JP2011105688A - Method for purifying monomer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for purifying an N-alkyl-substituted imide group-containing alicyclic olefin monomer which is a raw material monomer for a polar group-containing cyclic olefinic polymer useful as a sealing material and an insulating material for various optical parts and electronic parts. <P>SOLUTION: There is provided the method for purification by which the N-alkyl-substituted imide group-containing alicyclic olefin monomer which is N-(2-ethylhexyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide (NEHI) as a representative example is brought into contact with a mixed ion exchange resin comprising a cation exchange resin and an anion exchange resin. The ratio of the cation exchange resin and anion exchange resin in the mixed ion exchange resin is preferably (1:1) to (10:1) in terms of weight ratio of the cation exchange resin:anion exchange resin. The monomer is preferably brought into contact with the mixed ion exchange resin under conditions of 10-100°C. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention provides a method for purifying a predetermined N-substituted imide group-containing alicyclic olefin monomer, and a polarity obtained using the N-substituted imide group-containing alicyclic olefin monomer purified by the purification method. The present invention relates to a group-containing cyclic olefin polymer.

  Cyclic olefin polymers obtained by polymerizing cyclic olefin monomers have low hygroscopicity and excellent dielectric properties, and are therefore suitably used as sealing materials and insulating materials for various optical components and electronic components.

  For example, a technology for imparting photosensitivity and solvent solubility by introducing a polar group into such a cyclic olefin polymer to form a polar group-containing cyclic olefin polymer is known (for example, patents). Reference 1). Such a polar group-containing cyclic olefin-based polymer can be patterned by sensitizing it with radiation or the like and dissolving it with an alkaline solution or the like. Therefore, various types of organic EL elements, liquid crystal display devices, etc. It is suitably used as a resin material for forming a protective film for electronic components such as display elements, integrated circuit elements, solid-state imaging elements, color filters, and black matrices.

  On the other hand, in order to use such a polar group-containing cyclic olefin polymer as a material for forming a protective film for various display elements and electronic parts described above, polymerization conversion is performed to reduce the influence of residual unreacted monomers. It is necessary to increase the rate and remove impurities such as metals and polymerization inhibitors. On the other hand, for example, in Patent Document 2, in order to remove various impurities contained in the cyclic olefin monomer and polymerization inhibitors such as polymerization inhibitors, the cyclic olefin monomer is an inorganic adsorbent such as alumina or silica. The method of processing with is proposed.

  However, in the polar group-containing cyclic olefin polymer, the introduction of the polar group increases the types of impurities and polymerization inhibitors contained in the monomers that form the polar group-containing cyclic olefin polymer. Therefore, the method described in Patent Document 2 has a problem that impurities and polymerization inhibitors cannot be sufficiently removed.

  On the other hand, the present applicant has proposed to use a predetermined N-substituted imide group-containing alicyclic olefin monomer as a monomer for introducing a polar group into a cyclic olefin polymer ( (See Patent Document 3). Processing when patterning a polar group-containing cyclic olefin polymer obtained by using a predetermined N-substituted imide group-containing alicyclic olefin monomer as a monomer for introducing a polar group And excellent electrical properties. However, on the other hand, even when an N-substituted imide group-containing alicyclic olefin monomer is used, the obtained polar group-containing cyclic olefin polymer has a low polymerization conversion rate, so that unreacted monomers remain. There was a problem of doing.

  On the other hand, in order to remove impurities and polymerization inhibitors contained in the N-substituted imide group-containing alicyclic olefin monomer, conventionally used purification methods (for example, crystallization, distillation, extraction or extraction) A method of processing by ion exchange processing or the like is also conceivable (for example, see Patent Document 4 as an example of ion exchange processing). However, in these methods, there is a problem that the polymerization conversion rate of the obtained polymer cannot be increased, and even if the polymerization conversion rate can be increased to some extent, another problem occurs. there were.

JP 2007-264616 A JP-A-5-132523 International Publication No. 2004/029720 JP-A-8-310979

  As a result of investigation by the present inventor on the above problem, cation exchange is performed in order to remove the amine compound which is the main impurity among impurities contained in the N-substituted imide group-containing alicyclic olefin monomer. When the resin was used, it was found that although the polymerization conversion rate was improved, the transparency of the obtained polar group-containing cyclic olefin polymer was lowered.

  On the other hand, as a result of diligent research to solve such problems, the present inventor has found that the impurities contained in the N-substituted imide group-containing alicyclic olefin monomer are cation exchange resins. When it is removed by using a cation exchange resin, the transparency of the obtained polar group-containing cyclic olefin polymer is reduced. Furthermore, the cation exchange resin and the anion exchange resin are combined. The present inventors have found that the above-mentioned problems can be solved by using the mixed ion exchange resin.

（上記式（１）中、ｎは０〜３の整数であり、Ｒ^１は置換基を有していてもよい炭素数１〜１６の炭化水素基を表す。） That is, according to the present invention, a monomer represented by the following general formula (1) is brought into contact with a mixed ion exchange resin composed of a cation exchange resin and an anion exchange resin. A purification method is provided.

(In the above formula (1), n is an integer of 0 to 3, ^{R 1} represents a hydrocarbon group having 1 to 16 carbon atoms which may have a substituent.)

In the purification method of the present invention, the ratio of the cation exchange resin to the anion exchange resin in the mixed ion exchange resin is 1: 1 to 1 by weight ratio of “cation exchange resin: anion exchange resin”. 10: 1 is preferred.
In the purification method of the present invention, the monomer is preferably brought into contact with the mixed ion exchange resin under conditions of 10 to 100 ° C.
In the purification method of the present invention, the monomer is preferably brought into contact with 5 to 100 parts by weight of the mixed ion exchange resin with respect to 100 parts by weight of the monomer.
In the purification method of the present invention, it is preferable that the fluid containing the monomer is continuously contacted with the mixed ion exchange resin at a volume time space velocity (VHSV) of 0.01 to 2 hr ⁻¹ .

  Moreover, according to the present invention, a polar group-containing cyclic olefin polymer obtained by polymerizing a monomer mixture containing a monomer purified by any of the above methods, the polar group-containing cyclic olefin polymer, There are provided a laminate comprising a resin composition containing a solvent, a resin film formed using the resin composition, and a substrate.

  According to the purification method of the present invention, impurities in the N-substituted imide group-containing alicyclic olefin monomer as a raw material for forming the polar group-containing cyclic olefin polymer can be effectively removed. Therefore, according to the present invention, by using the N-substituted imide group-containing alicyclic olefin monomer purified by the purification method of the present invention, the polymerization conversion rate is high and the polarity has excellent transparency. A group-containing cyclic olefin polymer can be provided.

The purification method of the present invention is characterized in that a monomer represented by the following general formula (1) is brought into contact with a mixed ion exchange resin composed of a cation exchange resin and an anion exchange resin.
First, the monomer used in the purification method of the present invention will be described.

（上記式（１）中、ｎは０〜３の整数であり、Ｒ^１は置換基を有していてもよい炭素数１〜１６の炭化水素基を表す。） (Monomer)
The monomer used in the purification method of the present invention is a monomer represented by the following general formula (1).

(In the above formula (1), n is an integer of 0 to 3, ^{R 1} represents a hydrocarbon group having 1 to 16 carbon atoms which may have a substituent.)

  In said formula (1), n is an integer of 0-3, Preferably, n is 0.

R ¹ is an optionally substituted hydrocarbon group having 1 to 16 carbon atoms, preferably an alkyl group having 1 to 16 carbon atoms, a cycloalkyl group having 3 to 16 carbon atoms, or a carbon number. It is an 8-16 aryl group, More preferably, it is a C5-C16 branched alkyl group or a phenyl group.

  Examples of the branched alkyl group having 5 to 16 carbon atoms include 1-methylbutyl group, 2-methylbutyl group, 1-methylpentyl group, 1-ethylbutyl group, 2-methylhexyl group, 2-ethylhexyl group, and 4-methyl. A heptyl group, 1-methylnonyl group, 1-methyltridecyl group, 1-methyltetradecyl group and the like can be mentioned. Among these, a branched alkyl group having 6 to 14 carbon atoms is preferable, and a branched alkyl group having 7 to 10 carbon atoms is more preferable because of excellent heat resistance and solubility in a polar solvent. When the number of carbon atoms is 4 or less, the solubility in a polar solvent is inferior. When the number of carbon atoms is 17 or more, the heat resistance is inferior. Further, when a polar group-containing cyclic olefin polymer is formed, May melt and the pattern may disappear.

Further, the substituent is not particularly limited, but is a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or a functional group represented by —COOR ² (where R ² is a monovalent alkyl having 1 to 10 carbon atoms). Group, or a monovalent halogenated alkyl group having 1 to 10 carbon atoms). Among these, a functional group represented by —COOR ² is preferable.

  Specific examples of the monomer represented by the general formula (1) include N-phenyl-bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1- Methylbutyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-methylbutyl) -bicyclo [2.2.1] hept-5-ene-2,3 -Dicarboximide, N- (1-methylpentyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-methylpentyl) -bicyclo [2.2 .1] Hept-5-ene-2,3-dicarboximide, N- (1-ethylbutyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- ( 2-Ethylbutyl) -bicyclo [2.2.1] hept-5- -2,3-dicarboximide, N- (1-methylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-methylhexyl)- Bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (3-methylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-di Carboximide, N- (1-butylpentyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-butylpentyl) -bicyclo [2.2.1 ] Hept-5-ene-2,3-dicarboximide, N- (1-methylheptyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2 -Methylheptyl) -bicyclo [2.2.1] hept- -Ene-2,3-dicarboximide, N- (3-methylheptyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-methylheptyl) -Bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-ethylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-di Carboximide, N- (2-ethylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (3-ethylhexyl) -bicyclo [2.2.1] hept -5-ene-2,3-dicarboximide, N- (1-propylpentyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-propyl) Pentyl) -bicyclo [2.2.1 Hept-5-ene-2,3-dicarboximide, N- (1-methyloctyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2- Methyloctyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (3-methyloctyl) -bicyclo [2.2.1] hept-5-ene-2 , 3-dicarboximide, N- (4-methyloctyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-ethylheptyl) -bicyclo [2 2.1] hept-5-ene-2,3-dicarboximide, N- (2-ethylheptyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (3-ethylheptyl) -bicyclo [2.2 .1] Hept-5-ene-2,3-dicarboximide, N- (4-ethylheptyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-propylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-propylhexyl) -bicyclo [2.2.1] hept-5- Ene-2,3-dicarboximide, N- (3-propylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-methylnonyl) -bicyclo [2.2.1] Hept-5-ene-2,3-dicarboximide, N- (2-methylnonyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide , N- (3-methylnonyl) -bicyclo [ 2.1] hept-5-ene-2,3-dicarboximide, N- (4-methylnonyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N -(5-Methylnonyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-ethyloctyl) -bicyclo [2.2.1] hept-5 Ene-2,3-dicarboximide, N- (2-ethyloctyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (3-ethyloctyl)- Bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-ethyloctyl) -bicyclo [2.2.1] hept-5-ene-2,3-di Carboximide, N- (1-methyldecyl) -bicyclo [ 2.1] hept-5-ene-2,3-dicarboximide, N- (1-methyldodecyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-methylundecyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-methyldodecyl) -bicyclo [2.2.1] hept -5-ene-2,3-dicarboximide, N- (1-methyltridecyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1- Methyltetradecyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-methylpentadecyl) -bicyclo [2.2.1] hept-5-ene -2,3-dicarboximide and the like. These may be used alone or in combination of two or more.

When R ¹ has a functional group represented by —COOR ² , the monomer represented by the general formula (1) is represented by the following general formula (2). Is preferred.

In the general formula (2), R ² is a monovalent alkyl group having 1 to 10 carbon atoms or a monovalent halogenated alkyl group having 1 to 10 carbon atoms, and monovalent having 1 to 10 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a hexyl group, and a cyclohexyl group. Examples of the monovalent halogenated alkyl group having 1 to 10 carbon atoms include a fluoromethyl group, a chloromethyl group, a bromomethyl group, a difluoromethyl group, a dichloromethyl group, a difluoromethyl group, a trifluoromethyl group, a trichloromethyl group, Examples include 2,2,2-trifluoroethyl group, pentafluoroethyl group, heptafluoropropyl group, perfluorobutyl group, and perfluoropentyl group. Among these, because of excellent solubility in polar solvents, as R ^2, a methyl group and an ethyl group are preferred.

In the general formula (2), R ³ is a divalent alkylene group having 1 to ³ carbon atoms. Examples of the divalent alkylene group having 1 to 3 carbon atoms include a methylene group, an ethylene group, a propylene group, and An isopropylene group is mentioned. Among these, since a polymerization activity is favorable, a methylene group and an ethylene group are preferable.

  The monomer represented by the general formula (1) can be obtained, for example, by an amidation reaction between a corresponding amine and 5-norbornene-2,3-dicarboxylic acid anhydride. The obtained monomer can be efficiently isolated by separating and purifying the reaction solution of the amidation reaction by a known method.

(Mixed ion exchange resin)
Next, the mixed ion exchange resin used in the purification method of the present invention will be described. The mixed ion exchange resin used in the purification method of the present invention comprises a cation exchange resin and an anion exchange resin.

  The cation exchange resin is not particularly limited, but is a strongly acidic cation exchange resin having a styrene / divinylbenzene copolymer structure with sulfonic acid as a functional group (for example, Amberlite 200CT Na, manufactured by Organo), acrylic acid / Examples include weakly acidic cation exchange resins having a carboxylic acid as a functional group in the divinylbenzene copolymer structure (for example, Amberlite IRC76, manufactured by Organo Corporation).

  Further, the anion exchange resin is not particularly limited, but a strongly basic anion exchange resin having a quaternary ammonium base as a functional group in a styrene / divinylbenzene copolymer structure (for example, Amberlite IRA900J CL, Organo Corporation). And a weakly basic anion exchange resin having a primary to tertiary amino group as a functional group in the styrene / divinylbenzene copolymer structure (for example, Amberlite IRA96SB, manufactured by Organo Corporation).

  The mixed ion exchange resin used in the purification method of the present invention can be obtained by combining the cation exchange resin and the anion exchange resin described above, but as the mixed ion exchange resin used in the purification method of the present invention, cation exchange is possible. You may use what mixed resin and anion exchange resin previously (for example, Amberlyst MSPS2-1, the organo company make).

  The ratio of the cation exchange resin to the anion exchange resin in the mixed ion exchange resin used in the purification method of the present invention is preferably a weight ratio of “cation exchange resin: anion exchange resin”, preferably 1: 1 to 10. : 1, more preferably 1: 1 to 5: 1, still more preferably 1: 1 to 2: 1. If the proportion of the cation exchange resin is too large, the monomer represented by the general formula (1) may be polymerized to form a polar group-containing cyclic olefin polymer, which may reduce the transparency. is there. On the other hand, if the ratio of the anion exchange resin is too large, the polymerization conversion rate when the monomer represented by the general formula (1) is polymerized is not sufficiently high, and unreacted monomers remain. When applied to a display element or an electronic component, various characteristics may be deteriorated.

(Monomer purification method)
In the purification method of the present invention, the monomer represented by the general formula (1) is brought into contact with the mixed ion exchange resin described above.

  The contact method between the monomer represented by the general formula (1) and the mixed ion exchange resin may be either a batch method or a continuous method, and is not particularly limited.

  Although it does not specifically limit as a batch method, For example, the method etc. which stir the monomer represented by the said General formula (1) and mixed ion exchange resin using a stirring tank are mentioned. In this case, when the mixed ion exchange resin is charged into the stirring tank, the cation exchange resin and the anion exchange resin are separately charged into the stirring tank, and the mixed ion exchange resin may be used as the mixed ion exchange resin in the stirring tank. Or what mixed cation exchange resin and anion exchange resin beforehand may be thrown into a stirring tank. Furthermore, a combination of a cation exchange resin and an anion exchange resin previously mixed with a cation exchange resin and / or an anion exchange resin is used in combination, and these are separately put into a stirring tank and stirred. It is good also as mixed ion exchange resin in a tank.

  On the other hand, the continuous method is not particularly limited, and examples thereof include a method in which the monomer represented by the general formula (1) is passed through a packed bed made of a mixed ion exchange resin. The packed layer made of the mixed ion exchange resin may be formed of a single layer containing a cation exchange resin and an anion exchange resin, or a layer made of a cation exchange resin and an anion exchange resin. It is good also as a thing formed in combination with a layer. Furthermore, the packed layer may be a combination of a layer containing a cation exchange resin and an anion exchange resin and a layer made of a cation exchange resin and / or a layer made of an anion exchange resin. However, in the case where the packed layer is formed of a plurality of layers, the layer on the outlet side of the packed layer is a layer containing only the cation exchange resin. The layer on the outlet side is desirably a layer containing at least an anion exchange resin.

  The amount of the mixed ion exchange resin used when bringing the monomer represented by the general formula (1) into contact with the mixed ion exchange resin is 100 weights of the monomer represented by the general formula (1). The amount is preferably 5 to 100 parts by weight, more preferably 5 to 50 parts by weight, and still more preferably 10 to 20 parts by weight with respect to parts. If the ratio of the mixed ion exchange resin is too small, the effect of the present invention tends to be difficult to obtain, whereas if it is too large, the purification treatment cost may increase.

  Moreover, the temperature condition in contacting the monomer represented by the general formula (1) with the mixed ion exchange resin is not particularly limited, but is preferably 10 to 100 ° C, more preferably 10 to 60. ° C, more preferably 20-50 ° C. If the temperature is too low, the reactivity during polymerization tends to decrease. On the other hand, if the temperature is too high, the monomer represented by the general formula (1) is polymerized, and the resulting polymer is obtained. When the film is formed, the transmittance tends to decrease.

Moreover, the volume time space velocity (VHSV) showing the contact time of the monomer represented by the general formula (1) and the mixed ion exchange resin when using the continuous method is preferably 0.01 to 2 hr. ⁻¹ , more preferably 0.1 to ¹ hr ⁻¹ , and still more preferably 0.1 to 0.5 hr ⁻¹ . If the volume time space velocity is too small, the purification process cost may increase. On the other hand, if the volume time space velocity is too large, the effect of the present invention tends to be difficult to obtain. The volume hourly space velocity (VHSV) is a unit supply amount of the monomer represented by the general formula (1) supplied per unit time at 20 ° C. per unit volume of the mixed ion exchange resin (the general formula ( In the case where the monomer represented by 1) is dissolved in a solvent and brought into contact with the mixed ion exchange resin, the supply amount including the solvent, that is, the supply amount of the fluid containing the monomer is expressed.

  When the monomer represented by the general formula (1) is brought into contact with the mixed ion exchange resin, the monomer represented by the general formula (1) is previously dissolved in a solvent, You may make it contact with mixed ion exchange resin in the state dissolved in. Such a solvent is not particularly limited as long as it can dissolve the monomer represented by the general formula (1) satisfactorily. For example, methanol, ethanol, propanol, butanol, 3-methoxy- Alcohols such as 3-methylbutanol; cyclic ethers such as tetrahydrofuran and dioxane; cellosolv esters such as methyl cellosolve acetate and ethyl cellosolve acetate; ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol mono-t-butyl ether , Glycol ethers such as diethylene glycol ethyl methyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate (PGMEA); Aromatic hydrocarbons such as ethylene and xylene; ketones such as methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-peptanone, 4-hydroxy-4-methyl-2-pentanone; ethyl 2-hydroxypropionate, 2-hydroxy- Ethyl 2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, methyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, Esters such as ethyl acetate, butyl acetate, and ethyl lactate; N-methylformamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-methylacetamide, N, N-dimethylacetamide, dimethylsulfoxide, γ- Butyllacto And the like; an aprotic polar solvent such as. These solvents can be used alone or in combination of two or more.

  The amount used in the case of using a solvent is preferably 10 to 300 parts by weight, more preferably 30 to 150 parts by weight, more preferably 100 parts by weight of the monomer represented by the general formula (1). Preferably it is 40-100 weight part.

  Thus, according to the purification method of the present invention, the monomer represented by the general formula (1) is obtained by bringing the monomer represented by the general formula (1) into contact with the mixed ion exchange resin. It is possible to effectively remove various impurities such as impurities contained therein, specifically, main compounds such as amine compounds, polymerization catalysts, and other compounds derived from cation exchange resins. Therefore, according to the present invention, by using the monomer represented by the above general formula (1) purified by the purification method of the present invention, the polymerization conversion rate is high and the polarity has excellent transparency. It becomes possible to obtain a group-containing cyclic olefin polymer.

(Polar group-containing cyclic olefin polymer)
Next, the polar group-containing cyclic olefin polymer of the present invention will be described.

  The polar group-containing cyclic olefin polymer of the present invention is a polymer obtained by polymerizing a monomer mixture containing the monomer represented by the general formula (1). The polar group-containing cyclic olefin polymer of the present invention may be a homopolymer of the monomer represented by the general formula (1), or may be a single polymer represented by the general formula (1). It may be a copolymer of a monomer and a copolymerizable monomer.

  Examples of the copolymerizable monomer include a cyclic olefin monomer having a protic polar group (a1) and a polar group other than the protic polar group excluding the monomer represented by the general formula (1). Cyclic olefin monomer (a2), cyclic olefin monomer having no polar group (a3), and monomer other than cyclic olefin (a4) (hereinafter these monomers are simply referred to as monomer (a1) to (A4)). Here, the monomer (a4) may have a protic polar group or other polar group, and may not have a polar group at all.

  Here, the protic polar group refers to a group containing an atom in which a hydrogen atom is directly bonded to an atom belonging to Group 15 or 16 of the periodic table. The atom belonging to group 15 or 16 of the periodic table is preferably an atom belonging to the first or second period of group 15 or 16 of the periodic table, more preferably an oxygen atom, nitrogen atom or sulfur An atom, particularly preferably an oxygen atom.

Specific examples of such protic polar groups include polar groups having oxygen atoms such as hydroxyl groups, carboxy groups (hydroxycarbonyl groups), sulfonic acid groups, phosphoric acid groups; primary amino groups, secondary amino groups A polar group having a nitrogen atom such as a primary amide group or a secondary amide group (imide group); a polar group having a sulfur atom such as a thiol group; Among these, those having an oxygen atom are preferable, and a carboxy group is more preferable.
In the present invention, the number of protic polar groups bonded to the cyclic olefin resin having a protic polar group is not particularly limited, and different types of protic polar groups may be included.

Specific examples of the cyclic olefin monomer (a1) having a protic polar group include 5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene and 5-methyl-5-hydroxycarbonylbicyclo [2. 2.1] hept-2-ene, 5-carboxymethyl-5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-dihydroxycarbonylbicyclo [2.2.1] hept-2 -Ene, 8-hydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 9-hydroxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyl-9-hydroxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9,10-dihydroxycarbonyltetracyclo [6.2.1.1 ^3,6 . Carboxy group-containing cyclic olefin such as 0 ^2,7 ] dodec-4-ene; 5- (4-hydroxyphenyl) bicyclo [2.2.1] hept-2-ene, 5-methyl-5- (4-hydroxy Phenyl) bicyclo [2.2.1] hept-2-ene, 9- (4-hydroxyphenyl) tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyl-9- (4-hydroxyphenyl) tetracyclo [6.2.1.1 ^3,6 . Hydroxyl group-containing cyclic olefins such as 0 ^2,7 ] dodec-4-ene and the like can be mentioned, and among these, carboxy group-containing cyclic olefins are preferable from the viewpoint that adhesion to the substrate can be improved. These monomers (a1) may be used alone or in combination of two or more.

  Examples of the cyclic olefin monomer (a2) having a polar group other than the protic polar group excluding the monomer represented by the general formula (1) include an ester group, a cyano group, or a cyclic olefin having a halogen atom. It is done.

Examples of the cyclic olefin having an ester group include 5-acetoxybicyclo [2.2.1] hept-2-ene, 5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl- 5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 9-acetoxytetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-n-propoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-isopropoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-n-butoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyl-9-methoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyl-9-ethoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyl-9-n-propoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyl-9-isopropoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyl-9-n-butoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyl-9- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene and the like.

Examples of the cyclic olefin having a cyano group include 9-cyanotetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyl-9-cyanotetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 5-cyanobicyclo [2.2.1] hept-2-ene and the like.
Examples of the cyclic olefin having a halogen atom include 9-chlorotetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyl-9-chlorotetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene and the like.
These monomers (a2) may be used alone or in combination of two or more.

Specific examples of the cyclic olefin monomer (a3) having no polar group include bicyclo [2.2.1] hept-2-ene (also referred to as “norbornene”), 5-ethyl-bicyclo [2.2. .1] Hept-2-ene, 5-butyl-bicyclo [2.2.1] hept-2-ene, 5-ethylidene-bicyclo [2.2.1] hept-2-ene, 5-methylidene-bicyclo [2.2.1] hept-2-ene, 5-vinyl-bicyclo [2.2.1] hept-2-ene, tricyclo [5.2.1.0 ^2,6 ] deca-3,8- diene (common name: dicyclopentadiene), tetracyclo [10.2.1.0 ^2,11. 0 ^4,9 ] pentadeca-4,6,8,13-tetraene, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene (also referred to as “tetracyclododecene”), 9-methyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methylidene-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethylidene-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-vinyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-propenyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, pentacyclo [9.2.1.1 ^3,9 . 0 ^2,10] pentadeca-5,12-diene, cyclopentene, cyclopentadiene, 9-phenyl - tetracyclo [6.2.1.1 ^{3, 6.} 0 ^2,7] dodeca-4-ene, tetracyclo ^{[9.2.1.0 2,10.} 0 ^3,8 ] tetradeca-3,5,7,12-tetraene, pentacyclo [9.2.1.1 ^3,9 . 0 ^2,10] pentadeca-12-ene, and the like.
These monomers (a3) may be used alone or in combination of two or more.

Specific examples of the monomer (a4) other than the cyclic olefin include ethylene; propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3- Ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, An α-olefin having 2 to 20 carbon atoms such as 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene; Non-conjugated dienes such as hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene, and derivatives thereof; cyclobutene, Ropenten, cyclohexene, cyclooctene, 3a, 5,6,7A- tetrahydro-4,7-methano -1H- indene cycloolefin, etc., such as. Among these, an α-olefin, particularly ethylene is preferable.
Monomers (a4) other than these cyclic olefins may be used alone or in combination of two or more.

  Among the above copolymerizable monomers, the polar group-containing cyclic olefin-based polymer of the present invention can have a protic polar group, and as a result, has excellent heat resistance and adhesion. The cyclic olefin monomer (a1) having a protic polar group is preferable, and a carboxy group-containing cyclic olefin is particularly preferable.

  In the polar group-containing cyclic olefin polymer of the present invention, the content of the monomer unit represented by the general formula (1) is preferably 10 to 95% by weight based on the total monomer units. More preferably, it is 35-75 weight%, More preferably, it is 45-70 weight%. If the content ratio of the monomer unit represented by the general formula (1) is too small, the solubility of the polar group-containing cyclic olefin polymer in the polar solvent may be insufficient. When too much, the radiation sensitivity in the case of adding a radiation sensitive compound may fall.

In the present invention, a proton polar group is introduced into a polar group-containing cyclic olefin polymer by introducing a protic polar group into a polymer having no protic polar group using a known modifier. May be.
A polymer having no protic polar group can be obtained by polymerizing the above-described monomers (a2) to (a4) in any combination.

As the modifier for introducing a protic polar group, a compound having a protic polar group and a reactive carbon-carbon unsaturated bond in one molecule is usually used.
Specific examples of such compounds include acrylic acid, methacrylic acid, angelic acid, tiglic acid, oleic acid, elaidic acid, erucic acid, brassic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, atropaic acid. Unsaturated carboxylic acids such as acids and cinnamic acids; allyl alcohol, methyl vinyl methanol, crotyl alcohol, methallyl alcohol, 1-phenylethen-1-ol, 2-propen-1-ol, 3-butene-1- All, 3-buten-2-ol, 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, 2-methyl-3-buten-2-ol, 2-methyl- Saturation of 3-buten-1-ol, 4-penten-1-ol, 4-methyl-4-penten-1-ol, 2-hexen-1-ol, etc. Alcohol; and the like.
The modification reaction of the polymer using these modifiers may be performed according to a conventional method, and is usually performed in the presence of a radical generator.

  The weight average molecular weight of the polar group-containing cyclic olefin polymer of the present invention can be arbitrarily selected depending on the production purpose of the polymer, but is usually 1,000 to 1,000,000, preferably 1,500 to 1,000. 500,000, more preferably 2,000 to 50,000. The weight average molecular weight (Mw) of a polymer is a value calculated | required as a polystyrene conversion value by gel permeation chromatography (GPC).

  The polar group-containing cyclic olefin-based polymer of the present invention opens at least one of the monomers represented by the general formula (1) and a copolymerizable monomer used as necessary. A ring-opened polymer obtained by ring polymerization or an addition polymer obtained by addition polymerization of these monomers may be used, but various characteristics of the polymer can be improved. More preferred is a ring-opening polymer.

  The ring-opening polymer is obtained by opening at least one of the monomers represented by the general formula (1) and a copolymerizable monomer used as necessary in the presence of a metathesis reaction catalyst. It can be produced by metathesis polymerization.

  The metathesis reaction catalyst may be any catalyst as long as it is a group 3-11 transition metal compound of the periodic table and performs ring-opening metathesis polymerization of the monomer represented by the general formula (1). For example, as a metathesis reaction catalyst, one described in Olefin Metathesis and Metathesis Polymerization (KJ Ivinand JC Mol, Academic Press, San Diego 1997) can be used.

  As a metathesis reaction catalyst, a periodic table group 3-11 transition metal carbene complex catalyst is mentioned, for example. Among these, use of a ruthenium carbene complex catalyst is preferable.

  Examples of the periodic table Group 3-11 transition metal-carbene complex catalyst include a tungsten alkylidene complex catalyst, a molybdenum alkylidene complex catalyst, a rhenium alkylidene complex catalyst, and a ruthenium carbene complex catalyst.

Specific examples of the tungsten alkylidene complex ^{_{catalysts, W (N-2,6-Pr}} i 2 C 6 H 3) (CHBu t) (OBu t) 2, W (N-2,6-Pr i 2 C 6 H ^{_{3) (CHBu t) (OCMe}} 2 CF 3) 2, W (N-2,6-Pr i 2 C 6 H 3) (CHBu t) (OCMe (CF 3) 2) 2, W (N-2, ^{_{6-Pr i 2 C 6 H}} 3) (CHCMe 2 Ph) (OBu t) 2 W (N-2,6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) (OCMe 2 CF 3) 2, W ^{_{(N-2,6-Pr i 2}} C 6 H 3) (CHCMe 2 Ph) (OCMe (CF 3) 2) 2 and the like.

Specific examples of molybdenum alkylidene complex _{^{catalyst, Mo (N-2,6-Pr}} i 2 C 6 H 3) (CHBu t) (OBu t) 2, Mo (N-2,6-Pr i 2 C 6 H _{^{3) (CHBu t) (OCMe}} 2 CF 3) 2, Mo (N-2,6-Pr i 2 C 6 H 3) (CHBu t) (OCMe (CF 3) 2) 2, Mo (N-2, _{^{6-Pr i 2 C 6 H}} 3) (CHCMe 2 Ph) (OBu t) 2 Mo (N-2,6-Pr i 2 C 6 H 3) (CHCMe2Ph) (OCMe 2 CF 3) 2, Mo (N _{^{-2,6-Pr i 2 C 6 H}} 3) (CHCMe 2 Ph) (OCMe (CF 3) 2) 2, Mo (N-2,6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) ( BIPHEN), Mo (N-2,6 -Pr i 2 C ₆ H ₃ ) (CHCMe ₂ Ph) (BINO) (THF) and the like.

Specific examples of rhenium alkylidene complex ^{catalyst, Re (CBu t) (CHBu} t) (O-2,6-Pr i 2 C 6 H 3) 2, Re (CBu t) (CHBu t) (O-2- _{^{Bu t C 6 H 4) 2}} , Re (CBu t) (CHBu t) (OCMe 2 CF 3) 2, Re (CBu t) (CHBu t) (OCMe (CF 3) 2) 2, Re (CBu t) (CHBu ^t ) (O-2,6-Me ₂ C ₆ H ₃ ) _{2 and the} like.

In the above formula, the Pr ⁱ isopropyl group, a Bu ^t is tert- butyl group, Me is a a methyl group, Ph refers to a phenyl group, BIPHEN is 5,5 ', 6,6'-tetramethyl-3, 3′-di-tert-butyl-1,1′-biphenyl-2,2′-dioxy group, BINO represents 1,1′-dinaphthyl-2,2′-dioxy group, and THF represents tetrahydrofuran. .

  Further, specific examples of the ruthenium carbene complex catalyst include compounds represented by the following general formula (3) or general formula (4).

In the general formulas (3) and (4), ═CR ⁴ R ⁵ and ═C═CR ⁴ R ⁵ are carbene compounds containing a carbene carbon as a reaction center. R ⁴ and R ⁵ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain a halogen atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom or silicon atom, The carbene compound may or may not contain a heteroatom. L ¹ represents a heteroatom-containing carbene compound, and L ² represents a heteroatom-containing carbene compound or any neutral electron-donating compound.

Here, the hetero atom-containing carbene compound refers to a compound containing a carbene carbon and a hetero atom. Both L ¹ and L ² or L ¹ is a heteroatom-containing carbene compound, and a ruthenium metal atom is directly bonded to the carbene carbon contained therein, and a group containing a heteroatom is bonded.

L ³ and L ⁴ each independently represent an arbitrary anionic ligand. Also, two, three, four, five or six of R ⁴ , R ⁵ , L ¹ , L ² , L ³ and L ⁴ are bonded to each other to form a multidentate chelating ligand. May be. Specific examples of heteroatoms include N, O, P, S, As, and Se atoms. Among these, from the viewpoint of obtaining a stable carbene compound, N, O, P, S atoms and the like are preferable, and N atom is particularly preferable.

In the general formulas (3) and (4), the anionic (anionic) ligands L ³ and L ⁴ are ligands having a negative charge when separated from the central metal, for example, Halogen atoms such as fluorine, chlorine, bromine and iodine; hydrocarbons containing oxygen such as diketonate, alkoxy, aryloxy and carboxyl groups; substituted with halogen atoms such as cyclopentadienyl chloride And alicyclic hydrocarbon groups. Among these, a halogen atom is preferable and a chlorine atom is more preferable.

When L ² is a neutral electron donating compound, L ² may be any ligand as long as it has a neutral charge when separated from the central metal. Specific examples thereof include carbonyls, amines, pyridines, ethers, nitriles, esters, phosphines, thioethers, aromatic compounds, olefins, isocyanides, thiocyanates, and the like. Among these, phosphines and pyridines are preferable, and trialkylphosphine is more preferable.

  Examples of the ruthenium complex catalyst represented by the general formula (3) include benzylidene (1,3-dimesitymylimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3-dimesityl). Imidazolidine-2-ylidene) (3-methyl-2-butene-1-ylidene) (tricyclopentylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-octahydrobenzimidazol-2-ylidene) (tricyclohexylphosphine) Ruthenium dichloride, benzylidene [1,3-di (1-phenylethyl) -4-imidazoline-2-ylidene] (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-2,3-dihydrobenzimidazole-2 -B Den) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (tricyclohexylphosphine) (1,3,4-triphenyl-2,3,4,5-tetrahydro-1H-1,2,4-triazole-5-ylidene) Ruthenium dichloride, (1,3-diisopropylhexahydropyrimidin-2-ylidene) (ethoxymethylene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesitylimidazolidine-2-ylidene) pyridine ruthenium dichloride, etc. Ruthenium carbene complex in which a hetero atom-containing carbene compound and a neutral electron donating compound are bonded; benzylidenebis (1,3-dicyclohexylimidazolidine-2-ylidene) ruthenium dichloride, benzylidenebis (1,3 Ruthenium carbene complex-diisopropyl-4-imidazolin-2-ylidene) two hetero atom-containing carbene compounds such as ruthenium dichloride are bonded; and the like.

  Examples of the ruthenium carbene complex catalyst represented by the general formula (4) include (1,3-dimesitylimidazolidine-2-ylidene) (phenylvinylidene) (tricyclohexylphosphine) ruthenium dichloride, (t-butyl). Vinylidene) (1,3-diisopropyl-4-imidazoline-2-ylidene) (tricyclopentylphosphine) ruthenium dichloride, bis (1,3-dicyclohexyl-4-imidazoline-2-ylidene) phenylvinylidene ruthenium dichloride, and the like.

  The amount of the metathesis reaction catalyst used is the molar ratio of monomer to catalyst, catalyst: monomer = 1: 100 to 1: 2,000,000, preferably 1: 500 to 1: 1,000,000, More preferably, it is 1: 1,000-1: 500,000. If the amount of catalyst is too large, it may be difficult to remove the catalyst, and if it is too small, sufficient polymerization activity may not be obtained.

  Ring-opening polymerization using a metathesis reaction catalyst can be carried out in a solvent or without a solvent. When the hydrogenation reaction is carried out as it is without isolating the produced polymer after completion of the polymerization reaction, the polymerization is preferably carried out in a solvent.

  The solvent to be used is not particularly limited as long as it dissolves the produced polymer and does not inhibit the polymerization reaction. Examples of the solvent used include aliphatic hydrocarbons such as n-pentane, n-hexane, and n-heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, and bicyclo Alicyclic hydrocarbons such as heptane, tricyclodecane, hexahydroindene and cyclooctane; aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; nitrogen-containing compounds such as nitromethane, nitrobenzene, acetonitrile, propionitrile and benzonitrile Hydrocarbons; ethers such as diethyl ether, tetrahydrofuran, dioxane, etc .; acetone, ethyl methyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, etc. Ketones; methyl acetate, ethyl acetate, ethyl propionate, methyl benzoate, chloroform, dichloromethane, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, halogenated hydrocarbons such as chlorobenzene; and the like. Among these, the use of aromatic hydrocarbons, alicyclic hydrocarbons, ethers, ketones or esters is preferable.

  The concentration of the monomer composition in the solvent is preferably 1 to 50% by weight, more preferably 2 to 45% by weight, and still more preferably 5 to 40% by weight. If the concentration of the monomer composition is less than 1% by weight, the productivity of the polymer may be deteriorated. If it exceeds 50% by weight, the viscosity after polymerization is too high, and subsequent hydrogenation becomes difficult. There is.

  The metathesis reaction catalyst may be dissolved in a solvent and added to the reaction system, or may be added as it is without being dissolved. Examples of the solvent for preparing the catalyst solution include the same solvents as those used for the polymerization reaction.

  In the polymerization reaction, a molecular weight modifier can be added to the reaction system in order to adjust the molecular weight of the polymer. Examples of molecular weight modifiers include α-olefins such as 1-butene, 1-pentene, 1-hexene and 1-octene; styrenes such as styrene and vinyltoluene; ethers such as ethyl vinyl ether, isobutyl vinyl ether and allyl glycidyl ether; Halogen-containing vinyl compounds such as allyl chloride; oxygen-containing vinyl compounds such as allyl acetate, allyl alcohol and glycidyl methacrylate; nitrogen-containing vinyl compounds such as acrylonitrile and acrylamide can be used. A polymer having a desired molecular weight can be obtained by using 0.05 to 50 mol% of a molecular weight modifier with respect to the monomer mixture containing the monomer represented by the general formula (1). it can.

  The polymerization temperature is not particularly limited, but is usually −100 ° C. to + 200 ° C., preferably −50 ° C. to + 180 ° C., more preferably −30 ° C. to + 160 ° C., and further preferably 0 ° C. to + 140 ° C. The polymerization time is usually from 1 minute to 100 hours, and can be appropriately adjusted according to the progress of the reaction.

  On the other hand, the addition polymer coalescence is a known addition polymerization catalyst such as at least one monomer represented by the general formula (1) and a copolymerizable monomer used as necessary. It can be obtained by polymerization using a catalyst comprising a titanium, zirconium or vanadium compound and an organoaluminum compound. These polymerization catalysts can be used alone or in combination of two or more. The amount of the polymerization catalyst is a molar ratio of the metal compound to the monomer in the polymerization catalyst and is usually in the range of 1: 100 to 1: 2,000,000.

  Further, when the polar group-containing cyclic olefin polymer according to the present invention is a ring-opening polymer, a hydrogenation reaction is further performed, and hydrogen in which a carbon-carbon double bond contained in the main chain is hydrogenated. An additive is preferred. In the case where the polar group-containing cyclic olefin polymer is a hydrogenated product, the ratio of hydrogenated carbon-carbon double bonds (hydrogenation rate) is usually 50% or more, and from the viewpoint of heat resistance, 70 % Or more is preferable, 90% or more is more preferable, and 95% or more is further preferable.

Hydrogenation ratio of the hydrogenated product may, for example, carbon in the ^{1 H-NMR} spectrum of the ring-opening polymer - a peak intensity derived from the carbon-carbon double bond, carbon in the ^{1 H-NMR} spectrum of the hydrogenated product - carbon double It can obtain | require by comparing with the peak intensity derived from a coupling | bonding.

  The hydrogenation reaction can be performed, for example, by converting a carbon-carbon double bond in the main chain of the ring-opening polymer into a saturated single bond using hydrogen gas in the presence of a hydrogenation catalyst.

  The hydrogenation catalyst to be used is not particularly limited, such as a homogeneous catalyst and a heterogeneous catalyst, and those generally used for hydrogenation of olefin compounds can be used as appropriate.

  Examples of homogeneous catalysts include transitions such as cobalt acetate and triethylaluminum, nickel acetylacetonate and triisobutylaluminum, a combination of titanocene dichloride and n-butyllithium, zirconocene dichloride and sec-butyllithium, tetrabutoxytitanate and dimethylmagnesium, etc. Ziegler catalyst comprising a combination of a metal compound and an alkali metal compound; ruthenium carbene complex catalyst, dichlorotris (triphenylphosphine) rhodium described in the above section of ring-opening metathesis reaction catalyst, JP-A-7-2929, JP-A-7 -149823, JP-A-11-109460, JP-A-11-158256, JP-A-11-193323, JP-A-11-109460, etc. Noble metal complex catalyst consisting ruthenium compound; and the like.

  Examples of the heterogeneous catalyst include a hydrogenation catalyst in which a metal such as nickel, palladium, platinum, rhodium, and ruthenium is supported on a carrier such as carbon, silica, diatomaceous earth, alumina, and titanium oxide. More specifically, for example, nickel / silica, nickel / diatomaceous earth, nickel / alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth, palladium / alumina and the like can be used. These hydrogenation catalysts can be used alone or in combination of two or more.

  Among these, rhodium, ruthenium, and the like from the point that the carbon-carbon double bond in the polymer can be selectively hydrogenated without causing side reactions such as modification of the functional group contained in the ring-opening polymer. The use of a noble metal complex catalyst and a palladium supported catalyst such as palladium / carbon is preferred, and the use of a ruthenium carbene complex catalyst or a palladium supported catalyst is more preferred.

  The ruthenium carbene complex catalyst described above can be used as a ring-opening metathesis reaction catalyst and a hydrogenation catalyst. In this case, the ring-opening metathesis reaction and the hydrogenation reaction can be performed continuously.

  When a ring-opening metathesis reaction and a hydrogenation reaction are continuously performed using a ruthenium carbene complex catalyst, a vinyl compound such as ethyl vinyl ether or a catalyst modifier such as an α-olefin is added to activate the catalyst. Then, a method of starting the hydrogenation reaction is preferably employed. Furthermore, it is also preferable to employ a method of improving the activity by adding a base such as triethylamine or N, N-dimethylacetamide.

  The hydrogenation reaction is usually performed in an organic solvent. As an organic solvent, it can select suitably by the solubility of the hydride to produce | generate, The organic solvent similar to the said polymerization solvent can be used. Therefore, after the polymerization reaction, the hydrogenation catalyst can be added to the reaction solution or the filtrate obtained by filtering the metathesis reaction catalyst from the reaction solution without replacing the solvent.

  The conditions for the hydrogenation reaction may be appropriately selected according to the type of hydrogenation catalyst used. The amount of the hydrogenation catalyst used is usually 0.01 to 50 parts by weight, preferably 0.05 to 20 parts by weight, more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the ring-opening polymer. . The reaction temperature is usually −10 ° C. to + 250 ° C., preferably −10 ° C. to + 210 ° C., more preferably 0 ° C. to + 200 ° C. At a temperature lower than this range, the reaction rate becomes slow. Conversely, at a high temperature, a side reaction tends to occur. The pressure of hydrogen is usually 0.01 to 10.0 MPa, preferably 0.05 to 8.0 MPa, more preferably 0.1 to 6.0 MPa.

  The time for the hydrogenation reaction is appropriately selected in order to control the hydrogenation rate. The reaction time is usually in the range of 0.1 to 50 hours, and 50% or more, preferably 70% or more, more preferably 90% or more, most preferably, of the carbon-carbon double bonds of the main chain in the polymer. 95% or more can be hydrogenated.

  The polar group-containing cyclic olefin polymer obtained as described above is excellent in various electrical properties, low water absorption and adhesion, etc., which the polar group-containing cyclic olefin polymer has, It has a high rate and is excellent in transparency. Therefore, the polar group-containing cyclic olefin polymer of the present invention is used as a protective film for various display devices such as organic EL devices and liquid crystal display devices, integrated circuit devices, solid-state imaging devices, color filters, black matrices, and other various electronic components. It is suitable as a resin material for forming.

(Resin composition)
The resin composition of the present invention comprises the above-mentioned polar group-containing cyclic olefin polymer of the present invention and a solvent.

  The solvent is not particularly limited as long as it can dissolve the polar group-containing cyclic olefin polymer of the present invention satisfactorily. For example, acetone, methyl ethyl ketone, cyclopentanone, 2-hexanone, 3-hexanone, 2 -Linear ketones such as heptanone, 3-heptanone, 4-heptanone, 2-octanone, 3-octanone, 4-octanone; alcohols such as n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, cyclohexanol; Ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether and dioxane; alcohol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; propyl formate, butyl formate, propyl acetate, vinegar Esters such as butyl, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl lactate, ethyl lactate; cellosolv esters such as cellosolve acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve acetate; propylene Propylene glycols such as glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, die Diethylene glycols such as lenglycol methyl ethyl ether; saturated γ-lactones such as γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-caprolactone; halogenated hydrocarbons such as trichloroethylene; toluene, xylene, etc. Aromatic hydrocarbons; polar solvents such as dimethylacetamide, dimethylformamide, N-methylacetamide and the like. These solvents may be used alone or in combination of two or more. The content of the solvent is preferably 10 to 10000 parts by weight, more preferably 50 to 5000 parts by weight, and still more preferably 100 to 1000 parts by weight with respect to 100 parts by weight of the polar group-containing cyclic olefin polymer. .

  Moreover, it is preferable that the resin composition of this invention contains the crosslinking agent. Examples of the crosslinking agent include those that form a crosslinked structure between the crosslinking agent molecules by heating, and those that react with the polar group-containing cyclic olefin polymer to form a crosslinked structure between the resin molecules. Examples include compounds having two or more reactive groups. Examples of such a reactive group include an amino group, a carboxy group, a hydroxyl group, an epoxy group, and an isocyanate group, more preferably an amino group, an epoxy group, and an isocyanate group, and further preferably an amino group and an epoxy group. It is a group. Moreover, as an epoxy group, a terminal epoxy group and an alicyclic epoxy group are preferable, and an alicyclic epoxy group is more preferable.

  Although the molecular weight of a crosslinking agent is not specifically limited, Usually, it is 100-100,000, Preferably it is 300-50,000, More preferably, it is 500-10,000. A crosslinking agent can be used individually or in combination of 2 types or more, respectively.

  Specific examples of the crosslinking agent include aliphatic polyamines such as hexamethylenediamine; aromatic polyamines such as 4,4′-diaminodiphenyl ether and diaminodiphenylsulfone; 2,6-bis (4′-azidobenzal) cyclohexanone, 4 , 4′-diazidodiphenylsulfone and other azides; nylon, polyhexamethylenediamine terephthalamide, polyhexamethyleneisophthalamide and other polyamides; N, N, N ′, N ′, N ″, N ″ Melamines which may have a methylol group such as-(hexaalkoxyalkyl) melamine or an imino group (trade names "Cymel 303, Cymel 325, Cymel 370, Cymel 232, Cymel 235, Cymel 272, Cymel 212, Myel Coat 506 "{End, Cytec Indah Cymel series, Mycoat series, etc. manufactured by Torys Co., Ltd.]; N, N ′, N ″, N ′ ″-(tetraalkoxyalkyl) glycoluril and other methylol groups and imino groups Good glycolurils (trade name “Cymel 1170” {Cytech series manufactured by Cytec Industries, Inc.}); acrylate compounds such as ethylene glycol di (meth) acrylate; hexamethylene diisocyanate polyisocyanate, isophorone diisocyanate polyisocyanate , Isocyanate compounds such as tolylene diisocyanate polyisocyanate and hydrogenated diphenylmethane diisocyanate; 1,4-di- (hydroxymethyl) cyclohexane, 1,4-di- (hydroxymethyl) norbornane; 1,3,4 Trihydroxycyclohexane; bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, polyphenol type epoxy resin, cyclic aliphatic epoxy resin, aliphatic glycidyl ether, epoxy acrylate polymer, etc. And epoxy compounds.

  Specific examples of the epoxy compound include a trifunctional epoxy compound having a dicyclopentadiene skeleton (trade name “XD-1000”, manufactured by Nippon Kayaku Co., Ltd.), 2,2-bis (hydroxymethyl) 1-butanol. 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct (15-functional alicyclic epoxy resin having a cyclohexane skeleton and a terminal epoxy group, trade name “EHPE3150”, manufactured by Daicel Chemical Industries, Ltd.), epoxidation 3-cyclohexene-1,2-dicarboxylate bis (3-cyclohexenylmethyl) modified ε-caprolactone (aliphatic cyclic trifunctional epoxy resin, trade name “Epolide GT301”, manufactured by Daicel Chemical Industries), epoxidized butane Tetracarboxylic acid tetrakis (3-cyclohexenylmethyl) modified ε-caprolactone (fat An epoxy compound having an alicyclic structure such as an aliphatic cyclic tetrafunctional epoxy resin, trade name “Epolide GT401” manufactured by Daicel Chemical Industries, Ltd .;

  Aromatic amine type polyfunctional epoxy compound (trade name “H-434”, manufactured by Tohto Kasei Kogyo Co., Ltd.), cresol novolac type polyfunctional epoxy compound (trade name “EOCN-1020”, manufactured by Nippon Kayaku Co., Ltd.), phenol novolac type Polyfunctional epoxy compounds (Epicoat 152, 154, manufactured by Japan Epoxy Resin Co., Ltd.), polyfunctional epoxy compounds having a naphthalene skeleton (trade name EXA-4700, manufactured by Dainippon Ink & Chemicals, Inc.), chain alkyl polyfunctional epoxy compounds (products) Name “SR-TMP”, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., multifunctional epoxy polybutadiene (trade name “Epolide PB3600”, manufactured by Daicel Chemical Industries, Ltd.), glycerin glycidyl polyether compound (trade name “SR-GLG”, Sakamoto Yakuhin) Kogyo Co., Ltd.), diglycerin polyglycidyl ether compound ( Product name “SR-DGE”, Sakamoto Yakuhin Kogyo Co., Ltd., polyglycerol polyglycidyl ether compound (trade name “SR-4GL”, Sakamoto Yakuhin Kogyo Co., Ltd.) and other epoxy compounds having no alicyclic structure; be able to.

  Among the epoxy compounds, polyfunctional epoxy compounds having two or more epoxy groups are preferable, and the resin film obtained by using the resin composition of the present invention can be excellent in heat resistance shape retention. And a polyfunctional epoxy compound having 3 or more epoxy groups is particularly preferable.

  The content of the crosslinking agent in the resin composition of the present invention is not particularly limited, and is arbitrary in consideration of the degree of heat resistance required when a pattern is provided on the resin film obtained using the resin composition of the present invention. However, it is usually 1 to 500 parts by weight, preferably 5 to 300 parts by weight, more preferably 10 to 150 parts by weight with respect to 100 parts by weight of the polar group-containing cyclic olefin polymer. If the amount of the crosslinking agent is too much or too little, the heat resistance tends to decrease.

  Furthermore, the resin composition of the present invention may contain a radiation sensitive compound. A radiation-sensitive compound is a compound that can cause a chemical reaction upon irradiation with radiation such as ultraviolet rays or electron beams. By containing a radiation sensitive compound, the resin composition of the present invention can have radiation sensitivity. In the present invention, the radiation sensitive compound is preferably one that can control the alkali solubility of the resin film formed from the resin composition, and it is particularly preferable to use a photoacid generator.

  Examples of such radiation-sensitive compounds include azide compounds such as acetophenone compounds, triarylsulfonium salts, and quinonediazide compounds, with azide compounds being preferred, and quinonediazide compounds being particularly preferred.

As the quinonediazide compound, for example, an ester compound of a quinonediazidesulfonic acid halide and a compound having a phenolic hydroxyl group can be used. Specific examples of the quinone diazide sulfonic acid halide include 1,2-naphthoquinone diazide-5-sulfonic acid chloride, 1,2-naphthoquinone diazide-4-sulfonic acid chloride, 1,2-benzoquinone diazide-5-sulfonic acid chloride, and the like. Can be mentioned. Typical examples of the compound having a phenolic hydroxyl group include 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 4,4 ′-[1- [4- [1. -[4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and the like. Other compounds having a phenolic hydroxyl group include 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2-bis (4-hydroxyphenyl) propane, tris (4- Hydroxyphenyl) methane, 1,1,1-tris (4-hydroxy-3-methylphenyl) ethane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, novolac resin oligomer, phenolic hydroxyl group Examples thereof include oligomers obtained by copolymerizing one or more compounds and dicyclopentadiene.
Among these, a condensate of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and a compound having a phenolic hydroxyl group is preferable, and 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl)- A condensate of 3-phenylpropane (1 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (1.9 mol) is more preferred.

In addition to quinonediazide compounds, photoacid generators include onium salts, halogenated organic compounds, α, α′-bis (sulfonyl) diazomethane compounds, α-carbonyl-α′-sulfonyldiazomethane compounds, sulfone compounds, Known compounds such as organic acid ester compounds, organic acid amide compounds, and organic acid imide compounds can be used.
These radiation-sensitive compounds can be used alone or in combination of two or more.

  The content of the radiation sensitive compound in the resin composition of the present invention is preferably 10 to 100 parts by weight, more preferably 15 to 70 parts by weight, and still more preferably 100 parts by weight of the polar group-containing cyclic olefin polymer. Is in the range of 20-50 parts by weight. If the content of the radiation-sensitive compound is within this range, when patterning a resin film made of a resin composition, the difference in solubility in the developer between the radiation-irradiated part and the unirradiated part is increased, and the radiation sensitivity is also increased. This is preferable because it becomes high and patterning by development is easy.

  Furthermore, as long as the resin composition used in the present invention is within a range in which the effects of the present invention are not inhibited, a surfactant, an acidic compound, a coupling agent or a derivative thereof, a sensitizer, a latent acid generator, Other compounding agents such as an antioxidant, a light stabilizer, an antifoaming agent, a pigment, a dye, and a filler;

  The surfactant is used for the purpose of preventing striation (after application stripes) and improving developability. Specific examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, and the like. Polyoxyethylene aryl ethers; Nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; Fluorine surfactants; Silicone surfactants; Methacrylic acid copolymer System surfactants; acrylic acid copolymer system surfactants; and the like.

  The acidic compound is used for the purpose of improving the adhesion between the resin film made of the resin composition and each layer including the semiconductor layer constituting the semiconductor element substrate.

  As the acidic compound, an aliphatic compound having an acidic group, an aromatic compound, a heterocyclic compound, or the like can be used. The acidic group may be an acidic functional group, and specific examples thereof include strong acidic groups such as sulfonic acid group and phosphoric acid group; weak acidic groups such as carboxy group, thiol group and carboxymethylenethio group. It is done. Among these, a carboxy group, a thiol group or a carboxymethylenethio group is preferable, and a carboxy group is particularly preferable. Specific examples include methanoic acid, ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, glycolic acid, glyceric acid, ethanedioic acid (Also referred to as “oxalic acid”), propanedioic acid (also referred to as “malonic acid”), butanedioic acid (also referred to as “succinic acid”), pentanedioic acid, hexanedioic acid (also referred to as “adipic acid”) ), 1,2-cyclohexanedicarboxylic acid, 2-oxopropanoic acid, 2-hydroxybutanedioic acid, 2-hydroxypropanetricarboxylic acid, mercaptosuccinic acid, dimercaptosuccinic acid, 2,3-dimercapto-1-propanol, 1 2,3-trimercaptopropane, 2,3,4-trimercapto-1-butanol, 2,4-dimercapto-1,3-buta Diol, 1,3,4-trimercapto-2-butanol, 3,4-dimercapto-1,2-butanediol, aliphatic compounds such as 1,5-dimercapto-3-Chiapentan;

  Benzoic acid, p-hydroxybenzenecarboxylic acid, o-hydroxybenzenecarboxylic acid, 2-naphthalenecarboxylic acid, methylbenzoic acid, dimethylbenzoic acid, trimethylbenzoic acid, 3-phenylpropanoic acid, 2-hydroxybenzoic acid, dihydroxybenzoic acid , Dimethoxybenzoic acid, benzene-1,2-dicarboxylic acid (also referred to as “phthalic acid”), benzene-1,3-dicarboxylic acid (also referred to as “isophthalic acid”), benzene-1,4-dicarboxylic acid ( Also referred to as “terephthalic acid”), benzene-1,2,3-tricarboxylic acid, benzene-1,2,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, benzenehexacarboxylic acid, biphenyl-2 , 2'-dicarboxylic acid, 2- (carboxymethyl) benzoic acid, 3- (carboxymethyl) benzoic acid 4- (carboxymethyl) benzoic acid, 2- (carboxycarbonyl) benzoic acid, 3- (carboxycarbonyl) benzoic acid, 4- (carboxycarbonyl) benzoic acid, 2-mercaptobenzoic acid, 4-mercaptobenzoic acid, 2- Mercapto-6-naphthalenecarboxylic acid, 2-mercapto-7-naphthalenecarboxylic acid, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,4-naphthalenedithiol, 1 , 5-naphthalenedithiol, 2,6-naphthalenedithiol, 2,7-naphthalenedithiol, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris (mercaptomethyl) benzene, 1,2,4-tris (mercapto) Chill) benzene, 1,3,5-tris (mercaptomethyl) benzene, 1,2,3-tris (mercaptoethyl) benzene, 1,2,4-tris (mercaptoethyl) benzene, 1,3,5-tris Aromatic compounds such as (mercaptoethyl) benzene;

  Nicotinic acid, isonicotinic acid, 2-furoic acid, pyrrole-2,3-dicarboxylic acid, pyrrole-2,4-dicarboxylic acid, pyrrole-2,5-dicarboxylic acid, pyrrole-3,4-dicarboxylic acid, imidazole Five-membered nitrogen atoms such as 2,4-dicarboxylic acid, imidazole-2,5-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, pyrazole-3,5-dicarboxylic acid Heterocyclic compounds; thiophene-2,3-dicarboxylic acid, thiophene-2,4-dicarboxylic acid, thiophene-2,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, thiazole-2,4-dicarboxylic acid, thiazole -2,5-dicarboxylic acid, thiazole-4,5-dicarboxylic acid, isothiazole-3,4-dicarboxylic acid, isothiazole -3,5-dicarboxylic acid, 1,2,4-thiadiazole-2,5-dicarboxylic acid, 1,3,4-thiadiazole-2,5-dicarboxylic acid, 3-amino-5-mercapto-1,2, 4-thiadiazole, 2-amino-5-mercapto-1,3,4-thiadiazole, 3,5-dimercapto-1,2,4-thiadiazole, 2,5-dimercapto-1,3,4-thiadiazole, 3- (5-mercapto-1,2,4-thiadiazol-3-ylsulfanyl) succinic acid, 2- (5-mercapto-1,3,4-thiadiazol-2-ylsulfanyl) succinic acid, (5-mercapto-1 , 2,4-thiadiazol-3-ylthio) acetic acid, (5-mercapto-1,3,4-thiadiazol-2-ylthio) acetic acid, 3- (5-mercapto-1,2,4) Thiadiazol-3-ylthio) propionic acid, 2- (5-mercapto-1,3,4-thiadiazol-2-ylthio) propionic acid, 3- (5-mercapto-1,2,4-thiadiazol-3-ylthio) Succinic acid, 2- (5-mercapto-1,3,4-thiadiazol-2-ylthio) succinic acid, 4- (3-mercapto-1,2,4-thiadiazol-5-yl) thiobutanesulfonic acid, 4 -5-membered heterocyclic compound containing a nitrogen atom and a sulfur atom such as (2-mercapto-1,3,4-thiadiazol-5-yl) thiobutanesulfonic acid;

  Pyridine-2,3-dicarboxylic acid, pyridine-2,4-dicarboxylic acid, pyridine-2,5-dicarboxylic acid, pyridine-2,6-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, pyridine-3,5 -Dicarboxylic acid, pyridazine-3,4-dicarboxylic acid, pyridazine-3,5-dicarboxylic acid, pyridazine-3,6-dicarboxylic acid, pyridazine-4,5-dicarboxylic acid, pyrimidine-2,4-dicarboxylic acid, pyrimidine -2,5-dicarboxylic acid, pyrimidine-4,5-dicarboxylic acid, pyrimidine-4,6-dicarboxylic acid, pyrazine-2,3-dicarboxylic acid, pyrazine-2,5-dicarboxylic acid, pyridine-2,6- Dicarboxylic acid, triazine-2,4-dicarboxylic acid, 2-diethylamino-4,6-dimercapto-s-triazine, 2-dipropyl Mino-4,6-dimercapto-s-triazine, 2-dibutylamino-4,6-dimercapto-s-triazine, 2-anilino-4,6-dimercapto-s-triazine, 2,4,6-trimercapto- 6-membered heterocyclic compounds containing a nitrogen atom such as s-triazine.

Among these, the number of acidic groups is preferably 2 or more, and particularly preferably 2 from the viewpoint that adhesion between the resin film made of the resin composition and the substrate can be increased.
The compounds having two acidic groups include ethanedioic acid, propanedioic acid, butanedioic acid, pentanedioic acid, hexanedioic acid, 1,2-cyclohexanedicarboxylic acid, benzene-1,2-dicarboxylic acid (“phthalic acid”). ), Benzene-1,3-dicarboxylic acid (also referred to as “isophthalic acid”), benzene-1,4-dicarboxylic acid (also referred to as “terephthalic acid”), biphenyl-2,2′-dicarboxylic acid. 2- (carboxymethyl) benzoic acid, 3- (carboxymethyl) benzoic acid, 4- (carboxymethyl) benzoic acid, 2-mercaptobenzoic acid, 4-mercaptobenzoic acid, 2-mercapto-6-naphthalenecarboxylic acid, 2-mercapto-7-naphthalenecarboxylic acid, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, Aromatic compounds having two acidic groups of 1,4-naphthalenedithiol, 1,5-naphthalenedithiol, 2,6-naphthalenedithiol, and 2,7-naphthalenedithiol; pyrrole-2,3-dicarboxylic acid, pyrrole-2 , 4-dicarboxylic acid, pyrrole-2,5-dicarboxylic acid, pyrrole-3,4-dicarboxylic acid, imidazole-2,4-dicarboxylic acid-, imidazole-2,5-dicarboxylic acid, imidazole-4,5-dicarboxylic acid Acid, pyrazole-3,4-dicarboxylic acid, pyrazole-3,5-dicarboxylic acid, thiophene-2,3-dicarboxylic acid, thiophene-2,4-dicarboxylic acid, thiophene-2,5-dicarboxylic acid, thiophene-3, 4-dicarboxylic acid, thiazole-2,4-dicarboxylic acid, thiazole-2,5-dicarboxylic acid, thiazo -4,5-dicarboxylic acid, isothiazole-3,4-dicarboxylic acid, isothiazole-3,5-dicarboxylic acid, 1,2,4-thiadiazole-2,5-dicarboxylic acid, 1,3,4 -Thiadiazole-2,5-dicarboxylic acid, (5-mercapto-1,2,4-thiadiazol-3-ylthio) acetic acid, (5-mercapto-1,3,4-thiadiazol-2-ylthio) acetic acid, pyridine- 2,3-dicarboxylic acid, pyridine-2,4-dicarboxylic acid, pyridine-2,5-dicarboxylic acid, pyridine-2,6-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, pyridine-3,5-dicarboxylic acid Acid, pyridazine-3,4-dicarboxylic acid, pyridazine-3,5-dicarboxylic acid, pyridazine-3,6-dicarboxylic acid, pyridazine-4,5-dicarboxylic acid, Midine-2,4-dicarboxylic acid, pyrimidine-2,5-dicarboxylic acid, pyrimidine-4,5-dicarboxylic acid, pyrimidine-4,6-dicarboxylic acid, pyrazine-2,3-dicarboxylic acid, pyrazine-2,5 -A heterocyclic compound having two acidic groups of dicarboxylic acid, pyridine-2,6-dicarboxylic acid, and triazine-2,4-dicarboxylic acid.

  The coupling agent or derivative thereof has an effect of further improving the adhesion between the resin film made of the resin composition and the substrate. As the coupling agent or derivative thereof, a compound having one atom selected from a silicon atom, a titanium atom, an aluminum atom, and a zirconium atom and having a hydrocarbyloxy group or a hydroxy group bonded to the atom can be used.

As a coupling agent or a derivative thereof, for example,
Tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane,
Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n- Butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, n-decyltrimethoxysilane, p-styryl Trimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyl Nyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-amino Propyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyl Limethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyl Triethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-ethyl (trimethoxysilylpropoxymethyl) oxetane, 3-ethyl (triethoxysilylpropoxymethyl) Kisetan, 3-triethoxysilyl-N-(1,3-dimethyl - butylidene) propylamine, trialkoxysilanes such as bis (triethoxysilylpropyl) tetrasulfide,
Dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxy Silane, di-n-butyldimethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyl Dimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n-octyldiethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane, Diphenyldie Xysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropylmethyldiethoxysilane In addition to dialkoxysilanes such as N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane,
Silicon atoms such as methyltriacetyloxysilane, dimethyldiacetyloxysilane, trade names X-12-414, KBP-44 (manufactured by Shin-Etsu Chemical Co., Ltd.), 217FLAKE, 220FLAKE, 233FLAKE, z6018 (manufactured by Toray Dow Corning Co., Ltd.) Containing compounds;

(Tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetrakis (2-ethylhexyloxy) titanium, titanium-i-propoxyoctylene glycolate, di-i-propoxybis (acetylacetonato) titanium, propanedi Oxytitanium bis (ethylacetoacetate), tri-n-butoxytitanium monostearate, di-i-propoxytitanium distearate, titanium stearate, di-i-propoxytitanium diisostearate, (2-n-butoxycarbonyl Titanium atom-containing compounds such as benzoyloxy) tributoxytitanium, di-n-butoxy bis (triethanolaminato) titanium, as well as the preneact series (manufactured by Ajinomoto Fine Techno Co., Ltd.);
Aluminum atom-containing compounds such as (acetoalkoxyaluminum diisopropylate);
(Tetranormal propoxyzirconium, tetranormalbutoxyzirconium, zirconium tetraacetylacetonate, zirconium tributoxyacetylacetonate, zirconium butoxyacetylacetonate bis (ethylacetoacetate), zirconium dibutoxybis (ethylacetoacetate), zirconium tetraacetyl Zirconium atom-containing compounds such as acetonate and zirconium tributoxy systemate).

  Examples of light stabilizers include ultraviolet absorbers such as benzophenone-based, salicylic acid ester-based, benzotriazole-based, cyanoacrylate-based, and metal complex-based salts, hindered amine-based (HALS), and the like that capture radicals generated by light. Either is acceptable. Among these, HALS is a compound having a piperidine structure and is preferable because it is less colored with respect to the resin composition and has good stability. Specific compounds include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl 1,2,3,4 -Butanetetracarboxylate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate and the like.

  Specific examples of the sensitizer include 2H-pyrido- (3,2-b) -1,4-oxazin-3 (4H) -ones, 10H-pyrido- (3,2-b) -1,4. -Benzothiazines, urazoles, hydantoins, barbituric acids, glycine anhydrides, 1-hydroxybenzotriazoles, alloxans, maleimides and the like.

  The latent acid generator is used for the purpose of improving the heat resistance and chemical resistance of the resin composition used in the present invention. Specific examples thereof include sulfonium salts, benzothiazolium salts, ammonium salts, and phosphonium salts, which are cationic polymerization catalysts that generate an acid upon heating. Of these, sulfonium salts and benzothiazolium salts are preferred.

  As the antioxidant, there can be used phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, lactone antioxidants and the like used in ordinary polymers. For example, as phenols, 2,6-di-t-butyl-4-methylphenol, p-methoxyphenol, styrenated phenol, n-octadecyl-3- (3 ′, 5′-di-t-butyl-4 '-Hydroxyphenyl) propionate, 2,2'-methylene-bis (4-methyl-6-t-butylphenol), 2-t-butyl-6- (3'-t-butyl-5'-methyl-2' -Hydroxybenzyl) -4-methylphenyl acrylate, 4,4'-butylidene-bis- (3-methyl-6-tert-butylphenol), 4,4'-thio-bis (3-methyl-6-tert-butylphenol) ), Pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], alkylated bisphenols, etc. Can. Examples of the phosphorus-based antioxidant include triphenyl phosphite and tris (nonylphenyl) phosphite. Examples of the sulfur-based antioxidant include dilauryl thiodipropionate.

  Examples of light stabilizers include ultraviolet absorbers such as benzophenone-based, salicylic acid ester-based, benzotriazole-based, cyanoacrylate-based, and metal complex-based salts, hindered amine-based (HALS), and the like that capture radicals generated by light. Either is acceptable. Among these, HALS is a compound having a piperidine structure and is preferable because it is less colored with respect to the resin composition and has good stability. Specific compounds include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl 1,2,3,4 -Butanetetracarboxylate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate and the like.

The preparation method of the resin composition of this invention is not specifically limited, What is necessary is just to mix each component which comprises a resin composition by a well-known method.
The mixing method is not particularly limited, but it is preferable to mix a solution or dispersion obtained by dissolving or dispersing each component constituting the resin composition in a solvent. Thereby, a resin composition is obtained with the form of a solution or a dispersion liquid.

  A method for dissolving or dispersing each component constituting the resin composition in a solvent may follow a conventional method. Specifically, stirring using a stirrer and a magnetic stirrer, a high-speed homogenizer, a disper, a planetary stirrer, a twin-screw stirrer, a ball mill, a three-roll, etc. can be used. Further, after each component is dissolved or dispersed in a solvent, it may be filtered using, for example, a filter having a pore size of about 0.5 μm.

  The solid content concentration of the resin composition of the present invention is usually 1 to 70% by weight, preferably 5 to 60% by weight, and more preferably 10 to 50% by weight. If the solid content concentration is within this range, dissolution stability, coating properties, film thickness uniformity of the formed resin film, flatness, and the like can be highly balanced.

(Laminate)
The laminate of the present invention has a resin film formed from the resin composition of the present invention described above and a substrate. For example, the resin film of the present invention described above is used to form a resin film on the substrate. Then, it can be obtained by crosslinking the resin film as necessary.

  In the present invention, for example, a printed wiring board, a silicon wafer substrate, a glass substrate, a plastic substrate, or the like can be used as the substrate. The substrate surface may be physically and / or chemically surface treated, and may have a multiple layer structure in which other thin films are formed on the substrate surface. Further, a glass substrate, a plastic substrate, or the like used in the display field, in which various elements such as a thin transistor type liquid crystal display element, a thin film transistor, and an organic EL, a color filter, a black matrix, and the like are suitably used.

  The method for forming the resin film on the substrate is not particularly limited, and for example, a method such as a coating method or a film lamination method can be used.

  The application method is, for example, a method of removing a solvent by applying a resin composition and then drying by heating. As a method for applying the resin composition, for example, various methods such as a spray method, a spin coating method, a roll coating method, a die coating method, a doctor blade method, a spin coating method, a bar coating method, and a screen printing method may be adopted. Can do. The heating and drying conditions vary depending on the type and blending ratio of each component, but are usually 30 to 150 ° C., preferably 60 to 120 ° C., usually 0.5 to 90 minutes, preferably 1 to 60 minutes, and more. Preferably it may be performed in 1 to 30 minutes.

  In the film lamination method, the resin composition is applied onto a B-stage film-forming substrate such as a resin film or a metal film, and then the solvent is removed by heating and drying to obtain a B-stage film. And a method of laminating on a substrate. The heating and drying conditions can be appropriately selected according to the type and mixing ratio of each component, but the heating temperature is usually 30 to 150 ° C., and the heating time is usually 0.5 to 90 minutes. . Film lamination can be performed using a pressure laminator, a press, a vacuum laminator, a vacuum press, a roll laminator or the like.

  The thickness of the resin film formed on the substrate is not particularly limited and may be set as appropriate according to the application. The thickness of the resin film is preferably 0.1 to 100 μm, more preferably 0. It is 5-50 micrometers, More preferably, it is 0.5-30 micrometers.

  Moreover, when the resin composition of this invention contains a crosslinking agent, a crosslinking reaction can be performed about the resin film formed by the above-mentioned coating method or film lamination method. Such crosslinking may be appropriately selected according to the type of the crosslinking agent, but is usually performed by heating. The heating method can be performed using, for example, a hot plate or an oven. The heating temperature is usually 180 to 250 ° C., and the heating time is appropriately selected according to the area and thickness of the resin film, the equipment used, and the like. For example, when using a hot plate, the oven is usually used for 5 to 60 minutes. When used, it is usually in the range of 30 to 90 minutes. Heating may be performed in an inert gas atmosphere as necessary. Any inert gas may be used as long as it does not contain oxygen and does not oxidize the resin film. Examples thereof include nitrogen, argon, helium, neon, xenon, and krypton. Among these, nitrogen and argon are preferable, and nitrogen is particularly preferable. In particular, an inert gas having an oxygen content of 0.1% by volume or less, preferably 0.01% by volume or less, particularly nitrogen is suitable. These inert gases can be used alone or in combination of two or more.

Moreover, when the resin composition of this invention contains a radiation sensitive compound, the resin film formed using the resin composition of this invention may be patterned.
As a method of patterning the resin film, for example, the latent image pattern is formed by irradiating the resin film before patterning with active radiation, and then the developer is brought into contact with the resin film having the latent image pattern. The method of making it manifest is mentioned.

The actinic radiation is not particularly limited as long as it can activate the radiation-sensitive compound and change the alkali solubility of the resin composition containing the radiation-sensitive compound. Specifically, ultraviolet rays, ultraviolet rays having a single wavelength such as g-line or i-line, light rays such as KrF excimer laser light and ArF excimer laser light; particle beams such as electron beams; As a method for selectively irradiating these actinic radiations in a pattern to form a latent image pattern, a conventional method may be used. For example, ultraviolet, g-line, i-line, KrF excimer is used by a reduction projection exposure apparatus or the like. A method of irradiating a light beam such as laser light or ArF excimer laser light through a desired mask pattern or a method of drawing with a particle beam such as an electron beam can be used. When light is used as the active radiation, it may be single wavelength light or mixed wavelength light. Irradiation conditions may be appropriately selected depending on the active radiation to be used, for example, when using a light beam of wavelength 200 to 450 nm, the amount of irradiation is usually 10~1,000mJ / cm ^2, preferably 50 to 500 mJ / It is a range of cm ² and is determined according to irradiation time and illuminance. After irradiation with actinic radiation in this way, the protective film is heat-treated at a temperature of about 60 to 130 ° C. for about 1 to 2 minutes as necessary.

  Next, the latent image pattern formed on the resin film before patterning is developed and made visible. As the developer, an aqueous solution of an alkaline compound is usually used. As the alkaline compound, for example, an alkali metal salt, an amine, or an ammonium salt can be used. The alkaline compound may be an inorganic compound or an organic compound. Specific examples of these compounds include alkali metal salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate and sodium metasilicate; ammonia water; primary amines such as ethylamine and n-propylamine; diethylamine Secondary amines such as di-n-propylamine; tertiary amines such as triethylamine and methyldiethylamine; quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide and choline Alcohol alcohols such as dimethylethanolamine and triethanolamine; pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] nona-5 -En, N-Me Cyclic amines such as Rupiroridon; and the like. These alkaline compounds can be used alone or in combination of two or more.

As an aqueous medium of the alkaline aqueous solution, water; water-soluble organic solvents such as methanol and ethanol can be used. The alkaline aqueous solution may have a surfactant added in an appropriate amount.
As a method of bringing the developer into contact with the resin film having the latent image pattern, for example, a paddle method, a spray method, a dipping method, or the like is used. The development is usually appropriately selected in the range of 0 to 100 ° C, preferably 5 to 55 ° C, more preferably 10 to 30 ° C, and usually 30 to 180 seconds.

The resin film on which the target pattern is formed in this manner can be rinsed with a rinsing liquid in order to remove the development residue, if necessary. After the rinse treatment, the remaining rinse liquid is removed with compressed air or compressed nitrogen.
Further, if necessary, in order to deactivate the radiation sensitive compound, the entire surface of the substrate can be irradiated with actinic radiation. For irradiation with actinic radiation, the method exemplified in the formation of the latent image pattern can be used. The resin film may be heated simultaneously with irradiation or after irradiation. Examples of the heating method include a method of heating the substrate in a hot plate or an oven. The temperature is usually in the range of 100 to 300 ° C, preferably 120 to 200 ° C.

  In the present invention, the resin film can be subjected to a crosslinking reaction after being patterned. Crosslinking may be performed according to the method described above.

  According to the present invention, the resin film constituting the laminate is composed of the above-described polar group-containing cyclic olefin polymer of the present invention. In addition to the properties of excellent water absorption and adhesion, the polymerization conversion rate is high and the transparency can be improved. Therefore, the laminate of the present invention is suitable as various electronic components such as various display elements such as organic EL elements and liquid crystal display devices, integrated circuit elements, solid-state imaging elements, color filters, and black matrices.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. Parts and% in each example are based on weight unless otherwise specified.
In addition, the evaluation method of each characteristic is as follows.

<Polymerization conversion>
The residual monomer amount in the reaction solution after the polymerization reaction was measured using gas chromatography, and the polymerization conversion rate of the cyclic olefin polymer was calculated from the residual monomer amount.

<Hydrogen addition rate>
By measuring the number of moles of hydrogenated carbon-carbon double bonds by ¹ H-NMR spectrum and calculating the ratio to the number of moles of carbon-carbon double bonds before hydrogenation, the hydride of the cyclic olefin polymer The hydrogenation rate of was determined.

<Weight average molecular weight / number average molecular weight>
Using gel permeation chromatography (combined with three types of columns of Tosoh Corporation model number “HLC-8020”, TSKgel SuperH2000, TSKgel SuperH4000, TSKgel SuperH5000), the weight average molecular weight of the cyclic olefin polymer and its hydride The number average molecular weight was calculated in terms of polystyrene. Tetrahydrofuran was used as a developing solvent.

<Spectral transmittance>
A resin composition is applied on a glass substrate (Corning, product name Corning 1737) by spin coating, and is heated and dried (pre-baked) at 90 ° C. for 2 minutes using a hot plate, thereby a resin having a film thickness of 3.0 μm. A film was formed. Then, the laminated body was obtained by performing an oven baking process in air at the temperature of 230 degreeC and 1 hour conditions. And about the obtained laminated body, the spectral transmittance was measured with wavelength 400nm using the spectrophotometer (The JASCO Corporation make, "ultraviolet visible spectrophotometer V-560 (product name)".

Example 1
In a SUS reaction vessel equipped with a purification stirrer, 100 parts of N- (2-ethylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide (NEHI) and diethylene glycol ethyl 100 parts of methyl ether was charged, and then mixed ion exchange resin (Amberlyst MSPS2-1, manufactured by Organo Corporation, strongly acidic cation exchange resin: weakly basic anion exchange resin = 50: 50 (weight ratio) mixture) 20 parts were added, and the mixture was stirred at a temperature of 25 ° C. And after stirring for 20 hours, it filtered using a filter paper, N-phenyl-bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide (NEHI) and diethylene glycol ethyl. A filtrate containing methyl ether was obtained. The obtained filtrate was analyzed by gas chromatography. As a result, N- (2-ethylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide (NEHI) was obtained. As a decomposition product, 2-ethylhexylamine was below the detection limit (the same applies to Example 2 and Comparative Example 1 described later).

Polymerization reaction And 40 parts of N- (2-ethylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide (NEHI) purified above, 8-hydroxy Carbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene 60 parts, 1,5-hexadiene 6.5 parts, (1,3-dimesityrylimidazoline-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium chloride (Org. Lett. , Vol. 1, page 953, synthesized by the method described in 1999), 0.03 part and 400 parts of ethylene glycol ethyl methyl ether were charged into a nitrogen-substituted glass pressure-resistant reactor and stirred at 80 ° C. For 3 hours to obtain a polymerization reaction solution. The obtained cyclic olefin polymer had a polymerization conversion of 99.4%, a weight average molecular weight of 5,654, a number average molecular weight of 3,798, and a molecular weight distribution of 1.49.

Hydrogenation reaction The polymerization reaction liquid obtained above was put in an autoclave, 0.6 parts of nickel diatomaceous earth was added, and the mixture was stirred at 150 ° C. and a hydrogen pressure of 4 MPa for 5 hours, and the temperature was further raised to 190 ° C. Then, the hydrogenation reaction was carried out by stirring for 5 hours to obtain a resin composition containing a hydrogenated cyclic olefin polymer and diethylene glycol ethyl methyl ether. The obtained hydride had a weight average molecular weight of 5,671, a number average molecular weight of 3,822, a molecular weight distribution of 1.48, and a hydrogenation rate of 99.3%.

  Using the resin composition containing the hydride obtained above and diethylene glycol ethyl methyl ether, according to the above method, a laminate composed of a resin film and a glass substrate is formed, and the spectral transmittance of the resin film is measured. went. The results are shown in Table 1.

Example 2
N- (2-ethylhexyl) -bicyclo [2.2.1] is the same as Example 1 except that the addition amount of the mixed ion exchange resin (Amberlyst MSPS2-1) was changed from 20 parts to 10 parts. A purification treatment of hept-5-ene-2,3-dicarboximide (NEHI) was performed, and in the same manner, a polymer and a hydride were obtained and evaluated in the same manner. The results are shown in Table 1.

Example 3
A column having an inner diameter of 20 mm was packed with 20 parts of mixed ion exchange resin (Amberlyst MSPS2-1) to obtain a column filled with mixed ion exchange resin. Separately, in a SUS reaction vessel equipped with a stirrer, N- (2-ethylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide (NEHI) 100 parts and 100 parts of diethylene glycol ethyl methyl ether were mixed, and the resulting mixture was filled with the mixed ion exchange resin obtained above at a temperature of 25 ° C. and a volume hour space velocity of 0.5 hr ^−1. The refining process was performed by continuously feeding the water into the tank. And as a result of analyzing by gas chromatography about the liquid mixture after a refinement | purification process, N- (2-ethylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide ( NEHI) was decomposed to 2-ethylhexylamine below the detection limit (the same applies to Examples 3 to 5 described later).

  Then, using N- (2-ethylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide (NEHI) purified as described above, Example 1 and Similarly, a polymer and a hydride were obtained and evaluated in the same manner. The results are shown in Table 1.

Example 4
N- (2-Ethylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyx in the same manner as in Example 3 except that the temperature during the purification treatment was changed to 50 ° C. Imide (NEHI) was purified, and similarly, a polymer and a hydride were obtained and evaluated in the same manner. The results are shown in Table 1.

Example 5
Instead of 20 parts of mixed ion exchange resin (Amberlyst MSPS2-1), 4 parts of mixed ion exchange resin (Amberlyst MSPS2-1) and 16 parts of strongly acidic cation exchange resin (Amberlite 200CT Na, manufactured by Organo) And N- (2-ethylhexyl) -bicyclo [2.2.1] hept-5-ene- was used in the same manner as in Example 3 except that the volume hourly space velocity was changed to 1.0 hr ^−1. 2,3-Dicarboximide (NEHI) was subjected to purification treatment, and a polymer and a hydride were obtained in the same manner and evaluated in the same manner. The results are shown in Table 1.

<< Comparative Example 1 >>
In the same manner as in Example 1 except that 20 parts of strongly acidic cation exchange resin (Amberlite 200CT Na) was used instead of 20 parts of mixed ion exchange resin (Amberlyst MSPS2-1), N- (2- Ethylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide (NEHI) was purified to obtain a polymer and a hydride in the same manner. went. The results are shown in Table 1.

As shown in Table 1, N- (2-ethylhexyl) -bicyclo [2.2.1] hept-5-5 purified by contacting with a mixed ion exchange resin composed of a cation exchange resin and an anion exchange resin. When ene-2,3-dicarboximide (NEHI) was used, the polymerization conversion rate during polymerization could be increased, and the spectral transmittance of the resulting hydride was increased. (Examples 1-5).
On the other hand, when N- (2-ethylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide (NEHI) purified using only a cation exchange resin is used. The obtained hydride was inferior in spectral transmittance (Comparative Example 1).

Claims (8)

A monomer purification method comprising contacting a monomer represented by the following general formula (1) with a mixed ion exchange resin comprising a cation exchange resin and an anion exchange resin.

(In the above formula (1), n is an integer of 0 to 3, ^{R 1} represents a hydrocarbon group having 1 to 16 carbon atoms which may have a substituent.)   The ratio of the cation exchange resin and the anion exchange resin in the mixed ion exchange resin is 1: 1 to 10: 1 in a weight ratio of “cation exchange resin: anion exchange resin”. The method for purifying a monomer according to claim 1.   The method for purifying a monomer according to claim 1 or 2, wherein the monomer is brought into contact with the mixed ion exchange resin under a condition of 10 to 100 ° C.   The monomer according to any one of claims 1 to 3, wherein the monomer is brought into contact with 5 to 100 parts by weight of the mixed ion exchange resin with respect to 100 parts by weight of the monomer. Purification method. The fluid containing the monomer is continuously brought into contact with the mixed ion exchange resin at a volumetric hourly space velocity (VHSV) of 0.01 to 2 hr ⁻¹ . A method for purifying the monomer described in 1.   A polar group-containing cyclic olefin polymer obtained by polymerizing a monomer mixture containing the monomer purified by the method according to claim 1.   A resin composition comprising the polar group-containing cyclic olefin polymer according to claim 6 and a solvent.   The laminated body which has a resin film formed using the resin composition of Claim 7, and a board | substrate.