Composition of Cyclic Olefin Addition Copolymer and Cross-Linked Material

专利摘要:
The present invention provides a cyclic olefin addition copolymer containing a repeating unit (a) represented by the formula (1) and a repeating unit (b) represented by the following formula (2); And (A) a metal compound which acts as an acid when heated to a temperature of 50 ° C. or higher, (B) an alkoxy compound, an aryloxy compound, a carboxyl compound, a β-diketone compound, a halogen compound or an oxide, wherein the metal is Al, Ga, Sn, Ca, Ba, Zn, Sb, Ti, Zr, Sc, Y, Ce, Nd, Sm and Yb), and (C) organic carboxylic acid, organic phosphoric acid, organic sulfonic acid A composition comprising at least one compound selected from the group consisting of ammonia, primary to tertiary amine compounds and quaternary ammonium hydroxide compounds, cross-linked materials obtained by cross-linking the composition by siloxane bonds. And to films, sheets or coatings made from the composition. The composition exhibits excellent optical transparency, solvent resistance, dimensional stability, heat resistance, and adhesion to metals and inorganic materials, and is suitable for use in optical transparent materials and electronic material parts.
公开号:KR20020027217A
申请号:KR1020010061027
申请日:2001-09-29
公开日:2002-04-13
发明作者:노보루 오시마；요오이찌로 마루야마；노부유끼 사까베；가쯔또시 사와다；겐조 오끼따；유우이찌 하시구찌；다로우 가나모리；고우지 가와하라
申请人:마쯔모또 에이찌；제이에스알 가부시끼가이샤；
IPC主号:

专利说明:

Composition of Cyclic Olefin Addition Copolymer and Cross-Linked Material
[1] The present invention relates to compositions comprising addition copolymers of cyclic olefins having alkoxysilyl functionality, cross-linked materials prepared from the compositions, and films, sheets or coatings made from the compositions.
[2] More specifically, the present invention exhibits excellent optical transparency, solvent resistance, dimensional stability, heat resistance, and adhesion to metals and inorganic materials, and has alkoxysilyl functional groups suitable for use in optical transparent materials and electronic material parts. A composition comprising an additional copolymer of a click olefin, a cross-linked material obtained by cross-linking the composition by siloxane bonds, and a film, sheet or coating made from the composition.
[3] In recent years, in order to meet the requirements of lightening, miniaturization and pain synthesis of optical components and liquid crystal display devices, attempts to replace inorganic glass with transparent optical resins in these component fields continue. For this reason, it is desirable to further improve heat resistance, chemical resistance, dimensional stability, adhesion and adhesion in addition to the optical transparency of the resin material.
[4] Cyclic olefin compounds and ring-opening polymers of the compounds in which they are hydrogenated are commonly known as materials which exhibit good transparency. However, many of these polymers are unsuitable as glass substitutes because of their poor heat resistance due to low glass transition temperatures of 200 ° C. or lower.
[5] Conversely, glass transitions of addition copolymers of norbornene compounds disclosed in Japanese Patent Application Laid-Open Nos. 4-63807 and 8-198919, PCT Application Nos. 9-508649 and 11-505880 The temperature is above 200 ° C. and the addition copolymer shows good transparency.
[6] However, these addition (co) polymers are not only difficult to cross-link due to the absence of cross-linking points but also exhibit poor dimensional stability, solvent resistance and chemical resistance.
[7] Japanese Patent Application Laid-Open No. 2001-98206 introduces functional groups such as hydroxyl groups as cross-linking points in polymers and cross-linking polymers using polyfunctional cross-linking agents such as dicarboxylic acids such as maleic acid or epoxy resins. A method is disclosed. However, improvements in dimensional stability, solvent resistance and chemical resistance of the cross-linked films obtained using this method are insufficient. To improve these properties, polymer molecules must be directly cross-linked through the functional groups introduced into the polymer molecule without the use of cross-linkers.
[8] One specific method is to introduce unsaturated double bonds into polymer molecules and cross-linked polymers using peroxides. However, it is not possible to achieve a sufficient degree of cross-linking using this method, nor to obtain a product with improved resistance to oxidative degradation, which is an antioxidant added to prevent degradation of the polymer by oxidation. This is due to the reaction of with peroxide. It is possible to use a method of irradiating cross-linked unsaturated double bonds without UV peroxide. However, when the polymer is exposed to strong UV light of intensity that achieves a high degree of cross-linking, the polymer can oxidize and become yellow and impair transparency.
[9] The introduction of an alkoxysilyl functional group into the polymer and the cross-linked polymer via siloxane linkage by hydrolysis and condensation can reduce the effect of the antioxidant added to the polymer.
[10] US Pat. No. 5,912,313 discloses cross-linked polymers with improved solvent resistance, obtained by heating an addition (co) polymer of norbornene containing an alkoxysilyl functional group at 300 ° C. A problem with this technique is the degradation of the polymer due to oxidation that occurs when the polymer is heated at 300 ° C. under oxygen.
[11] WO 98/20394 discloses a composition comprising a norbornene addition copolymer containing an alkoxysilyl functional group and a photoacid generator (photoinitiator), wherein the spin-coated thin film of the composition is irradiated with UV light to form a cross-linked polymer. A method is disclosed. However, irradiation with strong UV light can change the color of the polymer to yellow. In addition, it is difficult to homogeneously apply the cross-linked polymer onto the entire film or sheet thicker than the thin film produced by the spin-coating. In addition, when the composition contains a photoacid generator, certain cross-linking conditions that block UV radiation must be met to prevent any problems due to cross-linking during storage of the composition or manufacture of the film or sheet. . Therefore, a more convenient cross-linking method is needed.
[12] In addition to these problems, cross-linking of polymers can lead to various changes in polymer properties, such as increased solvent resistance and reduced linear expansion coefficients (increased dimensional stability), which are properties not covered in US Pat. No. 5,912,313 as well as WO 98/20394. Entails).
[13] The present invention has been made to solve the above problems and an object of the present invention is to exhibit excellent optical transparency, solvent resistance, dimensional stability, heat resistance, and adhesion to metal and inorganic materials, and to be used for optical transparent materials and electronic material parts. Suitable compositions comprising addition copolymers of cyclic olefins with alkoxysilyl functionalities, cross-linked materials obtained by cross-linking the composition with siloxane bonds, cross-linked substantially free of degradation by oxidation A process for preparing a material, a process for producing a cross-linked material substantially free of degradation by oxidation by cross-linking the composition by siloxane bonds, a film comprising the composition or a cross-linked material, or To provide a sheet and a coating film comprising the cross-linked material.
[14] As a result of extensive research, the inventors have found that the problems caused by cross-linking during the storage of a composition or during the manufacture of a film or sheet can be solved by using the composition of the present invention without using specific cross-linking conditions that are blocked by UV radiation. It has been found that cross-linked materials substantially free from degradation by oxidation can be prepared by heating the composition above 50 ° C. and optionally contacting the composition with water or steam above 50 ° C.
[15] Accordingly, the present invention provides a cyclic olefin addition copolymer containing a repeating unit (a) represented by the following formula (1) and a repeating unit (b) represented by the following formula (2); And (A) a metal compound which acts as an acid when heated to a temperature of 50 ° C. or higher, (B) an alkoxy compound, an aryloxy compound, a carboxyl compound, a β-diketone compound, a halogen compound or an oxide, wherein the metal is Al, Ga, Sn, Ca, Ba, Zn, Sb, Ti, Zr, Sc, Y, Ce, Nd, Sm and Yb), and (C) organic carboxylic acid, organic phosphoric acid, organic sulfonic acid It provides a composition comprising at least one compound selected from the group consisting of ammonia, primary to tertiary amine compounds and quaternary ammonium hydroxide compounds.
[16]
[17] Wherein A ¹ to A ⁴ are independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a chemical formula-(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 ) or-(CR ¹ R ² ) _f C (O) O (CH ₂ ) _h Si (OR ³ ) _g An alkoxysilyl group or an aryloxysilyl group represented by R ⁴ _(3-g) , wherein R ¹ and R ² are independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R ³ is each having 10 carbon atoms An alkyl group, an alkenyl group, an aryl group or a cycloalkyl group of less than R ⁴ is a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, f and h are integers from 0 to 5, g is from 1 to 3 Integer), provided that at least one of A ¹ to A ⁴ is an alkoxysilyl group or an aryloxysilyl group, Y is -CH ₂ -or -O-, and m is 0 or 1.
[18]
[19] Wherein B ¹ , B ² , B ³ and B ⁴ independently represent a hydrogen atom or an alkyl group, aryl group, alkenyl group or cycloalkyl group, halogen atom, halogenated hydrocarbon group, each having 20 or less carbon atoms, or-(CH ₂ ) a polar group represented by _j X, wherein 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 20 or less carbon atoms Or derivatives of these groups or halogen-substituted groups of these groups; j is an integer from 0 to 5), or B ¹ and B ² , or B ³ and B ⁴ may be bonded to form an alkylidenyl group, or Or B ¹ and B ⁴ , B ¹ and B ³ , B ² and B ³ , or B ² and B ⁴ may be bonded to form a cycloalkylene group or a cycloalkenylene group, n is an integer from 0 to 2 .
[20] In the composition, the cyclic olefin addition copolymer preferably contains 0.1 to 30 mol% of the repeating unit (a) represented by the formula (1), and 70 to 99.9 mol% of the repeating unit (b) represented by the formula (2), The sum of the repeating unit a) and the repeating unit (b) is 100 mol%.
[21] In the composition, the glass transition temperature of the cyclic olefin addition copolymer is preferably 200 ° C. or higher.
[22] The composition preferably comprises at least one compound (A).
[23] In the above composition, it is preferable that the compound (A) is a phosphorous acid ester compound, a hypophosphorous acid ester compound or both.
[24] The composition preferably comprises at least one compound (B) selected from the group consisting of divalent tin compounds represented by the following formula (3), tetravalent tin compounds represented by the following formula (4), and tetravalent tin oxides represented by the following formula (5).
[25] Sn (R ⁷ ) ₂
[26] Sn (R ⁸ ) _4-n (R ⁷ ) _n
[27] (R ⁸ ) ₂ Sn = O or (R ⁸ ) ₂ (Y) -Sn-O-Sn (R ⁸ ) ₂ (X)
[28] Wherein R ⁷ is a carboxyl group having 1 to 20 carbon atoms, a β-diketone group, an alkoxy group having 1 to 15 carbon atoms, a phenoxy group or a halogen atom; R ⁸ is a hydrocarbon group or halogen atom having 1 to 15 carbon atoms; n is an integer from 0 to 4; X and Y independently represent a hydroxyl group, a halogen atom or an isothiocyanate group.
[29] The composition preferably further comprises at least one compound selected from the group consisting of organosilanes represented by the following formula (6), hydrolyzates of organosilanes and condensates of organosilanes.
[30] (R ⁹ ) _q Si (OR ¹⁰ ) _4-q
[31] Wherein, R ⁹ independently represents an organic group having 1 to 10 carbon atoms when two or more R ⁹ are present; R ¹⁰ independently represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 6 carbon atoms; q is an integer of 0-2.
[32] The composition preferably further comprises one or more metal oxide particles selected from the group consisting of silica, alumina, zirconia, titania, diatomite, montmorillonite and tin oxide.
[33] The present invention also provides a cyclic olefin addition copolymer containing a repeating unit (a) represented by the following formula (1) and a repeating unit (b) represented by the following formula (2); And (A) a metal compound which acts as an acid when heated to a temperature of 50 ° C. or higher, (B) an alkoxy compound, an aryloxy compound, a carboxyl compound, a β-diketone compound, a halogen compound or an oxide, wherein the metal is Al, Ga, Sn, Ca, Ba, Zn, Sb, Ti, Zr, Sc, Y, Ce, Nd, Sm and Yb), and (C) organic carboxylic acid, organic phosphoric acid, organic sulfonic acid Prepared by cross-linking cyclic olefin addition copolymers by siloxane bonding in a composition composition comprising at least one compound selected from the group consisting of ammonia, primary to tertiary amine compounds and quaternary ammonium hydroxide compounds. It provides a cross-linked material.
[34] <Formula 1>
[35]
[36] Wherein A ¹ to A ⁴ are independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a chemical formula-(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 ) or-(CR ¹ R ² ) _f C (O) O (CH ₂ ) _h Si (OR ³ ) _g An alkoxysilyl group or an aryloxysilyl group represented by R ⁴ _(3-g) , wherein R ¹ and R ² are independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R ³ is each having 10 carbon atoms An alkyl group, an alkenyl group, an aryl group or a cycloalkyl group of less than R ⁴ is a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, f and h are integers from 0 to 5, g is from 1 to 3 Integer), provided that at least one of A ¹ to A ⁴ is an alkoxysilyl group or an aryloxysilyl group, Y is -CH ₂ -or -O-, and m is 0 or 1.
[37] <Formula 2>
[38]
[39] Wherein B ¹ , B ² , B ³ and B ⁴ independently represent a hydrogen atom or an alkyl group, aryl group, alkenyl group or cycloalkyl group, halogen atom, halogenated hydrocarbon group, each having 20 or less carbon atoms, or-(CH ₂ ) a polar group represented by _j X, wherein 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 20 or less carbon atoms Or derivatives of these groups or halogen-substituted groups of these groups; j is an integer from 0 to 5), or B ¹ and B ² , or B ³ and B ⁴ may be bonded to form an alkylidenyl group, or Or B ¹ and B ⁴ , B ¹ and B ³ , B ² and B ³ , or B ² and B ⁴ may be bonded to form a cycloalkylene group or a cycloalkenylene group, n is an integer from 0 to 2 .
[40] The cross-linked material preferably comprises up to 10% by weight of toluene soluble components.
[41] The cross-linked material preferably has a swelling degree of 300% or less of toluene measured at 25 ° C.
[42] The cross-linked material preferably has a linear expansion coefficient measured at 80 ° C. of 70 ppm / ° C. or less.
[43] The cross-linked material is preferably a film, sheet or coating.
[44] Other objects, features and advantages of the present invention will become more apparent from the following detailed description.
[45] Detailed Description of the Invention and Preferred Embodiments
[46] The present invention is described in more detail below.
[47] In the cyclic olefin addition copolymer having an alkoxysilyl functional group of the present invention, the repeating unit (a) of Formula 1 is an addition polymerization of a cyclic olefin represented by the following Formula 1 '(hereinafter referred to as "specific cyclic olefin 1"). It can form by.
[48] <Formula 1 '>
[49]
[50] Wherein A ¹ to A ⁴ , Y and m are the same as defined in Chemical Formula 1.
[51] The following compounds are those which may serve as specific examples of the specific cyclic olefin 1.
[52] 5-trimethoxysilyl-2-norbornene,
[53] 5-trimethoxysilyl-7-oxa-2-norbornene,
[54] 5-dimethoxychlorosilyl-2-norbornene,
[55] 5-dimethoxychlorosilyl-7-oxa-2-norbornene,
[56] 5-methoxychloromethylsilyl-2-norbornene,
[57] 5-methoxyhydridemethylsilyl-2-norbornene,
[58] 5-dimethoxyhydridesilyl-2-norbornene,
[59] 5-methoxydimethylsilyl-2-norbornene,
[60] 5-triethoxysilyl-2-norbornene,
[61] 5-triethoxysilyl-7-oxa-2-norbornene,
[62] 5-diethoxychlorosilyl-2-norbornene,
[63] 5-ethoxychloro-methylsilyl-2-norbornene,
[64] 5-diethoxyhydridesilyl-2-norbornene,
[65] 5-ethoxydimethylsilyl-2-norbornene,
[66] 5-ethoxydiethylsilyl-7-oxa-2-norbornene,
[67] 5-propoxydimethylsilyl-2-norbornene,
[68] 5-tripropoxysilyl-2-norbornene,
[69] 5-triphenoxysilyl-2-norbornene,
[70] 5-trimethoxysilylmethyl-2-norbornene,
[71] 5- (2-trimethoxysilyl) ethyl-2-norbornene,
[72] 5- (2-dimethoxychlorosilyl) ethyl-2-norbornene,
[73] 5- (1-trimethoxysilyl) ethyl-2-norbornene,
[74] 5- (2-trimethoxysilyl) propyl-2-norbornene,
[75] 5- (1-trimethoxysilyl) propyl-2-norbornene,
[76] 5-triethoxysilylethyl-7-oxa-2-norbornene,
[77] 5-dimethoxymethylsilylmethyl-2-norbornene,
[78] 5-trimethoxypropylsilyl-2-norbornene,
[79] 5-triethoxysiloxy-dimethylsilyl-2-norbornene,
[80] 8-triethoxysilyl-3-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodeken,
[81] 8-methyldimethoxysilyl-3-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodeken,
[82] 8-triethoxysiloxy-dimethylsilyl-3-tetracyclo [4.4.O.1 ^2,5 .1 ^7,10 ] dodeken,
[83] 5-trimethoxysiloxy-dimethylsilyl-2-norbornene,
[84] 5-methyldimethoxysiloxy-dimethylsilyl-2-norbornene,
[85] Trimethoxysilylpropyl 5-norbornene-2-carboxylate,
[86] Triethoxysilylpropyl 5-norbornene-2-carboxylate,
[87] Dimethoxysilylpropyl 5-norbornene-2-carboxylate,
[88] Trimethoxysilylpropyl 2-methyl-5-norbornene-2-carboxylate,
[89] Triethoxysilylpropyl 2-methyl-5-norbornene-2-carboxylate, and
[90] Dimethoxysilylpropyl 5-methyl-5-norbornene-2-carboxylate.
[91] The content of the repeating unit (a) in the cyclic olefin addition copolymer having an alkoxysilyl functional group is 0.2 to 30 mol%, preferably 0.5 to 20 mol%, more preferably 1.0 to 10 mol%. If the content of the repeating unit (a) in the cyclic olefin addition copolymer having an alkoxysilyl functional group is less than 0.2 mol%, it is difficult to form a crosslinking product. When this content exceeds 30 mol%, moisture resistance and dimensional stability tend to fall.
[92] As another method for forming the repeating unit (a) of the formula (1), by copolymerization of a cyclic olefin having a trichlorosilyl group or a dichloroalkylsilyl group (hereinafter referred to as "specific cyclic olefin 2") and Or a method in which the trichlorosilyl group or dichloroalkylsilyl group in the resulting copolymer is reacted with an alkoxide compound or an aryloxide compound of an alkali metal or the copolymer is reacted with an alcohol or a phenol compound in the presence of an amine compound. Can be.
[93] The following compounds are those which may serve as specific examples of the specific cyclic olefins 2 above.
[94] 5-trichlorosilyl-2-norbornene,
[95] 5-trichlorosilyl-7-oxa-2-norbornene,
[96] 5-dichloromethylsilyl-2-norbornene,
[97] 5-dichloroethylsilyl-2-norbornene,
[98] Trichlorosilylpropyl 5-norbornene-2-carboxylate,
[99] Trichlorosilylpropyl 2-methyl-5-norbornene-2-carboxylate, and
[100] Dichloromethylsilylpropyl 5-norbornene-2-carboxylate.
[101] In the cyclic olefin addition copolymer having an alkoxysilyl functional group of the present invention, the repeating unit (b) of formula (2) used together with the repeating unit (a) of formula (1) may be a cyclic olefin represented by the following formula (2 '). It may be formed by addition polymerization of the cyclic olefin 3 ").
[102] <Formula 2 '>
[103]
[104] Wherein, B ¹ to B ⁴ , and n are as defined in formula (2).
[105] The following compounds are those which may serve as specific examples of the specific cyclic olefins 3 above.
[106] 2-norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene,
[107] 5-propyl-2-norbornene, 5-butyl-2-norbornene,
[108] 5-pentyl-2-norbornene, 5-hexyl-2-norbornene,
[109] 5-heptyl-2-norbornene, 5-octyl-2-norbornene,
[110] 5-decyl-2-norbornene, 5-dodecyl-2-norbornene,
[111] 5-vinyl-2-norbornene, 5-allyl-2-norbornene,
[112] 5-butenyl-2-norbornene, 5-methylidene-2-norbornene,
[113] 5-ethylidene-2-norbornene, 5-isopropylidene-2-norbornene,
[114] 5,6-dimethyl-2-norbornene, 5-methyl-5-ethyl-2-norbornene,
[115] 5,6-benz-2-norbornadiene, 5-phenyl-2-norbornene,
[116] 2,5-norbornadiene, 5-methyl-2,5-norbornadiene,
[117] 5-cyclohexyl-2-norbornene, 5-fluoro-2-norbornene,
[118] 5-chloro-2-norbornene, methyl 5-norbornene-2-carboxylate,
[119] Ethyl 5-norbornene-2-carboxylate,
[120] Butyl 5-norbornene-2-carboxylate,
[121] Methyl 2-methyl-5-norbornene-2-carboxylate,
[122] Ethyl 2-methyl-5-norbornene-2-carboxylate,
[123] Propyl 2-methyl-5-norbornene-2-carboxylate,
[124] Butyl 2-methyl-5-norbornene-2-carboxylate,
[125] Methyl 2-ethyl-5-norbornene-2-carboxylate,
[126] Trifluoroethyl 2-methyl-5-norbornene-2-carboxylate,
[127] Ethyl 2-methyl-5-norbornene-2-ylacetate,
[128] 5-norbornene-2-spiro-N-phenylsuccinimide,
[129] 5-norbornene-2-spiro-N-cyclohexylsuccinimide,
[130] 5-norbornene-2-spiro-N-methylsuccinimide,
[131] 5-norbornene-2,3-N-phenyldicarboxyimide,
[132] 5-norbornene-2,3-N-cyclohexyldicarboxyimide,
[133] 2-methyl-5-norbornene acrylate,
[134] 2-methyl-5-norbornene methacrylate,
[135] Dimethyl 5-norbornene-2,3-dicarboxylate,
[136] Diethyl 5-norbornene-2,3-dicarboxylate,
[137] 3-tricyclo [4.3.0.1 ^2,5 ] dekene,
[138] 3,7-tricyclo [4.3.0.1 ^2,5 ] decadiene (dicyclopentadiene),
[139] 3-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodeken,
[140] 8-methyl-3-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecene,
[141] 8-ethylidene-3-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodeken,
[142] 8-methyl-8-methoxycarbonyl-3-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodeken, and
[143] 8-methyl-8-ethoxycarbonyl-3-tetracyclo [4.4.O.1 ^2,5 .1 ^7,10 ] dodeken.
[144] The compound (represented by Formula 2 ') for forming the repeating unit (b) may be used independently or in combination of two or more thereof.
[145] The content of the repeating unit (b) in the cyclic olefin addition copolymer having an alkoxysilyl functional group is 70 to 99.8 mol%, preferably 80 to 99.5 mol%, even more preferably 90 to 99 mol%. If the content of the repeating unit (b) is less than 70 mol%, the glass transition temperature can be reduced. If this content exceeds 99.8 mol%, crosslinking becomes difficult.
[146] In addition, the repeating unit (a) represented by Formula 1 may be formed by changing the reaction product using the specific cyclic olefin compound represented by Formula 2 '. Examples that may be mentioned include one or more compounds selected from the group consisting of norbornadiene compounds, compounds containing alkenyl substituents, and compounds having vinylideneyl substituents by addition copolymerization (hereinafter referred to as "specific cyclic olefins"). 4 ") and reacting the unsaturated double bond in the resulting copolymer with an alkoxysilane compound having a Si-H bond in the presence of a catalyst such as a Pt compound, a Rh compound or a Ru compound.
[147] The following compounds are those which may serve as specific examples of the specific cyclic olefins 4 above.
[148] 2,5-norbornadiene, 7-oxa-2,5-norbornadiene,
[149] 5-methyl-2,5-norbornadiene, 5-vinyl-2-norbornene,
[150] 5-vinyl-7-oxa-2-norbornene, 5-allyl-2-norbornene,
[151] 5-butenyl-2-norbornene, 5-methylidene-2-norbornene,
[152] 5-ethylidene-2-norbornene, 5-ethylidene-7-oxa-2-norbornene,
[153] 5-isopropylidene-2-norbornene, and
[154] 8-ethylidene-3-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodeken.
[155] The following compounds are those which may serve as specific examples of the alkoxysilane compound having a Si—H bond.
[156] Trimethoxysilane, triethoxysilane, tripropoxysilane, dimethoxysilane, diethoxysilane, dimethoxychlorosilane, diethoxychlorosilane, dimethoxymethylsilane, diethoxymethylsilane, dimethoxyphenylsilane, diethoxy Phenylsilane, monomethoxydimethylsilane, monoethoxydimethylsilane and monoethoxydiethylsilane.
[157] Hydrosilylation catalysts include 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.
[158] The cyclic olefin copolymer of the present invention can be prepared by addition copolymerization of specific cyclic olefin 1 and specific cyclic olefin 3 having a reactive silyl group.
[159] This reaction is carried out as follows.
[160] (A) A multicomponent catalyst containing the following compounds 1), 2) and 3) is used.
[161] 1) transition metal compound:
[162] Organic carboxylates, organic phosphites, organic phosphates, organic sulfonates and β-diketonato of nickel, cobalt or palladium [examples of such compounds are nickel acetate, nickel octanoate, nickel 2-ethylhexano Nate, nickel naphthenate, nickel oleate, nickel stearate, nickel dibutyl phosphate, nickel dibutyl phosphate, nickel dioctylphosphate, nickel salts of dibutyl phosphate, nickel dodecylbenzenesulfonate, nickel p-toluenesulfo Nate, nickel bis (acetylacetonate), nickel bis (acetylacetate), cobalt (II) 2-ethylhexanoate, cobalt (III) 2-ethylhexanoate, cobalt (II) dodecanoate, cobalt (II ) Naphthenate, cobalt (II) versatate, cobalt (III) tris (acetylacetonate), palladium acetate, palladium 2-ethylhexanoate and palladium bis (ace That such butyl acetonate);
[163] Pre-formed compounds prepared from such organic carboxylates of nickel, cobalt or palladium and super acids such as hexafluoro antimonic acid, tetrafluoroboric acid, trifluoro acetic acid or hexafluoro acetone;
[164] Complexes in which dienes or trienes coordinate with nickel, for example nickel complexes of 1,5-cyclooctadiene, [(η ³ -crotyl) Ni (cyclooctadiene)] [B ((CF ₃ ) 2C ₆ H ₄ ) ₄ ], [cyclododecatriene] nickel, or bis [norbornadiene] nickel;
[165] Complexes in which ligands containing P, N or O atoms are coordinated with nickel, for example bis (triphenylphosphine) nickel dichloride, bis (triphenylphosphine) nickel dibromide, bis (triphenylphosph) Pin) cobalt dibromide, bis (tris-tolylphosphine) nickel dichloride, 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 with PPh ₃ = CHC (O) Ph, and (ArN = CHC ₆ H ₃ (O) (Anth)) (Ph) (PPh ₃ ) Ni [where Ar is 2,6 -(Pr) ₂ C ₆ H ₃ , Pr is isopropyl, Anth is 9-anthracene, Ph is phenyl, Cy is cyclohexyl and COD is 1,5-cyclooctadiene]
[166] At least one compound selected from the group consisting of.
[167] 2) organoaluminum compounds
[168] Methyl Aloxane, Ethyl Aloxane, Butyl Aloxane, Methyl Aloxane partially mixed with Trialkyl Aluminum, Trimethyl Aluminum, Triethyl Aluminum, Triisobutyl Aluminum, Diisobutyl Aluminum Hydride, Diethyl Aluminum Chloride, Ethyl Aluminum At least one compound selected from organoaluminum compounds such as sesquichloride, ethyl aluminum dichloride. Of these, organoaluminum compounds containing at least methyl acetate are preferred.
[169] 3) Compounds That Enhance Polymerization Activity
[170] Non-conjugated diene compounds such as 1,5-cyclooctadiene and 1,5,9-cyclododecatene. Lewis-acidic boron or aluminum compounds, such as ether, amine or phenol complexes with boron trifluoride, ether, amine or phenols and trifluoroaluminum, tri (pentafluorophenyl) Complexes such as borane, tri (3,5-di-trifluoromethylphenyl) borane and tri (pentafluorophenyl) aluminum. Triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (3,5-di-trifluoromethylphenyl) borate, tributylammonium tetrakis (pentafluorophenyl) borate, N, N At least one compound selected from ionic boron compounds such as dimethylanilinium tetrakis (pentafluorophenyl) borate and N, N-diethylanilinium tetrakis (pentafluorophenyl) borate.
[171] (B) The following compounds are those which may serve as examples of one-component catalysts.
[172] B-1) A compound represented by the following formula (7).
[173] [L ¹ L ² ML ³ ] ⁺ [A] ^-
[174] Wherein M is Ni, Co or Pd, and L ¹ , L ² and L ³ represent a ligand of M, where one ligand has one σ bond and one to three π bonds to all ligands Is retained, and A is a counter anion. Specifically, L ¹ , L ^2, and L ³ are cyclodiene having 6 to 20 carbon atoms, norbornadiene having 6 to 20 carbon atoms, cyclotriene having 10 to 20 carbon atoms, and 6 to 20 carbon atoms. And a compound selected from the group consisting of 20 aromatic compounds. As the counter anion represented by A is _{^{BF 4 -, PF 6 -,}} SbF 5 SO 3 F -, AlF 3 SO 3 CF 3 -, AsF 6 -, SbF 6 -, AsF 6 -, CF 3 CO 2 -, C 2 _{^{F 5 CO 2 -, CH 3}} C 6 H 4 SO 3 -, B [C 6 F 5] 4 - , and _{B [C 6 H 3 (CF} 3) 2] 4 - are preferable.
[175] B-2) arene complexes of Ni (C ₆ F ₅ ) ₂ or Ni (SiCl ₃ ) ₂ .
[176] B-3) Palladium complex represented by the following formula (8).
[177] [Pd (II) (L ⁴ ) ₄ ] [A] ₂
[178] Wherein A is as defined in B-1, and L ⁴ represents a nitrile compound, tertiary amine compound or triaryl phosphine compound.
[179] The following compounds are those which may serve as specific examples of B-1, B-2 and B-3.
[180] B-1)
[181] [(η ³ -crotyl) Ni (cycloocta-1,5-diene)] [B ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ ],
[182] [(η ³ -crotyl) Ni (cycloocta-1,5-diene)] [PF ₆ ],
[183] (PPh ₃ ) (C ₆ H ₅ ) Ni (Ph ₂ PCH = C (O) Ph),
[184] (6-methoxy-bicyclo [2.2.1] hept-2-ene-end-5σ, 2π) Pd (cycloocta-1,5-diene)] [PF ₆ ],
[185] [(6-methoxy-bicyclo [2.2.1] hept-2-ene-end-5σ, 2π) Pd (cycloocta-1,5-diene)] [SbF ₆ ],
[186] [(η ³ -ali) Pd] [SbF ₆ ] obtained from [(η ³ -ali) PdCl] ₂ and AgSbF ₆ ,
[187] [(η ³ -ali) Pd] [BF ₄ ] obtained from [(η ³ -ali) PdCl] ₂ and AgBF ₄ ,
[188] [(η ³ -crotyl) Pd (cycloocta-1,5-diene)] [PF ₆ ],
[189] [Ph ₃ PPdCH ₃ ] [B ((CF ₃ ) ₂ C ₆ H ₃ ) ₃ ], and
[190] [(Cycloocta-1,5-diene) Pd (CH ₃ ) Cl] [B ((CF ₃ ) ₂ C ₆ H ₃ ) ₃ ]
[191] B-2)
[192] TolueneNi (C ₆ F ₅ ) ₂ , xyleneNi (C ₆ F ₅ ) ₂ ,
[193] MesityleneNi (C ₆ F ₅ ) ₂ , and tolueneNi (SiCl ₃ ) ₂ .
[194] B-3)
[195] [Pd (CH ₃ CN) ₄ ] [BF ₄ ] ₂ , [Pd (C ₆ H ₅ CN) ₄ ] [BF ₄ ] ₂ ,
[196] [Pd (C ₆ H ₅ CN) ₄ ] [SbF ₆ ] ₂ .
[197] These catalyst components are used in amounts in the following ranges.
[198] Specifically, transition metal compounds such as nickel compounds, cobalt compounds and palladium compounds are used in an amount of 0.02 to 100 mm moles per mole of monomer, and organoaluminum compounds in an amount of 1 to 5000 moles per mole of atoms of the transition metal compound. Non-conjugated dienes, Lewis acids and ionic boron compounds are used in amounts of 0.2 to 100 moles per mole of nickel or cobalt atoms.
[199] The cyclic olefin copolymer of the present invention is a multicomponent or single component catalyst selected from catalysts 1) and 2) and, optionally, 3) alicyclic hydrocarbon solvents such as cyclohexane, cyclopentane and methylcyclopentane, hexane, heptane And aliphatic hydrocarbon solvents such as octane, aromatic hydrocarbon solvents such as toluene, benzene, xylene and mesitylene, and dichloromethane, 1,2-dichloroethylene, 1,1-dichloroethylene, tetrachloroethylene, chlorobenzene and dichlorobenzene It can be obtained by copolymerizing monomers using the same halogenated hydrocarbon solvent.
[200] Although the outline of the method for producing the addition copolymer of the cyclic olefin having the alkoxysilyl functional group of the present invention is described below, it should not be considered as limiting the present invention.
[201] The solvent, the cyclic olefin monomer and the molecular weight regulator are added to the reaction vessel under nitrogen or argon atmosphere. The temperature range of a polymerization reaction system is set to -20 degreeC-100 degreeC.
[202] The catalyst is then added and the polymerization is carried out at a temperature of -20 ° C to 100 ° C. The weight ratio of solvent and monomer is in the range of 1-20. The molecular weight of the desired copolymer is controlled by adjusting the amount of polymerization catalyst, the amount of molecular weight modifiers such as α-olefins, hydrogen or diphenyldihydrosilane, conversion and polymerization temperature. The polymerization reaction is terminated by addition of a compound selected from water, alcohols, organic acids and carbon dioxide. A mixture of an acid such as maleic acid, fumaric acid or oxalic acid and water or alcohol is added to the polymer solution to separate and remove the catalyst residue. The polymer can be obtained by placing the polymer solution in an alcohol such as methanol, ethanol or i-propanol and drying the aggregated polymer under reduced pressure. In addition, unreacted monomers remaining in the polymer solution can also be removed in this manner.
[203] In the cyclic olefin addition copolymer having an alkoxysilyl functional group of the present invention, the range of the number average molecular weight (hereinafter referred to as "Mn") without polystyrene is measured by gel permeation chromatography using an o-dichlorobenzene solvent. Is preferably 10,000 to 1,000,000, more preferably 50,000 to 500,000. The weight average molecular weight of the polymer minus polystyrene (hereinafter referred to as "Mw") is preferably 15,000 to 1,500,000, more preferably 70,000 to 700,000. If Mn is less than 10,000 or Mw is less than 15,000, the breaking strength may not be sufficient. On the other hand, if Mn is 1,000,000 or more, or Mw is 1,500,000 or more, the viscosity of the polymer solution is increased, so that when the sheet or film is produced by cast formation using a cyclic olefin copolymer solution, there is no flatness or warping, It becomes difficult to obtain a sheet or a film.
[204] The glass transition temperature of the cyclic olefin addition copolymer having the alkoxysilyl functional group thus obtained is preferably 200 ° C or higher, more preferably 250 ° C to 400 ° C. If the glass transition temperature is less than 200 ° C., the shape of the product formed by the heat generated during the crosslinking formation may be modified.
[205] The cyclic olefin addition copolymer having an alkoxysilyl functional group of the present invention contains at least one compound selected from the following compounds (A), (B) and (C). This compound promotes the formation of siloxane bonds through which the cyclic olefin addition copolymer is crosslinked.
[206] (A) The compound which acts as an acid when heated to 50 degreeC or more.
[207] (B) alkoxy compounds, aryloxy compounds, carboxyl compounds, β-diketonato compounds, halogen compounds or metal compounds of oxides, wherein the metal is Al, Ga, Sn, Ca, Ba, Zn, Sb, Ti, Zr , Sc, Y, Ce, Nd, Sm and Yb.
[208] (C) a compound selected from the group consisting of organic carboxylic acids, organic phosphoric acids, organic sulfonic acids, ammonia, primary to tertiary amine compounds, and quaternary ammonium hydroxide compounds.
[209] As the compound (A), one or more compounds selected from compounds which generate an acid by pyrolysis or compounds which generate an acid by hydrolysis in the presence of hot water or steam can be used. Pyrolysis or hydrolysis takes place at 50 to 300 ° C, preferably at 80 to 250 ° C, even more preferably at 100 to 200 ° C. When crosslinking the composition of the present invention using compound (A), the composition must be crosslinked at a temperature higher than the temperature at which compound (A) is pyrolyzed or hydrolyzed.
[210] Specific examples of the compound (A) are described below, but should not be taken as limiting the present invention.
[211] Examples of the compound that produces an acid by pyrolysis include benzyl sulfonium salts, benzyl ammonium salts, benzyl phosphonium salts, hydradinium salts, and the like.
[212] On the other hand, as a compound which produces | generates an acid by hydrolysis, phosphorous acid ester, hypophosphorous acid ester, iminophosphonate, organic carboxylic acid ester, organic sulfonate, organic sulfinic acid, etc. are mentioned.
[213] Ester of phosphorous acid or hypophosphorous acid can be obtained by reacting an organic compound having a hydroxyl group with phosphorous acid or hypophosphorous acid. Examples of the organic compound having a hydroxyl group reacting with phosphorous acid or hypophosphorous acid include alcohols obtained by substituting one or more hydrogen atoms with a hydroxyl group in a saturated or unsaturated aliphatic hydrocarbon having 1 to 40 carbon atoms, and having 5 to 5 carbon atoms. Alcohols obtained by substituting one or more hydrogen atoms with a hydroxyl group in a saturated or unsaturated alicyclic hydrocarbon of 40, and one or more hydrogen atoms in an alkyl-substituted or unsubstituted aromatic hydrocarbon having 6 to 40 carbon atoms. Phenol etc. which were obtained by substituting the said are mentioned.
[214] Specific examples of the phosphite ester obtained by reacting the organic compound having a hydroxyl group with phosphoric acid,
[215] Phosphoric acid triesters such as trimethyl phosphite, triethyl phosphite, tripropyl phosphite, tributyl phosphite, trihexyl phosphite, trioctyl phosphite, tridecyl phosphite, triphenyl phosphite, trinonylphenyl Phosphite, tristearyl phosphite, diphenyloctyl phosphite, diphenyldecyl phosphite, phenyldidecyl phosphite, (tetraphenyl) dipropylene glycol diphosphite, (tetraphenyl) tetra (tridecyl) pentaerythritol Tetraphosphite, tetra (tridecyl) -4,4'-isopropylidenediphenyl diphosphate, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphate, bis (2, 4-di-t-butylphenyl) pentaerythritol diphosphate, bis (2,4-di-t-cumylphenyl) pentaerythritol diphosphate, bis (2,6-di-t-cumylphenyl) penta Erythritol diphosphite, distearylpentaerythritol diphosphate, 2,2-methylenebis (4, 6-di-t-butylphenyl) octyl phosphite, tri (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, 1,1,3-tris (2-methyl-4-ditridecylphosphite- 5-t-butylphenyl) -butane, bis (tridecyl) pentaerythritol tetraphosphite, bis (nonylphenyl) pentaerythritol tetraphosphite, distearylpentaerythritol diphosphate, bis (2, 6-di-t-butyl-4-methoxycarbonylethylphenyl) pentaerythritol diphosphate, and bis (2,6-di-t-butyl-4-octadecyloxycarbonylethylphenyl) penta Rititol diphosphite;
[216] Phosphorous acid diesters such as dimethyl phosphite, diethyl phosphite, dipropyl phosphite, dibutyl phosphite, dihexyl phosphite, dioctyl phosphite, didecyl phosphite, dilauryl phosphite, dioleyl phosphate Pit, diphenyl phosphite, phenyloctyl phosphite and phenyldecyl phosphite; And
[217] Phosphorous acid monoesters such as methyl phosphite, ethyl phosphite, propyl phosphite, butyl phosphite, hexyl phosphite, octyl phosphite, decyl phosphite and phenyl phosphite.
[218] Specific examples of the hypophosphite ester formed by the reaction of the organic compound having a hydroxyl group with hypophosphorous acid,
[219] Hypophosphite diesters such as dimethylphenyl phosphonite, diethylphenyl phosphonite, dipropylphenyl phosphonite, dibutylphenyl phosphonite, dihexylphenyl phosphonite, dioctylphenyl phosphonite, Didecylphenyl phosphonite, methyldiphenyl phosphonite, ethyldiphenyl phosphonite, propyldiphenyl phosphonite, butyldiphenyl phosphonite, hexyldiphenyl phosphonite, octyldiphenyl phosphonite, de Sildiphenyl phosphonite, bis [bis (2,4-di-t-butyl-5-methylphenoxy) phosphino] biphenyl, and bis [bis (2,4-di-t-butylphenoxy) force Pino] biphenyl;
[220] Hypophosphorous acid monoesters such as methylphenyl phosphinate, ethylphenyl phosphinate, propylphenyl phosphinate, butylphenyl phosphinate, hexylphenyl phosphinate, octylphenyl phosphinate and decylphenyl phosphinate Included.
[221] Examples of other compounds that generate acids by hydrolysis include
[222] Organic carboxylic acid esters such as propyl acetate, butyl acetate, amyl acetate, propyl propionate, butyl propionate, amyl propionate, propyl 2-ethylhexanoate, butyl 2-ethylhexanoate, And amyl 2-ethylhexanoate;
[223] Organic sulfonic acid esters such as ethyl p-toluenesulfonate, propyl p-toluenesulfonate, butyl p-toluenesulfonate, amyl p-toluenesulfonate, ethyl decansulfonate, propyl decansulfonate, butyl decansulfonate And amyl decansulfonate;
[224] Organic sulfinic acid esters, for example ethyl p-toluenesulfinate, propyl p-toluenesulfinate, butyl p-toluenesulfinate, amyl p-toluenesulfinate, ethyl decansulfinate, propyl decansulfinate, butyl decansulfipi And amyl decanesulfinate; And
[225] Iminosulfonates, for example, 2,3,4-trihydronaphthyl-1-imino-N-phenylsulfonate, and the like.
[226] Among them, phosphorous acid esters and hypophosphorous acid esters are preferable in view of excellent storage stability of the composition. Among the phosphorous and hypophosphite esters, phosphorous esters are more preferable because of the high catalytic activity of the composition and excellent storage stability.
[227] Such crosslinking catalysts which act as acids by hydrolysis are 0.001 to 10 parts by weight, preferably 0.01 to 5.0 parts by weight, more preferably 0.05 to 5 parts by weight, per 100 parts by weight of the cyclic olefin addition copolymer having an alkoxysilyl functional group in the composition. It is used in the amount of 2.0 weight part. If the amount of the crosslinking catalyst is less than 0.001 part by weight, the catalytic effect will not be sufficient, but if it is 10 parts by weight or more, the transparency of the resulting crosslinking product may decrease, and the amount of volatile components may increase during heating. .
[228] Specific examples of the compound (B) are described below, but should not be considered as limiting the present invention.
[229] Specific examples of the aluminum compound,
[230] Organoaluminum compounds, for example, tri-i-propoxy aluminum, di-i-propoxy ethylacetoacetate aluminum, di-i-propoxy acetylacetonate aluminum, i-propoxy bis (ethylacetoacetate ) Aluminum, i-propoxy bis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum, and mono-acetylacetonate bis (ethylacetoacetate) aluminum;
[231] Specific examples of gallium compounds include tris (acetylacetonate) gallium, tri-i-propoxy gallium, di-i-propoxy acetylacetonate gallium, and i-propoxy bis (ethylacetoacetate) gallium .
[232] Specific examples of tin compounds are described below.
[233] Specific examples of calcium compounds include calcium acetate and calcium octanoate.
[234] Specific examples of barium compounds include barium acetate and barium octanoate.
[235] Specific examples of zinc compounds include zinc acetate and zinc octanoate.
[236] Specific examples of antimony compounds include antimony acetate and antimony ethylene glycoside.
[237] Specific examples of the titanium compound include tetra-i-propoxy titanium, di-i-propoxy bis (ethylacetoacetate) titanium, di-i-propoxy bis (acetylacetate) titanium and di-i-propoxy. Bis (acetylacetone) titanium is included.
[238] Specific examples of zirconium compounds include organic zirconium compounds such as tetra-n-butoxy zirconium, tri-n-butoxyethylacetoacetate zirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n Butoxy tris (ethylacetoacetate) zirconium, tetrakis (n-propylacetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium and tetrakis (ethylacetoacetate) zirconium.
[239] Specific examples of scandium compounds include scandium tri-i-propoxide.
[240] Specific examples of yttrium compounds include yttrium tri-i-propoxide and yttrium tris (aluminum tetra-i-propoxide).
[241] Specific examples of lanthanide compounds include iso-propoxide compounds and butoxide compounds of Gd, Nd, Sm or Yb.
[242] Among the above compounds, at least one compound selected from tin compounds represented by the following formulas (3), (4) and (5) is preferable.
[243] <Formula 3>
[244] Sn (R ⁷ ) ₂
[245] In the above formula, R ⁷ is a carboxyl group having 1 to 20 carbon atoms, a β-diketone group, an alkoxyl group having 1 to 15 carbon atoms, a phenoxy group, or a halogen atom.
[246] <Formula 4>
[247] Sn (R ⁸ ) _4-n (R ⁷ ) _n
[248] In the above formula, R ⁷ is as defined in formula (3), R ⁸ is a hydrocarbon group or halogen atom of 1 to 15 carbon atoms, n is an integer of 0 to 4.
[249] <Formula 5>
[250] (R ⁸ ) ₂ Sn = O or (R ⁸ ) ₂ (Y) -Sn-O-Sn (R ⁸ ) ₂ (X)
[251] Wherein R ⁸ is as defined in formula (4), and X and Y each represent a hydroxyl group, a halogen atom or an isothiocyanate group.
[252] Specific examples of the tin compound are as follows.
[253] Tin compound represented by the formula (1).
[254] Tin (II) diacetate, tin (II) dipropionate, tin (II) maleate, tin (II) fumarate, tin (II) dioctanoate, tin (II) decanoate, tin (II ) Dododecanoate, tin (II) dilaurate, tin (II) dioleate, tin (II) diversaticate, tin (II) naphthoate, tin (II) bisacetylacetonate, tin ( II) bis-ethylacetoacetate, tin (II) bis-butylacetoacetate, tin (II) dimethoxide, tin (II) diethoxide, tin (II) dipropoxide, tin (II) dibutoxide , Tin (II) diamyloxide, tin (II) diphenoxide, tin (II) bis (2,6-di-tert-butylphenoxide), tin (II) dinonylphenoxide, tin (II) di Chloride, tin (II) dibromide, and tin (II) dichlorolide dihydride.
[255] Tin compound represented by the formula (2).
[256] Dibutyltin (IV) dilaurate, dibutyltin (IV) dioleate, dibutyltin (IV) dioctoate, dibutyltin (IV) distearate, dihexyltin (IV) dilaurate, dihex Siltin (IV) dioleate, dioctyltin (IV) dilaurate, dioctyltin (IV) dioleate, dioctyltin (IV) diversaticate, dibutyltin (IV) maleate, dibutyltin (IV ) Fumarate, dioctyltin (IV) malate, dioctyltin (IV) acetylacetonate, dibutyltin (IV) acetylacetonate, dioctyltin (IV) ethylacetoacetate, dibutyltin (IV) dichloride, dioxane Tiltin (IV) dichloride, dioctyltin (IV) dibromide, tin (IV) tetrachloride, dibutyltin (IV) dibutoxide, dibutyltin (IV) dipropoxide, dibutyltin (IV) diee Toxide, dioctyltin (IV) diethoxide, dibutyltin (IV) diphenoxide, dibutyltin (IV) dinonylphenoxide, tributyltin (IV) chlora Tributyltin (IV) methoxide, tributyltin (IV) ethoxide, tributyltin (IV) butoxide, tributyltin (IV) acetate, tributyltin (IV) octoate, trioctyltin ( IV) chloride, and trioctyltin (IV) acetate.
[257] Tin compound represented by the formula (3).
[258] Diethyltin oxide, dibutyltin oxide, dioctyltin oxide, dinonyltin oxide, 1-hydroxy-3-chloro-1,1,3,3-tetrabutyl-distanoxane, 1-hydroxy 3-Chloro-1,1,3,3-tetramethyl-distanoxane, 1-hydroxy-3-chloro-1,1,3,3-tetraethyl-distanoxane, 1-hydroxy-3 i-thiocyanato-1,1,3,3-tetrabutyl-distanoxane, 1-hydroxy-3-chloro-1,1,3,3-tetraoctyl-distanoxane, and 1, 3-bis (isocyanate) -1,1,3,3-tetrabutyl-distanoxane.
[259] The tin compound is used in an amount of 0.001 to 5 parts by weight, preferably 0.005 to 1.0 parts by weight, more preferably 0.01 to 0.1 parts by weight, per 100 parts by weight of the cyclic olefin addition copolymer having an alkoxysilyl functional group in the composition. If the amount of the tin compound is less than 0.001 parts by weight, the catalytic effect will not be sufficient, but if it is 5 parts by weight or more, the storage stability of the composition may be lowered.
[260] Crosslinking of the composition of the present invention is carried out using the tin compound in the solid state under high humidity conditions as a water-soluble solution or as a suspension or emulsion of a polymer containing a dispersing or emulsifying agent. If the amount of water provided is not sufficient for the amount of alkoxysilane of the cyclic olefin addition copolymer having an alkoxysilyl functional group in the composition, the crosslinking may remain insufficient.
[261] Crosslinking formation is generally carried out at 0 to 300 ° C., preferably at 50 to 200 ° C. for 1 minute to 1,000 hours. However, the optimum temperature and reaction time depend on the degree of crosslink formation, reaction system conditions, polymer type, polymer concentration in solution, and catalyst type.
[262] The use of a divalent tin compound of formula (3) speeds up the crosslinking reaction, alcohols such as methanol, ethanol, propanol, butanol, octanol, or benzyl alcohol, or lactic acid derivatives having hydroxyl functional groups (e.g., L Lactide, D, L-methyl lactate, D, L-ethyl lactate, D, L-butyl lactate or D, L-octyl lactate can be used to reduce the amount of tin compounds used in small amounts. Can be. Such alcohol or lactic acid derivatives may be added in an amount of 0.1 to 500 moles per mole of divalent tin compound of formula (3).
[263] Specific examples of the compound (C) are described below, but should not be taken as limiting the present invention.
[264] Mono or di-phosphates, di- or phosphates of organic carboxylic acids such as formic acid, oxalic acid, acetic acid, hexanoic acid, octanoic acid, lactic acid, stearic acid, oleic acid, maleic acid and fumaric acid, dioctyl phosphate, dibutyl phosphate, lauxy polyethylene glycol Organic phosphoric acids such as butyl monophosphate, dibutyl diphosphate, dioctyl monophosphate, organic sulfonic acids such as dodecylbenzenesulfonic acid and nonylbenzenesulfonic acid, methylamine, ethylamine, butylamine, octylamine, ethylenediamine, diethylamine, Primary, secondary or tertiary amine compounds such as dibutylamine, pyridine, triethylenediamine, tetramethyl ethylenediamine and cyclohexylamine and tetramethylammonium hydroxide, tetrabutylammonium hydroxide and tetraoctylammonium hydroxide Quaternary ammonium hydroxide compounds such as seeds.
[265] The compounds (A) to (C) can be used independently or in combination of two or more. As used herein, the use of two or more combinations includes the use of two or more compounds of the same kind, eg, compound (A), as well as the use of other kinds, such as compound (A) and compound (B).
[266] The cross-linked product is cloudy when the composition comprises organosilanes, hydrolysates or condensates of organosilanes described below or fine particles of metal oxides such as silica, alumina, zirconia, titania, diatomite, montmorillonite and zinc oxide. Can be done. The combined use of compound (A) and compound (B) overcomes this problem and is effective in producing cross-linked materials having good reproducibility and good transparency.
[267] Although the details of the reaction mechanism are not very clear, the catalysis of compound (B) by grafting the copolymer with the above components improves the dispersion of the alkoxysilane or metal oxide particles in the cyclic olefin addition copolymer, and the compound (A It is assumed that the catalysis of) cross-links the molecules of the modified cyclic olefin addition copolymer. As a result, very transparent cross-linked materials can be easily produced.
[268] In order to improve the cross-linking degree, heat resistance and spatial stability of the cross-linked material of the present invention, at least one component is a hydrolyzate of organosilane (1). And a condensate of organosilane (1) may be added to the composition of the cyclic olefin addition copolymer having an alkoxysilyl functional group.
[269] <Formula 6>
[270] (R ⁹ ) _q Si (OR ¹⁰ ) _4-q
[271] Where
[272] R ⁹ independently represents an organic group having 1 to 10 carbon atoms, when two or more are present,
[273] R ¹⁰ independently represents an alkyl group having 1 to 5 carbon atoms or an acyl atom having 1 to 6 carbon atoms,
[274] q is an integer of 0-2.
[275] In the present invention, the hydrolyzate of organosilane (1) is not limited to a compound in which all OR ¹⁰ groups in the compound are hydrolyzed, but includes a compound in which one, two or more OR ¹⁰ groups are hydrolyzed and a mixture of such compounds. .
[276] In the same way, the condensates of organosilane (1), which means compounds formed by condensation of silanol groups on hydrolyzed organosilanes with Si—O—Si bonds, are not limited to compounds in which all silanol groups are condensed, but only It includes compounds in which a small amount of silanol groups are condensed as well as mixtures of compounds having different degrees of condensation.
[277] In the formula (6), the carbon atom content of the R ⁹ group is 1 to 10, preferably 1 to 8. Examples of the monovalent organic group represented by R ⁹ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group alkyl groups such as n-heptyl group, n-octyl group and 2-ethylhexyl group, acetyl group, propionyl group, butyryl group, valeryl group, acyl group such as benzoyl group, trioyl group and caproyl group, vinyl group, phenyl group Glycidyl groups, (meth) acryloxy groups, ureido groups, amide groups, fluoroacetamide groups and isocyanate groups as well as substituted derivatives of these groups can be given.
[278] Examples of the substituent of the R ⁹ group include a halogen atom, a substituted or unsubstituted amino group, a mercapto group, an isocyanate group, a glycidoxy group, a 3,4-epoxycyclohexyl group, a (meth) acryloxy group, a ureido group and an ammonium salt This can be given. The number of carbon atoms in the R ⁹ group containing such a substituent is 20 or less.
[279] When two or more R ⁹ groups are contained in the compound of formula (6), the groups may be the same or different.
[280] Examples of the alkyl group of R ¹⁰ having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl groups and the like can be given. As an example of the acyl group having 1 to 6 carbon atoms, an acetyl group, propionyl group, butyryl group, valeryl group and caproyl group may be given.
[281] The following compounds can be given as specific examples of organosilane (1).
[282] Tetra-alkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane and tetra-n-butoxysilane, methyltrimethoxysilane, methyltriethoxy Silane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n-butyltri Methoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, vinyltrimethoxysilane, Vinyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltrier Cysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropylethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3 -Isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-glycidoxyoxypropyltrimethoxysilane, 3-glycidoxyoxytriethoxysilane, 2- (3,4-epoxycyclohexyl) Ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3 Ureidopropyltrimethoxysilane and 3-ureidopropyltriethoxysilane Same trialkoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-i-propyl Dimethoxysilane, di-i-propyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di -n-hexyldimethoxysilane, di-n-hexyl diethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyl diethoxysilane, di-n-octyldimethoxysilane, di-n-octyldie Dialkoxysilanes such as methoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane and diphenyldiethoxysilane, methyltriacetyloxysilane and dimethyldiacetyloxy Silane.
[283] Of these organosilanes, tetramethoxysilane and tetraethoxysilane are preferred as tetraalkoxysilane, methyltrimethoxysilane and methyltriethoxysilane are preferred as trialkoxysilane, and dimethyldimethoxysilane and dityldiethoxysilane It is preferable as this dialkoxysilane.
[284] In the present invention, particularly preferred methods of using organosilanes are tetraalkoxysilanes, trialkoxysilanes or dialkoxysilanes alone or 10 to 90 mole percent tetraalkoxysilane, 10 to 90 mole percent trialkoxysilane and 10 to 90 moles. Combined use of 90 mole percent dialkoxysilane. Cross-linked materials having a small linear expansion coefficient or exhibiting good dimensional stability can be obtained by introducing such alkoxysilanes. Adhesion can also be improved.
[285] Organosilanes are used as hydrolysates and / or condensates.
[286] Hydrolysates and condensates can be used for the hydrolysis or condensation of organosilanes (1) as well as chlorosilanes such as methyltrichlorosilane, ethyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, diethyldichlorosilane or diphenyldichlorosilane. It can be obtained by hydrolysis or condensation of the compound.
[287] When organosilane (1) is used as a hydrolyzate and / or a condensate, the MW of the condensate is preferably 800 to 100,000, even more preferably 1,000 to 50,000.
[288] The hydrolyzate / condensate of organosilane (1) is MKC silicate manufactured by Mitsubishi Chemical Corp., ethyl silicate manufactured by Colcoat Co., Ltd., Toray-Dow Corning. Silicone resin manufactured by Dow Corning Co., Ltd., silicone resin manufactured by Shin-Etsu Chemical Co., Ltd., hydroxyl group manufactured by Dow Corning Asia Co. Commercially available as silicon oligomers prepared from -containing polydimethylsiloxane and Nippon Unica Co., Ltd. They are used as such or after condensation.
[289] These compounds of organosilane (1) are added to the composition of the present invention in an amount of 2 to 70 parts by weight, preferably 5 to 50 parts by weight, relative to 100 parts by weight of the cyclic olefin copolymer. When the amount of compound added is less than 2 parts by weight, the film or sheet prepared from the composition shows very slight improvement in solvent resistance and dimensional stability. If more than 70 parts by weight, transparency may be impaired.
[290] When organosilane (1) forms inorganic particles by hydrolysis / condensation, when the particle size of the inorganic particles is 100 μm or less, preferably 10 μm or less, the inorganic particles are dispersed in the polymer, thereby optically A composition which is transparent and exhibits excellent heat resistance and dimensional stability can be prepared.
[291] In order to increase the cross-linking degree and heat resistance of the cross-linked material of the present invention, at least one metal oxide selected from silica, alumina, zirconia, titanium dioxide, diatomite, montmorillonite and zinc dioxide has an alkoxysilyl functional group. It may be added to the composition of the click olefin addition copolymer.
[292] These metal oxide particles are added to the composition of the present invention in an amount of 2 to 70 parts by weight, preferably 5 to 50 parts by weight, relative to 100 parts by weight of the cyclic olefin copolymer having an alkoxysilyl functional group. When this amount is less than 2 parts by weight, the cross-linked material shows very slight improvement in solvent resistance and dimensional stability. If more than 70 parts by weight, transparency may be impaired.
[293] The particle diameter of the metal oxide particles is preferably 100 nm or less, more preferably 10 nm or less. The particle size ensures the production of optically clear cross-linked materials having good heat resistance and dimensional stability.
[294] The formed article can be prepared from the composition of the cyclic olefin addition copolymer having the alkoxysilyl functional group of the present invention according to the casting method. In particular, the film, sheet or coating film can be formed by casting a solution of the composition, removing the solvent and drying the coating. Since the solubility of the cyclic olefin addition copolymer having an alkoxysilyl functional group varies depending on the type of copolymer, the solvent used as the casting solvent cannot generally be specified, but one or more solvents are hydrocarbon compounds, halogenated hydrocarbon compounds. , Ethers, esters, ketones, amines, amides, alcohols, phenols and sulfoxides. The amount of solvent used is 1 to 10,000 parts by weight, preferably 10 to 5,000 parts by weight based on 100 parts by weight of the copolymer.
[295] Cross-linking can be completed by heating the formed product at 50 ° C. or higher and optionally contacting the formed product by generating water or steam at 50 ° C. or higher.
[296] Suitable cross-linking reaction conditions may be selected according to the desired degree of cross-linking, the state of the reaction system, the type of polymer, the type and amount of catalyst.
[297] The content of toluene soluble component in the cross-linked material of the present invention is preferably 10% by weight or less. Furthermore, the degree of swelling of the cross-linked material determined in toluene at 25 ° C. is preferably 300% or less.
[298] When the content of the toluene soluble component is at least 10% by weight and the degree of swelling is at least 300%, the cross-linked material does not have chemical resistance, solvent resistance and dimensional stability during heating sufficiently for use as the glass substrate. Swelling degree is a value determined by the method mentioned later. The swelling degree of the cross-linked material can be easily adjusted by the amount of the cross-linked catalyst, the reaction temperature and the reaction time.
[299] Moreover, the linear expansion coefficient of the cross-linked material determined at 80 ° C. is preferably 70 ppm / ° C. or less. If the linear expansion coefficient determined at 80 ° C. is 70 ppm / ° C. or higher, the thermal decomposition of the cross-linked material during post-treatment or use at high temperatures may be so great that the product after the process may be defective or cross-linked Problems may arise in products in which used materials are used.
[300] 2,6-di-t-butyl-4-methylphenol, 4,4'-thiolbis (3-methyl-6-t-butylphenol), 1,1'-bis (4-hydroxyphenyl) cyclohexane , 2,2'-methylenebis (4-methyl-6-t-butyl-6-butylphenol), 2,5-di-t-butylhydroquinone and pentaerythryl-tetrakis- [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate] is a composition of the present invention that increases the oxidative stability or composition of the cyclic olefin addition copolymer having an alkoxysilyl functional group. May be added to the cross-linked product.
[301] Due to the excellent light transmittance, heat resistance, adhesion and anti-hygroscopic properties, the composition of the cyclic olefin addition copolymer having the alkoxysilyl functional group of the present invention is suitably suitable for light conductive boards, polarizing films, liquid crystal panels, phase transfer films, transparent It can be used as a material for electronic parts such as conductive films, OHP films, optical discs, optical fibers and lenses, and as adhesives and coating materials.
[302] The cross-linked product prepared from the composition of the cyclic olefin addition copolymer having the alkoxysilyl functional group of the present invention may suitably be used as a substrate for a liquid crystal display device which is a glass substrate. Such a material is characterized in that when a TFT (film transistor) is formed on a liquid crystal substrate, the heat resistance, cleaning solution resistance, transparency, adhesion, dimensional stability, and liquid crystal resistance during liquid crystal injection required for the substrate material during the exposure, development, and etching processes Satisfy various such characteristics.
[303] <Example>
[304] The invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereby.
[305] Molecular weight, swelling degree, glass transition temperature, liquid crystal resistance, total light transmittance and solution viscosity were determined by the following method.
[306] (1) weight average molecular weight and number average molecular weight
[307] Molecular weight by Gel Permeation Chromatography (GPC) using o-dichlorobenzene as Waters Co. manufactured GPC apparatus type-150C, manufactured by Tosoh Corp., and solvent at 120 ° C. Was determined. The molecular weight determined is indicated by standard polystyrene-reduced values.
[308] (2) residual metal
[309] The residual metal in the copolymer was measured for atomic absorption using a Hitachi, Ltd. Z-9000 atomic spectrophotometer, and the measured value was measured using nickel and aluminum standard solutions (Wako Pure Chemical Co., Ltd.). Chemical Co., Ltd.) was applied to the calibration curve prepared.
[310] (3) swelling degree in toluene
[311] A 2 cm x 2 cm film having a thickness of 100 μm was immersed in toluene at 25 ° C. for 3 hours. The degree of swelling was determined from the weight ratio before and after dipping. Samples that appeared not to swell are graded as having a degree of non-swelling of 100%.
[312] (4) glass transition temperature
[313] Since the glass transition temperature of the cyclic olefin addition copolymer of the present invention is not always clearly determined by the differential scanning calorimetry (DSC method), tangent δ (storage modulus (E ')), which is the peak temperature determined by dynamic viscoelasticity measurement. Ratio (E '/ E ") of the loss modulus (E") was made into glass transition temperature.
[314] Dynamic viscoelasticity is achieved using a Leovibron DDV-01 FP (manufactured by Olientech Co., Ltd.) with a frequency of 10 Hz, a temperature rise rate of 4 ° C./min, a single wavelength forming vibration scheme and a vibration swing of 2.5 μm. Measured under conditions.
[315] (5) total light transmittance
[316] Total light transmittance was measured according to ASTM-D 1003 using a 100 μm thick film.
[317] (6) linear expansion coefficient
[318] Samples (3 cm × 10 mm × 100 μm) were safely stored in a mechanical thermal analyzer (TMA) SS6100 (manufactured by Seiko Instrument Co., Ltd.) at a chuck distance of 10 mm, The residual stress was measured by heating from room temperature to 200 ° C. Then, after cooling to room temperature, the sample was again heated to a temperature rise rate of 3 ° C./min to determine the linear expansion coefficient from elongation of the chuck distance.
[319] (7) liquid crystal resistance
[320] A drop of liquid crystal (approximately 20 mg) for TFT measurement (ZLI5081, manufactured by Merck Japan Inc.) was added dropwise onto the sample (2 cm × 2 cm × 50 to 500 μm) and 150 ° C. for 1 hour. It was heated under atmospheric pressure at and evaluated by visually observing a change on the film surface. Evaluation was made based on the following standards.
[321] ◎: No change in appearance
[322] O: Slight expansion is observed
[323] Δ: sample expanded
[324] ×: sample is deformed by dissolution or other action
[325] (8) adhesiveness and adhesion
[326] Aluminum was applied to the surface of the test film by vapor deposition. The aluminum surface was cut into 5 × 5 squares (each 1 mm × 1 mm) and a peel test was performed using an adhesive cellophane tape to determine the number of peeled squares out of 25 squares.
[327] Reference Example 1
[328] Synthesis of Copolymer (a)
[329] The reaction vessel (1 L) was 593.75 mmol of 2-norbornene, 31.25 mmol of 5-triethoxy-2-norbornene, 500 g of toluene as solvent and 0.25 m of molecular weight modifier (1,5-cyclooctadiene) It was filled with mol. The reaction system was maintained at 10 ° C. and a 1: 1 (molar ratio) mixture of nickel octoate and hexafluoro antimonite at −15 ° C., 2.25 mmol of trifluoroboron-diethyl ether complex and 2.5 mmol of triethyl aluminum The reaction was filled with 0.25 mmol of a nickel compound prepared in advance.
[330] After polymerization at 30 ° C. for 1 hour, isopropyl alcohol was added to terminate the polymerization reaction. The addition rate to the copolymer was 95%. 6 g of lactic acid was added to the copolymer solution to react with the catalyst component. The copolymer solution was poured into 4 l of isopropanol to coagulate the copolymer, thereby removing unreacted monomers and catalyst residues.
[331] The coagulated copolymer was dried to give copolymer (a).
[332] ¹ H-NMR analysis at 270 MHz (methylene absorption of ethoxy silyl group: 3.7 ppm, solvent: toluene D8, based on TMS). As a result, the copolymer (a) was 5-triethoxysilyl-2-nor It was found to contain 5.0 mol% of the structures derived from bornen. Mn and Mw of copolymer (a) were 87,000 and 211,000, respectively. The amount of residual nickel in the polymer was 0.1 ppm or less and the residual aluminum was 1.6 ppm.
[333] Reference Example 2
[334] Synthesis of Copolymer (b)
[335] Copolymer (b) was prepared in the same manner as in Reference Example 1, except that 562.5 mmol of 2-norbornene and 62.5 mmol of 5-triethoxy-2-norbornene were used as monomers.
[336] ¹ H-NMR analysis at 270 MHz (methylene absorption of ethoxy silyl group: 3.7 ppm, solvent: toluene D8, based on TMS). As a result, copolymer (b) was 5-triethoxysilyl-2-nor. It was found to contain 9.9 mol% of structures derived from bornen. Mn and Mw of copolymer (b) were 88,000 and 223,000, respectively. The amount of residual nickel in the polymer was 0.1 ppm or less and the residual aluminum was 1.2 ppm.
[337] Reference Example 3
[338] Synthesis of Copolymer (c)
[339] Copolymer (c) comprises 531.23 mmol of 2-norbornene, 62.50 mmol of 5-triethoxy-2-norbornene and 8-methyl-8-methoxycarbonyl-3-tetracyclo- [4.4 .0.1 ^2,5 1 ^7,10 ] The same procedure was followed as in Reference Example 1, except that 31.25 mmol of dodecene was used.
[340] ¹ H-NMR analysis at 270 MHz (methylene absorption of ethoxy silyl group: 3.7 ppm, solvent: toluene D8, based on TMS). As a result, the copolymer (c) was 5-triethoxysilyl-2-nor It was found to contain 9.9 mol% of structures derived from bornen. From the calibration curve of the characteristic IR absorption at 1730 cm ⁻¹ , 8-methyl-8-methoxycarbonyl-3-tetracyclo- [4.4.0.1 ^2,5 1 ^7,10 ] dodecene in copolymer (c) It was confirmed that the content of the structure derived from 4.9 mol%. Mn and Mw of copolymer (c) were 89,000 and 256,000, respectively. The amount of residual nickel in the polymer was 0.1 ppm or less, and the residual aluminum was also 0.1 ppm or less.
[341] Reference Example 4
[342] Synthesis of Copolymer (d)
[343] Copolymer (d) is a monomer of 2-norbornene 500 mmol, 5-n-hexyl-2-norbornene 93.75 mmol, 5-triethoxy-2-norbornene 62.50 mmol and 5-tri It was prepared in the same manner as in Reference Example 1 except that 31.25 mmol of ethoxysilyl-2-norbornene was used.
[344] ¹ H-NMR analysis at 270 MHz (methylene absorption of ethoxy silyl group: 3.7 ppm, solvent: toluene D8, based on TMS). As a result, the copolymer (d) was 5-triethoxysilyl-2-nor It was found to contain 4.8 mol% of the structures derived from bornen. From the calibration curve of the characteristic IR absorption at 721 cm ^-1 , it was confirmed that the content of the structure derived from 5-n-hexyl-2-norbornene in the copolymer (d) was 14.0 mol%. Mn and Mw of copolymer (d) were 220,000 and 350,000, respectively. The amount of residual nickel in the polymer was 0.1 ppm or less and the residual aluminum was 1.1 ppm.
[345] In the following examples, the following compounds were used as the compound (A).
[346] P1: tributoxy phosphite
[347] P2: bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite
[348] P3: phenyldidecyl phosphite
[349] P4: dibutyl phosphite
[350] P5: ethyl phosphite
[351] P6: diethylphenyl phosphonite
[352] P7: ethylphenyl phosphinate
[353] P8: 2,3,4-trihydronaphthyl-1-imino-N-phenylsulfonate
[354] Example 1
[355] Preparation of Cross-linked Film from Copolymer (a) (P Not Added, Only Sn Added)
[356] 10 g of copolymer (a) is dissolved in 40 g of toluene having a water content of 70 ppm, and as pentaerythritol tetrakis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) as an antioxidant Propionate] was added at 1.0 part by weight based on 100 parts by weight of the copolymer. After 0.05 parts by weight of tin (II) dioctanate was added as a cross-linking catalyst, the solution was spread on a PETRI dish and left at atmospheric temperature at 40 ° C. for 3 hours to obtain a film. The film was removed from the PETRI dish and dried under atmospheric pressure at 150 ° C. for 2 hours. The film was further dried under vacuum at 230 ° C. for 1 hour to obtain a colorless transparent film having a thickness of 100 μm. The properties of the resulting film are shown in Table 1 below.
[357] Example 2
[358] Preparation of Cross-linked Film from Copolymer (a) (P Added Only, Vapor Cross-link)
[359] 10 g of copolymer (a) is dissolved in 40 g of toluene having a water content of 70 ppm, and as pentaerythritol tetrakis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) as an antioxidant Propionate] was added at 1.0 part by weight based on 100 parts by weight of the copolymer. After 0.5 parts by weight of tributoxy phosphite was added as a cross-linking catalyst, the solution was spread on a PETRI dish and left for 3 hours at 40 ° C. under atmospheric pressure to obtain a film. The film was removed from the PETRI dish, dried at 150 ° C. for 2 hours at atmospheric pressure, and treated with steam at 150 ° C. for 4 hours. The film was further dried under vacuum at 230 ° C. for 1 hour to obtain a colorless transparent film having a thickness of 100 μm. The properties of the resulting film are shown in Table 1.
[360] Examples 3-9
[361] Preparation of Cross-linked Film from Copolymer (a) (P Added Only, Vapor Cross-link)
[362] A film was prepared in the same manner as in Example 3 except for using P2 to P8 instead of tributoxy phosphite (P1). The properties of the resulting film are shown in Table 1.
[363] Example 10
[364] 10 g of copolymer (a) is dissolved in 40 g of toluene having a water content of 70 ppm, and as pentaerythritol tetrakis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) as an antioxidant Propionate] was added at 1.0 part by weight based on 100 parts by weight of the copolymer. After 0.5 parts by weight of p-methoxybenzylsulfonium-SbF ₆ was added as a cross-linking catalyst, the solution was spread on a PETRI dish and left at atmospheric temperature at 40 ° C. for 3 hours to obtain a film. The film was removed from the PETRI dish, heated at 150 ° C. for 2 hours at atmospheric pressure, and dried under vacuum at 230 ° C. for 1 hour to give a colorless transparent film having a thickness of 100 μm. The properties of the resulting film are shown in Table 1.
[365] Example 11
[366] 10 g of copolymer (a) is dissolved in 40 g of toluene having a water content of 70 ppm, and as pentaerythritol tetrakis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) as an antioxidant Propionate] was added at 1.0 part by weight based on 100 parts by weight of the copolymer. After 0.5 parts by weight of dioctyl phosphate was added as a cross-linking catalyst, the solution was spread on a PETRI dish and left for 3 hours at 40 ° C. under atmospheric pressure to obtain a film. The film was removed from the PETRI dish, heated at 150 ° C. for 2 hours under atmospheric pressure, and dried under vacuum at 230 ° C. for 1 hour to give a colorless transparent film having a thickness of 100 μm. The properties of the resulting film are shown in Table 1.
[367] Example 12
[368] Preparation of cross-linked film from copolymer (a) (adds both P and Sn)
[369] A cross-linked film was prepared in the same manner as in Example 2 except for using the solution prepared by adding tin (II) dioctanate to the casting solution prepared in Example 2. The properties of the resulting film are shown in Table 1.
[370] Example 13
[371] Preparation of Cross-linked Films from Copolymer (a) and TEOS (P Not Added, Only Sn Added)
[372] A cross-linked film was prepared in the same manner as in Example 1 except for using the solution prepared by adding 2 g of tetraethoxy silane (TEOS) to the solution prepared in Example 1. The properties of the resulting film are shown in Table 1.
[373] Example 14
[374] Preparation of cross-linked film from copolymer (a) and TEOS (add only P)
[375] A cross-linked film was prepared in the same manner as in Example 2 except for using the solution prepared by adding 2 g of tetraethoxy silane (TEOS) to the solution prepared in Example 2. The film was slightly cloudy and the total light transmittance was 85%. The properties of the resulting film are shown in Table 1.
[376] Example 15
[377] Preparation of cross-linked film from copolymer (a) and TEOS (add both P and Sn)
[378] A film was prepared in the same manner as in Example 2, except for using the solution prepared by adding 2 g of tetraethoxy silane (TEOS) and 0.05 part by weight of tin (II) dioctanate to the solution prepared in Example 2. It was. The properties of the resulting film are shown in Table 1.
[379] Example 16
[380] Preparation of cross-linked film from copolymer (b) and TEOS (add both P and Sn)
[381] A film was prepared in the same manner as in Example 6 except for using the copolymer (b) instead of the copolymer (a). The properties of the resulting film are shown in Table 1.
[382] Example 17
[383] Preparation of cross-linked film from copolymer (c) and TEOS (add both P and Sn)
[384] A film was prepared in the same manner as in Example 6 except for using the copolymer (c) instead of the copolymer (a). The properties of the resulting film are shown in Table 1.
[385] Example 18
[386] Preparation of cross-linked film from copolymer (d) and TEOS (add both P and Sn)
[387] A film was prepared in the same manner as in Example 6 except for using the copolymer (d) instead of the copolymer (a). The properties of the resulting film are shown in Table 1.
[388] Comparative Example 1
[389] Preparation of cross-linked film from copolymer (a) (does not add both P and Sn)
[390] A film was prepared in the same manner as in Example 2, except that tributoxy phosphite was not added. Under this condition the polymer was not cross-linked at all. The properties of the resulting film are shown in Table 1.
[391] Comparative Example 2
[392] Preparation of cross-linked film from copolymer (a) (P added, Sn not added, treated with hot water at 40 ° C.)
[393] The film was prepared in the same manner as in Example 2 except that the film was treated with hot water at 40 ° C. instead of 150 ° C. steam. Under this condition the polymer was not cross-linked at all. The properties of the resulting film are shown in Table 1.
[394] Example One2345678910 Copolymer(a)(a)(a)(a)(a)(a)(a)(a)(a)(a) additivenonenonenonenonenonenonenonenonenonenone Water treatment (℃)150150150150150150150150150150 ^{* 1}Phosphoric acid catalystnoneP1P2P3P4P5P6P7P8 ^*2 Sn catalystaddingnonenonenonenonenonenonenonenone Specific swelling degree (%) in toluene500200210200200190240230210450 Tg (℃)338345345345345345345345345336 Total light transmittance (%)91919191918591919191 Linear expansion coefficient (ppm / ° C)81585858585858585865 Liquid crystal resistance test△◎◎◎◎◎◎◎◎△ Sticky0000000000 * 1: at atmospheric pressure * 2: sulfonium salt * 3: dioctyl phosphate * 4: dissolved * 5: number of exfoliated aluminum deposition blocks
[395] ExampleComparative example 1112131415161718One2 Copolymer(a)(a)(a)(a)(a)(b)(c)(d)(a)(a) additivenonenoneTEOSTEOSTEOSTEOSTEOSTEOSnonenone Water treatment (℃)150 ^{* 1} 15015015015015015015015040 Phosphoric acid catalyst ^{* 3}P1noneP1P1P1P1P1noneP1 Sn catalystaddingaddingnoneaddingaddingaddingaddingnonenone Specific swelling degree (%) in toluene250200190160150190200210 ^{*4 *4} Tg (℃)338338340340340340340320338338 Total light transmittance (%)91919185919191919191 Linear expansion coefficient (ppm / ° C)65545245455249588888 Liquid crystal resistance testO◎O◎◎◎◎◎×× Sticky0000000044 * 1: at atmospheric pressure * 2: sulfonium salt * 3: dioctyl phosphate * 4: dissolved * 5: number of exfoliated aluminum deposition blocks
[396] Example 19 and Comparative Example 3
[397] The composition solutions of Examples 1 to 18 and Comparative Examples 1 and 2 were applied to the polished surface of the crystal using a spin coater to prepare a coating film having a dry thickness of 5 μm, respectively. The coating was dried and cross-linked under the conditions of the examples or the comparative examples.
[398] Toluene Resistance Test:
[399] A drop of toluene (about 20 mg) was added dropwise to the coating film, and covered with a PETRI dish and sealed. The coating film was left at 20 ° C. for 24 hours and evaluated by visually observing the change on the film surface.
[400] ◎: No change in appearance
[401] O: slight staining is observed
[402] △: film is expanded
[403] ×: film is completely solvent
[404] Tackiness rating:
[405] The aluminum surface was cut into 5 × 5 squares (each 1 mm × 1 mm) and a peel test was performed using an adhesive cellophane tape to determine the number of peeled squares out of 25 squares.
[406] CopolymerCross-linking Conditions of CoatingsadditivePhosphoric acid catalystSn catalystToluene resistanceThickness ^{* 1}Example 19(a)Steam, 150 ℃nonenoneadding△0 (a)Steam, 150 ℃noneP1none◎0 (a)Steam, 150 ℃noneP2none◎0 (a)Steam, 150 ℃noneP3none◎0 (a)Steam, 150 ℃noneP4none◎0 (a)Steam, 150 ℃noneP5none◎0 (a)Steam, 150 ℃noneP6none◎0 (a)Steam, 150 ℃noneP7none◎0 (a)Steam, 150 ℃noneP8none◎0 (a)Atmospheric, 150 ℃noneSulfonium salts△0 (a)Atmospheric, 150 ℃noneDioctyl phosphateO0 (a)Steam, 150 ℃noneP1adding◎0 (a)Steam, 150 ℃TEOSnoneaddingO0 (a)Steam, 150 ℃TEOSP1none◎0 (a)Steam, 150 ℃TEOSP1adding◎0 (a)Steam, 150 ℃TEOSP1adding◎0 (c)Steam, 150 ℃TEOSP1adding◎0 (d)Steam, 150 ℃TEOSP1adding◎0 Comparative Example 3(a)Steam, 150 ℃nonenonenone×22 (a)Hot water, 40 ℃noneP1none×20 * 1: number of exfoliated aluminum deposition blocks
[407] The transparent optical materials obtained from the cyclic olefin copolymers of the present invention are excellent in optical clarity, heat resistance and adhesion, and exhibit cross-linkable and excellent solvent resistance, so that these materials are used in liquid crystal display substrates as glass substrates. Suitable for The material is characterized in that the heat resistance, cleaning solution resistance, transparency, adhesion, dimensional stability and liquid crystal injection required for the base material in the process of exposure, development, and etching when the TFT (film transistor) is formed on a commercially available liquid crystal. It satisfies various characteristics such as liquid crystal resistance.
[408] Because of the excellent optical transparency, heat resistance, adhesion, adhesion, and water absorption, the transparent optical materials obtained from the cyclic olefin copolymers of the present invention are photoconductive boards, polarizing films, liquid crystal panels, phase transition films, transparent conductive films, OHP films, optical It can be suitably used as materials for electronic parts such as disks, optical fibers and lenses, and materials such as medical containers.

权利要求:
Claims (19)
[1" claim-type="Currently amended] A cyclic olefin addition copolymer containing a repeating unit (a) represented by the following formula (1) and a repeating unit (b) represented by the following formula (2); And (A) a metal compound which acts as an acid when heated to a temperature of 50 ° C. or higher, (B) an alkoxy compound, an aryloxy compound, a carboxyl compound, a β-diketone compound, a halogen compound or an oxide, wherein the metal is Al, Ga, Sn, Ca, Ba, Zn, Sb, Ti, Zr, Sc, Y, Ce, Nd, Sm and Yb), and (C) organic carboxylic acid, organic phosphoric acid, organic sulfonic acid And at least one compound selected from the group consisting of ammonia, primary to tertiary amine compounds and quaternary ammonium hydroxide compounds.
<Formula 1>

Wherein A ¹ to A ⁴ are independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a chemical formula-(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 ) or-(CR ¹ R ² ) _f C (O) O (CH ₂ ) _h Si (OR ³ ) _g An alkoxysilyl group or an aryloxysilyl group represented by R ⁴ _(3-g) , wherein R ¹ and R ² are independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R ³ is each having 10 carbon atoms An alkyl group, an alkenyl group, an aryl group or a cycloalkyl group of less than R ⁴ is a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, f and h are integers from 0 to 5, g is from 1 to 3 Integer), provided that at least one of A ¹ to A ⁴ is an alkoxysilyl group or an aryloxysilyl group, Y is -CH ₂ -or -O-, and m is 0 or 1.
<Formula 2>

Wherein B ¹ , B ² , B ³ and B ⁴ independently represent a hydrogen atom or an alkyl group, aryl group, alkenyl group or cycloalkyl group, halogen atom, halogenated hydrocarbon group, each having 20 or less carbon atoms, or-(CH ₂ ) a polar group represented by _j X, wherein 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 20 or less carbon atoms Or derivatives of these groups or halogen-substituted groups of these groups; j is an integer from 0 to 5), or B ¹ and B ² , or B ³ and B ⁴ may be bonded to form an alkylidenyl group, or Or B ¹ and B ⁴ , B ¹ and B ³ , B ² and B ³ , or B ² and B ⁴ may be bonded to form a cycloalkylene group or a cycloalkenylene group, n is an integer from 0 to 2 .
[2" claim-type="Currently amended] The cyclic olefin addition copolymer according to claim 1, wherein the cyclic olefin addition copolymer contains 0.1 to 30 mol% of the repeating unit represented by the formula (1), and 70 to 99.9 mol% of the repeating unit represented by the formula (2) and the repeating unit a ) And the repeating unit (b) have a sum of 100 mol%.
[3" claim-type="Currently amended] The composition of claim 1 wherein the glass transition temperature of the cyclic olefin addition copolymer is at least 200 ° C.
[4" claim-type="Currently amended] The composition of claim 1 comprising at least one compound (A).
[5" claim-type="Currently amended] The composition according to claim 4, wherein the compound (A) is a phosphorous acid ester compound, a hypophosphorous acid ester compound or both.
[6" claim-type="Currently amended] The composition of claim 1, comprising at least one compound (B) selected from the group consisting of divalent tin compounds represented by formula (3), tetravalent tin compounds represented by formula (4), and tetravalent tin oxides represented by formula (5):
<Formula 3>
Sn (R ⁷ ) ₂
<Formula 4>
Sn (R ⁸ ) _4-n (R ⁷ ) _n
<Formula 5>
(R ⁸ ) ₂ Sn = O or (R ⁸ ) ₂ (Y) -Sn-O-Sn (R ⁸ ) ₂ (X)
Wherein R ⁷ is a carboxyl group having 1 to 20 carbon atoms, a β-diketone group, an alkoxy group having 1 to 15 carbon atoms, a phenoxy group or a halogen atom; R ⁸ is a hydrocarbon group or halogen atom having 1 to 15 carbon atoms; n is an integer from 0 to 4; X and Y independently represent a hydroxyl group, a halogen atom or an isothiocyanate group.
[7" claim-type="Currently amended] The composition of claim 1, further comprising at least one compound selected from the group consisting of organosilanes represented by Formula 6, hydrolyzates of organosilanes and condensates of organosilanes.
<Formula 6>
(R ⁹ ) _q Si (OR ¹⁰ ) _4-q
Wherein, R ⁹ independently represents an organic group having 1 to 10 carbon atoms when two or more R ⁹ are present; R ¹⁰ independently represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 6 carbon atoms; q is an integer of 0-2.
[8" claim-type="Currently amended] The composition of claim 1 further comprising at least one metal oxide particle selected from the group consisting of silica, alumina, zirconia, titania, diatomite, montmorillonite and tin oxide.
[9" claim-type="Currently amended] A film, sheet or coating comprising the composition of claim 1.
[10" claim-type="Currently amended] A cyclic olefin addition copolymer containing a repeating unit (a) represented by the following formula (1) and a repeating unit (b) represented by the following formula (2); And (A) a metal compound which acts as an acid when heated to a temperature of 50 ° C. or higher, (B) an alkoxy compound, an aryloxy compound, a carboxyl compound, a β-diketone compound, a halogen compound or an oxide, wherein the metal is Al, Ga, Sn, Ca, Ba, Zn, Sb, Ti, Zr, Sc, Y, Ce, Nd, Sm and Yb), and (C) organic carboxylic acid, organic phosphoric acid, organic sulfonic acid Crosslinked prepared by cross-linking by means of siloxane bonds a cyclic olefin addition copolymer in a composition comprising at least one compound selected from the group consisting of ammonia, primary to tertiary amine compounds and quaternary ammonium hydroxide compounds. Bound material.
<Formula 1>

Wherein A ¹ to A ⁴ are independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a chemical formula-(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 ) or-(CR ¹ R ² ) _f C (O) O (CH ₂ ) _h Si (OR ³ ) _g An alkoxysilyl group or an aryloxysilyl group represented by R ⁴ _(3-g) , wherein R ¹ and R ² are independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R ³ is each having 10 carbon atoms An alkyl group, an alkenyl group, an aryl group or a cycloalkyl group of less than R ⁴ is a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, f and h are integers from 0 to 5, g is from 1 to 3 Integer), provided that at least one of A ¹ to A ⁴ is an alkoxysilyl group or an aryloxysilyl group, Y is -CH ₂ -or -O-, and m is 0 or 1.
<Formula 2>

Wherein B ¹ , B ² , B ³ and B ⁴ independently represent a hydrogen atom or an alkyl group, aryl group, alkenyl group or cycloalkyl group, halogen atom, halogenated hydrocarbon group, each having 20 or less carbon atoms, or-(CH ₂ ) a polar group represented by _j X, wherein 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 20 or less carbon atoms Or derivatives of these groups or halogen-substituted groups of these groups; j is an integer from 0 to 5), or B ¹ and B ² , or B ³ and B ⁴ may be bonded to form an alkylidenyl group, or Or B ¹ and B ⁴ , B ¹ and B ³ , B ² and B ³ , or B ² and B ⁴ may be bonded to form a cycloalkylene group or a cycloalkenylene group, n is an integer from 0 to 2 .
[11" claim-type="Currently amended] The cross-linked material of claim 10, comprising up to 10% by weight of toluene soluble components.
[12" claim-type="Currently amended] The cross-linked material of claim 10, wherein the degree of swelling in toluene at 300 ° C. is 300% or less.
[13" claim-type="Currently amended] The cross-linked material of claim 10, wherein the linear expansion coefficient measured at 80 ° C. is 70 ppm / ° C. or less.
[14" claim-type="Currently amended] The cross-linked material of claim 10 in the form of a film, sheet or coating.
[15" claim-type="Currently amended] A transparent conductive substrate comprising a film or sheet made from the cross-linked material according to claim 10 and a transparent conductive layer formed on the film or sheet.
[16" claim-type="Currently amended] A process for preparing the cross-linked material according to claim 10, comprising heating the composition of claim 1 at 50 ° C. or higher.
[17" claim-type="Currently amended] A process for preparing a cross-linked material according to claim 10, comprising contacting the composition of claim 1 with hot water or steam of at least 50 ° C. 12.
[18" claim-type="Currently amended] A process for producing a film, sheet or coating according to claim 9 comprising heating the composition of claim 1 at 50 ° C. or higher.
[19" claim-type="Currently amended] A method of making a film, sheet or coating according to claim 9 comprising contacting the composition of claim 1 with hot water or steam of at least 50 ° C.

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同族专利:

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公开号 | 公开日

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TW539695B|2003-07-01|

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KR100816931B1|2008-03-25|

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CN1347939A|2002-05-08|

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US20020042461A1|2002-04-11|

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EP1195397B1|2004-04-14|

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EP1195397A1|2002-04-10|

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CN100478391C|2009-04-15|

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DE60102769D1|2004-05-19|

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US6639021B2|2003-10-28|

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DE60102769T2|2005-04-14|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
2000-10-04|Priority to JP2000305148A

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2000-10-04|Priority to JPJP-P-2000-00305148

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2000-12-22|Priority to JPJP-P-2000-00391021

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2000-12-22|Priority to JP2000391021

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2001-01-30|Priority to JP2001021743A

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2001-01-30|Priority to JPJP-P-2001-00021743

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2001-06-26|Priority to JP2001192802A

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2001-06-26|Priority to JPJP-P-2001-00192802

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2001-09-29|Application filed by 마쯔모또 에이찌, 제이에스알 가부시끼가이샤

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2002-04-13|Publication of KR20020027217A

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2008-03-25|Application granted

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2008-03-25|Publication of KR100816931B1

优先权:

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申请号 | 申请日 | 专利标题

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JP2000305148A|JP4626736B2|2000-10-04|2000-10-04|Optically transparent material and liquid crystal display substrate material containing cyclic olefin copolymer|

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JPJP-P-2000-00305148|2000-10-04|

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JPJP-P-2000-00391021|2000-12-22|

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JP2000391021|2000-12-22|

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JP2001021743A|JP4844704B2|2001-01-30|2001-01-30|Cyclic olefin polymer composition, crosslinked product thereof and method for producing the crosslinked product|

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JPJP-P-2001-00021743|2001-01-30|

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JP2001192802A|JP4821943B2|2001-05-30|2001-06-26|Crosslinked product of cyclic olefin addition type copolymer, composition for crosslinking, and method for producing crosslinked product|

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JPJP-P-2001-00192802|2001-06-26|