JP2007023184A - Film, method for producing the same and use thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a lightweight film of an organic/inorganic composite producible according to a simple method and having higher heat resistance and lower coefficient of linear expansion than those of conventional films, to provide a method for simply producing the film and to provide a laminated film, a transparent electroconductive film, a flat panel display device substrate and a liquid crystal display substrate having the film. <P>SOLUTION: The film is composed of the organic/inorganic composite composed of an organic polymeric material and inorganic micro-particles and is characterized as having ≥80% gel fraction and ≤5% elongation under 0.2 N/mm<SP>2</SP>load at 50-300°C measuring temperature. The method for producing the film comprises a step of molding a resin composition containing the organic polymeric material and inorganic micro-particles into a platy form and affording a platy body and a step of feeding the resultant platy body to a stretching treatment and an energy ray treatment. The laminated film, transparent electroconductive film, flat panel display device substrate and liquid crystal display substrate comprise the film. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a film, a production method thereof, and an application thereof. Specifically, the present invention relates to a film having high heat resistance and a low coefficient of linear expansion, a production method thereof, and an application thereof.

  A film made of a resin material can be obtained by appropriately selecting a material, and thus has excellent characteristics such as light weight, transparency, and low cost. Therefore, applications in a wide range of fields are being studied. However, organic / inorganic composites also have applications where their practical use is still difficult due to their high heat resistance and low coefficient of linear expansion.

  As an example, a case where a resin film is used in place of a glass substrate conventionally used as a substrate in the production of an active matrix liquid crystal display using TFTs (thin film transistors) will be described. As a method for forming a TFT array on a resin film substrate, a transfer method and a direct method have been proposed.

  The transfer method is a method in which a TFT array is once formed on a glass substrate, and then the TFT array layer is transferred onto a resin film substrate to remove the glass substrate. The manufacturing process of the TFT array is almost the same as the conventional method using a glass substrate, but the transfer process is essential, so that the manufacturing process is more complicated than the conventional method.

  In contrast, the direct method is a method of directly forming a TFT array on a resin film substrate without using a glass substrate. If the direct method becomes possible, it will be possible to manufacture a liquid crystal display at a low cost. However, the process temperature of amorphous silicon TFTs usually reaches a maximum of 300 to 350 ° C, so the heat resistance temperature is generally only about 100 to 200 ° C. Such a resin film cannot withstand the production of a TFT array by a direct method.

  Therefore, if it is possible to obtain a resin film having high heat resistance and low linear expansion coefficient that can withstand the manufacture of a TFT array by a direct method while having advantages such as low cost and light weight, the STN method or the like can be used for moving image display capability. An excellent TFT-type liquid crystal display that is lighter than a conventional glass substrate can be manufactured at low cost, and can have extremely high practical value. From such a point of view, there is a demand for a resin film that has both high heat resistance and a low linear expansion coefficient while having advantages such as fewer steps and light weight.

  As a technique for improving the heat resistance and the like of a resin film, an organic / inorganic composite film in which an inorganic compound is added to a resin has been proposed. For example, Patent Document 1 describes a film containing a specific organically modified layered silicate as an organic / inorganic composite film having heat resistance and gas barrier properties. However, as disclosed in Patent Document 1, even when an inorganic compound is added to a resin to form an organic / inorganic composite film, the film still has sufficient heat resistance, for example, to form the above-described direct method TFT array. Absent.

JP 2004-107541 A

  An object of the present invention is a film of an organic / inorganic composite that has an advantage such as light weight that can be manufactured by a simple method, and also has higher heat resistance and a lower linear expansion coefficient than conventional ones, and the like. Another object of the present invention is to provide a method for easily producing such a film, and a laminated film, a transparent conductive film and a display substrate provided with such a film.

  As a result of diligent research to solve the above problems, the present inventors have found that the gel fraction of the organic / inorganic composite and the elongation in a specific temperature range are important. And when the film of patent document 1 was measured, it turned out that a gel fraction is small and the elongation in a specific temperature range is large. Therefore, as a result of further diligent research, an organic / inorganic composite film having a specific gel fraction and a specific low value of elongation to a load at 50 to 300 ° C. is combined with a specific treatment. Based on this finding, the present invention has been completed.

That is, according to the present invention,
(1) A film comprising an organic polymer material and an organic / inorganic composite containing inorganic fine particles dispersed in the organic polymer material, having a gel fraction of 80% or more and a load of 0.2 N / mm ² , a film characterized in that the elongation at a measurement temperature of 50 to 300 ° C. is 5% or less;
(2) A resin composition containing an organic polymer material and inorganic fine particles is molded into a plate shape to obtain a plate body; the plate body is obtained by subjecting to a stretching treatment and an energy ray treatment, The film according to 1);
(3) The film according to (2), wherein the stretching treatment and the energy beam treatment include a step of stretching the plate-like body and then performing an energy beam treatment;
(4) The film according to (2), wherein the stretching treatment and energy beam treatment include a step of subjecting the plate-like body to energy beam treatment and then stretching treatment;
(5) A step of obtaining a plate-like body by molding a resin composition containing an organic polymer material and inorganic fine particles into a plate shape; and a step of subjecting the plate-like body to a stretching treatment and an energy ray treatment (1) ) Film production method;
(6) The manufacturing method according to (5), wherein the step of subjecting to the stretching treatment and the energy ray treatment includes a step of subjecting the plate-like body to a stretching treatment and then an energy ray treatment;
(7) The manufacturing method according to (5), wherein the step of subjecting to the stretching treatment and the energy ray treatment includes a step of subjecting the plate-like body to an energy ray treatment and then a stretching treatment;
(8) The manufacturing method according to any one of (5) to (7), wherein the step of obtaining the plate-like body includes a step of melt-extruding the resin composition;
(9) The manufacturing method according to any one of (5) to (8), wherein the energy beam is an electron beam;
(10) A laminated film including the layer of the film according to any one of (1) to (4) and an inorganic thin film layer provided thereon;
(11) A transparent conductive film comprising the layer of the film according to any one of (1) to (4) above, and a transparent conductive layer provided thereon;
(12) The flat panel display element substrate including the film according to any one of (1) to (4); and (13) The film according to any one of (1) to (4). Including a liquid crystal display substrate;
Are provided respectively.

The film of the present invention can be produced by a simple method, has both the advantages of conventional organic polymer materials such as light weight, and further has high heat resistance and low linear expansion coefficient, It is useful as a laminated film, a transparent conductive film, a flat panel display element substrate, etc. used for an organic EL display. Moreover, it can use suitably widely for the use used as a laminated body with metals other than the use for a display, such as a printed circuit board.
The production method of the film of the present invention can easily produce the film of the present invention by including specific treatments of stretching treatment and energy ray treatment.

The film of the present invention comprises an organic polymer material and an organic / inorganic composite containing inorganic fine particles dispersed in the organic polymer material.
Examples of the organic polymer material include various thermoplastic resins. The thermoplastic resin is not particularly limited as long as the inorganic fine particles can be uniformly dispersed. For example, alicyclic structure polymer, chain olefin polymer such as polyethylene and polypropylene, triacetyl cellulose, polyvinyl alcohol, polyimide, polyarylate, polyester, polycarbonate, polysulfone, polyethersulfone, amorphous polyolefin, modified acrylic polymer Etc. Among these, an alicyclic structure-containing polymer or a chain olefin polymer is preferable, and an alicyclic structure-containing polymer is particularly preferable from the viewpoints of transparency, low hygroscopicity, dimensional stability, and lightness.

  The organic polymer material is preferably a material capable of forming a crosslink by irradiation with energy rays to be described later. Specifically, a thermoplastic resin having a radical reactive unsaturated group is more preferable. By using a thermoplastic resin having a radical-reactive unsaturated group, a crosslinked product can be easily and efficiently obtained by a radical reaction after obtaining a molded product. Examples of the radical-reactive unsaturated group include an α-olefin group, a vinyl aromatic group, an unsaturated carboxylic acid group, and the like, and an unsaturated carboxylic acid group is preferable from the viewpoint of crosslinkability by energy ray irradiation. There is no restriction | limiting in particular in the method of obtaining the thermoplastic resin which has a radical reactive unsaturated group. For example, a method of reacting (modifying) a compound having a radical reactive unsaturated group with a thermoplastic resin having a reactive group such as a hydroxyl group, a carboxyl group, an epoxy group, a glycidyl group, an amino group, or a carbonyloxycarbonyl group. Is mentioned. By using such a resin, a film satisfying the requirements of the present invention such as a gel fraction described later can be easily produced.

  The inorganic fine particles used in the present invention are not particularly limited as long as they are uniformly dispersed in the organic polymer material. In the state dispersed in the organic / inorganic composite, (A) the number average thickness is 10 nm or less, It is preferable to use an inorganic layered compound having a number average particle size in the in-plane direction of 300 nm or less and an average aspect ratio of 5 or more, or (B) inorganic ultrafine particles having a number average particle size of 50 nm or less. By using such an inorganic layered compound or inorganic ultrafine particles, a film excellent in transparency, heat resistance and low linear expansion can be obtained.

  The inorganic layered compound (A) is a compound having a polycrystalline layer structure in which the compound is in a state (layered) having a structure arranged in a plane, and the planar structure is repeated in the vertical direction. . In this inorganic layered compound, a crystal layer is bonded to each other by van der Waals force or hydrogen bond force, and a crystal layer charged with a negative charge has a cation between each crystal layer. It can be roughly classified into those coupled by a weak electrostatic force through cations.

Specific examples of such inorganic layered compounds include transition metal dichalcogenides such as graphite, TiS ₂ , NbSe ₂ and MoS ₂ ; transition metal dichalcogenides such as CrPS ₄ ; transitions such as MoO ₃ and V ₂ O _5. Metal oxides; oxyhalides such as FeOCl, VOCl, CrOCl; hydroxides such as Zn (OH) ₂ and Cu (OH) ₂ ; Zr (HPO ₄ ) ₂ .nH ₂ O, Ti (HPO ₄ ) ₃ · nH ₂ O, Na (UO ₂ PO ₄ ) Phosphate such as ₃ · nH ₂ O; Titanate such as Na ₂ Ti ₃ O ₇ , KTiNbO ₅ , RbxMnxTi ₂ -xO ₄ ; Na ₂ U ₂ O ₇ , uranates such as K ₂ U ₂ O ₇ ; KV ₃ O ₈ , K ₃ V ₅ O ₁₄ , CaV ₆ O ₁₆ .nH ₂ O, Na (UO ₂ V ₃ O ₉ ) .nH ₂ O, etc. Vanadate; niobates such as KNb ₃ O ₃ and K ₄ Nb ₆ O ₁₇ ; N _{a 2 W 4 O 13, Ag} 4 W 10 O 13 tungstates such _{as; Mg 2 Mo 2 O 7,} Cs 2 Mo 5 O 16, Cs 2 Mo 7 O 22, Ag 4 molybdate such as Mo ₁₀ O ₃₃ Salt; montmorillonite, saponite, hydelite, hectorite, nontronite, stevensite, trioctahedral vermiculite, dioctahedral vermiculite, mascobite, phylogobite, biotite, lepidrite, baragonite, tetralithic mitite Silicates such as kaolinite, halloysite, dickite, H ₂ SiO ₅ , H ₂ Si ₁₄ O ₂₉ .5H ₂ O, or minerals composed of this silicate. These inorganic layered compounds can be used alone or in combination of two or more.

  Among these inorganic layered compounds, silicates, phosphates and molybdates are preferred from the viewpoints of dispersibility in organic polymer materials, heat resistance of the resulting film, and mechanical strength, and silicates are particularly preferred. preferable.

  The inorganic layered compound used in the present invention has a number average thickness of 10 nm or less, a number average particle diameter in the in-plane direction of 300 nm or less, an average aspect ratio of 5 or more, a number average thickness of 5 nm or less, and a number in the in-plane direction. Those having an average particle diameter of 200 nm or less and an average aspect ratio of 10 or more are preferred. The average aspect ratio is more preferably 100 or less, and even more preferably 50 or less. When the number average thickness is larger than 10 nm, the transparency of the obtained film may be inferior. Also, if the average aspect ratio is less than 5, the effect of improving heat resistance and mechanical strength may be reduced. If the average aspect ratio is greater than 50, the composition is inferior in transparency or solvent-removing property is deteriorated. Sometimes.

  The number average thickness, the number average particle diameter in the in-plane direction, and the average aspect ratio of the inorganic layered compound can be calculated by performing computer processing from an observation image with a transmission electron microscope (TEM).

  Here, the number average particle diameter in the in-plane direction is an arithmetic average value of the major axis and the minor axis in the in-plane direction. The major axis in the in-plane direction is the longest passing diameter in the in-plane direction, and the minor axis in the in-plane direction is the shortest passing diameter in the in-plane direction. The average aspect ratio is the ratio of the average particle diameter to the thickness in the in-plane direction.

  It is preferable to use an inorganic layered compound that can swell in an organic solvent. Here, the swelling means a phenomenon in which the inorganic layered compound absorbs the organic solvent to increase the volume, and at that time, the layer of the unit layer (hereinafter referred to as nanosheet) of the inorganic layered crystal constituting the inorganic layered compound is expanded.

  The interlayer distance of the swollen inorganic layered compound is preferably 3 nm or more, more preferably 5 nm or more, and further preferably 7 nm or more. If the interlayer distance is excessively small, uniform dispersion in the organic polymer material becomes insufficient. The interlayer distance can be measured using an X-ray diffraction method (XRD).

  When the inorganic layered compound is dispersed in the matrix of the organic polymer material, it is ideally uniformly dispersed in the state of the nanosheet, but the number average thickness even in the state where several nanosheets are overlapped May be 10 nm or less.

The inorganic layered compound used in the present invention is preferably subjected to an organic treatment in order to improve dispersibility. This organic treatment can be performed using, for example, a cationic surfactant. Examples of the cationic surfactant include a quaternary ammonium salt represented by R ¹ R ² R ³ R ⁴ N ⁺ X ⁻ , or a phosphonium described in JP-A Nos. 2004-29212 and 2005-97028. Mention may be made of salts.

Wherein ^{R 1 R 2 R 3 R 4} N + X - ^{in, R 1, R 2, R} 3 and R ⁴ are identical, respectively, may be different and saturated C1-30 Or represents an unsaturated hydrocarbon group. Examples of the saturated or unsaturated hydrocarbon group having 1 to 30 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, 2-ethylhexyl group, heptyl group, octyl group, nonyl group, decyl group. A saturated aliphatic hydrocarbon group such as a group, dodecyl group, hexadecyl group or octadecyl group; an unsaturated aliphatic hydrocarbon group such as a lauryl group or an oleyl group; an aromatic hydrocarbon group such as a phenyl group or a benzyl group. it can. Examples of X ⁻ include anions such as Cl ⁻ , Br ⁻ , NO ₃ ⁻ , OH ⁻ , and CH ₃ COO ⁻ .

  The inorganic layered compound is organically treated by, for example, preparing an inorganic layered compound dispersion by dispersing the inorganic layered compound in water, adding the cationic surfactant to the dispersion, and stirring at room temperature. Can be done by. At this time, the concentration of the inorganic layered compound in the inorganic layered compound dispersion is preferably adjusted to 0.01 to 70% by mass. Moreover, you may add the cationic surfactant to add as aqueous solution.

  In addition to the cationic surfactant used for organic treatment, functional organic compounds such as antioxidants, light stabilizers, ultraviolet absorbers, infrared absorbers, dyes and antistatic agents are intercalated. It is also possible to use those. The method for intercalating the functional organic compound is not particularly limited, and a known method can be adopted.

  The inorganic ultrafine particles having a number average particle size of (B) of 50 nm or less are dispersed in the organic polymer material, and if the number average particle size and average aspect ratio are within this range, the material and shape are as follows. There is no particular limitation.

  As the material of the inorganic ultrafine particles, metal oxide such as silicon oxide, aluminum oxide, titanium oxide, magnesium oxide, calcium oxide, cerium oxide, antimony oxide, tantalum oxide, niobium oxide, zirconium oxide, etc., composite metal oxide, gold, Examples thereof include transition metal alone such as platinum, silver, palladium, rhodium, and zinc, a semiconductor, and a metal salt.

  The shape of the inorganic ultrafine particles is not particularly limited, and may be appropriately selected according to the purpose, such as a spherical shape, a rod shape, a needle shape, or an indefinite shape.

  The number average particle diameter of the inorganic ultrafine particles is 50 nm or less, preferably 30 nm or less. When the number average particle diameter exceeds 50 nm, the transparency of the obtained film may be inferior. Further, the narrower the particle size distribution of the inorganic ultrafine particles, the better. When the particle size distribution is large, particles having a large particle size that cause light scattering are included, and thus the transparency of the film may be inferior.

  In order to obtain a film having excellent transparency, the proportion of inorganic fine particles having a particle size of 60 nm or more is usually 10% by volume or less, preferably 5% by volume or less, based on the volume of all inorganic fine particles. Volume% or less is more preferable.

  In addition, the smaller the particle size distribution of the inorganic ultrafine particles used in the present invention, the better the homogeneity of dispersibility and the lower haze, which is preferable. Therefore, the particle size distribution is usually 20% or less as a standard deviation, preferably 15% or less, and more preferably 10% or less.

  The number average particle size and particle size distribution of the inorganic ultrafine particles dispersed in the polymer can be measured from a transmission electron microscope (TEM) observation image.

  It is preferable to use inorganic ultrafine particles that have been surface-treated in order to achieve good uniform dispersion in an organic solvent, or in order to achieve good uniform dispersion in an organic polymer material.

  The surface treatment can be performed using an inorganic compound or an organic compound.

Examples of the inorganic compound used for the surface treatment include inorganic compounds containing cobalt (CoO ₂ , Co ₂ O ₃ , Co ₃ O _4, etc.), and inorganic compounds containing aluminum (Al ₂ O ₃ , Al (OH) ₃ ). Etc.), zirconium-containing inorganic compounds (ZrO ₂ , Zr (OH) ₄ etc.), silicon-containing compounds (SiO ₂ etc.), iron-containing compounds (Fe ₂ O ₃ etc.) and the like. Among these, an inorganic compound containing cobalt, an inorganic compound containing aluminum, and an inorganic compound containing zirconium are preferable, and an inorganic compound containing cobalt, Al (OH) ₃ , and Zr (OH) ₄ are more preferable.

  Examples of organic compounds used for the surface treatment include coupling agents such as polyols, alkanolamines, stearic acid, isocyanate compounds, organic silane compounds, organic titanium compounds, organic borane compounds, and epoxy compounds. Silane coupling agents are preferred.

  The organic silane coupling agent is not particularly limited. For example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-aminopropyltrimethoxysilane, γ-aminopropyl Methyldimethoxysilane, γ-aminopropyldimethylmethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyldimethylethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, Hexyltrimethoxysilane, hexyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacrylic Examples include loxypropyltrimethoxysilane and γ-methacryloxypropyltriethoxysilane.

  The inorganic ultrafine particles used in the present invention may have a heterogeneous structure such as a mixed crystal or a core-shell structure. In particular, when the core-shell structure has an unfavorable action such as, for example, the photocatalytic ability of the semiconductor crystal that is the core accelerates the decomposition of the resin, it can provide an excellent effect such as providing a shell structure of another substance to improve it. There is. Accordingly, it is preferable that a chemically relatively inactive substance constitutes the shell. Specifically, oxides of non-transition metals such as silica (silicon oxide) and alumina (aluminum oxide), and nitrides such as boron nitride Examples of preferable shell materials include carbon units such as graphitic carbon and amorphous carbon, and noble metals (silver, gold, platinum, copper, etc.).

  As the inorganic fine particles used in the present invention, those modified with a compound having a radical reactive unsaturated group are preferably used. By using inorganic fine particles modified with a compound having a radical reactive unsaturated group, a bond can be formed on the surface of the inorganic fine particles by irradiation with energy rays, and the film has high heat resistance and low linear expansion. be able to.

  The radical reactive unsaturated group is not particularly limited as long as it is an unsaturated group having a property of causing a radical reaction when irradiated with energy rays. For example, an α-olefin group, a vinyl aromatic group, an unsaturated carboxylic acid group, and the like can be given.

  The compound having a radical-reactive unsaturated group that modifies the surface of the inorganic fine particles is not particularly limited as long as it has at least one radical-reactive unsaturated group.

  Specific examples of the compound having a radical reactive unsaturated group to be used include α-olefins such as ethylene and propylene; conjugated diene compounds such as butadiene and isoprene; styrene, α-methylstyrene, t-butylstyrene, divinylbenzene, 4 -Radical reactive aromatic compounds such as vinylpyridine; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid, maleic acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid; acrylic acid chloride, methacrylic acid chloride A halide of the unsaturated carboxylic acid such as chlorai maleate; an amide or imide derivative of the unsaturated carboxylic acid such as acrylamide, methacrylamide or maleimide; an anhydride of the unsaturated carboxylic acid such as maleic anhydride or citraconic anhydride Maleic acid mono Methyl, dimethyl maleate, (meth) acrylic acid amide, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, dimethylamino (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, allyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (Meth) acrylate, hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tricyclodecane di (meth) a Ester derivatives of the above unsaturated carboxylic acids such as relate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate; vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane , Silane compounds having a radical unsaturated group such as 3- (meth) acryloxypropyltrimethoxysilane and 3- (meth) acryloxypropyltriethoxysilane.

  The modification of the inorganic fine particles in the present invention is a state where a compound having a radical reactive unsaturated group is adsorbed on the surface of the inorganic fine particles by an affinity such as electrostatic force, or a compound having inorganic fine particles and a radical reactive unsaturated group A state in which a covalent bond is formed between the two. Examples of the method for modifying the inorganic fine particles with the compound having a radical reactive unsaturated group include a method of bringing the inorganic fine particles into contact with the above compound in a solution.

  The content ratio of the organic polymer material and the inorganic fine particles in the organic / inorganic composite is preferably 1 to 100 parts by weight, more preferably 1 to 50 parts by weight, with respect to 100 parts by weight of the organic polymer material. More preferably, it can be 5-20 weight part. By setting the blending ratio, a molded body having excellent heat resistance and mechanical strength can be obtained.

  In addition to the organic polymer material and the inorganic fine particles, the organic / inorganic composite may include, as optional components, an anti-aging agent such as a phenol type or a phosphorus type, an antistatic agent, an ultraviolet absorber, and a leveling agent. The content ratio of these optional components is usually 10 to 10,000 ppm, preferably 100 to 5,000 ppm.

The film of the present invention has a gel fraction of 80% or more, preferably 80 to 100%. By setting the gel fraction to 80% or more, a film having desired characteristics such as heat resistance can be obtained. Here, the gel fraction was measured by immersing 2 g of a film sample in xylene heated to 110 ° C. and taking it out after 8 hours, distilling off xylene remaining in the sample, and drying the sample from which xylene was distilled off. It can be obtained by weighing and calculating according to the following formula.
Gel fraction (%) = 100 × (sample mass after thermal xylene treatment / sample mass before thermal xylene treatment)

The film of the present invention has a load of 0.2 N / mm ² and an elongation at a measurement temperature of 30 to 300 ° C. of 5% or less, preferably 0% to 5%. The elongation is measured using a thermomechanical analyzer (trade name: TMA / SDTA840) manufactured by METTLER TOLEDO, with a predetermined load applied to the sample of the film under a nitrogen stream at a heating rate of 10 ° C./min. After measuring in the temperature range from 30 ° C. to 300 ° C., it can be obtained by measuring the amount of change in the length of the sample at 50 to 300 ° C.

  The thickness of the film of the present invention can be appropriately determined according to the use. For example, the thickness that can be suitably used for the use of a laminated film, a transparent conductive film, a display substrate and the like described later is 10 to 500 μm. It is a range, More preferably, it is the range of 10-200 micrometers. If the thickness is less than 10 μm, the strength is insufficient and handling becomes difficult, and if the thickness is more than 500 μm, the transparency tends to deteriorate and the flexibility tends to be impaired.

  The film of the present invention can be obtained by molding a resin composition containing the organic polymer material and inorganic fine particles into a plate shape to obtain a plate-like body, and subjecting it to stretching treatment and energy ray treatment.

  The method for preparing the resin composition is not particularly limited. For example, (α) each predetermined amount of an organic polymer material and inorganic fine particles, and each predetermined amount of one or two or more additives blended as necessary. Directly blended and kneaded at room temperature or under heating, (β) each predetermined amount of organic polymer material and inorganic fine particles, and one or more additives blended as necessary (Γ) A master batch in which a predetermined amount or more of inorganic fine particles are blended in advance with the above organic polymer material and kneaded in advance. The master batch, the remainder of the predetermined amount of the organic polymer material, and each predetermined amount of one or more additives blended as necessary are kneaded at room temperature or under heating. Or a masterbatch method of mixing in a solvent, ( ) Mixing a mixture containing a predetermined amount of organic polymer material and inorganic fine particles, a predetermined amount of one or more additives blended as necessary, and an organic compound having a boiling point of 50 ° C. to 200 ° C. The method including the process of using and kneading, etc. are mentioned. Among these, the methods (γ) and (δ) are preferable.

  In the master batch method of (γ) above, a master batch in which inorganic fine particles are blended with an organic polymer material, and a master batch dilution containing the organic polymer material used when the master batch is diluted to a predetermined inorganic fine particle concentration The resin composition for use may be the same composition or a different composition.

  The blending amount of the inorganic fine particles in the masterbatch method is not particularly limited, but the preferable lower limit with respect to 100 parts by weight of the organic polymer material is 1 part by weight, and the upper limit is 500 parts by weight. When the amount is less than 1 part by weight, the convenience as a master batch that can be diluted to an arbitrary concentration is reduced. If it exceeds 500 parts by weight, the dispersibility in the master batch itself, and particularly the dispersibility of the inorganic fine particles when diluted to a predetermined blending amount by the master batch dilution resin composition may be deteriorated. A more preferred lower limit is 5 parts by weight and an upper limit is 300 parts by weight.

  A mixture containing each predetermined amount of the organic polymer material and inorganic fine particles and the predetermined amount of one or more additives and an organic compound having a boiling point of 50 ° C. to 200 ° C. The organic compound is inert to the polar part of the organic agent used to obtain the organic polymer material and the inorganic fine particles and is liquid at room temperature. The boiling point is not particularly limited as long as it has a boiling point of 50 ° C to 200 ° C.

  Examples of organic compounds include aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, halogenated hydrocarbon solvents, ether solvents, ketone solvents, ester solvents, nitrile solvents. Solvents, alcohol solvents, nitrobenzene, sulfolane and the like can be mentioned. These can be used individually by 1 type or in combination of 2 or more types.

  Among these, the use of an aromatic hydrocarbon solvent or an ether solvent is preferable in that the dispersibility of the inorganic layered compound (A) can be further improved, and the aromatic layered compound (A) swells. A group hydrocarbon solvent or an ether solvent is particularly preferable.

  The swelling mentioned here refers to a phenomenon in which the inorganic layered compound (A) absorbs an organic solvent and increases its volume, and a combination of an inorganic layered compound and an organic compound having a degree of swelling of 1 cc / g or more is preferable. . The degree of swelling can be measured, for example, by the sedimentation volume method (clay handbook, page 513). Further, when the swelling properties of the inorganic layered compound (A) and the organic compound are very good, the inorganic layered compound (A) swells infinitely in the organic compound, and does not settle and cannot be measured. However, this state is the most preferred combination that swells very well.

  The kneading apparatus is not particularly limited, and can be carried out using, for example, a screw extruder, a Banbury mixer, a mixing roll, etc., but a screw extruder is preferable and a twin-screw kneading extruder is particularly preferable because of easy operation. In the case of using a twin-screw kneading extruder, the organic compound in the organic-inorganic composite can be removed by heating the solution in the barrel of the extruder and setting the vent port under reduced pressure.

The kneading temperature and vent port pressure can be appropriately adjusted according to the boiling point of the organic compound used. More specifically, the kneading temperature can be in the range of 150 ° C to 300 ° C, preferably 200 ° C to 270 ° C. Moreover, the pressure of a vent port can be 1.3 * 10 < ² > -9.3 * 10 < ³ > Pa, Preferably it can be set as the range of 6.6 * 10 < ² > -2.7 * 10 < ³ > Pa.

  The kneading is performed under the condition that the specific energy of the kneading apparatus is 0.1 to 0.4 kW · hr / kg, preferably 0.15 to 0.35 kW · hr / kg. The specific energy of the kneading device means the energy given to the resin per unit weight (1 kg) from the kneading equipment for the kneading effect when the resin is melt-kneaded. When the numerical value is large, the kneading effect is high. It will be. For example, in the case of an extruder, it is approximately represented by the power consumption of a screw driving motor required to extrude 1 kg of resin.

  For example, in the case of a roll-type kneader such as a Banbury mixer, it is approximately represented by the power consumption of a roll driving motor necessary for processing 1 kg of resin. Specifically, an ammeter, a voltmeter, etc. are attached to the motor of the extruder, and the power consumption of the motor is obtained from this, and this is multiplied by the power factor of the motor (usually about 0.85) and added to 1 kg of resin. A kneading force (W · hr / kg) is obtained.

  It is preferable that the content of the organic compound remaining in the composition after the kneading is removed to 5000 ppm or less, preferably 3000 ppm or less, more preferably 1000 ppm or less. If the content of the remaining organic compound is too large, molding defects such as silver streaks, voids, and foaming and coloring occur in the molded body, which is not preferable. The content of the organic compound can be determined by dispersing the kneaded composition in a solvent and subjecting the composition to an internal standard method using gas chromatography.

  Using a kneading apparatus, a mixture containing each predetermined amount of organic polymer material and inorganic fine particles, each predetermined amount of one or more additives blended as necessary, and an organic compound having a boiling point of 50 to 200 ° C. Specific examples of the kneading procedure include the following two procedures.

(Procedure 1) (1-A) Each predetermined amount of organic polymer material and inorganic fine particles, and each predetermined amount of one or more additives blended as necessary, and an organic compound having a boiling point of 50 ° C. to 200 ° C. And (1-B) a step of kneading the mixture (la) with a kneading apparatus.
(Procedure 2) (2-A) a step of previously mixing an organic compound and an inorganic layered compound (A) to obtain a mixture (2a); and (2-B) the mixture (2a), an organic polymer material and necessary A step of mixing one or two or more additives blended according to the conditions and kneading with a kneading apparatus.

  The mixing method of each component in step (1-A) of the above procedure 1 is a method of mixing each component using a stirring tank: a method of mixing each component using a blender: using a high speed mixer such as a Henschel mixer. The method of mixing each component: etc. are mentioned. In that case, you may add an ultrasonic wave or heat it to the temperature below the boiling point of a solvent.

  The kneading in the step (1-B) can be performed by the kneading method as described above. Thereby, kneading | mixing can be achieved, removing an organic compound.

  The mixing of each component in the step (2-A) can be performed by the same method as in the step (1-A). Thus, after mixing an organic compound and an inorganic layered compound (a) beforehand, an inorganic layered compound (A) can be swollen and can use for the following process.

  The kneading in the step (2-B) is performed using a feeder so that the mixture (2a), the organic polymer material, and one or two or more additives blended as necessary have a desired blending ratio. It can be introduced into a kneading apparatus and carried out by the kneading method as described above. Thereby, kneading | mixing can be achieved, removing an organic compound. Various additives described later can be added at the time of this kneading as required.

  The step of obtaining the plate-like body can be performed by molding the resin composition obtained as described above by a known molding method. Examples of the molding method include an injection molding method, a melt extrusion molding method, a press molding method, a blow molding method, and a cast molding method. From the viewpoint of productivity of the plate-like body, a melt extrusion molding method is preferable.

  Either the stretching treatment or the energy beam treatment can be performed first. That is, the plate-like body can be stretched and then subjected to energy beam treatment, while the plate-like body can be subjected to energy beam treatment and then stretched.

  As a specific method of the stretching treatment, a uniaxial stretching method such as a method of uniaxial stretching in the longitudinal direction using a difference in peripheral speed on the roll side, a method of uniaxial stretching in the transverse direction using a tenter stretching machine; At the same time as stretching in the vertical direction with a gap between the clips, simultaneously stretching in the longitudinal direction using the simultaneous biaxial stretching method that stretches in the lateral direction according to the spread angle of the guide rail and the difference in peripheral speed between the rolls, A biaxial stretching method such as a sequential biaxial stretching method in which both end portions are clipped and stretched in the transverse direction using a tenter stretching machine; And a method of continuously and obliquely stretching in the direction of an arbitrary angle θ with respect to the width direction of the film using a tenter stretching machine that can be added. A biaxial stretching method is preferred as the stretching method from the viewpoint of isotropic film properties.

  When the glass transition temperature of the organic polymer material is Tg, the stretching temperature is preferably between (Tg-30 ° C) and (Tg + 60 ° C), more preferably (Tg-10 ° C) to (Tg + 50 ° C). Temperature range. Moreover, a draw ratio is 1.01-30 times normally, Preferably it is 1.01-10 times, More preferably, it is 1.01-5 times. It is preferable to perform stretching by 1.01 times or more because the linear expansion coefficient can be kept low. Moreover, when performing biaxial stretching, that is, stretching in two orthogonal directions in the plane, the difference in the stretching ratio is 0 to 5%, preferably 0 to 2%. It is preferable in obtaining.

  The energy beam treatment can be performed by irradiating the energy beam to the plate before stretching or after stretching. Examples of energy rays include ultraviolet rays, electron beams, and microwaves. Among these, electron beam irradiation is preferable from the viewpoint of minimizing deformation of the film. The irradiation intensity is preferably 30 to 500 kGy, more preferably 50 to 400 kGy. The irradiation temperature is not particularly limited as long as it is between room temperature and the deformation temperature of the support, preferably 30 to 200 ° C, more preferably 50 to 150 ° C.

The laminated film and the transparent conductive film of the present invention include the layer of the film of the present invention and an inorganic thin film layer or a transparent conductive layer provided thereon. Examples of the material constituting the inorganic thin film layer or transparent conductive layer include metals such as Au, Ag, Pd, Pt, Al, and Cr, ITO, IZO, ATO, In ₂ O ₃ , SnO ₂ , and Cd ₂ SnO ₄ . Examples thereof include metal oxides and multilayer films such as TiO ₂ / Ag / TiO ₂ . Although the thickness of an inorganic thin film layer and a transparent conductive layer is not specifically limited, The range of 5 nm-1 micrometer is preferable.

  The method for providing the inorganic thin film layer or the transparent conductive layer on the film layer is not particularly limited, and for example, a metal oxide film can be formed by a vapor deposition method, a sputtering method, a sol-gel method, a spray method, or the like.

  The flat panel display element substrate of the present invention and the liquid crystal display substrate of the present invention include the film of the present invention. These substrates of the present invention may contain the above-mentioned inorganic thin film layer, transparent conductive layer and the like in addition to the film of the present invention.

  The substrate of the present invention can be a substrate for a display of any type, and particularly preferably a substrate for a liquid crystal display of a TFT (thin layer transistor) type. Specifically, for example, a TFT array is directly formed on the film of the present invention as a substrate, or a TFT array formed on another substrate such as a glass substrate is transferred to manufacture a liquid crystal display device. can do. In particular, since the film of the present invention has little elongation at high temperature, it is suitable for directly forming a TFT array on the film, and a liquid crystal display having excellent performance can be easily produced.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to the following Example. In the following examples, the quantitative ratio indicates a mass ratio unless otherwise specified.

  Various physical properties in the examples were measured as follows.

(1) Modification amount of resin and introduction amount of unsaturated groups and epoxy groups, etc.
^It measured by the method of WO99 / 1519 using < ¹ > H-NMR.
(2) Molecular Weight of Resin Using gel permeation chromatography, the converted molecular weight of standard polystyrene was taken as the molecular weight of the resin.
(3) Gel fraction 2 g of the produced film was introduced into xylene heated to 110 ° C. After 8 hours, the test sample was taken out, the residual xylene was distilled off and dried, and the gel fraction was calculated according to the following formula.
Gel fraction (%) = 100 × (sample mass after thermal xylene treatment / sample mass before thermal xylene treatment)
(4) Elongation The film was cut out so that the produced film had a length of 15 mm and a cross-sectional area of 0.5 mm ² and measured using a thermomechanical analyzer (trade name: TMA / SDTA840) manufactured by METTLER TOLEDO. In this invention, after measuring in the temperature range from 30 degreeC to 300 degreeC by load 0.1N and temperature increase rate 10 degree-C / min under nitrogen stream, the amount of change of 50-300 degreeC was made into the elongation of a film. .
(5) Inorganic laminate durability test An inorganic laminate (1-5) obtained by laminating an ITO layer on the produced film was subjected to 90 RH% at −30 ° C., 30 minutes → 25 ° C., 5 minutes → 80 ° C., 30 minutes. -> 25 degreeC, 5 minutes was made into 1 cycle, the surface resistance after performing this cycle 200 cycles was measured, and the change of the resistance value before and behind a test was measured.

(Production Example 1) Production of unsaturated group-containing alicyclic structure polymer Under nitrogen atmosphere, dehydrated cyclohexane 500 parts, 1-hexene 0.82 parts, dibutyl ether 0.15 parts and triisobutylaluminum 0.30 parts Were mixed in a reactor at room temperature, and then maintained at 45 ° C. while maintaining 9-ethylidene-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene (hereinafter abbreviated as “ETCD”) and 100 parts of tungsten hexachloride 0.7 mass% toluene solution were continuously added over 2 hours for polymerization. To the polymerization solution, 1.06 part of butyl glycidyl ether and 0.52 part of isopropyl alcohol were added to inactivate the polymerization catalyst, and the polymerization reaction was stopped to obtain a reaction solution containing a ring-opening polymer. Further, 270 parts of cyclohexane was added to 100 parts of the reaction solution containing the obtained ring-opening polymer, and 5 parts of a nickel-alumina catalyst (manufactured by JGC Chemical Co., Ltd.) was added as a hydrogenation catalyst, and the pressure was increased to 5 MPa with hydrogen. Then, the mixture was heated to 200 ° C. with stirring and reacted for 4 hours to obtain a reaction solution containing 20% by mass of ETCD ring-opening copolymer hydride. After removing the hydrogenation catalyst by filtration, the hydride is melted while removing the solvent cyclohexane and other volatile components at a temperature of 270 ° C. and a pressure of 1 kPa or less using a cylindrical concentrating dryer (manufactured by Hitachi, Ltd.). In the state, it was extruded into a strand form from an extruder, pelletized after cooling, and ETCD ring-opening copolymer hydride pellets were recovered. The obtained ETCD ring-opening copolymer hydride had a mass average molecular weight of 35,000 and a hydrogenation rate of 99.9%.

Subsequently, 13.0 parts of maleic anhydride, 2 parts of dicumyl peroxide and 250 parts of tert-butylbenzene were mixed with 100 parts of the ETCD ring-opened polymer hydride obtained above, and 135 ° C. in an autoclave. After the reaction for 6 hours, the resin was precipitated by adding it to a large amount of acetone, and the resin was recovered by filtration. The recovered resin was dried at 100 ° C. and 1 Torr or less for 48 hours to obtain 121 parts of a maleic anhydride-modified alicyclic structure polymer. The obtained maleic anhydride-modified alicyclic structure polymer had a mass average molecular weight of 39,000. Moreover, when measured by ¹ H-NMR, the amount of maleic anhydride modification (ratio of the number of polymerized units modified with maleic anhydride to the total number of polymerized units in the polymer) was 19.5 mol%.

Next, 5.5 parts of allylamine, 200 parts of toluene and 200 parts of tetrahydrofuran were mixed with 100 parts of the maleic anhydride-modified alicyclic structure polymer obtained above, and the peak derived from acid anhydride disappeared by IR. The reaction was carried out at room temperature until Thereafter, the resin was precipitated by adding it to a large amount of acetone, and the resin was recovered by filtration. The recovered resin was dried at 100 ° C. and 1 Torr or less for 48 hours to obtain 99 parts of an unsaturated group-containing alicyclic structure polymer. The unsaturated group-containing alicyclic structure polymer thus obtained had a mass average molecular weight of 39,000. Moreover, when measured by ¹ H-NMR, the amount of unsaturated groups introduced (ratio of the number of polymerized units introduced with unsaturated groups to the total number of polymerized units in the polymer) was 19.5 mol%.

(Production Example 2) Production of unsaturated group-containing acrylic resin In a four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, 200.0 parts of xylene was charged as an initial charge solvent, and heated with stirring to 100 ° C. Kept. On the other hand, 65.5 parts of glycidyl acrylate, 373.0 parts of isoboryl acrylate, 61.5 parts of lauryl acrylate, 10.0 parts of azobisisobutyronitrile and 200.0 parts of acetic acid normal butyl ester were mixed and dissolved. did. Subsequently, the dropping component was dropped at a constant rate into the four-necked flask kept at 100 ° C. with a dropping funnel over 2 hours. After completion of the dropping, the temperature of 100 ° C. is maintained for 1 hour, an additional catalyst component in which 1.0 part of azobisisobutyronitrile is dissolved in 15.0 parts of acetic acid normal butyl ester is added, and the temperature of 100 ° C. is further increased. Left for 2 hours. The obtained resin solution is melted with a cylindrical concentrating dryer (manufactured by Hitachi, Ltd.) at a temperature of 200 ° C. and a pressure of 1 kPa or less while removing xylene, normal butyl acetate and other volatile components as solvents. In the state, it was extruded into a strand form from an extruder, cooled and pelletized to recover acrylic resin pellets. The obtained acrylic resin had a weight average molecular weight of 25,000. The measured by ¹ H-NMR, epoxy weight (to the total number of polymerization units of the polymer, the ratio of the number of polymerized units having an epoxy group) was 19.8mol%.

Next, 5.5 parts of allylamine, 200 parts of xylene and 200 parts of tetrahydrofuran were mixed with 100 parts of the obtained acrylic resin, and reacted at room temperature until the peak derived from the epoxy group disappeared by IR. Thereafter, the resin was precipitated by adding it into a large amount of acetone / methanol mixed solution, and the resin was recovered by filtration. The collected resin was dried at 80 ° C. and 1 Torr or less for 48 hours to obtain 100 parts of an unsaturated group-containing acrylic resin. The obtained unsaturated group-containing acrylic resin had a mass average molecular weight of 25,000. Moreover, when measured by ¹ H-NMR, the amount of unsaturated groups introduced was 19.8 mol%.

Example 1
A mixture obtained by adding 15 parts of an organically treated saponite (manufactured by Coop Chemical, product name “Lucentite SAN”) and 185 parts of the unsaturated group-containing alicyclic structure polymer obtained in Production Example 1 Made of TEM-35B, screw diameter 37 mm, L / D = 32, screw rotation speed 150 rpm, resin temperature 240 ° C., field rate 10 kg / hour), the resin composition is extruded into strands, cooled with water and cut with a pelletizer And pelletized.

  Next, using a T-die type film melt extruder having a resin melt kneader equipped with a 10 μm polymer filter and a 65 mmφ screw, the above was obtained under molding conditions of a melt resin temperature of 240 ° C. and a T die width of 350 mm. A film was obtained by extruding the pellets to a thickness of 100 μm. The obtained film was stretched 1.3 times both vertically and horizontally by biaxial stretching at a stretching speed of 100 mm / second and a stretching temperature of 150 ° C. Subsequently, the crosslinked film 1 was obtained by irradiating the stretched film with an electron beam with an acceleration voltage of 3 MeV at 200 kGy. When the gel fraction and elongation of the obtained crosslinked film 1 were measured, the gel fraction was 99% and the elongation was 1.3%.

  Next, an oxide composed of 90% by mass of indium oxide and 10% by mass of stannic oxide is used as a target, and the sputtering apparatus is used in an atmosphere of a mixed gas of argon and oxygen (volume ratio of argon and oxygen; 99: 1). Then, an inorganic laminate 1 was obtained by forming a transparent conductive thin film made of ITO having a thickness of 100 nm on the surface of the previously obtained crosslinked film 1. The appearance of the obtained inorganic laminate 1 and the change in surface resistance in a moist heat resistance test were measured. As a result, the inorganic laminate 1 did not show any planar defects, and the amount of change in surface resistance before and after the wet heat resistance test was 2Ω / □, indicating excellent durability.

A Cr film having a thickness of 200 nm was formed on the crosslinked film 1 by a sputtering method, and a gate wiring was processed by a photolithography process. Next, the obtained film was placed in a plasma CVD apparatus, a SiN film (source gas: SiH ₄ , NH ₃ , H ₂ mixed gas) as a gate insulating layer was 350 nm, and an a-Si film as a semiconductor layer ( raw material gas were formed SiH _4, and H ₂ gas mixture) 200 nm, further n + a-Si film is a contact layer (SiH _4, H ₂ mixed gas to a gas obtained by adding PH ₃₎ to a thickness of 30 nm. Next, a-Si and n + a-Si were processed into islands by a photolithography process to form a TFT portion. Next, a Cr film having a thickness of 200 nm was formed by sputtering and processed into a drain wiring and a source electrode by a photolithography process. Thereafter, the n + a-Si film was removed by dry etching. A protective insulating layer was formed thereon by plasma CVD. A photosensitive organic resin (manufactured by JSR, product name “Optomer PC”) was formed thereon by a coating method. Next, through holes are formed by exposure and development using a mask having a grid pattern, and contacts of the source electrode, drain wiring terminal portion, and gate wiring terminal portion are formed on the gate insulating layer and the protective insulating layer SiN by dry etching. A hole was formed. Further, an ITO film was formed to a thickness of 140 nm by a sputtering method, and the ITO film was processed by a photolithography process to form pixel electrode and wiring terminal portion coatings, thereby producing an active matrix substrate. An orientation film was formed by printing on the produced active matrix substrate, and then orientation treatment was performed by rotating rubbing using a rayon cloth. Next, an ultraviolet curable sealing resin mixed with 1.0% by mass of glass fiber was prepared, and an active matrix substrate was produced by printing the ultraviolet curable sealing resin around the substrate. On the other hand, after forming a color filter layer and a black matrix on another crosslinked film 1, an overcoat layer was formed. Thereafter, an ITO film as a counter electrode was formed to a thickness of 140 nm by a sputtering method. After the orientation film is printed on the produced counter electrode substrate, orientation treatment is performed by rotational rubbing using a rayon cloth, and resin beads having a predetermined diameter are dispersed at a rate of 200 pieces / mm ^2. Was made. Then, both substrates were bonded and the sealing resin was cured by ultraviolet irradiation. Thereafter, a mixed liquid crystal in which a predetermined amount of chiral agent was mixed with an ester nematic liquid crystal having n = 0.14 was vacuum-injected and sealed with an ultraviolet curable resin. And after hardening by ultraviolet irradiation, it heat-processed and the liquid crystal cell was formed. Next, a light diffusing sheet, a polarizing plate, a prepared liquid crystal cell, and a polarizing plate are sequentially arranged on the exit surface side of the light guide plate in which the cold cathode tube is disposed on the incident end surface side and the light reflecting sheet is provided on the back surface side. A transmissive liquid crystal display device was produced. When this liquid crystal display device was observed from the light exit surface side in the white / black display mode, good display was achieved over the entire display surface.

(Example 2)
Uniform mixture of 50 parts of silica fine particle toluene slurry (solid content concentration: 20% by mass) having a particle size of 20 nm, 190 parts of unsaturated group-containing alicyclic structure polymer obtained in Production Example 1 and 1000 parts of toluene The composition solution was obtained by stirring until it became. Further, the composition solution was extruded into a strand shape in a molten state while removing the solvent at a temperature of 270 ° C. and a pressure of 1 kPa or less using a cylindrical concentration dryer (manufactured by Hitachi, Ltd.), and water-cooled. And then pelletized by cutting with a pelletizer. Next, using a T-die type film melt extruder having a resin melt kneader equipped with a 10 μm polymer filter and a 65 mmφ screw, the above was obtained under molding conditions of a melt resin temperature of 240 ° C. and a T die width of 350 mm. A film was obtained by extruding the pellets to a thickness of 100 μm. The obtained film was irradiated with an electron beam with an acceleration voltage of 3 MeV at 300 kGy, and further subjected to a 1.3-fold stretching treatment by a uniaxial stretching at a stretching speed of 100 mm / second and a stretching temperature of 150 ° C. Got. When the gel fraction and elongation of the obtained crosslinked film 2 were measured, the gel fraction was 99% and the elongation was 2.8%.

  Next, an inorganic laminate 2 was produced in the same manner as in Example 1 except that the crosslinked film 2 was used instead of the crosslinked film 1. The appearance of the obtained inorganic laminate 2 and the change in surface resistance in the wet heat resistance test were measured. As a result, the inorganic laminate 2 did not show any planar defects, and the amount of change in surface resistance before and after the wet heat resistance test was 3Ω / □, indicating excellent durability.

  Subsequently, an active matrix substrate was produced in the same manner as in Example 1 except that the crosslinked film 2 was used instead of the crosslinked film 1, and a liquid crystal cell and a transmissive liquid crystal display device were produced. When this liquid crystal display device was observed from the light exit surface side in the white / black display mode, good display was achieved over the entire display surface.

(Example 3)
A crosslinked film 3 was obtained in the same manner as in Example 1 except that the unsaturated group-containing alicyclic structure polymer in Example 1 was changed to the unsaturated group-containing acrylic resin obtained in Production Example 2. When the gel fraction and elongation of the obtained crosslinked film 3 were measured, the gel fraction was 99% and the elongation was 3.7%.

  Next, an inorganic laminate 3 was produced in the same manner as in Example 1 except that the crosslinked film 3 was used instead of the crosslinked film 1. The appearance of the obtained inorganic laminate 3 and the change in surface resistance in the wet heat resistance test were measured. As a result, the inorganic laminate 3 did not show any planar defects, and the amount of change in surface resistance before and after the wet heat test was 6Ω / □, indicating excellent durability.

  Subsequently, an active matrix substrate was produced in the same manner as in Example 1 except that the crosslinked film 3 was used instead of the crosslinked film 1, and a liquid crystal cell and a transmissive liquid crystal display device were produced. When this liquid crystal display device was observed from the light exit surface side in the white / black display mode, good display was achieved over the entire display surface.

(Comparative Example 1)
In place of the unsaturated group-containing alicyclic structure polymer obtained in Production Example 1, the ETCD ring-opening copolymer hydride produced as an intermediate product in Production Example 1 was used. An uncrosslinked film 4 was produced. When the gel fraction and elongation of the obtained uncrosslinked film 4 were measured, the gel fraction was 0%, and when the elongation was measured, the film was broken.

  Next, a comparative example inorganic laminate 4 was produced in the same manner as in Example 1 except that the uncrosslinked film 4 was used instead of the crosslinked film 1. The appearance of the comparative inorganic laminate 4 thus obtained was measured for changes in surface resistance in a moist heat resistance test. As a result, it was confirmed that the comparative inorganic laminate 4 had surface defects such as swelling on the front surface of the film, and the surface resistance change amount was 26 Ω / □ before and after the wet heat resistance test and was inferior in durability.

(Comparative Example 2)
In place of the mixture of the unsaturated group-containing alicyclic structure polymer obtained in Production Example 1 and the organically-treated saponite, only the unsaturated group-containing alicyclic structure polymer produced in Production Example 1 was used. By operating in the same manner as in Example 1, Comparative Example Crosslinked Film 5 was obtained. When the gel fraction and elongation of the obtained Comparative Example crosslinked film 5 were measured, the gel fraction was 99% and the elongation was 10.6%.

  Next, a comparative example inorganic laminate 5 was produced in the same manner as in Example 1 except that the comparative example crosslinked film 5 was used instead of the crosslinked film 1. The appearance of the comparative inorganic laminate 5 thus obtained was measured for changes in surface resistance in a moist heat resistance test. As a result, Comparative Example inorganic laminate 5 did not show any planar defects, and the surface resistance change before and after the wet heat resistance test was 3Ω / □, indicating excellent durability.

  Subsequently, an active matrix substrate was produced in the same manner as in Example 1 except that the comparative example crosslinked film 5 was used instead of the crosslinked film 1 to produce a liquid crystal cell and a transmissive liquid crystal display device. When this liquid crystal display device was observed in the white / black display mode from the light exit surface side, a display defect was observed on a part of the entire display surface.

Claims (13)

A film comprising an organic polymer material and an organic / inorganic composite containing inorganic fine particles dispersed in the organic polymer material,
The gel fraction is 80% or more,
A film having a load of 0.2 N / mm ² and an elongation at a measurement temperature of 50 to 300 ° C. of 5% or less. A resin composition containing an organic polymer material and inorganic fine particles is molded into a plate shape to obtain a plate body;
The film according to claim 1, obtained by subjecting the plate-like body to a stretching treatment and an energy ray treatment.   The film according to claim 2, wherein the stretching treatment and the energy ray treatment include a step of subjecting the plate-like body to a stretching treatment and then an energy ray treatment.   The film according to claim 2, wherein the stretching treatment and energy beam treatment include a step of subjecting the plate-like body to energy beam treatment and then stretching treatment. Forming a plate-like body by molding a resin composition containing an organic polymer material and inorganic fine particles into a plate shape;
The manufacturing method of the film of Claim 1 including the process which uses the said plate-shaped object for an extending | stretching process and an energy-beam process.   The manufacturing method according to claim 5, wherein the step of subjecting to the stretching treatment and the energy ray treatment includes a step of subjecting the plate-like body to a stretching treatment and then an energy ray treatment.   The manufacturing method according to claim 5, wherein the step of subjecting to the stretching treatment and the energy ray treatment includes a step of subjecting the plate-like body to an energy ray treatment and then a stretching treatment.   The manufacturing method according to any one of claims 5 to 7, wherein the step of obtaining the plate-like body includes a step of melt-extruding the resin composition.   The manufacturing method according to claim 5, wherein the energy beam is an electron beam.   The laminated film containing the layer of the film of any one of Claims 1-4, and the inorganic thin film layer provided on it.   The transparent conductive film containing the layer of the film of any one of Claims 1-4, and the transparent conductive layer provided on it.   The flat panel display element board | substrate containing the film of any one of Claims 1-4.   The liquid crystal display substrate containing the film of any one of Claims 1-4.