KR20030022166A - Process for the production of block copolymers, block copolymers produced by the process, and use of the copolymers - Google Patents

Abstract

The present invention is initially performed when the metathesis polymerization reaction of the metathesis polymerizable unsaturated monocyclic compound (A) and the metathesis polymerizable unsaturated polycyclic compound (B) is carried out using a metal calbene complex catalyst (C). A method for producing a block copolymer in which the entire amount of the unsaturated monocyclic compound (A) and the required metal calben complex catalyst (C) is mixed and then reacted with addition of the unsaturated polycyclic compound (B), and the block air obtained by the production method To provide coalescence and its use.

Description

Process for producing block copolymer, block copolymer obtained and its use {PROCESS FOR THE PRODUCTION OF BLOCK COPOLYMERS, BLOCK COPOLYMERS PRODUCED BY THE PROCESS, AND USE OF THE COPOLYMERS}

Using a two-component metathesis polymerization catalyst (a chloride of tungsten or molybdenum and an activator thereof), two kinds of metathesis polymerization monomers having a carbon-carbon double bond are alternately added to each other to form a block copolymer. Synthesis | combination is known (for example, Unexamined-Japanese-Patent No. 52-51500).

In addition, examples of synthesizing block copolymers of metathesis polymerizable monomers having similar structures using metal calben complexes of metathesis polymerization catalysts are known (Macrololecules Vol. 28, p. 4709, 1995, Macrololecules Vol. 30, page 3137, 1997, Journal of the American Chemical Society, Vol. 118, page 784, 1996).

In the electronic field, the characteristics of materials (semiconductor package materials, optical materials, etc.) used for the components are increasingly higher with the recent technological advancements in information communication, multimedia, and personal computers. The items of the required characteristics are, for example, adhesive materials for electronic materials, such as low temperature adhesiveness, short time adhesiveness, moisture resistance, embedding resistance, film forming ability, and the like, and these characteristics must satisfy high levels at the same time.

It is also known that block copolymers having two molecular chains in which each block (the monomer of the block source) of the block copolymers are not mixed (different in nature) form a microphase separation structure and exhibit specific properties. . As one example, the styrene-butadiene-styrene block copolymer (SBS resin) is a block air forming a microphase separation structure consisting of a rigid molecular chain (hard segment) derived from polystyrene and a flexible molecular chain (soft segment) derived from polybutadiene. It is coalescing. This SBS resin is one of thermoplastic resins in which hard segments act as crosslinking points and soft segments act as rubber components at room temperature (see Polymer Society, Polymer Data Handbook Application, Baifu Can, 1986, p. 299-307). .

Examples of polyethylene-polyethylene glycol block copolymers are nonionic polymer surfactants having non-polar molecular chains and polar molecular chains, which are used as emulsifiers and antifoaming agents (Sigma-Aldority Co., Ltd. homepage and CAS registry). No .: 97953-22-5).

The method described in Japanese Patent Application Laid-Open No. 52-51500 has problems in handling such as instability to air and moisture of the catalyst after two-component mixing and requires a dry nitrogen atmosphere, and can be used as a functional group or solvent of a raw material monomer. There is also a limit to the choice of. In addition, raw material monomers (or solvents) having high functional groups, formyl groups, ketone groups, or ester groups having high proton releasing ability are not used in this reaction system because they cause a stoppage reaction and become a catalyst poison. (1), page 393 (public publication, issued in 1990).

Moreover, in the synthesis | combination of the block copolymer using a metal carbene complex, the synthesis example from the two types of monomers with similar structure is known, but the manufacturing method of the block copolymer using the two types of monomers which differ greatly in structure is not known yet. .

When a block copolymer is obtained from two kinds of metathesis polymerizable monomers having significantly different structures and / or polarities from each other, the block copolymer has a microphase separation structure forming ability and a polymer region composed of a molecular chain having a polar group. It can be expected to promote the adhesion with the silver metal. In addition, a polymer region composed of nonpolar molecular chains such as polyalkylene chains can also be expected to act as an elastomer to lower the polymer itself and to contribute to enhanced adhesion.

Further, by changing the kinds of the two raw material monomers in various ways, it is also possible to further improve the physical properties such as low water absorption, low dielectric constant, low elasticity, transparency of the block copolymer. Furthermore, it is also possible to control the physical properties minutely by changing the input amount of the raw material monomer.

The present invention relates to a method for producing a homogeneous block copolymer using a metathesis polymerization reaction, a block copolymer obtained by the production method and the use of the block copolymer. The block copolymer obtained in the present invention is usefully used for adhesives for circuit connections used in electrical and electronic parts such as semiconductor packages, and other uses.

1 is GPC chromatography of a polymer obtained in Example 1 and a polymer obtained in Comparative Example.

2 is a ¹ H-NMR spectrum of the polymer obtained in Example 1. FIG.

Best Mode for Carrying Out the Invention

First, the manufacturing method of a block copolymer is demonstrated. The manufacturing method usually consists of the following steps (iii) and (ii).

Step (iii): The total amount of the necessary amount of the metathesis-polymerizable unsaturated monocyclic compound (A; monomer A; also referred to as molecular species A) and the metal carbene complex catalyst (also referred to as C; catalyst) is added and mixed, and the ring-opening metathesis is mixed. Cis polymerization. A molecular chain (ie, Cata-AAA… AAA-lyst) having a catalytically active site (Cata) derived from a metal calben complex catalyst at its end is produced. In addition, Cata means the site | part containing a metal in the catalytically active site | part derived from a metal calben complex catalyst, and lyst means the residue.

Step (ii); Subsequently, a metathesis-polymerizable unsaturated polycyclic compound (B; monomer B; also referred to as molecular species B) is added to the reaction system and mixed. Monomer B is sequentially blown from the catalytic active site (Cata) end of the molecular chain (Cata-AAA ... AAA), and the BBB. The BBB chain elongates to form a diblock copolymer (Cata-BBB ... BBB-AAA ... AAA-lyst) having a catalytically active site (Cata) at its end.

Even if the entire amount of the monomer B and the catalyst (C) is added, mixed and reacted, and then the monomer A is added and reacted, a homogeneous diblock copolymer is not produced. In addition, the reverse Cata-AAA… AAA-BBB… The yield or yield is low even if the diblock copolymer represented by BBB-lyst is partially produced.

In the production method of the present invention, the reason why such a diblock copolymer (Cata-BBB ... BBB-AAA ... AAA-lyst) can be synthesized with good yield is that the polymerization initiation reaction rate of monomer A promoted by catalyst (C) Is larger than the polymerization elongation reaction rate, so that most of the product of the process is Cata-AAA. It is estimated that it is AAA-lyst and does not remain as a single catalyst (C).

On the other hand, since the polymerization elongation reaction rate of monomer B promoted by catalyst (C) is greater than the polymerization initiation reaction rate, in the case of adding the entire amount of monomer B and catalyst (C) in the reverse order, i.e. Cata-BBB… unreacted catalyst (C) BBB-lyst will generate it. The remaining catalyst (C) becomes a reaction catalyst in the next step (ii), whereby Cata-AAA... AAA-lyst is produced and the yield of diblock copolymers (Cata-AAA ... AAA-BBB ... BBB-lyst) is lowered, and the product is considered to be a heterogeneous polymer.

Further, following step (ii), when monomer A is further added to the reaction system, monomer A is sequentially blown from the catalytically active site of the diblock copolymer (Cata-BBB ... BBB-AAA ... AAA-lyst), It is also possible to produce triblock copolymers (Cata-AAA ... AAA-BBB ... BBB-AAA ... AAA-lyst).

Furthermore, following the said process (ii), the process (step (iii)) which preferably adds a reaction terminator and stops a metathesis polymerization reaction is added.

As the reaction terminating agent, the metathesis polymerization reaction is stopped and the catalytically active site derived from the catalyst (C) bonded to one end of the polymer is also excluded. For example, it has a double bond at the end of the molecule and has electron aspiration at its adjacent position. Vinylolefin compounds such as vinyl acetate, ethyl vinyl ether, phenyl vinyl sulfide and N-vinyl pyrrolidone having a group, and coordination compounds having high electron donating ability such as 4-vinylpyridine, or exomethylene compounds. Among these, vinyl acetate and ethyl vinyl ether are used preferably. In addition, there are imidazole, 2,2'-bipyridine, 4-methylpyridine, and the like, in which the metathesis polymerization reaction is stopped or the catalytically active site derived from the catalyst (C) bonded to one end of the polymer is not excluded. .

Below, monomer A, monomer B, and catalyst (C) used for this invention are demonstrated in order.

As an unsaturated monocyclic compound (monomer A) used for this invention, the compound which can provide ring-opening metathesis polymerization and which does not have a ring structure during ring-opening polymerization is mentioned. Preferably, the substituted or unsubstituted cycloalkene derivative which has a carbon-carbon double bond in a molecule | numerator is mentioned.

The elements constituting the cyclo ring of the cycloalkene derivative are usually 3 to 14 carbon atoms, preferably 4 to 9 carbon atoms, and some of the carbon atoms may be substituted with silicon atoms or boron atoms. Instead of some of the carbon atoms constituting the cyclo ring, an oxygen atom, a sulfur atom, a nitrogen atom or a person may be used. In this case, the molecular chain mA (block A) shows polarity.

Examples of the substituent Y ² in the case where there is a substituent on the cyclo ring include an alkyl group having 1 to 20 carbon atoms, a halogen atom and the like, but are preferably an alkyl group having 1 to 20 carbon atoms.

Carbonyl group, cyano group, isocyano group, nitro group, siloxy group, alkoxycarbonyl group having 2 to 20 carbon atoms, alkylcarbonyloxy group having 2 to 20 carbon atoms, amino group, amide group, formyl group, hydroxyl group and carbon source 1-20 hydroxyalkyl groups, alkoxyalkyl groups having 2 to 20 carbon atoms, acyloxyalkyl groups having 3 to 20 carbon atoms, cyanoalkyl groups having 2 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, and 1 carbon atom An alkylthio group having 20 to 20 carbon atoms, an alkylsulfinyl group having 1 to 20 carbon atoms, an alkylsulfonyl group having 1 to 20 carbon atoms, an alkyl serenyl group having 1 to 20 carbon atoms, an alkyl sereninyl group having 6 to 20 carbon atoms, or a carbon source And alkyl serenyl groups having 1 to 20 embroidery. In this case the molecular chain mA (block A) shows polarity.

Specific examples of the cycloalkene derivatives used in the present invention include cyclobutene, cyclopentene, cyclooctene, cyclododecene, 5-methoxy-1-cyclooctene, 5-bromo-1-cyclooctene, and 5-iso. Cyclo such as propoxy-1-cyclooctene, 5-formyl-1-cyclooctene, ethylcycloocto-1-ene-5-carboxylate, trimethylsilyl-cycloocto-1-ene-5-carboxylate Olefins etc. are mentioned, Preferably cyclopentene and / or cyclooctene is used.

In addition, unsaturated monocyclic compounds having two or more double bonds can also be used. Examples of such unsaturated monocyclic compounds include 1,5-cyclooctadiene, 1,3,5,7-cyclooctatetraene, 1,5,7-cyclododecatene, and the like.

Examples of the unsaturated polycyclic compound (B) used in the present invention include a compound capable of metathesis polymerization and providing a polymer having a ring structure in the main chain even after ring-opening polymerization. As such a compound, one preferable thing is a substituted or unsubstituted norbornene derivative, For example, what is represented by following formula (III) is mentioned.

In formula (III), m represents the integer of 0-3, 0-2 are preferable and 0 or 1 is more preferable.

R ⁵ to R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogen atom. Carbonyl group, cyano group, isocyano group, nitro group, siloxy group, alkoxycarbonyl group having 2 to 20 carbon atoms, alkylcarbonyloxy group having 2 to 20 carbon atoms, amino group, amide group, formyl group, hydroxyl group, 1 to 1 carbon atom 20 hydroxyalkyl groups, alkoxyalkyl groups having 2 to 20 carbon atoms, acyloxyalkyl groups having 3 to 20 carbon atoms, cyanoalkyl groups having 2 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, and 1-20 carbon atoms Alkylthio group, C1-C20 alkylsulfinyl group, C1-C20 alkylsulfonyl group, C1-C20 alkyl serene group, C1-C20 alkyl serenininyl group, and C1-C20 carbon atom It is selected from the alkyl cerenyl group of 20, and at least 1 is a hydrogen atom. Among them, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, a halogen atom, a carbonyl group, a cyano group, a nitro group, a siloxy group, and 2 to 10 carbon atoms It is preferable that it is selected from the alkoxycarbonyl group, the amide group, the formyl group, and the hydroxyl group of, and it is more preferable to select from the hydrogen atom, the carbonyl group, the siloxy group, the alkoxycarbonyl group of 2-10 carbon atoms, and the amide group.

In addition, R ⁵ ~R ⁸ of which two are combined to one set or two sets group -CO-O-CO- (acid anhydride), -CO-O- group (lactone), -CO-NR ⁹ -CO- group It may be a group selected from (imide) and -CO-NR ⁹ -group (lactam). R ⁹ is selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 20 carbon atoms. Especially, -CO-O-CO- group (acid anhydride) or -CO-NR ⁹ -CO- group (imide) is preferable, and in the case of imide, R <^9> is a hydrogen atom and a C1-C4 alkyl group. Or an aryl group having 6 to 12 carbon atoms is preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable.

X ⁵ and X ⁶ are each independently selected from an oxygen atom, a sulfur atom and C (R ¹⁰ ) ₂ . The two R ¹⁰ may be the same or different and are each selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 20 carbon atoms. Two R ^{10 's} may be bonded to each other to form a ring structure of 3 to 8 membered ring, or may form a spiro ring. R ¹⁰ may be substituted with any one of an alkyl group having 1 to 3 carbon atoms, a halogen atom, a cyano group, a carboxyl group, an amino group and an amide group, except for a hydrogen atom or a halogen atom. Among them, an oxygen atom or C (R ¹⁰ ) ₂ is preferable, R ¹⁰ is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms, and more preferably a hydrogen atom or a methyl group. . In addition, X ⁵ and X ⁶ are preferably the same.

As a specific compound represented by Formula (III), for example, norbornene, methyl norbornene, dimethyl norbornene, ethyl norbornene, ethylidene norbornene, butyl norbornene, 5-acetyl-2-norbornene, N-hydroxy- 5-norbornene-2,3-dicarboxyimide, 5-norbornene-2-carbonitrile, 5-norbornene-2-carbonaldehyde, 5-norbornene-2,3-dicarboxylic acid monomethyl ester, 5 -Norbornene-2,3-dicarboxylic acid dimethyl ester, 5-norbornene-2,3-dicarboxylic acid diethyl ester, 5-norbornene-2,3-dicarboxylic acid di-n-butyl ester, 5-norbornene -2,3-dicarboxylic acid dicyclohexyl ester, 5-norbornene-2,3-dicarboxylic acid dibenzyl ester, 5-norbornene-2,3-dicarboxylic acid anhydride, 5-norbornene-2,3-dica Main acid, 5-norbornene-2-methanol, 5-norbornene-2,3-dimethanol, 2,3-bis (methoxymethyl) -5-norbornene, N-methyl-5-norbornene-2, Bicyclic norbornene, dicyclopentadiene (dimer of cyclopentadiene) such as 3-carboxyimide, 6-triethoxysilyl-2-norbornene, 5-norbornene-2-ol, Tricyclic norbornenes such as dihydrodicyclopentadiene, methyldicyclopentadiene and dimethyldicyclopentadiene; tetracyclic pentadienes such as tetracyclododecene, methyltetracyclododecene and dimethylcyclotetradodecene; and tricyclopentadiene Compounds having two or more norbornene groups such as norbornene, tetracyclododecadiene, symmetric tricyclopentadiene or the like such as (trimer of cyclopentadiene), tetracyclopentadiene (tetramer of cyclopentadiene) Can be mentioned.

Especially, 5-norbornene-2,3-dicarboxylic acid monomethyl ester which has a polar group and is not highly reactive, 5-norbornene-2,3-dicarboxylic acid dimethyl ester, 5-norbornene-2,3-dica Diethyl ester of this acid, 5-norbornene-2,3-dicarboxylic acid dicyclohexyl ester, and 5-norbornene-2,3-dicarboxylic acid dibenzyl ester are preferable, and 5-norbornene-2,3-dicarboxylic acid Dimethyl ester, 5-norbornene-2,3-dicarboxylic acid diethyl ester, and 5-norbornene-2,3-dicarboxylic acid dicyclohexyl ester are more preferable.

In addition, 7-oxabicyclo [2.2.1] hepta-5-ene-2,3-dicarboxylic acid anhydride, 7-oxabicyclo [2.2.1] hepta-5-ene-2,3-dicarboxylic acid, 2-carboxy-3-methoxycarbonyl-7-oxabicyclo [2.2.1] hepta-5-ene, 2,3-dimethoxycarbonyl-7-oxabicyclo [2.2.1] hepta-5- N, 2,3-diethoxycarbonyl-7-oxabicyclo [2.2.1] hepta-5-ene, 2,3-dihexyloxycarbonyl-7-oxabicyclo [2.2.1] hepta-5 -Ene, 2,3-dibenzyloxycarbonyl-7-oxabicyclo [2.2.1] hepta-5-ene, 2,3-bis (hydroxymethyl) -7-oxabicyclo [2.2.1] Hepta-5-ene, 2,3-bis (methoxymethyl) -7-oxabicyclo [2.2.1] hepta-5-ene, N-methyl-7-oxabicyclo [2.2.1] hepta-5 -Ene-2,3-carboxyimide, 7-thiabicyclo [2.2.1] hepta-5-ene-2,3-dicarboxylic acid anhydride, 2-carboxy-3-methoxycarbonyl-7-thiabicyclo [2.2.1] hepta-5-ene, 2,3-dimethoxycarbonyl-7-thiasabicyclo [2.2.1] hepta-5-ene, 2,3-bis (hydroxymethyl) -7-thia Bicyclo [2.2.1] Other 5-ene can be cited as specific compounds of the formula etc. (Ⅲ).

Further, 2,3-bis (methoxycarbonyl) bicyclo [2.2.1] hepta-2,5-diene, 2,3-bis (methoxycarbonyl) -7-oxabicyclo [2.2.1] Two or more double bonds such as hepta-2,5-diene, 2,3-bis (methoxycarbonyl) -7-thiabicyclo [2.2.1] hepta-2,5-diene Compounds are also used.

When the compound represented by formula (III) is used as a monomer, carbon-carbon double bonds represented by the following formula (IIIa) exist in the molecular chain that is ring-opened by the metathesis polymerization reaction.

In formula, m, R <^5> -R <^8> , X <^5> , X <^6> is the same as in Formula (III).

What is necessary is just to determine each usage-amount of an unsaturated monocyclic compound (A) and an unsaturated polycyclic compound (B) according to the target block copolymer. At this time, it is considered that a block copolymer having a composition ratio (A / B) almost equal to the molar ratio of the unsaturated monocyclic compound (A) and the unsaturated polycyclic compound (B) used is obtained.

It is preferable that the metal calben complex catalyst (C) used in the present invention catalyze the metathesis polymerization reaction using the unsaturated monocyclic compound (A) and the unsaturated polycyclic compound (B) as raw materials. As a preferable thing, the compound represented by following formula (I) or formula (II) is mentioned. These compounds are stable to oxygen and moisture and are excellent in copolymerization of two monomers having different properties. Therefore, the polymerization reaction can be carried out not only in the inert gas atmosphere but also in the atmosphere. The metal calben complex catalyst (C) may be used alone or in combination of a plurality of them.

In formulas (I) and (II), M is ruthenium, osmium or iron, preferably ruthenium.

X ^{1 to} X ⁴ are anionic ligands (atoms or atom groups) capable of coordinating with the central metal M and having negative charges on their coordinating members, for example, hydrogen atoms, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms and the like. Halogen atom of, CF ₃ CO _2- , CH ₃ CO _2- , CF ₂ HCO _2- , CFH ₂ CO _2- , (CH ₃ ) ₃ CO-, (CF ₃ ) ₂ (CH ₃ ) CO-, (CF ₃ ) (CH ₃ ) ₂ CO-, a straight or branched alkoxy group having 1 to 5 carbon atoms, a substituted or unsubstituted phenoxy group, a trifluoromethanesulfonate group, and the like, among others, a halogen atom is preferable, Chlorine atoms are more preferred. It is more preferable that both X ¹ and X ² and X ³ and X ⁴ are halogen atoms (such as chlorine atoms).

L ^{1 to} L ⁴ represent a neutral electron donating group which can be coordinated with the central metal M, and for example, PR ¹¹ R ¹² R ¹³ (here, R ¹¹ to R ¹³ are each independently substituted or unsubstituted 6 to 20 carbon atoms. Phosphine, substituted or unsubstituted pyridine, 1,3-disubstituted imidazole, and the like represented by an aryl group, a linear or branched alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms; And imidazole compounds. Among them, phosphines such as tricyclohexylphosphine, tricyclopentylphosphine, triisopropylphosphine, 1,3-dimethylimidazole-2-iridene, 4,5-dihydro-1,3-dimethyl Imidazole compounds, such as imidazole-2- iridene, are preferable, and tricyclohexyl phosphine is more preferable.

R ¹ to R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 1 carbon atom Carboxylate group having 20 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, alkenyloxy group having 2 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, alkoxycarbonyl group having 2 to 20 carbon atoms, and 1 to 20 carbon atoms An alkylthio group having 20 carbon atoms, an alkylsulfonyl group having 1 to 20 carbon atoms, an alkylsulfinyl group having 1 to 20 carbon atoms, an alkyl serenyl group having 1 to 20 carbon atoms, an alkylhenenyl group having 1 to 20 carbon atoms, or a carbon atom having 1 to 20 carbon atoms It is selected from the alkyl cerenyl group of 20, each may be substituted by an alkyl group having 1 to 5 carbon atoms, a halogen atom, an alkoxy group having 1 to 5 carbon atoms or an aryl group having 6 to 20 carbon atoms, and the aryl group is halogen Atom, alkyl group of 1 to 5 carbon atoms It may be substituted alkoxy group of 1 to 5 carbon atoms.

As a specific compound represented by said Formula (I) or Formula (II), the compound etc. which are represented by following formula (V)-(XIV), etc. are mentioned, for example, Especially, formula (V), (VI), (VIII) Or the compound represented by (iii) is used preferably.

The amount of the metal calben complex catalyst (C) used is determined in consideration of the molecular weight of the desired block copolymer. The larger the amount used, the smaller the molecular weight of the block copolymer. With respect to 100 weight part of total amounts of an unsaturated monocyclic compound (A) and an unsaturated polycyclic compound (B), it is 0.001-20 weight part normally, Preferably it is 0.001-10 weight part, More preferably, it is 0.05-10 weight part.

In the polymerization reaction in the present invention, the entire amount of the unsaturated monocyclic compound (A) and the necessary metal calbene complex catalyst (C) is initially mixed and reacted, and then the unsaturated polycyclic compound (B) is added to the reaction system for reaction. General polymerization conditions can be used.

The reaction time of the polymerization reaction is not particularly limited as long as a block copolymer is obtained. The reaction time is 10 minutes to 6 hours in the process (i), preferably 0.5 to 2 hours. In the process (ii), 1 to 6 hours after the reaction in (i), preferably 2 to 6 hours. React time.

The reaction temperature of the polymerization reaction is not particularly limited as long as a block copolymer is obtained, and from the viewpoint of reactivity, it is preferably -20 to 200 ° C, more preferably 0 to 100 ° C.

In the polymerization reaction, it is preferable to use a solvent. The solvent used in the present invention is not particularly limited as long as it can dissolve an unsaturated monocyclic compound (A), an unsaturated polycyclic compound (B) and a catalyst (C). Examples of such a solvent include ketones such as acetone, 2-butanone, 2-pentanone, 3-pentanone, 4-methyl-3-pentanone, cyclopentanone, cyclohexanone, cycloheptanone, and cyclooctanone. And ether solvents such as diethyl ether, methyl-tert-butyl ether, tetrahydrofuran, 1,4-dioxane, and ethylene glycol dimethyl ether.

In the case of using a solvent, the amount of the solvent is preferably 60 to 95% by weight, more preferably 70 to 90, based on the entire reaction system (the total amount of monomers A and B, the catalyst and the solvent) from the viewpoint of ease of polymerization. Wt%, particularly preferably 80-90 wt%. If the catalyst (C) is left in the solvent for a long time, the decomposition reaction proceeds little by little. Therefore, after the unsaturated monocyclic compound (A) is dissolved in the solvent (powdered), the catalyst (C) is added or the monocyclic compound (A) It is preferable to use a catalyst solution dissolved in the same solvent (small amount) as the solvent used for dissolution.

Carbon-carbon double bonds are also present in the copolymer synthesized through the steps (iii), (ii) and (iv). In order to avoid the slight change (deterioration by oxidation, crosslinking reaction with other molecules, etc.) due to this double bond, it is preferable to further hydrogenate the obtained copolymer and to saturate the unsaturated bond remaining in the polymer molecule.

The hydrogenation reaction can be carried out using a known method such as a catalytic reduction method using a known metal catalyst or a hydrazine reduction method.

The block copolymer obtained by the above production method is a nonpolar and flexible molecular chain (mA, i.e., in which a molecular species (A) having a methylene group substituted in an unsubstituted or nonpolar group in the main chain is connected in m chains by selecting a raw material monomer). AAA ... AAA-), and any one cyclo ring structure of a cycloalkane derivative, a cycloalkene derivative, an oxacycloalkane derivative, an oxacycloalkene derivative, a thiacycloalkane derivative or a thiacycloalkene derivative is included in the main chain. The molecular species (B) having a polar substituent group on the above is composed of a block copolymer comprising a polar and rigid molecular chain (nB, that is, -BBB ... BBB-) connected in n chains. The block copolymer which shows the homogeneity of the dispersion degree of 1.0-2.5 is obtained. These include modified block copolymers, that is, block copolymers (triblock copolymers) such as molecular chain mA-molecular chain nB-molecular chain mA and the like.

The repetition number m of the molecular species (A) of such a block copolymer (diblock copolymer) and the repetition number n of the molecular species (B) are basically used amounts of raw materials (monomer A, monomer B and catalyst C). Determined by The repeating number m and n are usually 5-5000, respectively, Preferably they are 10-1000. If it is less than 5, it becomes difficult to exhibit the characteristics of the molecular chain mA and the molecular chain nB, that is, the flexibility (soft segment) of the molecular chain mA and the rigidity (hard segment) of the molecular chain nB, respectively. In addition, it is also difficult to exhibit the polarity of the molecular chain mA and the nonpolarity of the molecular chain nB, respectively. On the other hand, when it exceeds 5000, a synthesis reaction takes time. In addition, the ratio (m / n) of the repeating number m and n is a number balanced with each other, and is usually 95/5 to 5/95, preferably 90/10 to 10/90.

Regarding the polarity of the molecular chain mA and the molecular chain nB, the raw material monomer can be selected based on the organic diagram. Organic conceptual maps are an effective method for predicting various physicochemical properties from the chemical structure of organic compounds (see Koda Zenser, Organic Conceptual Maps-Foundations and Applications, Sampok Publishing (1984)). That is, an organic conceptual diagram divides the property of a compound into "the organic value which shows a covalent bond", and "the inorganic value which shows an ionic bondability", and divides the whole organic compound into one point on a rectangular coordinate called an organic axis and an inorganic axis. It is shown by positioning. Accordingly, as the organic value, the magnitude of the organic value can be measured in units of methylene groups in the molecule, and can be measured by the number of carbon atoms representing the methylene group, and the basic number of carbon atoms is 5 to 5 carbon atoms of the linear compound. Since one carbon in 10 vicinity is added, the average value of boiling point rise is 20 degreeC, and this is the value set to 20 on the basis of this. On the other hand, as an inorganic value, when the magnitude | size of the influence to the boiling point of various substituents is set based on a hydroxyl group, when the boiling point difference between the boiling point curve of a linear alcohol and the boiling point curve of a linear paraffin is set in the vicinity of carbon number 5, it will be about 100 Since it becomes ° C, it is the value which set the influence of one hydroxyl group to the numerical value 100. Based on this, the influence of another functional group is also determined as a value compared with this. These inorganic values and organic values are determined to correspond one-to-one on the graph. The inorganic and organic values of the organic compound are calculated from these values. Organic compounds having a high inorganic value have high polarity, and organic compounds having a high organic value have low polarity.

When the organic concept is guided, the inorganic to organic ratio (inorganic / organic) of the molecular species (A) in the present invention is usually 0 to 0.3, preferably 0 to 0.25. It is meant that the ratio of inorganic to organic when the molecular species (A) is methylene is 0, and the polymethylene chain of the molecular chain mA is nonpolar and has flexible properties.

Further, in the molecular chain (nB), the polar substituent on the cyclo ring can select "substituent constant based on the polar group effect" bh separated from Hammett's substituent constant б (M. Charton, Prog. Phys). Org. Chem., 13, 119-251 (1981). бI is a hydrogen atom of 0, and the higher the polarity of the substituent, the larger the value. In the molecular chain (nB), бI of the cyclocyclic polar substituent is usually +0.05 to +0.80, preferably +0.10 to +0.80.

The ratio of inorganic to organic on the organic conceptual diagram of the molecular species (B) is usually 0.4 to 10.0, preferably 0.45 to 7.5.

As a use of the obtained block copolymer, a curable compound and a hardening agent are added to this, a base resin and other additives are appropriately added as needed, and it can be set as the adhesive material for circuit connections. The adhesive material may be in various forms, for example, in the form of a film, a sheet, a tape, a liquid, or a paste, depending on the use.

Moreover, when preparing the adhesive agent for circuit connection, each compounding ratio may mix | blend about 100 weight part with respect to 100 weight part of curable compounds, and when it uses about 1 to about 100 weight part (when using a microcapsulated thing, it may mix | blend more than 100 weight part. ), And the block copolymer is about 5 to about 500 parts by weight.

Iii) curable compounds

The curable compound is a substance having a functional group polymerizable by a curing agent (described below), and may be a monomer or an oligomer. Specifically, an ion polymerizable epoxy compound, a radical polymerizable acrylate compound or a methacrylate compound may be used. Can be mentioned.

Ii) curing agent

A hardener is a compound which initiates superposition | polymerization of the curable compound mentioned above. Usually, the hardening | curing agent which generate | occur | produces a polymeric active species by heating or irradiation of an energy ray is used. As such a hardening | curing agent, the radically polymerizable monomer which generate | occur | produces a radical by heating with ion-polymerizable monomers, such as an imidazole derivative (some microcapsulated) and sulfonium salts, organic peroxide, azo compounds, etc. which have a potential. Etc.

베이스) Base resin

As the base resin, a film having high film forming ability, excellent stress relaxation during curing, and high adhesiveness can be used. As such resin, phenoxy resin of the molecular weight 10,000 or more which has a hydroxyl group in a molecule | numerator, etc. are mentioned, for example.

Iii) other additives

The conductive particles can be added and dispersed to absorb the height or deviation of the circuit electrode or to actively impart anisotropic conductivity. In addition, coupling agents, fillers, anti-aging agents, and the like may be added for the purpose of improving connection reliability and the like.

SUMMARY OF THE INVENTION An object of the present invention is to provide a manufacturing method which can easily synthesize a homogeneous block copolymer even when two kinds of metathesis polymerizable monomers having significantly different structures and / or polarities are used as raw materials. Moreover, it aims at using the block copolymer obtained by this for adhesive materials for circuit connection of electrical / electronic components, such as a semiconductor package.

The inventors of the present invention initially react the entire amount of cycloalkene and the necessary ruthenium carbene complex catalyst when copolymerizing a norbornene derivative, which is a synthetic raw material, with a cycloalkene, using a stable and highly active ruthenium carbene complex catalyst. When the norbornene derivative was added and reacted later, it was found that the desired homogeneous block copolymer was stably obtained. This led to the completion of the following invention.

In the present invention, when the metathesis-polymerizable unsaturated monocyclic compound (A) and the metathesis-polymerizable unsaturated polycyclic compound (B) are subjected to metathesis polymerization using a metal calbene complex catalyst (C), the unsaturated monocyclic ring is initially A method for producing a block copolymer in which the entire amount of the compound (A) and the required metal calben complex catalyst (C) is mixed and reacted, followed by addition of an unsaturated polycyclic compound (B) to react.

At this time, after the reaction, a reaction terminator is added to stop the polymerization reaction, and at the same time, the catalytically active site derived from the catalyst (C) bound to one end of the polymer is removed, and a halogen assigned to the central metal of the catalyst (C) is obtained. It is preferable to remove atoms and the like.

The present invention also relates to a block copolymer produced by the above production method.

One type of block copolymer to be produced is a molecular chain (mA; -AAA...) In which one of the blocks of the copolymer has a molecular species (A) having an unsubstituted or substituted methylene group as its main chain. AAA-; block A), and another block is composed of molecular chains (nB; -BBB ... BBB-; block B) in which molecular species (B) having a cyclo ring structure as a main chain are connected in n chains. One end of this copolymer molecule is a block copolymer to which residues other than the catalytically active site derived from a metal calben complex catalyst (C) are bonded.

Another type of block copolymer to be produced is a copolymer in which a catalytically active site derived from a metal calben complex catalyst (C) is further bonded to the other end of the copolymer molecule.

In the production method of the present invention, in the case of using a polymerization terminator which can stop the polymerization reaction and remove the catalytically active portion of the catalyst (C), the former type block copolymer is provided.

In the above production method, a reaction terminator which does not exclude the catalytically active site derived from the catalyst (C) before or after the addition of the reaction terminator or without the addition of the reaction terminator, or which terminates the polymerization reaction or is bound to one end of the polymer When used, the latter type of copolymer is provided.

The degree of dispersion of the molecular weight distribution of the block copolymer is usually 1.0 or more and 2.5 or less, preferably 1.0 or more and 2.0 or less. Here, the dispersion degree of the molecular weight distribution is a value calculated from the ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn).

Moreover, it is preferable also regarding any one of the above block copolymers that the non-polar and flexible molecular species (A) having a methylene group substituted with an unsubstituted or nonpolar group as one block of the block copolymer as a main chain are connected in m chains. It consists of a molecular chain (mA), and the other block contains a cyclocyclic structure in the main chain, and a molecular and rigid molecular chain (nB) in which molecular species (B) having a polar substituent on the cyclo ring are connected in n chains. It is a block copolymer consisting of

In addition, the present invention provides a nonpolar and flexible molecular chain (mA) in which a molecular species (A) having a methylene group substituted with an unsubstituted or nonpolar group as its main chain is connected in m chains, a cycloalkane derivative, a cycloalkene derivative, and an oxcyclo Molecular species (B) having any one cyclo ring structure of an alkane derivative, an oxacycloalkene derivative, a thiacycloalkane derivative or a thiacycloalkene derivative in the main chain, and having a polar substituent on the cyclo ring are connected in n chains. It is a block copolymer comprising a polar and rigid molecular chain (nB).

Moreover, this invention relates also to the adhesive agent for circuit connections containing the said block copolymer.

Example 1 (A / B = 50/50 (molar ratio) of injection monomer, solvent used: cyclohexanone)

In a 100 ml glass three-necked flask, 0.791 g (7.13 mmol) of cyclooctene as monomer A was dissolved in 8 ml of cyclohexanone, heated to 60 ° C., and 39.2 mg (0.048 mmol) of ruthenium carbene complex (manufactured by STREM CHEMICAL) of formula (V). ) Was added and reacted for 1 hour while stirring with a mechanical stirrer at 60 ° C (step). During the reaction, a small amount of the reaction solution was taken out of the reaction system, and vinyl acetate was added thereto to stop the reaction as a sample for GPC measurement.

Thereafter, 1.50 g (7.13 mmol) of endo-5-norbornene-2,3-dimethylester (endo-DME, manufactured by Lancaster) as the monomer B was added thereto, and the mixture was further reacted for 2 hours (step (ii)). During the reaction, a small amount of the reaction solution was taken out of the reaction system, and vinyl acetate was added to stop the reaction as a sample for GPC measurement.

Thereafter, 0.55 ml (6.0 mmol) of vinyl acetate and 6 ml of cyclohexanone were added to react for 5 minutes (step), and the cooled reaction solution was poured into 200 ml of methanol to obtain a white precipitate (polymer). Yield 63%.

The obtained polymer was dissolved in tetrahydrofuran (available for Wako Pure Chemical Industries, HPLC), and molecular weight was measured by GPC using tetrahydrofuran as eluent. , The degree of dispersion of the molecular weight distribution was 1.93. The GPC was measured at a flow rate of 1 cm 3 / min and a column temperature of 40 ° C. using a GL-A150 column (gel pack manufactured by Hitachi Kasei, exclusion limit 5 × 10 ⁵ ). GPC chromatogram is shown in FIG. 1.

Furthermore, the obtained polymer was made into the heavy chloroform solution, and the ¹ H-NMR spectrum was measured. The results are shown in FIG.

From the ratio of cyclooctene the integrated value of the ring-opening to generate methylene hydrogen H ^a and endo-DME is more broad-methyl-integration of the hydrogens of the methoxy group part value, a result of calculation for each raw material component mole ratio in the polymer, cyclooctene The molar ratio of / endo-DME was 52/48.

In the poly (cyclooctene) -block-poly (dimethyl endo-5-norbornene-2,3-dicarboxylic acid) of the obtained polymer, the inorganic / organic value on the organic conceptual diagram of the cyclooctene ring-opening polymerization chain is calculated to be 0.01. The substituent constant bI based on the polar group effect of the cyclohexane cyclic methoxycarbonyl group is +0.32.

Example 2 (A / B = 20/80 (molar ratio) of injection monomer)

A polymer was obtained in the same manner as in Example 1 except that 0.319 g (2.85 mmol) of cyclooctene was used and 2.41 g (11.4 mmol) of endo-5-norbornene-2,3-dimethylester. The yield was 82%, Mn was 52,000, Mw was 105,560 and the degree of dispersion of the molecular weight distribution was 2.03. In addition, the molar ratio of cyclooctene / endo-DME in the polymer was 18/82 as a result of calculating the molar ratio of each raw material component in the same manner as in Example 1.

Example 3 (A / B = 80/20 (molar ratio) of injection monomer)

A polymer was obtained in the same manner as in Example 1 except that the amount of cyclooctene used was 1.257 g (11.4 mmol) and the amount of endo-5-norbornene-2,3-dimethylester was 0.60 g (2.85 mmol). The yield was 86%, Mn in terms of standard polystyrene was 60,700, Mw was 105,618, and the dispersion degree of the molecular weight distribution was 1.74. In addition, the molar ratio of cyclooctene / endo-DME was 81/19 when the molar ratio of each raw material component was calculated in the same manner as in Example 1.

Comparative Example 1

In a 100 ml glass three-necked flask, 1.50 g (7.13 mmol) of endo-5-norbornene-2,3-dimethyl ester (endo-DME, manufactured by Lancaster) as monomer B was dissolved in 8 ml of cyclohexanone and heated to 60 ° C. Thereafter, 39.2 mg (0.048 mmol) of the ruthenium calben complex (manufactured by STREM CHEMICAL) of formula (V) was added thereto, and the mixture was allowed to react for 1 hour while stirring at 60 ° C with a mechanical stirrer. Thereafter, 0.791 g (7.13 mmol) of cyclooctene as monomer A was added thereto, followed by further reaction for 2 hours, and then 0.55 ml (6.0 mmol) of vinyl acetate and 6 ml of cyclohexanone were added as a reaction terminator, followed by reaction for 5 minutes. Thereafter, the cooled reaction solution was poured into 200 ml of methanol to obtain a white precipitate (polymer).

The GPC chromatogram of the polymer of Comparative Example 1 measured in the same manner as in Example is shown in FIG. 1. In addition, the molar ratio of cyclooctene / endo-DME in the polymer measured similarly to Example 1 was 46/54.

Comparative Example 2

In a 100 ml glass three-necked flask, 0.791 g (7.13 mmol) of cyclooctene as monomer A was dissolved in 8 ml of cyclohexanone and heated to 60 ° C, followed by 39.2 mg (0.048 mg) of ruthenium carbene complex (manufactured by STREM CHEMICAL) mmol), and the mixture was reacted for 1 hour while stirring with a mechanical stirrer at 60 ° C. Then, 0.55 ml (6.0 mmol) of vinyl acetate and 6 ml of cyclohexanone were added as a reaction terminator, followed by reaction for 5 minutes. The liquid was poured into 200 ml of methanol to obtain a white precipitate (polymer from monomer A).

The GPC chromatogram of the polymer of Comparative Example 2 measured in the same manner as in Example is shown in FIG. 1.

Since two peaks were found in the comparative example 1, it turns out that these are a mixture of two types of polymers (homopolymer or copolymer), and at least a homogeneous block copolymer is not obtained. On the other hand, in Example 1, since it consists of one peak shifted to the higher molecular weight side than the comparative example 2 (polymerization of only monomer A), it was confirmed that the copolymer which is not a mixture of monomer A and monomer B is obtained. . Further, the polymer of Example 1 was filmed and the glass transition temperature (Tg) was measured using a dynamic viscoelasticity measuring device (manufactured by Lehometric), and as a result, it was at two points around -55 ° C and 108 ° C. It was confirmed that the polymer of Example 1 was not a random copolymer but a block copolymer.

It was confirmed that the polymers of Examples 2 and 3 were also block copolymers from the measurement results of GPC and Tg in the same manner as in Example 1.

Further, in Examples 1 to 3, block copolymers having a material component molar ratio (copolymerization ratio) almost the same as the input molar ratio of the raw material monomer were obtained.

Example 4 (A / B = 50/50 (molar ratio) of injected monomer, solvent used: tetrahydrofuran)

Tetrahydrofuran was used as the solvent, the amount of cyclooctene was 11 g (100 mmol), the amount of endo-5-norbornene-2,3-dimethyl ester was 21 g (100 mol), and the formula (V) was used. The ruthenium calben complex used 0.27 g (0.33 mmol) in the same manner as in Example 1 to obtain a polymer. The yield was 90%, Mn in terms of standard polystyrene was 103,000, and the degree of dispersion in the molecular weight distribution was 1.91. In addition, the molar ratio of cyclooctene / endo-DME in the polymer was 50:50 when the molar ratio of each raw material component was calculated in the same manner as in Example 1. This was in accordance with the input cost of the moles.

Example 5 (A / B = 80/20 (molar ratio) of injection monomer)

Ruthenium of Formula (V) was carried out in the same manner as in Example 4 except that the amount of cyclooctene was 70 g (640 mmol) and the amount of endo-5-norbornene-2,3-dimethyl ester was 34 g (160 mmol). The usage-amount of a calben complex was 0.33 mmol), and the polymer was obtained. The yield was 85%, Mn in terms of standard polystyrene was 75,000, and dispersion degree of molecular weight distribution was 1.6. In addition, the molar ratio of cyclooctene / endo-DME in the polymer was 78:22 as a result of calculating the molar ratio of each raw material component in the same manner as in Example 1.

Example 6 (A / B = 50/50 (molar ratio) of injection monomer, using a large amount of catalyst)

A polymer was obtained in the same manner as in Example 4 except that the amount of the ruthenium calben complex of formula (V) was set to 3.3 mmol, which is 10 times the amount of Example 4. The yield was 90%, Mn in terms of standard polystyrene was 33,000, and dispersion degree of molecular weight distribution was 1.9. In addition, the molar ratio of cyclooctene / endo-DME in the polymer was 53:47 when the molar ratio of each raw material component was calculated in the same manner as in Example 1.

Example 7 (A / B = 80/20 (molar ratio) of injection monomer, using a large amount of catalyst)

A polymer was obtained in the same manner as in Example 5 except that the amount of the ruthenium calben complex used was 10 g (13 mmol). The yield was 88%, Mn in terms of standard polystyrene was 24,000, and the degree of dispersion of the molecular weight distribution was 1.9. In addition, the molar ratio of cyclooctene / endo-DME in the polymer was 79:21 as a result of calculating the molar ratio of each raw material component in the same manner as in Example 4.

Example 8 Preparation of Film-like Adhesive for Circuit Connection

20 g of PKHC (phenoxy resin, Union Carbide Co., Ltd.), 30 g of Epicoat YL-983U (bisphenol F type liquid epoxy resin, Emulsified Cell Epoxy Co., Ltd.) and the block copolymer prepared in Example 4 (number average molecular weight 103,000, molecular weight distribution) 1.91) 20g was weighed and dissolved in a mixed solvent of toluene / ethyl acetate = 50/50 (weight ratio) to obtain a solution having a solid content of 40%. To this, 30 g of Novacure HX-3941HP (a latent curing agent, manufactured by Asahi Chiba Co., Ltd.) was added and mixed, and 1.5 g of an epoxy silane compound (A-187, manufactured by Nippon Unicar Company) as a silane coupling agent was added and mixed. Thereafter, conductive particles having an average particle diameter of 10 μm and a specific gravity of 2.0 (a nickel layer having a thickness of 0.2 μm was provided on the surface of particles made of polystyrene as a nucleus, and a metal having a thickness of 0.02 μm was provided outside the nickel layer. 3% by volume (relative to solids), and the mixed solution is applied to a fluororesin film having a thickness of 80 µm using a milling tool, followed by hot air drying at 70 캜 for 10 minutes to form the fluorine resin film. Film adhesive material for connection for circuits whose thickness is 25 micrometers was obtained.

Example 9 Fabrication of Circuit Connector

A flexible circuit board having 500 copper circuits having a line width of 50 μm, a pitch of 100 μm, and a thickness of 18 μm, using a film adhesive (25 μm thick) for circuit connection, in which one side obtained above is covered on a fluororesin film ( FPC) and a glass (thickness of 1.1 mm, surface resistance of 20 Ω) having a thin layer of 0.2 μm of indium oxide (ITO) were heated and pressed at 180 ° C. and 4 MPa for 20 seconds to connect a width of 2 mm.

At this time, first, the adhesive surface of the film adhesive was heated and pressurized at 70 ° C. and 0.5 MPa for 5 seconds on the ITO glass, and the fluororesin film was peeled off and connected to FPC, which is another adherend, to form a connecting body.

As a result of measuring the resistance value between adjacent circuits of the obtained connection body, the average of 150 resistance between adjacent circuits was 2.7 ohms, and showed favorable connection characteristic.

In addition, the adhesive strength of this connector was measured by a 90-degree peeling method according to JIS-Z0237, and as a result, the adhesive strength was 800 N / m, indicating sufficient adhesive strength. In addition, Tensilon UTM-4 (peel rate 50mm / min, 25 degreeC) by Dongyang Baldwin Co., Ltd. was used for the measuring apparatus of adhesive strength.

According to the method for producing a block copolymer of the present invention, using two different raw material monomers (A, B), a block copolymer in which molecular species A and molecular species B are lumped together in a chain can be easily obtained. In addition, the structures of the two different raw material monomers A and B may be quite different. In addition, since the two molecular species A and molecular species B entering the copolymer reflect the input amount (moles) of the monomer, it is easy to manage the product (block copolymer). Moreover, the structural design of the polymer (block copolymer) is also easy, and the desired block copolymer can be effectively produced.

The block copolymer obtained in the present invention is a novel block copolymer. In addition, it has a low elasticity and is excellent in high strength, low stress, high adhesion, moisture resistance, heat resistance, film formation, and further compatibility with other components. Therefore, it can be widely used in the field of adhesive materials for electronic materials, such as a semiconductor package, a compatibilizer, a flexible agent, or a nonionic polymer surfactant, and its industrial value is large.

The adhesive material for a circuit connection of this invention is used for the circuit connection of electrical / electronic components, such as a semiconductor package, and shows favorable connection characteristic and adhesive strength.

Claims (14)

When the metathesis polymerizable unsaturated monocyclic compound (A) and the metathesis polymerizable unsaturated polycyclic compound (B) are subjected to metathesis polymerization reaction using a metal calbene complex catalyst (C), the monocyclic compound (A ) And the entire amount of the necessary metal calben complex catalyst (C) are mixed and reacted, and then the polycyclic compound (B) is added to react. The method of claim 1, further comprising the step of adding a reaction terminator to stop the polymerization reaction and at the same time removing the catalytically active site derived from the catalyst (C) bonded to one end of the polymer. Way. The method for producing a block copolymer according to claim 2, further comprising a step of saturating the remaining unsaturated double bond by hydrogenation. The method for producing a block copolymer according to claim 1, wherein the unsaturated monocyclic compound (A) is a substituted or unsubstituted cycloalkene compound. The method for producing a block copolymer according to claim 1, wherein the unsaturated polycyclic compound (B) is a substituted or unsubstituted norbornene compound. The block copolymer manufactured by the manufacturing method in any one of Claims 1-5. One block of the block copolymer consists of a molecular chain (mA) in which the molecular species (A) having an unsubstituted or substituted methylene group in the main chain are connected in m chains, A block copolymer comprising a molecular chain (nB) in which another molecular block has a cyclocyclic structure in its main chain, and the molecular species (B) are linked in n chains. One end of the copolymer molecule is a block copolymer, characterized in that residues other than the catalytically active site derived from the metal calben complex catalyst (C) are bonded. 8. The block copolymer according to claim 7, wherein a catalytically active site derived from a metal calben complex catalyst (C) is further bonded to the other end of the copolymer molecule. The block copolymer according to claim 7 or 8, wherein the degree of dispersion (weight average molecular weight / number average molecular weight) of the molecular weight distribution of the copolymer is 1.0 or more and 2.5 or less. The method according to claim 7, wherein one block of the block copolymer is a molecular species (A) having a methylene group substituted in the unsubstituted or a non-polar group in the main chain is connected in m chains made of a nonpolar and flexible molecular chain (mA) , The other block comprises a cyclocyclic structure in the main chain, and the molecular species (B) having a polar substituent on the cyclo ring are linked in n chains and constitute a polar and rigid molecular chain (nB). Copolymer. 11. The molecular species (A) has an inorganic to organic ratio in the organic conceptual diagram of 0 or more and 0.3 or less, and the cyclocyclic polar substituents of the molecular species (B) have a substituent constant (бI) of 0.05 or more and 0.80. The block copolymer characterized by the following group. A molecular species (A) having a methylene group in the main chain substituted with an unsubstituted or nonpolar group is connected in m chains to form a nonpolar and flexible molecular chain (mA), A molecular species having any one cyclocyclic structure of a cycloalkane compound, a cycloalkene compound, an oxacycloalkane compound, an oxacycloalkene compound, a thiacycloalkane compound or a thiacycloalkene compound in the main chain and having a polar substituent on the cyclocyclic ring A block copolymer, wherein (B) comprises a molecular chain (nB) which is connected in n chains and is polar and rigid. 13. The molecular species (A) of claim 12, wherein the inorganic to organic ratio in the organic conceptual diagram is 0 or more and 0.3 or less, and the cyclocyclic polar substituent of the molecular species (B) has a substituent constant (бI) of 0.05 or more, Block copolymer characterized in that the group is 0.80 or less. The block copolymer adhesive material as described in any one of Claims 6-13 characterized by the above-mentioned.