, inorganic metal salts, metal organic compounds are preferable.
[0047]
Preferable examples of the metal organic compound include a titanium organic compound, a zirconium organic compound, an aluminum organic compound, and a silicon organic compound. Among them, a metal organic compound having a chelating ligand such as an acetylacetonate and having a coordination bond with the high hydrogen bonding resin is preferable because the crosslinking reactivity is moderate.
[0048]
<Plastics board (1)>
The plastic substrate (1) is composed of a base film layer (11), a core material layer (12), a curable resin cured material layer (13), an air-proof layer (14), and an air-proof and moisture-proof layer (15). A substrate having a multilayer structure including at least one layer, in which at least one layer is composed of a layer (A) including a layered compound.
[0049]
Examples of the base film layer (11) include polycarbonate film, polyarylate film, polyethersulfone film, polysulfone film, amorphous polyolefin (bicycloolefin-based polyolefin, norbornene-based resin) film, polyamideimide-based resin film, and polyimide-based resin. Examples thereof include a single layer or a multilayer film including a film, a silicone-based resin film, and a film including at least one layer (A) including the above layered compound. The thickness of the base film layer (11) is often 10 to 1000 μm or more. When laminating other layers on the base film layer (11), the base film layer (11) may have been subjected to adhesion improvement treatment such as corona discharge treatment, plasma treatment, solvent treatment in advance, An anchor coating layer (ac) may be formed.
[0050]
The method for forming the base film is not particularly limited as long as it is a method capable of obtaining a uniform film with few defects, but the solvent casting method is preferably used in terms of few defects such as optical uniformity and gel. . In addition, for a resin that does not have a solvent suitable for using the solvent casting method, a film having excellent uniformity can be produced by using a precision extrusion method capable of reducing the residual stress. Moreover, the film which performed the biaxial stretching by uniaxial stretching by longitudinal uniaxial stretching between rolls, tenter lateral stretching, and these as needed can also be used.
[0051]
As the core material layer (12), in addition to the layer (A) comprising the above layered compound, for example, an active energy ray curable resin layer of the curable resin cured product layer (13) described below is used. Can be mentioned. The core material layer (12) may be the same as the base film layer (11). For example, the core material layer (12) is cured by interposing a curable resin between two single-layer or multi-layer films to form a core material. In such a case, the base film layer (11) may be difficult to call, so it will be referred to as the core material layer (12). The thickness of the core material layer (12) is not particularly limited, but is often 5 to 1000 μm or more.
[0052]
The cured resin layer (13) includes various non-solvent type active energy ray curable resin layers such as silicone acrylate, epoxy acrylate, ester acrylate and urethane acrylate, and thermosetting resin having heat resistance. A layer of the cured product, a layer obtained by applying an internal cross-linking means (mixing of a cross-linking agent) or an external cross-linking means (active energy ray irradiation) to a polyamide-imide resin or amorphous polyolefin is preferably used. The curable resin cured product layer (13) may be a layer (A) comprising the above layered compound.
The curable resin cured product layer (13) can be not only a single layer but also a plurality of layers. The thickness of the curable resin cured product layer (13) is not particularly limited, but it is often 1 to 300 μm or more, particularly 2 to 100 μm, more preferably 3 to 50 μm per layer. The non-solvent type does not exclude a case where a nominal amount of solvent is included.
[0053]
The air-proof layer (14) is preferably composed of the layer (A) comprising the above-mentioned layered compound, but in addition, polyvinyl alcohol or a copolymerized modified product thereof, a graft product, a polymer alloy, and an ethylene content of 15 to A layer made of an organic polymer such as a vinyl alcohol resin layer such as a 50 mol% ethylene-vinyl alcohol copolymer, a vinylidene chloride resin layer, or a high acrylonitrile resin layer is also used. A layer of a resin composition containing an agent and a water-soluble natural polymer is also preferable. The layer thickness of the air barrier layer (14) is often about 2 to 30 μm (preferably about 5 to 15 μm) per layer. This air barrier layer (14) is usually formed by a casting method.
[0054]
As the air and moisture proof layer (15), a layer (A) comprising a layered compound is used. Also preferably an inorganic thin film, for example, SiOx (where 1≤x≤2, preferably 1.5≤x <2), MgO, Al₂O_Three, InO₂, SnO₂, ZnO alone or a mixture of two or more of these is also preferred. Not only oxides but also nitrides, carbides, borides and the like can be used. This air-proof and moisture-proof layer (15) is formed by sputtering, in particular, in the case of an inorganic thin film, such as sputtering, vacuum deposition, ion plating, atmospheric pressure plasma, and sol-gel coating. . The thickness of the air-proof and moisture-proof layer (15) is arbitrary as long as the transparency can be secured, but usually about 30 to 2000 angstroms (preferably about 50 to 500 angstroms) per layer is appropriate. However, when heatless glass is obtained by a coating method, it is allowed up to about 10 μm. These air-proof and moisture-proof layers (15) also serve as air-proof layers, moisture-proof layers, heat resistant layers, under layers for forming transparent electrodes, and the like.
[0055]
Each of the above layers is usually required to be transparent and have optical isotropy. However, depending on the application, for example, in the case of an electrode substrate that also serves as a polarizing plate or an electrode substrate that also serves as a phase plate, It may contain a non-sexual layer.
[0056]
An adhesive layer (ad) or an anchor coating layer (ac) can be interposed between adjacent layers as necessary.
[0057]
The layer structure of the plastic substrate (1) can be various and can be symmetric or asymmetric. Some examples of symmetrical layer configurations are as follows. The meanings of the symbols are as follows: (11) is a base film layer, (12) is a core material layer, (13) is a cured resin cured material layer, (14) is an air-proof layer, and (15) is an air-proof and moisture-proof material. Layer (ad) is an adhesive layer.
[0058]
(13) / (14) / (11) / (14) / (13)
(13) / (14) / (ad) / (14) / (13)
(13) / (15) / (14) / (11) / (14) / (15) / (13)
(13) / (15) / (14) / (12) / (14) / (15) / (13)
(15) / (13) / (14) / (11) / (14) / (13) / (15)
(13) / (15) / (12) / (15) / (13)
(15) / (13) / (12) / (13) / (15)
(13) / (15) / (14) / (15) / (13)
(15) / (13) / (14) / (13) / (15)
(13) / (14) / (12) / (14) / (13)
(15) / (14) / (15)
(15) / (14) / (14) / (15)
(15) / (12) / (15)
(15) / (14) / (11) / (14) / (15)
(15) / (14) / (11) / (ad) / (11) / (14) / (15)
[0059]
As described above, in the present invention, at least one layer among (11) to (15) has a structure composed of the layer (A) containing a layered compound. In particular, a structure in which (14) and / or (15) is composed of the layer (A) is preferable.
[0060]
An optical plastic substrate having such a structure is usually required to be excellent in transparency and optical isotropy. As the transparency of the optical plastic substrate of the present invention, the average transmittance in the visible light region is preferably 60% or more, more preferably 70% or more, and particularly preferably 80% or more. Further, as optical isotropy, the in-plane retardation value of the substrate is preferably 50 nm or less, more preferably 30 nm or less, and further preferably 10 nm or less.
Even when used as an electrode substrate of a liquid crystal cell, optical isotropy is usually required, but those having a retardation value can be used as necessary. In addition, when a polarizing plate is used as an electrode substrate also serving as a protective film or an electrode substrate also serving as a retardation plate, those having a retardation value can be used. Although the retardation value depends on the type of liquid crystal display device to be applied, the retardation value in the substrate surface is usually 50 nm to 2000 nm.
[0061]
<Layers provided on the plastic substrate (1)>
A transparent electrode (3) represented by ITO can be formed on the plastic substrate (1). In this case, metal oxide prior to the formation of the transparent electrode (3) is used to improve the adhesion of the transparent electrode (3) or to prevent curling and improve reliability in the patterning process and washing process of the transparent electrode (3). It is preferable to form an undercoat layer (2) of an object or the like. In many cases, the undercoat layer (2) is of the same type as the above air-proof and moisture-proof layer (15) (in particular, an inorganic thin film).
[0062]
The optical plastic substrate of the present invention is particularly useful as an electrode substrate of a liquid crystal cell constituting a liquid crystal display element. In addition, an electrode substrate that also serves as a polarizing plate, an electrode substrate that also serves as a phase plate, a film with a transparent electrode for a touch panel (including those laminated on the polarizing plate as well as the polarizing plate), and an electromagnetic wave shielding plate for CRT It can also be used for applications such as plasma display panels (PDP), backlights, light guide plates, color filters, optical cards, optical tapes, optical disks, solar cell covers, EL substrates, and active elements.
[0063]
【The invention's effect】
In the optical plastics substrate of the present invention, the layer (A) containing the layered compound contained in the substrate (1) is an air-proofing layer made of a vinyl alcohol resin or the like that has been proposed or used conventionally. Compared to the layer, it has outstanding heat resistance, hardness and moisture resistance. For this reason, if a surface layer with excellent heat resistance and hardness is selected, the heat resistance and hardness of the air-proof layer, which is the internal scaffolding, is excellent, so that the conventional plastic substrate cannot be reached. It can withstand ACF crimp connection under harsh conditions.
[0064]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited at all by these.
Measurement methods for various physical properties are described below.
[0065]
(Particle size measurement)
Using a laser diffraction / scattering particle size distribution measuring apparatus (LA910, manufactured by Horiba, Ltd.), the volume-based median diameter of particles considered to be a layered compound present in the resin matrix of the medium was measured as the particle diameter L. The dispersion of the layered compound was measured by a flow cell method with an optical path length of 4 mm.
[0066]
[Aspect ratio calculation: When using resin]
Using an X-ray diffractometer (XD-5A, manufactured by Shimadzu Corporation), diffraction measurement was performed by a powder method of a composition containing a layered compound alone and a resin. Thereby, the unit thickness a of the layered compound was obtained, and further, from the diffraction measurement of the composition containing the resin, it was confirmed that there was a portion where the interplanar spacing d of the layered compound was widened. Using the particle diameter L obtained by the above method, the aspect ratio (Z) was calculated by the formula Z = L / a.
[0067]
Example 1
A dispersion kettle with a stirrer (trade name: Despa MH-L, manufactured by Asada Tekko Co., Ltd.), 1000 g of ion-exchanged water (specific electric conductivity 1 μs / cm or less) and polyvinyl alcohol (PVA117H; Kuraray Co., Ltd.) as a resin Manufactured, saponification degree: 99.6%, polymerization degree 1,700) 100 g, heated to 95 ° C. under low speed stirring (1,500 rpm, peripheral speed about 4 m / sec), stirred for 1 hour Dissolved to obtain a solution (A). The temperature was lowered to 65 ° C. while stirring the solution (A), and then an alcohol aqueous solution in which 400 g of ion exchange water and 94 g of isopropanol were mixed in advance was slowly added dropwise. After completion of dropping, 50 g of high-purity natural montmorillonite (trade name: Kunipia F; manufactured by Kunimine Kogyo Co., Ltd.) as a layered compound was added as a powder at 65 ° C. Subsequently, the stirring conditions were switched to high speed stirring (3000 rpm, peripheral speed about 8 m / sec) and dispersed for 90 minutes to obtain a mixed liquid (B).
[0068]
Next, the above mixed liquid (B) is passed through a high-pressure dispersion device (trade name: ultrahigh-pressure homogenizer M110-E / H, manufactured by Microfluidics Corporation) to obtain 1,750 kgf / cm.²1 treatment was performed to obtain a uniform dispersion (C) with good dispersibility. The solid content concentration of the dispersion (C) was about 7.6% by weight. The dispersion composed of the PVA and montmorillonite was dried and solidified and then pulverized, followed by powder X-ray analysis, and the interplanar spacing d of the natural montmorillonite (Kunipia F) swollen and cleaved was measured. The natural montmorillonite (Kunipia F) was sufficiently cleaved. The aspect ratio of the natural montmorillonite (Kunipia F) at this time was 200 or more. The dispersion (C) was cast on a polyester film and dried at 60 ° C. to obtain a film (thickness: about 5 μm) composed of a layered compound and a resin. About this film, oxygen permeability (measuring device: OXTRAN 10 / 50A manufactured by Modern Control, Inc .; measurement conditions: 23 ° C., 50% RH; unit: cc / m²-24 hr) was measured, it was less than 0.1 and excellent in air-proofing properties. Furthermore, when heat-treated at 180 ° C. for 30 minutes as an index of heat resistance, the film maintained flatness and was excellent in heat resistance.
[0069]
(Example 2)
25 g of polyvinyl alcohol (PVA117H; manufactured by Kuraray Co., Ltd., saponification degree: 99.6%, polymerization degree 1,700), high-purity natural montmorillonite as a layered compound (trade name: Kunipia G; manufactured by Kunimine Kogyo Co., Ltd.) A film (thickness of about 5 μm) made of a layered compound and a resin was obtained in the same manner as in Example 1 except that 50 g of the powder was used. About this film, oxygen permeability (measuring device: OXTRAN 10 / 50A manufactured by Modern Control Co., Ltd .; measurement conditions: 23 ° C., 50% RH; unit: cc / m²-24 hr) was measured, it was less than 0.1 and excellent in air-proofing properties. Furthermore, when heat-treated at 180 ° C. for 30 minutes as an index of heat resistance, the film maintained flatness and was excellent in heat resistance.
[0070]
(Comparative Example 1)
A film (thickness of about 5 μm) was obtained in the same manner as in Example 1 except that the layered compound was not used. About this film, oxygen transmission rate (measuring device: OXTRAN 10 / 50A manufactured by Modern Control, Inc .; measurement conditions: 30 ° C., 50% RH; unit: cc / m²When 24 hours) was measured, 0.4 was inferior in air-proofing property, and when heat-treated at 180 ° C. for 30 minutes as an index of heat resistance, the film was significantly shrunk and inferior in heat resistance.
[0071]
Therefore, an example of a plastic substrate (1) including a layer having such basic characteristics is shown below.
(Reference Example 1)
FIG. 1 is an explanatory view showing an example of an optical plastic substrate of the present invention. FIG. 2 is an explanatory view showing an example of a usage pattern of the optical plastic substrate of FIG.
As shown below, an optical plastic substrate and a liquid crystal cell using the same can be obtained according to the method disclosed in JP-A-2000-6259.
[0072]
A solvent solution of a resin composition in which a phenol novolac epoxy resin is mixed at a ratio of 10: 1 with a polyamideimide resin is cast, dried with hot air, and then at a temperature of 120 ° C. and further at a temperature of 150 to 180 ° C. By heat treatment, a polyamideimide resin film having a thickness of 40 μm and an extremely small retardation value can be obtained.
[0073]
This polyamide-imide resin film is used as an optically isotropic substrate film layer (11), and a water-soluble polyester urethane anchor coating agent having a solid content of 5% by weight is cast on one side of the film and dried, cured. By doing so, an anchor coating layer (ac) having a thickness of 1 μm can be formed.
[0074]
Subsequently, the dispersion liquid (C) of Example 1 was cast on the anchor coating layer (ac) and dried at 70 to 90 ° C. to form an air barrier layer (14) having a thickness of 8 μm in the same manner. Thus, an anchor coating layer (ac) having a thickness of 1 μm and an air-proof layer (14) having a thickness of 8 μm can be formed on the other surface of the base film layer (11). Thereby, the laminated film 1 having the layer structure of (14) / (ac) / (11) / (ac) / (14) is obtained.
[0075]
Non-solvent type silicone acrylate UV curable resin liquid is mixed with polyisocyanate compound ("Coronate HK" manufactured by Nippon Polyurethane Industry Co., Ltd.) at a weight ratio of 100: 30 to cure non-solvent type active energy ray. A mold composition can be prepared.
[0076]
The laminated film 1 is supplied to one roll of a pair of rolls arranged in parallel with a slight gap, and a mold film (S) is formed of a biaxially stretched polyethylene terephthalate film having a thickness of 100 μm on the other roll. Then, the active energy ray-curable composition is discharged toward the gap between the two rolls, and the rolls are rotated in a direction to bite each other, whereby the laminated film 1 and the mold film (S) The above composition is sandwiched between the two, and then, in the sandwiched state, ultraviolet irradiation is performed under the conditions of an output of 120 W / cm, one lamp, a lamp distance of 150 mm, and an integrated light quantity of 1000 mJ / cm 2. Is cured to form a cured resin layer (13) having a thickness of 15 μm, and further heat-treated at a temperature of 130 ° C. for 10 minutes, to obtain a laminated film 1 / cured type resin. Cured layer (13) / laminate film 2 having a layer structure of the mold film (S) is obtained. This time, the above operation is repeated using this laminated film 2 and another mold film (S). As a result, a symmetrical mold film (S ), (S) -attached optical laminated sheet is obtained.
[0077]
The layer structure of the plastics substrate (1) obtained by peeling and removing the mold film (S) and (S) at an appropriate stage thereafter is (13) / (14) # / (ac) / (11) / (ac) / (14) # / (13) (see FIG. 1), and the air barrier layers (14) # and (14) # marked with # are the layers (A) containing the layered compound. It is configured.
[0078]
Next, an undercoat layer (2) (also an air-proof and moisture-proof layer (15)) having a thickness of 50 Å made of a metal oxide mainly composed of SiOx is sputtered on one surface of the plastic substrate (1) obtained above. After forming by the method, a transparent electrode (3) made of an ITO layer having a thickness of 500 angstroms is formed to have a configuration of (1) / (2) / (3) (see FIG. 2). Then, in accordance with a conventional method, resist formation, exposure, development, etching, and removal of the cured resist can be performed to form a patterned electrode.
[0079]
A liquid crystal cell can be manufactured using a substrate made of an optical laminated sheet with a pattern electrode. In this case, a batch connection between the pattern electrode and the outer lead (TCP or FPC) of the control IC is made between the two. 180 ° C x 20 sec x 20 kg / cm with an anisotropic conductive sheet (ACF) interposed²Even under such severe conditions, it is possible to perform thermocompression bonding.
[0080]
The optical plastic substrate thus obtained has a glass-like property close to that of a conventional glass substrate, and is extremely useful as an electrode substrate for a liquid crystal cell of a liquid crystal display element.
[0081]
(Reference Example 2)
FIG. 3 is an explanatory view showing another example of the optical plastic substrate of the present invention.
According to Reference Example 1, a plastic substrate (1) having a layer structure of (13) / (15) / (12) # / (15) / (13) can be produced using the following layers. The core material layer (12) marked with # is composed of a layer (A) containing a layered compound.
[0082]
(Reference Example 3)
FIG. 4 is an explanatory view showing still another example of the optical plastic substrate of the present invention.
According to Reference Example 1, a plastic substrate (1) having a layer structure of (15) / (13) / (12) # / (13) / (15) can be produced using the following layers. The core material layer (12) marked with # is composed of a layer (A) containing a layered compound.
[Brief description of the drawings]
FIG. 1 is an explanatory view showing an example of an optical plastic substrate of the present invention.
2 is an explanatory view showing an example of a usage pattern of the optical plastic substrate of FIG. 1. FIG.
FIG. 3 is an explanatory view showing another example of the optical plastic substrate of the present invention.
FIG. 4 is an explanatory view showing still another example of the optical plastic substrate of the present invention.
[Explanation of symbols]
1 Plastics substrate
11 Base film layer
12 Core material layer
13 Curable resin cured product layer
14 Organic air barrier
15 Inorganic air and moisture barrier
ac anchor coating layer
ad adhesive layer
2 Undercoat layer
3 Transparent electrodes

Claims (5)

An electrode substrate comprising a plastic substrate (1) having a multilayer structure selected from the group consisting of the following multilayer structure (B) to the following multilayer structure (P ), and a transparent electrode ,
At least one of the base film layer (11), the core material layer (12), the curable resin cured material layer (13), the air-proof layer (14), and the air-proof and moisture-proof layer (15) constituting the multilayer structure. Is a layer (A) comprising a layered compound .
Multilayer structure (B): (13) / (14) / (11) / (14) / (13)
Multilayer structure (C): (13) / (14) / (ad) / (14) / (13)
Multilayer structure (D): (13) / (15) / (14) / (11) / (14) / (15) / (13)
Multilayer structure (E): (13) / (15) / (14) / (12) / (14) / (15) / (13)
Multilayer structure (F): (15) / (13) / (14) / (11) / (14) / (13) / (15)
Multilayer structure (G): (13) / (15) / (12) / (15) / (13)
Multilayer structure (H): (15) / (13) / (12) / (13) / (15)
Multilayer structure (I): (13) / (15) / (14) / (15) / (13)
Multilayer structure (J): (15) / (13) / (14) / (13) / (15)
Multilayer structure (K): (13) / (14) / (12) / (14) / (13)
Multilayer structure (L): (15) / (14) / (15)
Multilayer structure (M): (15) / (14) / (14) / (15)
Multilayer structure (N): (15) / (12) / (15)
Multilayer structure (O): (15) / (14) / (11) / (14) / (15)
Multilayer structure (P): (15) / (14) / (11) / (ad) / (11) / (14) / (15)
(Here, (11) is a base film layer, (12) is a core material layer, (13) is a curable resin cured material layer, (14) is an air-proof layer, (15) is an air-proof and moisture-proof layer, ( ad) is an adhesive layer.)   The resin composition wherein the layer (A) comprising the layered compound is composed of the layered compound (a) and the resin (b), and the weight ratio of (layered compound / resin) is in the range of 1/100 to 100/1. The electrode substrate according to claim 1, comprising: as a main component.   The electrode substrate according to claim 1, wherein the layered compound is an inorganic layered compound.   The electrode substrate according to any one of claims 1 to 3, wherein the layered compound is a clay mineral.   A liquid crystal display device using the electrode substrate according to claim 1.

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