JP4737451B2 - Crosslinked resin film and use thereof - Google Patents

Description

The present invention comprises a cyclic olefin addition copolymer composition containing a cyclic olefin addition copolymer having an alkoxysilyl group, and further containing an organosilane compound and a metal oxide as necessary. The film thus obtained is related to a resin film crosslinked with a siloxane bond.
Furthermore, the present invention is for liquid crystal display devices and EL display devices using the above-mentioned crosslinked resin film, which are excellent in optical transparency, heat resistance, water absorption resistance, liquid crystal resistance, dimensional stability, adhesion and adhesion, and the like. The present invention relates to a substrate film, a polarizing film, a surface protective film, a retardation film, a transparent conductive film, and a light diffusion film.

  Liquid crystal and EL display devices have features such as high image quality, thinness, light weight, and low power consumption. Many products such as calculators, watches, mobile phones, personal computers, TVs, projectors, ATMs, navigation displays, and other in-vehicle display devices. It is used for. Liquid crystal and EL display devices are composed of various parts and materials. In the liquid crystal display device, liquid crystal, liquid crystal alignment film, liquid crystal substrate, transparent electrode, color filter, polarizing film, light guide plate, transparent conductive film, retardation film, surface protective film, light diffusion film, prism sheet, spacer, sealant Etc. These are assembled, and further, module parts such as a driving IC, a printed circuit board, and a backlight are attached to form a liquid crystal display device. Moreover, in EL display devices, EL (electroluminescence), a polarizing film, a retardation film, a transparent electrode, etc. are mentioned, These are assembled and it becomes an EL display device.

  Conventionally, a glass substrate has been mainly used as a liquid crystal substrate. The glass substrate has problems such as difficulty in thinning because the mechanical strength of glass is weak, lack of flexibility due to lack of flexibility, and difficulty in productivity because it is easily broken. 2. Description of the Related Art In recent years, liquid crystal display devices used for highly portable devices such as portable information terminals such as mobile phones, notebook personal computers, sub-notebook personal computers, and liquid crystal substrates used therefor are lightweight, thin, It is required not to break. In view of this, in a liquid crystal display device for applications in which light weight, thinness, and non-breaking are important, a liquid crystal substrate film made of a transparent resin is used instead of a glass substrate. In a glass substrate, the applied alignment film is baked at a high temperature of 200 ° C. or higher. Conventionally, the heat resistance of a liquid crystal substrate film made of a transparent resin PES (polyethersulfone) often used for this purpose is 160 to There is a demand for a transparent resin film having a limit of 170 ° C. and higher heat resistance.

  The polarizing film has a function of separating incident light into two polarization components orthogonal to each other, allowing only one of them to pass, and absorbing or dispersing the other components. As this polarizing film, a film in which a film of polyvinyl alcohol or the like is molecularly arranged in a certain direction and a dichroic substance such as polyiodine or a dye is adsorbed thereon is used. However, these polarizing films have weak mechanical strength in the direction of the transmission axis and have problems such as shrinkage due to heat and moisture. Usually, a surface protective film is provided as a protective layer on both surfaces of the polarizing film.

  The surface protective film is required to have performances such as low birefringence, heat resistance, low hygroscopicity, mechanical strength, surface smoothness, high resolution, and adhesiveness with an adhesive. Conventionally, as a surface protective film, a TAC (triacetyl cellulose) film manufactured by a casting method having excellent low birefringence and surface smoothness has been used. The TAC film has a problem that it is inferior in durability under high temperature and high humidity, heat resistance, mechanical strength, low birefringence, and adhesiveness with an adhesive, and a material having higher heat resistance is required. .

The retardation film is used in a STN liquid crystal display device for the purpose of compensating for the wavelength-dependent coloring of the refractive index that is generated when the liquid crystal molecules are twisted. In order to obtain a clear color and a fine image, the retardation film is required to have uniform birefringence over the entire surface, and optical properties do not change even under severe conditions such as high temperature and high humidity. The retardation film is used in a liquid crystal display device in a form in which a polarizing film is laminated via an adhesive layer. As the retardation film, a film obtained by stretching and orienting a PC (polycarbonate) film is usually used. However, since the PC film has a large photoelastic coefficient of 9 × 10 ⁻¹² cm ² / dyn, it is birefringent. There is a problem that the birefringence becomes too large, the birefringence becomes non-uniform, and the birefringence changes due to a slight stress caused by the assembly or environmental change. In addition, since the PC film has a small surface hardness, there is a problem at the time of film production and device assembly, and a new material is demanded instead.

  The transparent conductive film has a configuration in which a transparent conductive film is laminated on a transparent film substrate. This transparent film substrate is required to be excellent in heat resistance, surface smoothness, optical properties, and moisture resistance, and PES (polyethersulfone) and PAR (polyarylate) are conventionally used, A film made of PES is inferior in transparency, and PAR is also susceptible to optical distortion, and a complicated technique is required to obtain a transparent and optically uniform film.

  A light diffusion film is laminated on a backlight for the purpose of light diffusion or brightness improvement in a liquid crystal display device, and generally forms a fine pattern on the surface of a transparent sheet or film by an embossing process or application of a photocurable resin. It will be. PC and PET (polyethylene terephthalate) are commonly used as the base material for the light diffusion film. However, the film made of PC has a low surface hardness, so the film is easily damaged. There is a problem that the transparency is lost due to the film being damaged in the assembly work. In addition, a film made of PET is inferior in transparency, and a liquid crystal display device using such a film has a problem that the image is difficult to see due to lack of brightness. Further, the heat resistance is not sufficient, and it is difficult to form a uniform fine pattern such as warping of the film during the formation of the fine pattern.

  The prism sheet is a film for collecting the light diffused through the light diffusion film at the viewing angle of the liquid crystal display device and improving the luminance of the liquid crystal display device, and is used for large color STN and color TFT. This is a PC film with a prism angle, and there is a demand for further improvement in the luminance of the liquid crystal display device by improving the optical non-uniformity and the light transmittance.

  Various films having a thickness of about 10 to 500 m, which are used in liquid crystal and EL display devices, are manufactured from transparent resins that satisfy the required properties. As the transparent resin, acrylic resin such as polymethyl methacrylate, PC (polycarbonate) resin, PET (polyethylene terephthalate) resin, PES (polyethersulfone) resin, PAR (polyarylate) resin are used, but PC resin The polyester resin has a large birefringence, the acrylic resin has insufficient heat resistance and moisture resistance, and the heat resistance of the PES film is limited to 160 to 170 ° C.

  As a substrate film for the antireflection film, a film made of a transparent resin such as PET, PC, or polymethyl methacrylate (PMMA) is widely used. The antireflection film formed on this film may be a single layer or a multilayer structure of two or more layers, and as the number of layers increases, antireflection in a wide wavelength region becomes possible, but many layers are formed. The transparency of the substrate decreases with time, and thus the transparency of the substrate is particularly required. In addition, these antireflection films are often used for display applications, but since it is difficult to obtain a good image such as a display image being distorted if the film has a large birefringence, the birefringence is low throughout the film. It is required to be a uniform film.

In addition, the following hydrides and addition polymers of ring-opening polymers have been proposed as optical component materials such as plastic substrate materials.
(1) Hydrogenated product of ring-opening polymer (1-1) Hydrogenated product of ring-opening copolymer of tetracyclododecene compound (Patent Document 1: JP-A-60-26024, Patent Document 2: Patent No. 2) No. 3050196)
(1-2) A hydride of a ring-opening copolymer of a norbornene-based or tetracyclododecene-containing compound containing an ester group (Patent Document 3: JP-A-1-132625, Patent Document 4: JP-A-1-132626) (Publication)
(2) Addition polymer (2-1) Copolymer of ethylene and norbornene compound or tetracyclododecene compound [Patent Document 5: Japanese Patent Application Laid-Open No. 61-292601, Non-Patent Document 1: Makromol. Chem. Macromol. Symp. Vol. 47, 83 (1991)]
(2-2) Norbornene addition polymer, addition type copolymer of norbornene and alkyl-substituted norbornene (Non-patent Document 2: MetCon97, June 4-5, 1997, B. Goodall et al., Patent Document 6: Japanese Patent Laid-Open No. Hei 4 -63807, Patent Document 7: JP-A-8-198919)
(2-3) Norbornene carboxylic acid addition polymer, addition type copolymer of norbornene and norbornene carboxylic acid ester, norbornene carboxylic acid addition polymer [Non-patent Document 3: Macromolecule, Vol. 29, 2755 (1996), Non-Patent Document 4: Macromol. Rapid. Commun. Vol. 19, 251 (1998), and Patent Document 8: International Patent Publication No. WO96 / 37526]

However, regarding the hydrides of the ring-opening copolymers (1-1) and (1-2) above, the ring-opening copolymer has a relative glass transition temperature relative to that of the addition polymer even if it is the same monomer. In particular, it is difficult to obtain a polymer having a low glass transition temperature. Further, the ring-opening copolymer is difficult to be completely hydrogenated, and the hydride contains a small amount of unsaturated bonds in the polymer. When forming into a film or sheet, it may be colored, which is not always sufficient in terms of heat resistance.
In addition, the copolymer of ethylene and norbornene compound or tetracyclododecene compound of (2-1) has a distribution in the ethylene chain, and crystallizes when the ethylene chain is as long as possible. In many cases, this is insufficient, and since it does not contain a polar group, it is insufficient in terms of adhesion and adhesion.

On the other hand, the addition polymer (2-2) has a high glass transition temperature and high heat resistance, but is insufficient in terms of solvent resistance. Further, since the addition polymer of norbornene carboxylic acid ester (2-3), the addition type copolymer of norbornene and norbornene carboxylic acid ester, and the addition polymer of norbornene carboxylic acid contain many polar groups, Although excellent in terms of adhesiveness and adhesion, it is insufficient in terms of moisture absorption resistance and lacks dimensional stability.
JP 60-26024 A Japanese Patent No. 3050196 Japanese Patent Laid-Open No. 1-132625 JP-A-1-132626 JP 61-292601 A Makromol. Chem. Macromol. Symp. Vol. 47, 83 (1991) MetCon97, June 4-5, 1997 B.I. L. Goodall et al. JP-A-4-63807 JP-A-8-198919 Macromolecule, Vol. 29, 2755 (1996) Macromol. Rapid. Commun. Vol. 19,251 (1998) International Patent Publication WO96 / 37526

  As a result of intensive studies, the present inventors have obtained a liquid crystal having excellent heat resistance, solvent resistance, dimensional stability and excellent transparency by using a cyclic olefin copolymer having a specific structure and using a crosslinked product thereof. The present invention has been completed by finding that a liquid crystal alignment film-formed substrate for forming a display element can be obtained.

  The present invention has been made to solve the above problems, and has been conventionally used as a film for a display device. Cyclic olefin copolymer (ring-opening polymerization) resin, PC (polycarbonate) resin, TAC (triacetyl cellulose) ) An object of the present invention is to provide a film for a liquid crystal and EL display device using a new resin instead of a resin such as a resin, a PES (polyether sulfone) resin, or a PET resin. The present invention also provides a substrate film, a polarizing film, a surface protective film, a retardation film, a transparent conductive film, and a light diffusion film for a liquid crystal display device characterized by using the film of the present invention. It is for the purpose.

  The present invention includes a cyclic olefin addition type copolymer containing a cyclic olefin addition type copolymer comprising a repeating unit (a) represented by the following formula (1) and a repeating unit (b) represented by the following formula (2). The present invention relates to a crosslinked resin film obtained by crosslinking a resin film obtained by molding a copolymer composition with a siloxane bond.

Wherein ^(1), A 1 ~A ⁴ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or
_{^{- (CR 1 R 2) f}} Si (OR 3) g R 4 (3-g),
_{^{- (CR 1 R 2) f}} Si (R 3 R 4) OSi (OR 3) g R 4 (3-g),
_{^{- (CR 1 R 2) f}} C (O) O (CH 2) h Si (OR 3) g R 4 (3-g)
And at least one of A ^{1 to} A ⁴ represents an alkoxysilyl group or an allyloxysilyl group. Here, R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ³ represents an alkyl group, alkenyl group, aryl group or cycloalkyl group having 1 to 10 carbon atoms. R ⁴ represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, f and h are integers of 0 to 5, and g is an integer of 1 to 3. Y represents —CH ₂ — or —O—, and m represents 0 or 1. ]

[In the formula (2), B ¹ , B ² , B ³ and B ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkenyl group, a cycloalkyl group, a halogen atom, a halogen atom. And a polar group represented by — (CH ₂ ) _j X. Here, X is —C (O) OR ⁵ , or —OC (O) R ⁶ , and R ⁵ and R ⁶ are each an alkyl group, alkenyl group, aryl group, cycloalkyl group having 1 to 20 carbon atoms, or These halogen substituents, j represents an integer of 0 to 5. Further, B ^{1 to} B ⁴ include an alkylidenyl group formed of B ¹ and B ² or B ³ and B ⁴ , a cyclohexane formed of B ¹ and B ⁴ , B ¹ and B ³ , or B ² and B ^4. An alkylene group and a cycloalkenylene group are also included. n represents an integer of 0 to 2. ]

The crosslinked resin film is selected from the group consisting of the following compound (A) [organosilane represented by the following formula (3), a hydrolyzate of the organosilane, or a condensate of the organosilane. At least one compound (hereinafter also referred to as “organosilanes”) and the following compound (B) [at least one metal oxide selected from the group consisting of silica, alumina, zirconia and titania]. It may be.
(R ⁷ ) _p Si (OR ⁸ ) _4-p
……… (3)
[In Formula (3), R ⁷ is the same or different when two are present, and represents an organic group having 1 to 10 carbon atoms; R ⁸ is the same or different and is an alkyl group or carbon having 1 to 5 carbon atoms; The acyl group of number 1-6 is shown, p is an integer of 0-2. ]

Furthermore, in the crosslinked resin film of the present invention, the compound such as the above-mentioned organosilanes and metal oxides and the cyclic olefin addition copolymer are grafted at the time of casting or before,
At least one metal compound selected from the group consisting of Al, Zr, Sn, Zn, Ca, Ba, Ti, Sc, Gd, Yb, Sm, Nd, Sb, Y, and Ce may be blended.

  The crosslinked resin film of the present invention is obtained by heating the cyclic olefin-based addition copolymer composition to a temperature of 50 ° C. or higher, or with hot water or steam after forming the film by a solution casting method. It is obtained by forming a siloxane bond and crosslinking.

Moreover, the crosslinked resin film of this invention can be preferably used as a film for liquid crystal display devices and a film for EL display devices.
Moreover, the crosslinked resin film of the present invention can be preferably used as a liquid crystal substrate film, a polarizing film, a surface protective film, a retardation film, a transparent conductive film, a light diffusion film, and an antireflection film of a liquid crystal display device.

  The film for a display device using a transparent crosslinked resin film comprising the composition containing the cyclic olefin addition type copolymer of the present invention has optical transparency, heat resistance, liquid crystal resistance, dimensional stability, and adhesiveness. In addition to being suitably used as a substitute for substrate glass in liquid crystal display devices and EL display devices, polarizing films, surface protective films, retardation films, transparent conductive films, light diffusion films, EL displays for these devices It can be used for an apparatus film, a transparent conductive composite material, an antireflection film, and the like.

The crosslinked resin film useful for the film for a display device of the present invention is a cyclic olefin type containing a cyclic olefin type addition copolymer containing the repeating unit (a) represented by the formula (1) and the repeating unit (b). A resin film obtained by molding an addition-type copolymer composition is a crosslinked resin film crosslinked with a siloxane bond.
The repeating unit (a) used in the cyclic olefin addition copolymer of the present invention is an addition of a cyclic olefin represented by the following formula (1) ′ (hereinafter sometimes referred to as “specific cyclic olefin (1)”). It can be formed by polymerization.

[In Formula (1) ′, A ^{1 to} A ⁴ , Y, and m are the same as those shown in Formula (1) above. ]

Specific examples of such “specific cyclic olefin (1)” include
5-trimethoxysilyl-2-norbornene,
5-trimethoxysilyl-7-oxa-2-norbornene,
5-dimethoxychlorosilyl-2-norbornene,
5-dimethoxychlorosilyl-7-oxa-2-norbornene,
5-methoxychloromethylsilyl-2-norbornene,
5-dimethoxychlorosilyl-2-norbornene,
5-methoxyhydridomethylsilyl-2-norbornene,
5-dimethoxyhydridosilyl-2-norbornene,
5-methoxydimethylsilyl-2-norbornene,
5-triethoxysilyl-2-norbornene,
5-triethoxysilyl-7-oxa-2-norbornene,
5-diethoxychlorosilyl-2-norbornene,
5-ethoxychloro-methylsilyl-2-norbornene,
5-diethoxyhydridosilyl-2-norbornene,
5-ethoxydimethylsilyl-2-norbornene,
5-ethoxydiethylsilyl-7-oxa-2-norbornene,
5-propoxydimethylsilyl-2-norbornene,
5-tripropoxysilyl-2-norbornene,
5-triphenoxysilyl-2-norbornene,
5-trimethoxysilylmethyl-2-norbornene,
5- (2-trimethoxysilyl) ethyl-2-norbornene,
5- (2-dimethoxychlorosilyl) ethyl-2-norbornene,
5- (1-trimethoxysilyl) ethyl-2-norbornene,
5- (2-trimethoxysilyl) propyl-2-norbornene,
5- (1-trimethoxysilyl) propyl-2-norbornene,
5-triethoxysilylethyl-7-oxa-2-norbornene,
5-dimethoxymethylsilylmethyl-2-norbornene,
5-trimethoxypropylsilyl-2-norbornene,
5-triethoxysiloxy-dimethylsilyl-2-norbornene,
8-triethoxysilyl-3-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecene,
8-methyldimethoxysilyl-3-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecene,
8-triethoxysiloxy-dimethylsilyl-3-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecene,
5-trimethoxysiloxy-dimethylsilyl-2-norbornene,
5-triethoxysiloxy-dimethylsilyl-2-norbornene,
5-methyldimethoxysiloxy-dimethylsilyl-2-norbornene,
Trimethoxysilylpropyl 5-norbornene-2-carboxylate,
Triethoxysilylpropyl 5-norbornene-2-carboxylate,
Dimethoxymethylsilylpropyl 5-norbornene-2-carboxylate,
Trimethoxysilylpropyl 2-methyl-5-norbornene-2-carboxylate,
Trimethylsilylpropyl 2-methyl-5-norbornene-2-carboxylate,
Dimethoxymethylsilylpropyl 5-methyl-5-norbornene-2-carboxylate,
Etc.

  The ratio of the repeating unit (a) in the cyclic olefin addition copolymer is 0.2 to 30 mol%, preferably 0.5 to 20 mol%, more preferably 1.0 to 10 mol%. When the proportion of the repeating unit (a) in the cyclic olefin addition copolymer is less than 0.2 mol%, it is difficult to form a crosslinked product. On the other hand, when the proportion exceeds 30 mol%, moisture absorption resistance and dimensions Stability is reduced.

  In addition, as another method for forming the repeating unit (a) represented by the formula (1), a cyclic olefin having a trichlorosilyl group or a dichloroalkylsilyl group (hereinafter referred to as “specific cyclic olefin (2)”). After addition copolymerization, the trichlorosilyl group or dichloroalkylsilyl group in the obtained copolymer is reacted with an alkali metal alkoxide compound or allyloxide compound, or reacted with an alcohol or phenol in the presence of an amine compound. Can be mentioned.

Specific examples of such “specific cyclic olefin (2)” include 5-trichlorosilyl-2-norbornene,
5-trichlorosilyl-7-oxa-2-norbornene,
5-dichloromethylsilyl-2-norbornene,
5-dichloroethylsilyl-2-norbornene,
Trichlorosilylpropyl 5-norbornene-2-carboxylate,
Trichlorosilylpropyl 2-methyl-5-norbornene-2-carboxylate,
Dichloromethylsilylpropyl 5-norbornene-2-carboxylate,
Etc.

  In the copolymer of the present invention, the repeating unit (b) represented by the formula (2) used together with the repeating unit (a) represented by the formula (1) is a cyclic olefin (hereinafter referred to as the following formula (2) ′). It is formed by addition copolymerization of “specific cyclic olefin (3)”.

[In Formula (2) ′, B ^{1 to} B ⁴ and n are the same as those in Formula (2). ]

Specific examples of such “specific cyclic olefin (3)” include
2-norbornene, 5-methyl-2-norbornene,
5-ethyl-2-norbornene, 5-propyl-2-norbornene,
5-butyl-2-norbornene, 5-pentyl-2-norbornene,
5-hexyl-2-norbornene, 5-heptyl-2-norbornene,
5-octyl-2-norbornene, 5-decyl-2-norbornene,
5-dodecyl-2-norbornene, 5-vinyl-2-norbornene,
5-allyl-2-norbornene, 5-butenyl-2-norbornene,
5-methylidene-2-norbornene, 5-ethylidene-2-norbornene,
5-isopropylidene-2-norbornene,
5,6-dimethyl-2-norbornene,
5-methyl, 5-ethyl-2-norbornene,
5,6-benzo-2-norbornadiene,
5-phenyl-2-norbornene, 2,5-norbornadiene,
2,5-norbornadiene,
5-methyl-2,5-norbornadiene,
5-cyclohexyl-2-norbornene,
5-fluoro-2-norbornene, 5-chloro-2-norbornene,
Methyl 5-norbornene-2-carboxylate,
Ethyl 5-norbornene-2-carboxylate,
Butyl 5-norbornene-2-carboxylate,
Methyl 2-methyl-5-norbornene-2-carboxylate,
Ethyl 2-methyl-5-norbornene-2-carboxylate,
Propyl 2-methyl-5-norbornene-2-carboxylate,
Butyl 2-methyl-5-norbornene-2-carboxylate,
Methyl 2-ethyl-5-norbornene-2-carboxylate,
Trifluoroethyl 2-methyl-5-norbornene-2-carboxylate,
2-methyl-5-norbornen-2-yl ethyl acetate,
5-norbornene-2-spiro-N-phenylsuccinimide,
5-norbornene-2-spiro-N-cyclohexylsuccinimide,
5-norbornene-2-spiro-N-methylsuccinimide,
5-norbornene-2,3-N-phenyldicarboximide,
5-norbornene-2,3-N-cyclohexyldicarboximide,
2-methyl-5-norbornene acrylate,
2-methyl-5-norbornene methacrylate,
Dimethyl 5-norbornene-2,3-dicarboxylate,
Diethyl 5-norbornene-2,3-dicarboxylate,
3-tricyclo [4.3.0.1 ^2,5 ] decene,
3,7-tricyclo [4.3.0.1 ^2,5 ] decadiene (dicyclopentadiene),
3-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecene,
8-methyl, 3-tetracyclo [4.4.0.1 ^2,5 1 ^7,10 ] dodecene,
8-ethylidene-3-tetracyclo [4.4.0.1 ^2,5 1 ^7,10 ] dodecene,
8-methyl-8-methoxycarbonyl-3-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecene,
8-methyl-8-ethoxycarbonyl-3-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecene,
And so on.

The compound represented by the formula (2) ′ forming the repeating unit (b) can be used alone or in combination of two or more.
The ratio of the repeating unit (b) in the cyclic olefin addition copolymer of the present invention is 70 to 99.8 mol%, preferably 80 to 99.5 mol%, more preferably 90 to 90% in all repeating units. 99 mol%. If the proportion of (b) is less than 70 mol%, the glass transition temperature may be lowered, whereas if it exceeds 99.8 mol%, crosslinking becomes difficult.

  In addition, the repeating unit (a) represented by Formula (1) can also be formed by modifying | denaturing using the specific thing in the cyclic olefin shown by said Formula (2) '. For example, it is obtained after addition copolymerization of at least one selected from the group of norbornadiene compounds, compounds having an alkenyl substituent and compounds having a vinylidenyl substituent (hereinafter referred to as “specific cyclic olefin (4)”). Further, there can be mentioned a method in which an alkoxysilane compound having an unsaturated double bond and a Si—H bond in a copolymer is subjected to a hydrosilylation reaction using a compound such as Pt, Rh, or Ru as a catalyst.

As a specific example of such “specific cyclic olefin (4)”,
2,5-norbornadiene, 7-oxa-2,5-norbornadiene,
5-methyl-2,5-norbornadiene, 5-vinyl-2-norbornene,
5-vinyl-7-oxa-2-norbornene, 5-allyl-2-norbornene,
5-butenyl-2-norbornene, 5-methylidene-2-norbornene,
5-ethylidene-2-norbornene,
5-ethylidene-7-oxa-2-norbornene,
5-isopropylidene-2-norbornene,
8-ethylidene-3-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecene,
Etc.

As a specific example of an alkoxysilane compound having a Si-H bond,
Trimethoxysilane, triethoxysilane,
Tripropoxysilane, dimethoxysilane,
Diethoxysilane, dimethoxychlorosilane,
Diethoxychlorosilane, dimethoxymethylsilane,
Diethoxymethylsilane, dimethoxyphenylsilane,
Diethoxyphenylsilane, monomethoxydimethylsilane,
Monoethoxydimethylsilane, monoethoxydiethylsilane,
Etc.

As the hydrosilylation _{catalyst, H 2 PtCl 6 · H 2} O, Pt / Al 2 O 3, RhCl (PPh 3) 2, Rh / Al 2 O 3, RuCl 3, IrCl 3, FeCl 3, AlCl 3 , PdCl ₂ .2H ₂ O, NiCl ₂ , TiCl _{4 and the} like.

As the polymerization catalyst used in the cyclic olefin addition copolymer of the present invention, multicomponent catalysts listed in the following 1), 2) and 3) are used.
1) Transition metal compound An organic carboxylate of nickel or cobalt, an organic phosphite, an organic phosphate, an organic sulfonate, a β-diketone compound, or an organic carboxylate of nickel or cobalt Super strong acid modified compounds such as hexafluoroantimonic acid, boron tetrafluoride, trifluoroacetic acid, hexafluoroacetone,
1,5-cyclooctadiene complex of nickel,
[(Η ³ -crotyl) Ni (cyclooctadiene)] [B ((CF ₃ ) ₂ C ₆ H ₄ ) ₄ ],
A cyclododecatriene complex of nickel,
A diene or triene coordinated complex, such as a norbornadiene complex of nickel,
Bis (triarylphosphine) dihalogen complexes of nickel or cobalt,
[(Η ³ -Crotyl) Ni (cyclooctadiene)] [B ((CF ₃ ) ₂ C ₆ H ₄ ) ₄ ]
Bis [N- (3-tert-butylsalicylidene) phenylaminato] Ni
Ni [PhC (O) CHPPh ₂ ] (Ph) (PPh ₃ )
Ni (OC (O) (C 6 H 4) PPh 2) (H) (PCy 3)
Ni [OC (O) (C 6 H 4) PPh 2] (H) (PPh 3)
Reaction product of Ni (COD) ₂ and PPh ₃ = CHC (O) Ph [(ArN = CHC ₆ H ₃ (O) (Anth)] (Ph) (PPh ₃ ) Ni
(Ar: 2,6- (Pr) 2C 6 H 3, Pr: isopropyl, Anth: 9-anthracene,
(Ph: phenyl, Cy: Cyclohexyl)
Complexes with bidentate or tridentate ligands such as

2) Organoaluminum compounds methylalumoxane, ethylalumoxane, butylalumoxane,
Methylalumoxane partially mixed with trialkylaluminum,
Trimethylaluminum, triethylaluminum,
Triisobutylaluminum, diisobutylaluminum hydride,
Diethylaluminum chloride, ethylaluminum sesquichloride,
Organoaluminum compounds such as ethylaluminum dichloride

3) Further, non-conjugated diene compounds such as 1,5-cyclooctadiene and 1,5,9-cyclododecatriene, which can be added to improve polymerization activity,
Boron trifluoride ethers, amines, phenols and other complexes,
Tri (pentafluorophenyl) borane,
Tri (3,5-di-trifluoromethylphenyl) borane,
Lewis acid compounds such as tri (pentafluorophenyl) aluminum.
Triphenylcarbenium tetrakis (pentafluorophenyl) borate,
Triphenylcarbenium tetrakis (3,5-di-trifluoromethyl-phenyl) borate,
Tributylammonium tetrakis (pentafluorophenyl) borate,
N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate,
N, N-diethylanilinium tetrakis (pentafluorophenyl) borate,
Ionic boron compounds such as.

  These catalyst components are used in amounts used within the following ranges. That is, the nickel or cobalt compound is 0.02 to 100 millimol atom per mole of monomer, the organoaluminum compound is 1 to 5,000 mole per mole atom of nickel or cobalt, non-conjugated diene, Lewis An acid compound and an ionic boron compound are 0.2-100 mol with respect to 1 mol atom of nickel or cobalt.

  As a solvent for the polymerization reaction of the cyclic olefin addition copolymer of the present invention, aliphatic hydrocarbons such as pentane, hexane, heptane, butene, 2-methylbutene, alicyclic such as cyclohexane, cyclopentane, methylcyclopentane, etc. Hydrocarbons, aromatic hydrocarbons such as toluene, benzene, xylene and mesitylene, halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chlorobenzene and o-dichlorobenzene, ethyl acetate, butyl acetate, γ-butyrolactone, nitromethane, etc. One or two or more polar solvents are selected and used.

Below, although the outline | summary of the method of obtaining the cyclic olefin type addition type copolymer of this invention is illustrated, it is not necessarily limited to this illustration.
That is, in a nitrogen or argon atmosphere, a monomer composed of a solvent and a cyclic olefin and a molecular weight regulator are charged in a reaction vessel, and the polymerization system is set to a temperature in the range of −20 ° C. to 100 ° C.
Next, the said catalyst component is added and it superposes | polymerizes in the range of -20 degreeC-100 degreeC. The solvent / monomer weight ratio is in the range of 1-20. The molecular weight is adjusted to the target molecular weight by the amount of the polymerization catalyst, the addition amount of a molecular weight regulator such as α-olefin, hydrogen, diphenyldihydrosilane, the conversion rate to the polymer and the polymerization temperature. The polymerization is stopped by a compound selected from water, alcohol, organic acid, carbon dioxide gas and the like. By adding a water / alcohol mixture of an acid selected from maleic acid, fumaric acid and oxalic acid to the polymer solution, the catalyst residue is separated and removed from the polymer solution. The polymer is obtained by putting the polymer solution in an alcohol selected from methanol, ethanol, isopropanol, and the like, coagulating and drying under reduced pressure. In this step, unreacted monomers remaining in the polymer solution are also removed.

The cyclic olefin addition copolymer of the present invention preferably has a number average molecular weight in terms of polystyrene measured by gel permeation chromatography using o-dichlorobenzene as a solvent, preferably 10,000 to 1,000,000, More preferably, it is 50,000-500,000. Moreover, the weight average molecular weight of polystyrene conversion becomes like this. Preferably it is 15,000-1500,000, More preferably, it is 70,000-700,000. If the number average molecular weight in terms of polystyrene is less than 10,000 and the weight average molecular weight is less than 15,000, the fracture strength may be insufficient. On the other hand, when the polystyrene-equivalent number average molecular weight exceeds 1,000,000 and the weight average molecular weight exceeds 1,500,000, the sheet or film is cast using a solution of a cyclic olefin addition copolymer. When producing a substrate, the solution viscosity becomes high, and it may be difficult to produce a sheet or film having good smoothness without waviness or warpage.
Moreover, the glass transition temperature (Tg) of the cyclic olefin addition type copolymer of the present invention obtained as described above is preferably 200 ° C. or higher, more preferably 250 ° C. to 400 ° C. If it is lower than 200 ° C., deformation may occur with respect to the heat load during crosslinking.

  The crosslinking reaction of the resin film containing the cyclic olefin addition copolymer of the present invention proceeds with an acid catalyst. As the acid catalyst, at least one compound selected from a compound that generates an acid by thermal decomposition or a compound that generates an acid by hydrolysis in the presence of hot water or steam is used. The temperature at which thermal decomposition or hydrolysis proceeds is 50 ° C. or higher, preferably 80 ° C. or higher, more preferably 100 ° C. or higher.

Examples of the compound (acid generator) that generates an acid by thermal decomposition include benzylsulfonium salt, benzylammonium salt, benzylphosphonium salt, and hydrazinium salt.
On the other hand, examples of the compound that generates an acid by hydrolysis include phosphite, hypophosphite, iminophosphonate, organic carboxylic acid ester, organic sulfonic acid ester, and organic sulfinic acid.
Of these, phosphites and hypophosphites are preferred from the viewpoint of storage stability.

There are three types of phosphites: monoesters, diesters, and triesters. In the range from room temperature to around 100 ° C, triesters are often neutral, and mono- and diesters are often very weakly acidic. The action as a crosslinking catalyst is weak.
On the other hand, it is known that mono- and diesters isomerize into stronger tautomers under conditions of heating to high temperatures. Further, the triester is hydrolyzed in the presence of hot water or water vapor, and changes to a mono- or diester to exhibit a function as an acid.
In the case of hypophosphorous acid ester, the same is true, and a diester showing neutrality is hydrolyzed and converted into a monoester showing acidity at high temperature and hypophosphorous acid.
By this reaction mechanism, it is considered that the crosslinking catalyst function of phosphite ester and hypophosphite ester is developed in the presence of hot water and water vapor.

  The phosphite ester or hypophosphite ester is obtained by reacting an organic compound having a hydroxy group with phosphorous acid or hypophosphorous acid. Examples of the organic compound having a hydroxy group to be reacted with phosphorous acid or hypophosphorous acid include alcohols in which one or more hydroxy groups are substituted on a saturated or unsaturated aliphatic hydrocarbon having 1 to 40 carbon atoms, carbon number 5 Alcohol substituted with one or more hydroxy groups on saturated or unsaturated alicyclic hydrocarbon of ˜40, and one or more hydroxy groups on alkyl group-substituted or unsubstituted aromatic hydrocarbon having 6 to 40 carbon atoms Examples include substituted phenols.

Specific examples of the phosphite ester formed by the reaction of these organic compounds having a hydroxy group and phosphorous acid include:
[Specific examples of phosphorous acid triesters]
Trimethyl phosphite, triethyl phosphite,
Tripropyl phosphite, tributyl phosphite,
Trihexyl phosphite, trioctyl phosphite,
Tridecyl phosphite, triphenyl phosphite,
Trinonylphenyl phosphite, tristearyl phosphite,
Diphenyl octyl phosphite, diphenyl decyl phosphite,
Phenyldidecyl phosphite,
(Tetraphenyl) dipropylene glycol diphosphite,
(Tetraphenyl) tetra (tridecyl) pentaerythritol tetraphosphite,
Tetra (tridecyl) -4,4′-isopropylidene diphenyl diphosphite,
Bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-diphosphite,
Bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite,
Bis (2,4-di-cumylphenyl) pentaerythritol diphosphite,
Bis (2,6-di-cumylphenyl) pentaerythritol diphosphite,
Distearyl pentaerythritol diphosphite,
2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite,
Tri (nonylphenyl) phosphite,
Tris (di-nonyl-phenyl) phosphite,
1,1,3-tris (2-methyl-4-ditridecylphosphite 5-t-butylphenyl) butane,
Bis (tridecyl) pentaerythritol diphosphite,
Bis (nonylphenyl) pentaerythritol diphosphite,
Distearyl pentaerythritol diphosphite,
Bis (2,6-di-t-butyl-4-methoxycarbonylethyl-phenyl) pentaerythritol diphosphite,
Bis (2,6-di-t-butyl-4-octadecyloxycarbonylethyl-phenyl) pentaerythritol diphosphite,

[Specific examples of phosphorous acid diester]
Dimethyl phosphite, diethyl phosphite, dipropyl phosphite,
Dibutyl phosphite, dihexyl phosphite, dioctyl phosphite,
Didecyl phosphite, dilauryl phosphite, dioleyl phosphite,
Diphenyl phosphite, phenyl octyl phosphite, phenyl decyl phosphite,

[Specific examples of phosphorous acid monoester]
Methyl phosphite, ethyl phosphite, propyl phosphite,
Butyl phosphite, hexyl phosphite, octyl phosphite,
Decyl phosphite, phenyl phosphite,
Etc.

On the other hand, as a specific example of hypophosphite,
[Specific examples of hypophosphorous acid diester]
Dimethyl-phenylphosphonite, diethyl-phenylphosphonite,
Dipropyl-phenylphosphonite, dibutyl-phenylphosphonite,
Dihexyl-phenylphosphonite, dioctyl-phenylphosphonite,
Didecyl-phenylphosphonite, methyl-diphenylphosphonite,
Ethyl-diphenylphosphonite, propyl-diphenylphosphonite,
Butyl-diphenylphosphonite, hexyl-diphenylphosphonite,
Octyl-diphenylphosphonite, decyl-diphenylphosphonite,
Bis [bis (2,4-di-t-butyl-5-methylphenoxy) phosphino] biphenyl,
Bis [bis (2,4-di-t-butylphenoxy) phosphino] biphenyl,

[Specific examples of hypophosphorous acid monoester]
Methyl-phenylphosphinate, ethyl-phenylphosphinate,
Propyl-phenylphosphinate, butyl-phenylphosphinate,
Hexyl-phenyl phosphinate, octyl-phenyl phosphinate, decyl-phenyl phosphinate,
Etc.

  Of the phosphites and hypophosphites, phosphites are preferred from the viewpoints of both catalytic activity and storage stability, and phosphites triesters are more preferred.

Moreover, the following example is mentioned as another compound which generate | occur | produces an acid by a hydrolysis.
[Specific examples of organic carboxylic acid esters]
Acetic acid-propyl ester, acetic acid-butyl ester, acetic acid-amyl ester,
Propionic acid-propyl ester, propionic acid-butyl ester, propionic acid-amyl ester, 2-ethylhexanoic acid-propyl ester, 2-ethylhexanoic acid-butyl ester, 2-ethylhexanoic acid-amyl ester,

[Specific examples of organic sulfonate esters]
p-toluenesulfonic acid-ethyl ester, p-toluenesulfonic acid-propyl ester,
p-toluenesulfonic acid-butyl ester, p-toluenesulfonic acid-amyl ester, decanesulfonic acid-ethyl ester, decanesulfonic acid-propyl ester, decanesulfonic acid-butyl ester, decanesulfonic acid-amyl ester

[Specific examples of organic sulfinic acid esters]
p-toluenesulfinic acid-ethyl ester, p-toluenesulfinic acid-propyl ester,
p-toluenesulfinic acid-butyl ester, p-toluenesulfinic acid-amyl ester, decanesulfinic acid-ethyl ester, decanesulfinic acid-propyl ester, decanesulfinic acid-butyl ester, decanesulfinic acid-amyl ester

[Specific examples of iminosulfonate]
2,3,4-Trihydronaphthyl-1-imino-N-phenylsulfonate

  These acid catalysts that hydrolyze and act as acids (crosslinking catalysts) are in the range of 0.001 to 10 parts by weight, preferably 0.01 to 5.0 parts by weight, per 100 parts by weight of the polymer. Preferably it is used in the range of 0.05 to 2.0 parts by weight. When the amount of the acid catalyst used is less than 0.001 part by weight, the effect as a crosslinking catalyst is insufficient. On the other hand, when the amount exceeds 10 parts by weight, the transparency of the resulting crosslinked resin film is reduced, and the volatile components are heated. Increase, etc. is not preferable.

Examples of the compound which is mixed and / or condensed with the cyclic olefin addition copolymer of the present invention to form the resin film include the following compounds (A) and (B) (these compounds are generic names). (Hereinafter referred to as “Compound (1)”).

Compound (A):
At least one selected from organosilane represented by the following formula (3) (hereinafter referred to as “organosilane (1)”), hydrolyzate of organosilane (1), and condensate of organosilane (1). Species (R ⁷ ) _p Si (OR ⁸ ) _4-p (3)
[In Formula (3), R ⁷ is the same or different when two are present, and represents an organic group having 1 to 10 carbon atoms; R ⁸ is the same or different and is an alkyl group or carbon having 1 to 5 carbon atoms; The acyl group of number 1-6 is shown, p is an integer of 0-2. ]
Compound (B):
At least one metal oxide selected from the group of silica, alumina, zirconia and titania

  By adding these blends (1), there is an effect that a film sheet having a small linear expansion coefficient, that is, having good dimensional stability can be obtained.

Here, the hydrolyzate of the organosilane (1) does not have to be decomposed all of R ⁸ contained in the organosilane (1). For example, only one is hydrolyzed. One or more of them may be hydrolyzed, or a mixture thereof.
The organosilane (1) condensate is formed by condensation of silanol groups of the hydrolyzate of organosilane (1) to form Si—O—Si bonds. It is not necessary to condense all of them, and it is a concept including a mixture of a small part of silanol groups or a mixture of those having different degrees of condensation.

In the formula (3), R ⁷ has 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms. Examples of the monovalent organic group for R ¹ include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n -Alkyl groups such as hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, acyl groups such as acetyl group, propionyl group, butyryl group, valeryl group, benzoyl group, trioyl group, caproyl group, vinyl Groups, allyl groups, cyclohexyl groups, phenyl groups, glycidyl groups, (meth) acryloxy groups, ureido groups, amide groups, fluoroacetamide groups, isocyanate groups, and substituted derivatives of these groups. .

Examples of the substituent in the substituted derivative of R ⁷ include a halogen atom, a substituted or unsubstituted amino group, a hydroxyl group, a mercapto group, an isocyanate group, a glycidoxy group, a 3,4-epoxycyclohexyl group, and a (meth) acryloxy group. Ureido group, ammonium base and the like. However, the number of carbon atoms of R ⁷ consisting of substituted derivatives thereof is 20 or less, including the carbon atoms in the substituent.
In Formula (3), when two R ⁷ are present, they may be the same as or different from each other.
The alkyl group having 1 to 5 carbon atoms for ^{R 8,} for example, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl group, sec- butyl group, t- butyl radical, n -A pentyl group etc. can be mentioned, As a C1-C6 acyl group, an acetyl group, a propionyl group, a butyryl group, a valeryl group, a caproyl group etc. can be mentioned, for example.

Specific examples of such organosilane (1) include
Tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane; methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, Ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyl Trimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, cyclohexyltrimethoxysilane Cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3- Trifluoropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxy Propyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrie Xysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) Ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3-ureidopropyltri Trialkoxysilanes such as methoxysilane and 3-ureidopropyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxy Sisilane, di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyl Dimethoxysilane, di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n- In addition to dialkoxysilanes such as octyldimethoxysilane, di-n-octyldiethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane and diphenyldiethoxysilane, methyltriacetyl Oxysilane, dimethyldiacetyl Or the like can be mentioned Kishishiran.
Of these, the tetraalkoxysilanes are preferably tetramethoxysilane and tetraethoxysilane, the trialkoxysilanes are preferably methyltrimethoxysilane and methyltriethoxysilane, and the dialkoxysilanes are preferably dimethyl Dimethoxysilane and dimethyldiethoxysilane are preferred.

  In the present invention, the organosilane (1) is particularly preferably tetraalkoxysilane alone, trialkoxysilane alone, or a combination of 10 to 90 mol% tetraalkoxysilane and 10 to 90 mol% trialkoxysilane. By introducing tetraalkoxysilane or trialkoxysilane, the degree of crosslinking of the resulting coating film can be increased, and the adhesion can be improved.

Organosilane (1) is used as it is or as a hydrolyzate and / or condensate.
The hydrolysis condensate is not only obtained by hydrolysis / condensation of organosilane (1), but also methyltrichlorosilane, ethyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, diethyldichlorosilane, diphenyldichlorosilane. It can also be obtained by hydrolysis and condensation of chlorosilane compounds such as

  When the organosilane (1) is used as a hydrolysis / condensation product, the polystyrene-equivalent weight average molecular weight (hereinafter referred to as “Mw”) of the condensation product is preferably 800 to 100,000, more preferably. 1,000 to 50,000.

  Commercially available products of hydrolysis / condensation products of organosilane (1) include MKC silicate manufactured by Mitsubishi Chemical Corporation, ethyl silicate manufactured by Colcoat, silicone resin manufactured by Toray Dow Corning, manufactured by Toshiba Silicone Co., Ltd. Silicone resin, Shin-Etsu Chemical Co., Ltd. silicone resin, Dow Corning Asia Co., Ltd. hydroxyl group-containing polydimethylsiloxane, Nippon Unica Co., Ltd. silicone oligomer, etc. You may use it.

  In these compositions, the proportion of the blend (1) is 2-70 parts by weight, preferably 5-50 parts by weight, with respect to 100 parts by weight of the cyclic olefin addition copolymer of the present invention. Partly formulated. When the proportion of the compound to be blended is less than 2 parts by weight, there are few effects such as solvent resistance and dimensional stability when formed into a film or sheet. On the other hand, if it exceeds 70 parts by weight, the transparency is often impaired.

  When the compound (1) generates inorganic particles by hydrolysis / condensation, the composition is optically transparent by being dispersed in the polymer with a particle size of 100 μm or less, preferably 10 μm or less. In addition, heat resistance and dimensional stability are good.

  In the crosslinked resin film of cyclic olefin addition type copolymer containing said compound (1), it may sometimes become cloudy. In order to solve this problem and produce a highly transparent crosslinked resin film with good reproducibility, the cyclic olefin addition-type copolymer and the compound (1) are grafted at the time of casting or before, and a polymer is obtained. A technique for improving the dispersion ratio of the blend (1) therein can be employed. Specifically, grafting of the alkoxysilyl group contained in the copolymer and the compound (1) proceeds by the action of the following metal catalyst (1) (hydrolysis / condensation reaction of alkoxysilyl group).

Metal catalyst (1)
Aluminum (Al) compound, zirconium (Zr) compound, tin (Sn) compound, zinc (Zn) compound, calcium (Ca) compound, barium (Ba) compound, titanium (Ti) compound, scandium (Sc) compound, lanthanide ( Gd, Yb, Sm, Nd, etc.) compounds, antimony (Sb) compounds, yttrium (Y) compounds, cerium (Ce) compounds, etc.

As a specific example,
[Specific examples of aluminum compounds]
Tri-i-propoxyaluminum, di-i-propoxyethyl acetoacetate aluminum, di-i-propoxy acetylacetonate aluminum, i-propoxy bis (ethylacetoacetate) aluminum, i-propoxy bis (acetylacetonate) ) Organoaluminum compounds such as aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum, monoacetylacetonate bis (ethylacetoacetate) aluminum

[Specific examples of zirconium compounds]
Tetra-n-butoxyzirconium, tri-n-butoxyethylacetoacetatezirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate) zirconium, tetrakis (n-propylacetate) Organic zirconium compounds such as acetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium;

[Specific examples of tin compounds]
Sn (OCOCH ₃ ) ₂ ,
Sn (OCOC ₂ H ₅ ) ₂ ,
Sn (OCOC ₃ H ₇ ) ₂ ,
Sn (OCOC ₄ H ₉ ) ₂ ,
Sn (OCOC ₅ H ₁₁ ) ₂ ,
Sn (OCOC ₆ H ₁₃ ) ₂ ,
Sn (OCOC ₇ H ₁₅ ) ₂ ,
Sn (OCOC ₈ H ₁₇ ) ₂ ,
Sn (OCOC ₉ H ₁₉ ) ₂ ,
Sn (OCOC ₁₀ H ₂₁ ) ₂ ,
Sn (OCOC ₁₁ H ₂₃ ) ₂ ,
Sn (OCOCH = CHCOOCH ₃ ) ₂ ,
Sn (OCOCH = CHCOOC ₄ H ₉ ) ₂
Sn (OCOCH = CHCOOC ₈ H ₁₇ ) ₂
Sn (OCOCH = CHCOOC ₁₆ H ₃₃ ) ₂
Sn (OCOCH = CHCOOC ₁₇ H ₃₅ ) ₂
Sn (OCOCH = CHCOOC ₁₈ H ₃₇ ) ₂
Sn (OCOCH = CHCOOC ₂₀ H ₄₁ ) ₂
(C ₄ H ₉ ) ₂ Sn (OCOC ₁₁ H ₂₃ ) ₂ ,
_{(C 4 H 9) 2 Sn} (OCOCH = CHCOOCH 3) 2,
_{(C 4 H 9) 2 Sn} (OCOCH = CHCOOC 4 H 9) 2,
(C ₈ H ₁₇ ) ₂ Sn (OCOC ₈ H ₁₇ ) ₂ ,
(C ₈ H ₁₇ ) ₂ Sn (OCOC ₁₁ H ₂₃ ) ₂ , 1
_{(C 8 H 17) 2 Sn} (OCOCH = CHCOOCH 3) 2,
_{(C 8 H 17) 2 Sn} (OCOCH = CHCOOC 4 H 9) 2,
_{(C 8 H 17) 2 Sn} (OCOCH = CHCOOC 8 H 17) 2,
_{(C 8 H 17) 2 Sn} (OCOCH = CHCOOC 16 H 33) 2,
_{(C 8 H 17) 2 Sn} (OCOCH = CHCOOC 17 H 35) 2,
_{(C 8 H 17) 2 Sn} (OCOCH = CHCOOC 18 H 37) 2,
(C ₈ H ₁₇ ) ₂ Sn (OCOCH═CHCOOC ₂₀ H ₄₁ ) ₂
(C ₄ H ₉ ) ₂ SnOCOCH ₃
｜
O
｜
(C ₄ H ₉ ) ₂ SnOCOCH ₃ ,
_{(C 4 H 9) Sn (} OCOC 11 H 23) 3,
(C ₄ H ₉ ) Sn (OCONa) ₃
Carboxylic acid type organotin compounds such as;

_{(C 4 H 9) 2 Sn} (SCH 2 COOC 8 H 17) 2,
_{(C 4 H 9) 2 Sn} (SCH 2 CH 2 COOC 8 H 17) 2,
_{(C 8 H 17) 2 Sn} (SCH 2 COOC 8 H 17) 2,
_{(C 8 H 17) 2 Sn} (SCH 2 CH 2 COOC 8 H 17) 2,
_{(C 8 H 17) 2 Sn} (SCH 2 COOC 12 H 25) 2,
_{(C 8 H 17) 2 Sn} (SCH 2 CH 2 COOC 12 H 25) 2,
_{(C 4 H 9) Sn (} SCOCH = CHCOOC 8 H 17) 3,
_{(C 8 H 17) Sn (} SCOCH = CHCOOC 8 H 17) 3,

(C ₄ H ₉ ) ₂ Sn (SCH ₂ COOC ₈ H ₁₇ )
｜
O
｜
(C ₄ H ₉ ) ₂ Sn (SCH ₂ COOC ₈ H ₁₇ )
Mercaptide-type organotin compounds such as

(C ₄ H ₉ ) ₂ Sn = S, (C ₈ H ₁₇ ) ₂ Sn = S,

(C ₄ H ₉ ) ₂ Sn = S
｜
O
｜
(C ₄ H ₉ ) ₂ Sn = S
Sulfide-type organotin compounds such as;

(C ₄ H ₉ ) SnCl ₃ , (C ₄ H ₉ ) ₂ SnCl ₂ ,
(C ₈ H ₁₇ ) ₂ SnCl ₂ ,
_{(C 4 H 9) 2 Sn} -Cl
｜
O
｜
_{(C 4 H 9) 2 Sn} -Cl
Chloride-type organotin compounds such as

Reaction of organotin oxides such as (C ₄ H ₉ ) ₂ SnO, (C ₈ H ₁₇ ) ₂ SnO, and ester compounds such as silicates, dimethyl maleate, diethyl maleate and dioctyl phthalate Product

[Specific examples of tin compounds]
Zinc acetate, zinc octoate

[Specific examples of calcium compounds]
Calcium acetate, calcium octoate

[Specific examples of barium compounds]
Barium acetate, barium octoate

[Specific examples of titanium compounds]
Tetra-i-propoxy titanium, di-i-propoxy bis (ethylacetoacetate) titanium, di-i-propoxy bis (acetylacetate) titanium, di-i-propoxy bis (acetylacetone) titanium

[Specific examples of scandium compounds]
Scandium triisopropoxide

[Specific examples of lanthanide compounds]
Isopropoxide and butoxide such as Gd, Yb, Sm, Nd

[Specific examples of antimony compounds]
Antimony acetate, antimony ethylene glycoloxide

[Specific examples of yttrium compounds]
Yttrium triisopropoxide, Yttrium tris (aluminum tetraisopropoxide)

[Specific examples of cerium compounds]
Examples include triisopropoxycerium and cerium trichloride.

  A metal catalyst (1) can be used individually or in mixture of 2 or more types, and can also be used in mixture with a zinc compound and another reaction retarder.

The amount of the metal catalyst (1) used is usually 0 to 10 mol, preferably 0.001 to 7 mol, more preferably, with respect to 1 mol of OR ⁸ contained in the aforementioned organosilane (1). 0.001 to 5 mol. In this case, when the amount of the organometallic compound (1) used is within 10 moles, the composition has excellent storage stability and also has excellent coating film strength and is less prone to cracking.

The resin film containing the cyclic olefin addition type copolymer of the present invention can be produced by a solution casting method (solution casting method).
The production of a film by the casting method involves the production of an acid in an organic solvent (such as a polymerization solvent for the copolymer) of a cyclic olefin addition copolymer and an acid catalyst (for example, hydrolysis). Compound), if necessary, the above-mentioned formulation (1), and if necessary, a solution obtained by uniformly mixing the above-mentioned metal catalyst (1), reacting or aging at a predetermined temperature for a predetermined time, If necessary, concentrate or dilute to a suitable concentration for casting, and then cast it on a smooth fluororesin plate or glass plate using a T-shaped die, etc., and remove the solvent by evaporation. Further heating is performed. Solvents used as casting solvents differ in solubility depending on the type of polymer, but hydrocarbon compounds, halogenated hydrocarbon compounds, ethers, esters, ketones, amines, amides, alcohols, phenols , Sulfoxides and the like are selected and used. The amount of the solvent is 1 to 10,000 parts by weight, preferably 10 to 5,000 parts by weight per 100 parts by weight of the polymer.
Moreover, in order to adjust the solubility and viscosity of each component before casting, or to facilitate casting, a part or all of the solvent can be replaced with another solvent.

The cross-linking reaction of the cast film is performed by heating the film under water or steam as described above. In the case where the above-mentioned acid catalyst (crosslinking catalyst) is not added, no siloxane bond is formed even when heated under steam, and no crosslinking is performed. In addition, if sufficient water is not supplied with respect to the alkoxysilane content of the polymer, crosslinking is insufficient. The reaction temperature is 50 ° C. or higher, preferably 60 ° C. to 300 ° C., more preferably 80 ° C. to 250 ° C., and particularly preferably 100 ° C. to 200 ° C. At temperatures below 50 ° C., it is hardly crosslinked, while at temperatures above 300 ° C., the polymer is more likely to be thermally decomposed.
The time for the cross-linking reaction is appropriately selected depending on the desired degree of cross-linking, the state of the reaction system, the type of polymer, the amount of catalyst, and the type of catalyst, but is usually 1 minute to 1,000 hours, preferably 5 Minutes to 100 hours, more preferably 10 minutes to 50 hours.

In the crosslinked resin film of the present invention, the degree of swelling measured with toluene at 25 ° C. is preferably less than 500%, and more preferably 300% or less.
When the toluene swelling degree is 500% or more, when used as a glass substitute, chemical resistance, solvent resistance, dimensional stability during heating, etc. may be insufficient. In addition, the measurement of this swelling degree is the value measured by the method mentioned later. The degree of swelling of the crosslinked product can be easily adjusted by the amount of the crosslinking catalyst, the reaction temperature, and the reaction time.

  Moreover, from the film use shown below, the linear expansion coefficient of the crosslinked resin film of the present invention is preferably 65 (ppm / ° C.) or less, more preferably 60 (ppm / ° C.) or less.

  Since the transparent cross-linked resin film of the present invention has a silyl group, it has a high affinity with glass, and the ratio of peeled blocks in an adhesion test to quartz glass is 25 blocks, preferably 5 blocks or less, more preferably 3 No more than blocks, particularly preferably no more than one block.

  The composition used in the present invention includes known antioxidants such as 2,6-di-tert-butyl, 4-methylphenol, 4,4′-thiobis- (6-tert-butyl-3-methylphenol). ), 1,1′-bis (4-hydroxyphenyl) cyclohexane, 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,5-di-tert-butylhydroquinone, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate and other phenolic and hydroquinone antioxidants; tris (4-methoxy-3,5-diphenyl) phosphite, tris ( Nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, bis (2,6-di-t-butyl-4-methylpheny) ) Pentaerythritol diphosphite, with the addition of phosphorus-based antioxidants such as bis (2,4-di -t- butyl-phenyl) pentaerythritol diphosphite, it is possible to improve the oxidation stability. The amount of these antioxidants to be added is usually 0.1 to 5 parts by weight, preferably 0.005 parts per 100 parts by weight in total of the cyclic olefin addition copolymer of the present invention and the blend (1). 2 to 3 parts by weight. When the amount of the antioxidant used is too small, the effect of improving the durability is insufficient, and when it is too large, problems such as bleeding of the molding surface and a decrease in transparency are undesirable.

  The composition used in the present invention can be stabilized by adding an ultraviolet absorber such as 2,4-dihydroxybenzophenone or 2-hydroxy-4-methoxybenzophenone. Further, additives such as a lubricant can be added for the purpose of improving processability.

  As described above, the crosslinked resin film obtained using the transparent resin comprising the cyclic olefin addition copolymer composition of the present invention is used as it is as a film for a display device such as a liquid crystal display device or an EL display device. it can.

  The thickness of the film for a display device of the present invention is usually 5 to 600 μm, preferably 10 to 500 μm, more preferably 25 to 400 μm, and is appropriately determined depending on the application. The film for a display device of the present invention desirably has a small variation in retardation, and the variation in retardation at a wavelength of 633 nm is preferably ± 20% or less. When the variation in retardation is outside the range of ± 20%, it is difficult to say that the film is optically uniform, and when used in a display device, it is difficult to obtain good display performance such as distortion of the display image. . In the present invention, the retardation value is a value measured with light having a wavelength of 633 nm using an ellipsometer [DVA-36LS manufactured by Mizoji Optical Co., Ltd.].

  The liquid crystal substrate film of the present invention is formed by using the above-mentioned film for a display device. Usually, the thickness is 25 to 400 μm, the thickness unevenness is ± 30% or less of the entire thickness, and the Rmax value is 0.2 μm. The thickness unevenness is preferably ± 20% or less of the thickness over the entire surface, and the Rmax value is 0.1 μm or less. When the thickness unevenness is large or the surface smoothness is poor, the screen of the liquid crystal display device is distorted.

  The polarizing film of the present invention can be produced by bonding the display device film of the present invention as a protective layer to a polarizing film based on a PVA film or the like. The thickness of the protective layer is usually 5 to 500 μm, preferably 10 to 300 μm, and more preferably 20 to 200 μm. In order to laminate the protective layer on the polarizing film of the polarizing film, an adhesive or an adhesive can be used. These pressure-sensitive adhesives and adhesives are preferably excellent in transparency. Specific examples include natural rubber, synthetic rubber, vinyl acetate / vinyl chloride copolymer, polyvinyl ether, acrylic, modified polyolefin, and isocyanates. Examples thereof include a curable pressure-sensitive adhesive to which a curing agent such as nate is added, an adhesive for dry lamination in which a polyurethane resin solution and a polyisocyanate resin solution are mixed, a synthetic rubber adhesive, and an epoxy adhesive.

  The polarizing film used in the present invention is not particularly limited as long as it has a function as a polarizer. For example, a PVA / iodine polarizing film, a dye-based polarizing film in which a dichroic dye is adsorbed and oriented on a PVA film, a dehydration reaction is induced from a PVA film, or a dehydrochlorination reaction of a polyvinyl chloride film, Examples include a polyene polarizing film in which a polyene is formed, and a polarizing film having a dichroic dye on the surface and / or inside of a PVA film made of modified PVA containing a cationic group in the molecule. The manufacturing method of the polarizing film is not particularly limited. For example, a method of adsorbing iodine ions after stretching a PVA film, a method of stretching a PVA film after dyeing with a dichroic dye, a method of dyeing a PVA film with a dichroic dye after stretching, a dichroic dye Well-known methods such as a method of stretching after printing on a PVA-based film and a method of printing a dichroic dye after stretching a PVA-based film can be mentioned. More specifically, iodine is dissolved in a potassium iodide solution to form higher-order iodine ions, and these ions are adsorbed on a PVA film and stretched. Then, a bath temperature of 30 wt. A method for producing a polarizing film by immersing at ~ 40 ° C, or treating a PVA film with boric acid in the same manner and stretching it about 3 to 7 times in a uniaxial direction to form a 0.05 to 5% by weight dichroic dye aqueous solution There is a method in which a dye is adsorbed by dipping at a bath temperature of 30 to 40 ° C., dried at 80 to 100 ° C., and heat-fixed to produce a polarizing film.

  The surface protective film used in the present invention is the same as the film bonded to the polarizing film in the production of the polarizing film described above. In order to protect the surface of a thin film component for a display device, it is used by being bonded to one side or both sides of the component.

  The retardation film used in the present invention is obtained by using the above-described film for a display device, and can be produced by stretching orientation or surface pressing. The thickness of the sheet before stretching is usually 25 to 500 μm, preferably 50 to 400 μm, and more preferably 100 to 300 μm. As a stretching method, a known uniaxial stretching method, that is, a horizontal uniaxial stretching method by a tenter method, a compression stretching method between rolls, or a longitudinal uniaxial stretching method using rolls having different peripheral edges can be used. Moreover, after extending | stretching in the range which does not affect the orientation of a molecule | numerator, the biaxial stretching which extends | stretches to a uniaxial direction in order to orient a molecule | numerator may be sufficient. The film obtained as described above is oriented with molecules by stretching and has a certain retardation value, but the retardation is the retardation and stretching ratio of the sheet before stretching, the stretching temperature, the thickness of the stretched oriented film. Can be controlled. When the sheet before stretching has a certain thickness, the absolute value of retardation tends to increase as the stretching ratio of the film increases. Therefore, it is possible to obtain a stretched oriented film having a desired retardation by changing the stretching ratio. it can.

In the present invention, the film obtained by the above-mentioned method has a preferable retardation range depending on the type and shape of the liquid crystal display in which the measured value of the retardation with a polarizing microscope is 5 to 900 nm. In the polarizing film used in the liquid crystal display device according to the above, it is necessary that the transparency is particularly high, and an optically uniform film having a small retardation of 10 to 80 nm is preferably used.

  The transparent conductive film of the present invention is obtained by forming a transparent conductive layer on a film made of the transparent resin of the present invention. As a material for forming the transparent conductive layer, metals such as Sn, In, Ti, Pb, Au, Pt, and Ag, or oxides thereof are generally used. These metals are usually formed on a liquid crystal substrate film by a plasma method, sputtering method, vacuum deposition method, plating, ion plating method, spray method, electrolytic deposition method, etc. Is coated to 50 to 5,000 angstroms. When a metal simple substance is formed on a film, it can also be oxidized after that as needed. There is also a method of depositing as an oxide layer from the beginning, but at first, a film is formed in the form of a single metal or a lower oxide, and then subjected to an oxidation treatment such as heat oxidation, anodization or liquid phase oxidation to be transparent. It can also be converted. The specific resistance of the transparent conductive film is preferably 100 ohm cm or less.

The light diffusing film of the present invention can be produced by forming a pattern having a diffusing function on one side of a film made of the transparent resin of the present invention. Here, the pattern having a diffusion function can be formed by applying various coating materials in addition to embossing or a method of forming a pattern by applying a photocurable resin such as ultraviolet rays.
Examples of the photocurable resin used for forming a pattern on the film of the present invention include one or more compounds having at least one ethylenic double bond such as a (meth) acryloyl group in the molecule. A composition comprising a photopolymerization initiator, a composition comprising at least one compound having at least one group having ring-opening reactivity such as an epoxy group in the molecule, and a photocationic initiator, gelatin, Examples thereof include a composition containing a dichromate, a composition containing a cyclized rubber and a bisazide photosensitizer, and a composition containing a novolac resin and a quinone azide photosensitizer. In addition, the surface of the film is subjected to physical ground treatment such as plasma treatment, or conventional rubber-based, resin-based, especially acrylic-based, silicone-based, etc., in order to control its adhesion before applying the photocurable resin. Chemical base treatment with various coating materials such as a system may be performed.

The prism sheet for collecting the light diffused through the light diffusing film at the viewing angle of the display device and improving the brightness of the display device has a transparent prism surface with a small prism angle. In the same manner as the light diffusing film, the prism surface pattern is embossed on the film surface made of the transparent resin of the present invention, or a pattern is formed by applying a photocurable resin such as ultraviolet rays. can do.
The crosslinked resin film of the present invention is also useful as a film for an EL display device. Examples of the EL display device film include a substrate film, a polarizing film, a surface protective film, and a transparent conductive film, which are also used in the liquid crystal display device. Of course, the characteristics of these films are not always the same as those for liquid crystal display devices.
Moreover, it can be used as a transparent conductive composite material by forming a transparent conductive film on the surface of the crosslinked resin film of the present invention. As this transparent conductive composite material, in addition to the electrode film for the liquid crystal display device or EL display device, it is also useful as an electromagnetic wave prevention film for electronic devices such as CRT.
Furthermore, on the surface of the crosslinked resin film of the present invention, an antireflection film in which the layer in contact with the surface of the film is made of SiO _x (0.8 ≦ x ≦ 1.8) and the outermost layer is made of SiO ₂ By forming it, it can be used as an antireflection film. Since this antireflection film is excellent in heat resistance, it is useful not only for the liquid crystal display device or EL display device, but also for a plasma display, a field emission display, and the like.

When the various films for a display device of the present invention are used adjacent to each other, if they are integrated in advance, there are advantages such as a reduction in the number of parts, a reduction in the thickness of the display device, and weight reduction. For example, a liquid crystal substrate film and a polarizing film, a retardation film and a transparent conductive film, a light diffusion film and a prism sheet, a polarizing film and a light diffusion film, and the like. For the integration, an adhesive layer and / or an anchor coat layer is formed between the two films and bonded. Examples of the adhesive layer include heat-resistant resins such as epoxy resin, polyimide, polybutadiene, phenol resin, and polyetheretherketone. Moreover, as an anchor coat layer, what contains what is called acrylic prepolymers, such as epoxy diacrylate, urethane diacrylate, and polyester diacrylate, are used. As a curing method, a known method can be used, and for example, UV curing, thermal curing, or the like is used.
The display device film of the present invention has excellent optical transparency, heat resistance, moisture absorption resistance, liquid crystal resistance, dimensional stability, and adhesion / adhesion, and is therefore suitable for the production of liquid crystal display devices and EL display devices. These display devices can be used for personal computers, televisions, mobile phones, digital information terminals, pagers, navigation, liquid crystal monitors, light control panels, displays for OA devices, displays for AV devices, and the like.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by these examples.
Moreover, molecular weight, swelling degree, glass transition temperature, liquid crystal resistance, total light transmittance, and birefringence were measured by the following methods.

(1) Weight average molecular weight, number average molecular weight Using a H type column manufactured by Tosoh Corporation with a 150C type gel permeation chromatography (GPC) manufactured by WATERS, using o-dichlorobenzene as a solvent, Measured at 120 ° C. The obtained molecular weight shows a standard polystyrene conversion value.
(2) Metal atomic weight Copolymer based on a calibration curve prepared with a standard solution of nickel and aluminum [Wako Pure Chemical Industries, Ltd.] using Hitachi Z-9000 atomic absorption spectrophotometer Residual metal atoms were quantified.
(3) Swelling degree of toluene A film or sheet having a thickness of 50 to 500 microns and a length of 2 cm × width 2 cm was immersed in toluene at 25 ° C. for 3 hours, and the degree of swelling was calculated from the weight ratio before and after the immersion. The thing which does not swell at all was made into 100%.
(4) Glass transition temperature The glass transition temperature of the cyclic olefin addition copolymer of the present invention is often unclear and not measured in the scanning differential calorimetry (DSC) measurement. It was defined by the peak temperature of measured Tan δ (ratio E ′ / E ″ = Tan δ of storage elastic modulus E ′ and loss elastic modulus E ″). Dynamic viscoelasticity was measured using Leo Vibron DDV-01FP (Orientec). The measurement frequency was 10 Hz, the heating rate was 4 ° C./min, the excitation mode was a single waveform, and the excitation amplitude was 2.5 μm.
(5) Total light transmittance Based on ASTM-D1003, the total light transmittance of the 100-micrometer-thick film was measured.
(6) Linear expansion coefficient TMA (Thermal Mechanical
Analysis) / SS6100 (manufactured by Seiko Instruments Inc.), fixing a sample with a film thickness of 100 μm, a width of 3 mm, and a length of 10 cm with a distance between chucks of 10 mm,
After raising the temperature to about 1 ° C. to remove residual strain, the temperature was raised from room temperature at 3 ° C./min., And the linear expansion coefficient was obtained from the elongation of the distance between chucks.
(7) Liquid crystal resistance This evaluation sample having a thickness of 50 to 500 microns and a length and width of 2 cm × 2 cm is immersed in a liquid crystal for TFT [ZLI5081 manufactured by Merck Japan Ltd.], and 1 drop (about 20 mg) is dropped into the atmosphere. The change of the film surface after heating at 150 ° C. for 1 hour was visually evaluated. The evaluation criteria are as follows.
A: No change in shape.
○: Slightly swollen.
Δ: Swells.
X: The shape is lost due to dissolution or the like.
(8) Adhesiveness / adhesion:
Aluminum is vapor-deposited on the film for evaluation, and this vapor-deposited film is cut with a cutter so that 10 × 10 grids of 1 mm × 1 mm are formed, and a peel test using a cellophane tape is performed. The number of peeled blocks in 25 blocks was measured. In the evaluation of adhesion to quartz glass, the composition of the present invention was applied to quartz glass so as to have a dry coating film thickness of 5 to 10 μm, dried and cured at 90 ° C., and then subjected to the same peeling test using a cellophane tape. .
(9) Birefringence (nm)
It was measured with an ellipsometer (manufactured by Mizojiri Optical Co., Ltd.).

Reference Example 1 (Synthesis of copolymer a)
2-norbornene 593.75 mmol as a monomer, 5-triethoxysilyl-2-norbornene 31.25 mmol, toluene 500 g as a solvent, molecular weight regulator (1,5-cyclooctadiene) 0.25 mmol in volume 1 A liter reactor was charged under nitrogen. The reaction system was brought to 10 ° C., and 0.25 mmol of a nickel compound obtained by reacting nickel octanoate [Ni (octate) ₂ ] and hexafluoroantimonic acid in a molar ratio of 1: 1 at −15 ° C. in advance, trifluoroboron Polymerization was carried out by charging 2.25 mmol of diethyl ether complex and 2.5 mmol of triethylaluminum.
Polymerization was carried out at 30 ° C. for 1 hour, and the polymerization was stopped with isopropyl alcohol. The addition rate to the copolymer was 95%. 6 g of lactic acid was added to the copolymer solution and reacted with the catalyst component. The copolymer solution was put into 4 liters of isopropanol to solidify the copolymer, and unreacted monomers and catalyst residues were removed.
The coagulated copolymer was dried to obtain a copolymer a.
Derived from 5-triethoxysilyl-2-norbornene by analysis of copolymer a by 270 MHz ¹ H-NMR (3.8 to 4.0 ppm ethoxysilyl group methylene absorption, solvent is toluene dated, TMS standard) The content of the structure was 5.0 mol%. Moreover, the number average molecular weight of polystyrene conversion of the copolymer a was 87,000, and the weight average molecular weight was 211,000. The residual nickel in the polymer was 0.1 ppm or less, and the residual aluminum was 1.6 ppm.

Reference Example 2 (Synthesis of copolymer b)
Polymerization was carried out in the same manner as in Reference Example 4 except that 562.5 mmol of 2-norbornene and 62.5 mmol of 5-triethoxysilyl-2-norbornene were used as monomers to obtain a copolymer b.
The content of the structure derived from 5-triethoxysilyl-2-norbornene is determined by analysis of copolymer b by 270 MHz ¹ H-NMR (absorption of 4 ppm ethoxysilyl group methylene, solvent is d-toluene, TMS standard). It was 9.9 mol%. The copolymer b had a polystyrene-equivalent number average molecular weight of 88,000 and a weight average molecular weight of 223,000. The residual nickel in the polymer was 0.1 ppm or less, and the residual aluminum was 1.2 ppm.

Reference Example 3 (Synthesis of copolymer c)
As monomers, 2-norbornene 531.23 mmol, 5-triethoxysilyl-2-norbornene 62.50 mmol, 8-methyl-8-methoxycarbonyl-3-tetracyclo [4.4.0.1 ^2,5 1 ^7,10 ] Dodecene Polymerization was carried out in the same manner as in Reference Example 4 except that the amount was 31.25 mmol to obtain copolymer c.
The content of the structure derived from 5-triethoxysilyl-2-norbornene is determined by analysis of copolymer c by 270 MHz ¹ H-NMR (4 ppm ethoxysilyl group methylene absorption, solvent is d-toluene, TMS standard). It was 9.9 mol%. The ratio of the structure derived from 8-methyl, 8-methoxycarbonyl-3-tetracyclo [4.4.0.1 ^2,5 1 ^7,10 ] dodecene in copolymer c was determined by infrared analysis at 1,730 cm. It was 4.9 mol% from the calibration curve by the characteristic absorption of -1. Moreover, the number average molecular weight of polystyrene conversion of the copolymer c was 89,000, and the weight average molecular weight was 256,000. Residual nickel in the polymer was 0.1 ppm or less, and residual aluminum was also 0.1 ppm or less.

Reference Example 4 [Creating crosslinked film of copolymer a (P added, no Sn)]
10 g of copolymer a was dissolved in 40 g of toluene containing 70 ppm of water, and pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4 was used as an antioxidant with respect to 100 parts by weight of copolymer. -Hydroxyphenyl) propionate] 1.0 part by weight was added. After adding 0.5 part by weight of tributoxyphosphite as an acid catalyst (crosslinking catalyst), this solution was poured into a stainless steel petri dish and cast at 40 ° C. for 3 hours. The produced film was dried at 150 ° C. for 2 hours, and then heat-treated under steam at 150 ° C. for 4 hours. Then, it dried at 230 degreeC under vacuum for 1 hour, and obtained the 100-micrometer-thick colorless transparent film. Table 1 shows the film production conditions, the state of the obtained film, and the degree of swelling.

Reference Example 5 [Creating crosslinked film of copolymer a (P, Sn added)]
A crosslinked film was prepared under the same conditions as in Reference Example 4 except that dioctyltin (II) was further added to the cast solution prepared in Reference Example 4 . The results are shown in Table 1.

Example 3 [Creation of Copolymer a + TEOS Composite Crosslinked Film (P Addition Sn Addition)]
A film was prepared under the same conditions as in Reference Example 4 except that 2 g of tetraethoxysilane (TEOS) and dioctyltin (II) were further added to the cast solution prepared in Reference Example 4 . The toluene swelling degree of the film is 160%, and the linear expansion coefficient is 45 ppm / ℃
It became. The results are shown in Table 1.

Example 4 [Preparation of crosslinked film of copolymer a + TEOS composite (addition of P, no Sn)]
A crosslinked film was prepared under the same conditions as in Reference Example 4 except that 2 g of tetraethoxysilane (TEOS) was further added to the cast solution prepared in Reference Example 4 . This film was slightly cloudy and had a total light transmittance of 85%. The results are shown in Table 1.

Example 5 [Preparation of crosslinked film of copolymer b + TEOS composite (addition of P, Sn)]
A film was prepared under the same conditions as in Reference Example 5 except that copolymer b was used instead of copolymer a. The results are shown in Table 1.

Example 6 [Crosslinked film of copolymer c + TEOS composite system (addition of P, Sn)]
A film was prepared under the same conditions as in Reference Example 4 except that copolymer c was used instead of copolymer a. The results are shown in Table 1.

Comparative Example 1 [Creating a crosslinked film of copolymer a (no P, no Sn)]
A film was prepared under the same conditions as in Reference Example 4 except that tributoxyphosphite was not added. Under these conditions, no crosslinking occurred. The results are shown in Table 1.

Comparative Example 2 [Creating a crosslinked film of copolymer a (no P, Sn added)]
A film was prepared under the same conditions as in Reference Example 4 except that tritoxyphosphite was not added and dioctyltin (II) was added instead. Under these conditions, there was almost no crosslinking. The results are shown in Table 1.

Comparative Example 3 [Creating a crosslinked film of copolymer a (P, Sn added, 40 ° C. hot water treatment)]
A film was prepared by the same operation as in Reference Example 4 except that the film was heated in 40 ° C. warm water instead of water vapor (150 ° C.). Under these conditions, no crosslinking occurred. The results are shown in Table 1.

Comparative Example 4 [Creation of crosslinked film of copolymer a + TEOS composite (no P, Sn added)]
A film was prepared under the same conditions as in Reference Example 5 , except that tributoxyphosphite was not added. Under these conditions, there was almost no crosslinking. The results are shown in Table 1.

Example 7
Production of film for liquid crystal display device and liquid crystal substrate film: Variation in retardation of the crosslinked film (1) prepared in Example 3 at a wavelength of 633 nm was ± 5%. An anchor agent solution composed of an ionic polymer complex [Toyobein 210K manufactured by Tosoh Corporation] having water / alcohol (50/50 weight ratio) as a solvent component is applied to the obtained film, and dried at 90 ° C. for 5 minutes. Thus, an aqueous anchor coat layer (2) was formed. On this water-based anchor coat layer, an adhesive layer composed of a urethane-based adhesive [Takelac A-371 made by Takeda Pharmaceutical Co., Ltd.] and a curing agent [Takenet A-10 made by Takeda Pharmaceutical Co., Ltd.] 3) was formed. Further, an ethylene-vinyl alcohol copolymer / dichroic dye-based polarizing film (4) was layered on the adhesive layer, and laminated and integrated by hot pressing at 80 ° C. and a pressure of 3 kg / cm ² . Next, a transparent conductive layer (5) was formed on the polarizing film surface by sputtering using a target made of indium oxide / tin oxide (weight ratio 95: 5). As a result, a liquid crystal display panel having a laminated structure composed of transparent electrode (5) / polarizing film (4) / adhesive layer (3) / aqueous anchor coat layer (2) / substrate layer (1) was obtained. The adhesion between the substrate layer (1) and the polarizing film layer (4) of this laminate was good, and no peeling was observed. Further, when a durability test was performed under the conditions of 80 ° C. and 90% relative humidity, no abnormality was observed in the laminate at a stage of 1,000 hours, and the durability was good.

Example 8
Production of surface protective film: 1 part by weight of stearyl-β- (3.5-di-t-butyl-4-hydroxyphenyl) propionate was added to the mixed solution prepared in Example 3 with respect to 100 parts by weight in total. 0.1 parts by weight of tris (2,4-di-t-butylphenyl) phosphite was added, and a film having a thickness of 80 μm was prepared by a casting method to obtain a protective film. The glass transition temperature of this film was 340 ° C. Further, the variation in retardation at a wavelength of 633 nm was as small as ± 5%.

Example 9
Production of polarizing film: A polyvinyl alcohol film having a thickness of 50 μm was uniaxially stretched up to 4 times in about 5 minutes while being immersed in a bath at 40 ° C. composed of 5.0 g of iodine, 250 g of potassium iodide, 10 g of boric acid, and 1,000 g of water. . The surface of the obtained film was washed with alcohol while keeping tension, and then air-dried to obtain a polarizing film. To this polyvinyl alcohol polarizing film, 100 parts by weight of an acrylic resin consisting of 90% by weight of n-butyl acrylate, 7% by weight of ethyl acrylate and 3% by weight of acrylic acid and trimethylolpropane (1 mol) of tolylene diisocyanate (3 mol) Mol) The above protective film was laminated using an adhesive obtained by mixing a crosslinking agent comprising 2 parts by weight of a 75% by weight ethyl acetate solution of the adduct. The adhesion of both layers of this laminate was good and no peeling was observed. In addition, when a durability test was performed at 80 ° C. and a relative humidity of 90%, no abnormality was observed in the polarizing film at the stage of 1,000 hours, and the durability was good.

Example 10
Production of retardation film: Using the mixed solution prepared in Example 3, a film having a thickness of 100 μm was produced by a casting method. This film was stretched in a uniaxial direction at a temperature of 300 ° C. to obtain a retardation film having a thickness of 80 μm. The retardation of this film at a wavelength of 633 nm was 136 μm, and the variation in retardation was as small as ± 5%. The wavelength dispersion (α) of retardation in the wavelength range of 450 nm to 750 nm was 1.01.

Example 11
Production of transparent conductive film: A film having a length of 200 mm, a width of 200 mm, and a thickness of 0.1 mm was prepared by the method of Example 3. An indium-tin oxide (ITO) film was formed on the obtained film under the following conditions using a sputtering machine (Chuai Furnace Industries).
Power supply High frequency power supply of MHz Substrate temperature 70 ℃
Target In ₂ O ₃ / SnO ₂ = 90/10 (weight ratio) Atmosphere At argon gas inflow Sputter speed 270 Å / min Sputter pressure 10 ^-2 Torr
The thickness of the obtained ITO film is 2,500 angstroms, the specific resistance is 1.5 × 10 ^-3 ohm cm, 400-800 of transparent conductive composite material
The light transmittance at nm was 84%. When the adhesion between the obtained transparent conductive composite material and the ITO film was tested according to JIS K-5400 (8th, 5th and 2nd test), no peeling was observed. Further, no changes were observed in the conductive properties and appearance after the obtained transparent conductive composite material was stored for one week under conditions of a temperature of 90 ° C. and a humidity of 95%.

Example 12
Manufacture of EL display device: After applying a quinolinol complex solution on a 5 cm square glass substrate on which an ITO film was formed, the solvent was removed to form an electroluminescence layer having a thickness of 50 nm. Next, a 60 nm thick electron transport light emitting layer made of triskinolinolatoaluminum is formed on the electroluminescent layer, and a 100 mm thick 5 mm square magnesium / silver alloy (by a vapor deposition method) is formed on this electron transport light emitting layer. A 10: 1 weight ratio film (cathode layer) was formed. Furthermore, on the side opposite to the ITO film of the glass substrate on which the ITO film is formed, a laminate of the above retardation film and a commercially available polarizing film [NPF-F1225DU manufactured by Nitto Denko Corporation] is laminated to form an EL display device. Manufactured.
The manufactured EL display device was evaluated as follows: color tone; black, quality; no reflection of outside scenery, light reflectance (%); 0.2, adhesion; no peeling, durability at high temperature and high humidity; It was a result. As described above, the EL display device using the retardation film of the present invention can block the reflected light from the back electrode so that the external scenery is not reflected, and is very easy to see even in a bright place. Could get.

Example 13
Production of light diffusion composite sheet: A film having a thickness of 0.1 mm was prepared by the method of Example 3. On the obtained film, a solution of 10 g of vinyl chloride-vinyl acetate copolymer containing methyl ethyl ketone / ethylene glycol (40 / 0.1 weight ratio) as a solvent component was applied and dried to form a resin film having a thickness of 30 μm. Formed. Next, this film was immersed in hot water at 80 ° C. for 45 minutes and then taken out and dried to obtain a 130 μm thick light diffusion composite sheet. In this case, the light transmittance of the transparent resin film was 75%, and it was a single cell having a particle size in the range of 2 to 8 μm.

Example 14
Production of antireflection film: A film having a thickness of 100 μm was produced by the casting method using the mixed solution prepared in Example 3. On the surface of this film, SiO was deposited to a thickness of 825 nm under a vacuum of 10 ⁻⁴ Torr. Next, SiO ₂ was deposited with a film thickness of 130 nm. Further, a mixture of ZrO ₂ and TiO ₂ was deposited with a film thickness of 130 nm. Further, the SiO ₂ was vapor-deposited in a thickness of 248nm as an outermost layer to obtain an antireflection film. The light transmittance of this antireflection film was 90%, and the birefringence was as small as 2 nm.

Claims (11)

Cyclic olefin addition type copolymer composition containing cyclic olefin type addition type copolymer containing repeating unit (a) shown by following formula (1), and repeating unit (b) shown by following formula (2) Furthermore, a crosslinked resin film obtained by crosslinking a resin film obtained by molding a composition containing the following compound (A) and / or (B) with a siloxane bond.
Compound (A):
At least one selected from the group consisting of an organosilane represented by the following formula (3), a hydrolyzate of the organosilane, and a condensate of the organosilane (R ⁷ ) _p Si (OR ⁸ ) _4-p. ... (3)
[In Formula (3), R ⁷ is the same or different when two are present, and represents an organic group having 1 to 10 carbon atoms; R ⁸ is the same or different and is an alkyl group or carbon having 1 to 5 carbon atoms; The acyl group of number 1-6 is shown, p is an integer of 0-2. ]
Compound (B):
At least one metal oxide selected from the group of silica, alumina, zirconia and titania

[In formula (1), A ^{1 to} A ⁴ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or
_{^{- (CR 1 R 2) f}} Si (OR 3) g R 4 (3-g),
_{^{- (CR 1 R 2) f}} Si (R 3 R 4) OSi (OR 3) g R 4 (3-g),
_{^{- (CR 1 R 2) f}} C (O) O (CH 2) h Si (OR 3) g R 4 (3-g)
And at least one of A ^{1 to} A ⁴ represents an alkoxysilyl group or an allyloxysilyl group. Here, R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ³ represents an alkyl group, alkenyl group, aryl group or cycloalkyl group having 1 to 10 carbon atoms. R ⁴ represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, f and h are integers of 0 to 5, and g is an integer of 1 to 3. Y represents —CH ₂ — or —O—, and m represents 0 or 1. ]

[In the formula (2), B ¹ , B ² , B ³ and B ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkenyl group, a cycloalkyl group, a halogen atom, a halogen atom. And a polar group represented by — (CH ₂ ) _j X. Here, X is —C (O) OR ⁵ , or —OC (O) R ⁶ , and R ⁵ and R ⁶ are each an alkyl group, alkenyl group, aryl group, cycloalkyl group having 1 to 20 carbon atoms, or These halogen substituents, j represents an integer of 0 to 5. Further, B ^{1 to} B ⁴ include an alkylidenyl group formed of B ¹ and B ² or B ³ and B ⁴ , a cyclohexane formed of B ¹ and B ⁴ , B ¹ and B ³ , or B ² and B ^4. An alkylene group and a cycloalkenylene group are also included. n represents an integer of 0 to 2. ]   The cyclic olefin addition copolymer composition according to claim 1 is mixed with an organic solvent to form a solution, which is then formed into a film by a solution casting method, and then heated to 50 ° C. or higher, or heated with hot water or steam. The crosslinked resin film of Claim 1 obtained by the manufacturing method including the process of forming a siloxane bond and bridge | crosslinking by this.   A liquid crystal substrate film for a liquid crystal display device, wherein the cross-linked resin film according to claim 1 is used.   A polarizing film for a liquid crystal display device comprising the crosslinked resin film according to claim 1.   A surface protective film for a liquid crystal display device comprising the crosslinked resin film according to claim 1.   A retardation film for a liquid crystal display device, wherein the crosslinked resin film according to claim 1 is used.   A transparent conductive film for a liquid crystal display device, wherein the crosslinked resin film according to claim 1 is used.   A light diffusion film for a liquid crystal display device, wherein the crosslinked resin film according to claim 1 is used. EL display film, characterized by using a crosslinked resin film according to claim 1 or 2 any one of claims.   A transparent conductive composite material comprising a transparent conductive film formed on the surface of the crosslinked resin film according to claim 1. On the surface of the crosslinked resin film of any one of claims 1-2, the layer layer in contact with the surface of the film is made of _{SiO x (0.8 ≦ x ≦ 1.8} ), the outermost layer is made of SiO ₂ An antireflection film comprising an antireflection film as described above.