JP2002363265A - New block copolymer, method for producing the same and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new block copolymer usable e.g. as an adhesive material for connecting the circuit of an electric or electronic part such as a semiconductor package, and provide a method for the production of the copolymer. SOLUTION: A block of the block copolymer is composed of a molecular chain (mA; -AAA...AAA-; block A) containing linearly bonded (m) molecular species (A) having non-substituted or substituted methylene groups in the main chain, the other block of the copolymer is composed of a molecular chain (nB; -BBB...BBB-; block B) containing linearly bonded (n) molecular species (B) having cyclic ring structure in the main chain and a residue other than the catalytically active site derived from a metal carbene complex catalyst (C) is bonded to an end of the copolymer molecule. This invention further provides a copolymer containing a catalytically active site derived from the metal carbene complex catalyst (C) and bonded to the other end of the copolymer molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel block copolymer, its production method and use. INDUSTRIAL APPLICABILITY The block copolymer of the present invention is useful for adhesives for circuit connection of electric / electronic parts such as semiconductor packages and other uses.

[0002]

2. Description of the Related Art Electronic materials used for electric and electronic parts,
The required characteristics of semiconductor packages, optical materials, and the like have become increasingly severe on a daily basis with recent technological advances in information communication, multimedia, personal computers, and the like. Taking the adhesive material for electronic materials as an example, the required properties include low-temperature adhesion, short-time adhesion, high moisture resistance, embedding property, film forming property, etc., and these properties must simultaneously reach a high level. Can be

On the other hand, a block copolymer having two molecular chains (different properties) in which each block of the block copolymer (in other words, each monomer of the block source) does not mix with each other has a microphase-separated structure. It is known to form and exhibit unique properties. As an example, styrene-butadiene-styrene block copolymer (SBS resin) is
Rigid molecular chains derived from polystyrene (hard segments)
And a flexible molecular chain (soft segment) derived from polybutadiene to form a microphase-separated structure. This SBS resin is one of thermoplastic resins in which a hard segment acts as a crosslinking point at room temperature and a soft segment acts as a rubber component (edited by the Society of Polymer Science, edited by Handbook of Polymer Data, Baifukan, 19
86, pp. 299-307).

[0004] As another example, a polyethylene-polyethylene glycol block copolymer is a nonionic polymer surfactant having a nonpolar molecular chain and a polar molecular chain.
It is used as an emulsifier and an antifoam (Sigma-
Aldrich website, product information (http: //www.s
igma-aldrich.com/saws.nsf/Technical+Library?OpenFr
ameset) and CAS Registry Number: 97953-22
-5).

[0005]

SUMMARY OF THE INVENTION The present invention provides a novel block copolymer and a method for producing the same, and also provides an adhesive used for circuit connection of electric / electronic parts such as semiconductor packages. The purpose is to do.

[0006]

Means for Solving the Problems The present inventors have proposed a non-polar
If a block copolymer in which a flexible molecular chain (molecular chain mA) and a polar / rigid molecular chain (molecular chain nB) are linked in a chain can be obtained, this would be a new property not seen before. From the idea that it must have a function, various studies have been made to complete the present invention.

That is, the present invention relates to some of the following block copolymers. One type of the block copolymer in the present invention is a molecular chain in which one of the blocks of the copolymer has m-chains of molecular species (A) having an unsubstituted or substituted methylene group in the main chain. (MA; -AAA
... AAA-; block A), the other blocks are:
The molecular species (B) having a cyclocyclic structure in the main chain is composed of n molecular chains (nB; -BBB ... BBB-; block B), and one end of the copolymer molecule has It is a block copolymer to which a residue other than the catalytically active site derived from the metal carbene complex catalyst (C) is bonded.

[0008] Another type of block copolymer in the present invention comprises, at the other end of the copolymer molecule,
It is a copolymer to which a catalytically active site derived from the metal carbene complex catalyst (C) is bonded.

Here, in the case of using a "polymerization reaction terminator" which can stop the polymerization reaction and remove the catalytically active site of the catalyst (C) during the polymerization reaction, the former type is used. Is obtained. In addition, before adding a reaction terminator or when no reaction terminator is added, or a “reaction terminator” that stops the polymerization reaction but cannot remove the catalytically active site derived from the catalyst (C) bonded to one end of the polymer. When used, the latter type of copolymer is obtained.

Furthermore, one of the preferable block copolymers is one block (block A) of the copolymer.
Is composed of a nonpolar and flexible molecular chain (mA) in which the molecular species (A) having a methylene group substituted or unsubstituted with a nonpolar group in the main chain are connected in m chains, and the other block (block B) Is a block copolymer comprising a polar and rigid molecular chain (nB) in which a molecular species (B) having a polar substituent on the cyclo ring has a cyclocyclic structure in its main chain and is connected in n chains. It is.

The present invention also relates to a method for producing these block copolymers, that is, a method for producing a block copolymer comprising the following steps (i) and (ii). (I) First, a step of mixing and reacting the unsubstituted or substituted unsaturated monocyclic compound (A) capable of ring-opening metathesis polymerization with the entire amount of the required metal carbene complex catalyst (C). (Ii) Subsequently, a step of adding an unsaturated polycyclic compound (B) capable of ring-opening metathesis polymerization and having a polar substituent on a ring to the reaction system and reacting.

Here, after the above reaction, a reaction terminator is further added to stop the polymerization reaction, and the catalytically active site derived from the catalyst (C) bonded to one end of the polymer is removed (accordingly, the central metal of the catalyst is Excluding coordinated halogen atoms)
Is preferred.

It is preferable to further hydrogenate the copolymer obtained here. This is for the purpose of saturating the carbon-carbon double bond still existing in the polymer molecule and improving the stability over time.

[0014] The present invention also relates to an adhesive for circuit connection containing the above block copolymer.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, a method for producing a block copolymer will be described. The production method usually comprises the following step (i) and step (ii). Step (i): A metathesis-polymerizable unsaturated monocyclic compound (A; monomer A; also referred to as molecular species A) and a required amount of a metal carbene complex catalyst (C; also referred to as Catalyst) are added and mixed, Ring-opening metathesis polymerization is performed. A molecular chain having a catalytically active site (Cata) derived from a metal carbene complex catalyst at the terminal (that is, Cata-AAA... AAA-lyst) is generated. Cata means a site containing a metal in a catalytically active site derived from a metal carbene complex catalyst, and lyst means its residue.

Step (ii): Subsequently, an unsaturated polycyclic compound capable of metathesis polymerization (B; monomer B; also referred to as molecular species B) is added to the above reaction system and mixed. The molecular chain (Cata
-AAA ... from the catalytically active site (Cata) end of AAA)
BBB ... BBB by sequentially taking in monomer B
A diblock copolymer (Cata-BBB ... BBB-AAA ... AAA-) having a chain extending and having a catalytically active site (Cata) at the end.
lyst).

Even if monomer B and the entire amount of catalyst (C) are added, mixed and reacted, and then monomer A is added and reacted, a homogeneous diblock copolymer is not formed. Also,
Even if the diblock copolymer represented by Cata-AAA... AAA-BBB... BBB-lyst is partially formed, the yield (or yield) is low.

The reason that such a diblock copolymer (Cata-BBB... BBB-AAA... AAA-lyst) can be synthesized in good yield by this production method is that the polymerization of monomer A promoted by catalyst (C) is started. The reaction rate is greater than the polymerization extension reaction rate, so that the majority of the product of step (i) is Cat-A
AA ... AAA-lyst, which is presumed to be not left as a single catalyst (C). On the other hand, since the polymerization elongation reaction rate of the monomer B promoted by the catalyst (C) is higher than the polymerization initiation reaction rate, when the monomer B and the total amount of the catalyst (C) are added first, the process ( In i), Cata-BBB ... BBB-ly while leaving unreacted catalyst (C)
st will be generated. The remaining catalyst (C) becomes a reaction catalyst in the next step (ii) and becomes Cata-AAA ... AAA-ly
st to form a diblock copolymer (Cata-AAA ... A
It is believed that the yield of AA-BBB... BBB-lyst) is reduced and the product is a heterogeneous polymer.

Following step (ii), monomer A
Is added to the reaction system, the diblock copolymer (Cata
-BBB ... BBB-AAA ... AAA-lyst), the monomer A is sequentially incorporated from the catalytically active site, and a triblock copolymer (Cata-AAA ... AAA-BBB ... BBB-AAA)
.. AAA-lyst) can also be generated.

Subsequent to the above step (ii), preferably, a step of adding a reaction terminator to terminate the metathesis polymerization reaction (step (iii)) is added. As the reaction terminator, one that stops the metathesis polymerization reaction and also removes the catalytically active site derived from the catalyst (C) bonded to one end of the polymer, for example, has a double bond at the molecular end and has an electron withdrawing position adjacent thereto Vinyl olefin compounds such as vinyl acetate, ethyl vinyl ether, phenyl vinyl sulfide, and N-vinyl pyrrolidone having a functional group; coordinating compounds having a large electron donating ability such as 4-vinyl pyridine; and exomethylene compounds. Vinyl acetate and ethyl vinyl ether are preferably used. In addition, imidazole, 2,2 ′ may be used to terminate the metathesis polymerization reaction but not remove the catalytically active site derived from the catalyst (C) bonded to one end of the polymer.
-Bipyridine, 4-methylpyridine and the like.

Hereinafter, the monomer A, the monomer B, and the catalyst (C) used will be described in order. The unsaturated monocyclic compound (monomer A) to be used is a compound capable of ring-opening metathesis polymerization and giving a polymer having no ring structure after ring-opening polymerization. Preferably, it is a substituted or unsubstituted cycloalkene derivative (having a carbon-carbon double bond in the molecule). The element constituting the cyclo ring of the cycloalkene derivative usually has 3 to 14 (preferably 4 to 9) carbon atoms, and some of the carbon atoms may be replaced by silicon or boron. An oxygen atom, a sulfur atom, a nitrogen atom, or a phosphorus atom may be used instead of some of the carbon atoms constituting the cyclo ring. In this case, the molecular chain mA (block A) shows polarity. Examples of the cycloalkene derivative include a compound represented by the following formula (1).

[0022]

Embedded image In the formula (1), Y ¹ represents a divalent organic group (preferably, an organic group having 1 to 12 carbon atoms), and Y ² represents a hydrogen atom, a halogen, or an alkyl group having 1 to 20 carbon atoms (preferably, , A hydrogen atom or an alkyl group having 1 to 10 carbon atoms). The hydrogen bonded to the carbon of the unsaturated monocyclic compound may be unsubstituted or substituted with an alkyl group having 1 to 20 carbon atoms or halogen.

Specific compounds of the formula (1) include cyclobutene, cyclopentene, cyclooctene, cyclododecene, 1,5-cyclooctadiene, 1,3,5,7-
Cyclooctatetraene, 1,5,7-cyclododecatriene, 5,6-epoxy-1-cyclooctene, 3,
4-epoxy-1-cyclooctene, 5-bromo-1-
There are cycloolefins such as cyclooctene, and among them, cyclopentene, cyclooctene and 1,5-cyclooctadiene are preferably used.

The metal carbene complex catalyst (C) used will be described later.

In the molecular chain synthesized by the ring-opening metathesis polymerization reaction in the step (i), a carbon-carbon double bond exists as shown by the following formula (2).

Embedded image [In Formula (2), Y ¹ and Y ² have the same meanings as in Formula (1). ]

The unsaturated polycyclic compound (B) used in the next step (ii) is a compound capable of metathesis polymerization and giving a polymer having a ring structure in the main chain even after ring-opening polymerization. One of the preferable examples of such a compound is a substituted or unsubstituted norbornene derivative.
It is shown by.

[0027]

Embedded image

In the formula, p is an integer of 0 to 3 (preferably 0 to 3).
It is an integer of 2, more preferably 0 or 1). Also, R
¹~ R^FourAre each independently a hydrogen atom, a carbon number of 1-20.
An alkyl group, a cycloalkyl group having 3 to 20 carbon atoms,
An aryl group having 6 to 20 prime numbers, a halogen, a carbonyl group,
Cyano group, isocyano group, nitro group, siloxy group, carbon
An alkoxycarbonyl group having 2 to 20 carbon atoms, 2 to 20 carbon atoms
An alkylcarbonyloxy group, an amino group, an amide group,
Formyl group, hydroxyl group, hydroxyal having 1 to 20 carbon atoms
Kill group, alkoxyalkyl group having 1 to 20 carbon atoms, carbon
An acyloxyalkyl group having 1 to 20 carbon atoms and 2 to 20 carbon atoms
Cyanoalkyl group, alkoxy group having 1 to 20 carbon atoms, charcoal
An alkylthio group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms
Killsulfinyl group, alkylsulfo having 1 to 20 carbon atoms
Nyl group, alkyl seleno group having 1 to 20 carbon atoms, 1 carbon atom
To 20 alkyl seleninyl groups, or 1 to 20 carbon atoms
And at least one is water
And at least one is a polar group. R¹~
R^FourOne or two of them are combined to form -C
O-O-CO- group (acid anhydride), -CO-O- group (
Ton), -CO-NR ^Five-CO- group (imide) or -C
O-NR^Five-It may be a group (lactam).

Here, R ⁵ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms [preferably, —CO—O—C
An O- group (acid anhydride) or -CO-NR ⁵ -CO- group (imide)], in the case of the imide, R ⁵ is a hydrogen atom, 6-12 alkyl group carbon atoms or 1 to 4 carbon atoms Is an aryl group.

X ¹ and X ² are each independently an oxygen atom, a sulfur atom or C (R ⁶ ) ₂ ;
⁶ is a hydrogen atom, a halogen, an alkyl group having 1 to 4 carbon atoms,
It is selected from a cycloalkyl group having 3 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms, which may be the same or different. Further, two R ^{6 's} may be bonded to form a 3- to 8-membered ring structure, or may form a spiro ring. When R ⁶ is neither a hydrogen atom nor a halogen, the hydrogen atom bonded to the carbon atom is an alkyl group having 1 to 3 carbon atoms,
It may be substituted with a halogen, a cyano group, a carboxyl group, an amino group or an amide group. Among them, an oxygen atom or C (R ⁶ ) ₂ is preferable, and R ⁶ is a hydrogen atom and has 1 to 1 carbon atoms.
An alkyl group of 4 or a cycloalkyl group having 3 to 6 carbon atoms is preferable, and a hydrogen atom or a methyl group is more preferable. X ¹ and X ² are preferably the same.

Specific compounds of the above formula (2) include:
For example, 5-acetyl-2-norbornene, N-hydroxy-5-norbornene-2,3-dicarboximide, 5-norbornene-2-carbonitrile, 5-norbornene-2-carbaldehyde, 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 diisopropyl 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 anhydride, 5-
Norbornene-2,3-dicarboxylic acid, 5-norbornene-2-methanol, 6-triethoxysilyl-2-norbornene, 5-norbornen-2-ol, 5-norbornene-2,3-dimethanol, 2,3- Bicyclic norbornene such as bis (methoxymethyl) -5-norbornene and N-methyl-5-norbornene-2,3-carboximide; tricyclic norbornene having a polar group; tetracyclododecene having a polar group; Tetracyclic dobornene having a polar group such as methyltetracyclododecene having polar groups, dimethylcyclotetradodecene having a polar group, norbornene having five or more rings having a polar group, tetracyclododecadiene having a polar group, and symmetric having a polar group Compounds having two or more norbornene groups such as tricyclopentadiene It is.

In addition, 7-oxabicyclo [2.2.
1] hepta-5-ene-2,3-dicarboxylic anhydride,
7-oxabicyclo [2.2.1] hept-5-ene-
2,3-dicarboxylic acid, 2-carboxy-3-methoxycarbonyl-7-oxabicyclo [2.2.1] hept-5-ene, 2,3-dimethoxycarbonyl-7-oxabicyclo [2.2.1] Hepta-5-ene, 2,3-
Diethoxycarbonyl-7-oxabicyclo [2.2.
1] Hept-5-ene, 2,3-dihexyloxycarbonyl-7-oxabicyclo [2.2.1] hepta-5
-Ene, 2,3-dibenzyloxycarbonyl-7-oxabicyclo [2.2.1] hept-5-ene, 2,3
-Bis (hydroxymethyl) -7-oxabicyclo [2.2.1] hept-5-ene, 2,3-bis (methoxymethyl) -7-oxabicyclo [2.2.1] hept-5-ene , N-methyl-7-oxabicyclo [2.
2.1] Hept-5-ene-2,3-carboximide, 7-thiabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic anhydride, 2-carboxy-3-
Methoxycarbonyl-7-thiabicyclo [2.2.1]
Hepta-5-ene, 2,3-dimethoxycarbonyl-7
-Thiabicyclo [2.2.1] hept-5-ene,
2,3-bis (hydroxymethyl) -7-thiabicyclo [2.2.1] hept-5-ene and the like can also be exemplified as the specific compound of the formula (2).

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

In the molecular chain synthesized by the ring-opening metathesis polymerization reaction in the step (ii), a carbon-carbon double bond exists as shown in the following formula (4).

Embedded image [In the formula (4), p, R ^{1 to} R ⁴ , X ¹ and X ² have the same meanings as in the formula (3). ]

The amount of each of the unsaturated monocyclic compound (A) and the unsaturated polycyclic compound (B) may be determined according to the intended block copolymer. At this time, it is considered that a block copolymer having a constitution ratio (A / B) substantially equal to the molar ratio of the unsaturated monocyclic compound (A) and the unsaturated polycyclic compound (B) used is obtained.

The metathesis polymerization catalyst (C) used in the polymerization reaction is a metal carbene complex catalyst (TM.) Which allows the reaction to proceed without deactivation even if various polar functional groups are present.
Trnka and R.A. H. Grubbs, Acc.
Chem. Res. , Vol. 34, 18 (2001)
Is preferably used.

As such a metal carbene complex catalyst, there are compounds represented by the formulas (5) and (6). Excellent in copolymerization of monomers having different properties. Unlike various organometallic polymerization catalysts, it is stable to oxygen and moisture. Therefore, the polymerization reaction is not only in an inert gas atmosphere,
It is possible even in the atmosphere. These may be used alone or in combination.

[0038]

Embedded imageHere, in the formulas (5) and (6), M is ruthenium, male
X or M, preferably ruthenium; X^Three
~ X⁶Is capable of coordinating to the central metal M and having a shadow on its coordinating atom
A charged anionic ligand (atom or atomic group)
For example, hydrogen atom, fluorine, chlorine, bromine, iodine, etc.
Halogen, CF_ThreeCO_Two-, CH_ThreeCO_Two-, CF_TwoHC
O_Two-, CFH_TwoCO_Two−, (CH_Three)_ThreeCO-, (CF_Three)
_Two(CH_Three) CO-, (CF_Three) (CH_Three) _TwoCO-, carbon
1-5 linear or branched alkoxy groups, substituted or unsubstituted
Phenoxy group, trifluoromethanesulfonate group, etc.
Halogen is preferable, and chlorine is more preferable.
Good. X^ThreeAnd X^Four, And X^FiveAnd X⁶And both (chlorine, etc.)
Is more preferred.

L ^{1 to} L ^{4 each} represent a neutral electron donating group capable of coordinating to the central metal M, for example, PR ¹¹ R ¹² R ¹³ (where,
R ^{11 to} R ¹³ are each independently selected from a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a linear or branched alkyl group having 1 to 10 carbon atoms, and a cycloalkyl group having 3 to 10 carbon atoms. ), Substituted or unsubstituted pyridine, and imidazole compounds such as 1,3-disubstituted imidazole. Among them, phosphines such as tricyclohexylphosphine, tricyclopentylphosphine, and triisopropylphosphine, 1,3-dimesitylimidazole-2-ylidene, and 4,5-dihydro-
Imidazole compounds such as 1,3-dimesitylimidazole-2-ylidene are preferred, and tricyclohexylphosphine is more preferred.

R ^{7 to} R ¹⁰ each independently represent 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,
Aryl group having 20 to 20 carbon atoms, carboxylate group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, 2 to 20 carbon atoms
An alkenyloxy group, an aryloxy group having 6 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkylsulfonyl group having 1 to 20 carbon atoms, and having 1 to 20 carbon atoms Alkylsulfinyl group, C1-20 alkylseleno group, C1
20 alkyl seleninyl groups, or an alkyl selenonyl group having 1 to 20 carbon atoms, each of which has 1 to 1 carbon atoms.
5 alkyl groups, halogen, an alkoxy group having 1 to 5 carbon atoms or an aryl group having 6 to 20 carbon atoms, wherein the aryl group is a halogen, an alkyl group having 1 to 5 carbon atoms or 1 carbon atom. 5 to 5 alkoxy groups.

Specific examples of the compound represented by the above formula (5) or (6) include, for example, the following formulas (7) to (16)
In particular, there are compounds represented by the formulas (7), (8),
The compound represented by (9), (10) or (16) is preferably used.

[0042]

Embedded image

[0043]

Embedded image

The amount of the metal carbene complex catalyst (C) used is
It is determined in consideration of the desired molecular weight of the block copolymer.
The larger the amount used, the smaller the molecular weight of the block copolymer. Usually, 0.001 to 100 parts by weight of the total amount of the unsaturated monocyclic compound (A) and the unsaturated polycyclic compound (B).
To 20 parts by weight, preferably 0.001 to 10 parts by weight, more preferably 0.05 to 5 parts by weight.

In the polymerization reaction of the present invention, first, the whole amount of the unsaturated monocyclic compound (A) and the required metal carbene complex catalyst (C) are mixed and reacted, and then the unsaturated polycyclic compound is added to the reaction system. Other than adding (B) and reacting,
General polymerization reaction conditions can be used. Regarding the temperature and reaction time of the metathesis polymerization, in the step (i), a molecule having a catalytically active site derived from a metal carbene complex at the molecular chain terminal using an unsaturated monocyclic compound (A) as a raw material by ring-opening metathesis polymerization. Any condition may be used as long as a chain mA can be obtained. In the step (ii), the molecular chain mA is used.
The ring-opening metathesis polymerization of an unsaturated polycyclic compound (molecular species B) from the catalytically active site of
The molecular chain nB is synthesized following the molecular chain mA (molecular chain mA).
Any condition may be used as long as a block copolymer having a molecular chain of nB) can be obtained. The reaction time of the polymerization reaction is 10 minutes to 6 hours (preferably 0.5 to 2 hours) in the step (i), and 1 to 6 hours after the reaction in the step (ii). The reaction is carried out for a time (preferably 2 to 6 hours). The reaction temperature of the polymerization reaction is usually -20 to 200C, preferably 0 to 100C.

The atmosphere for the metathesis polymerization can be carried out under an atmosphere of an inert gas such as argon or nitrogen, but may also be carried out in the air. The reaction apparatus is simplified and advantageous.

If necessary, a solvent such as a metal carbene complex catalyst or a solvent capable of dissolving an unsaturated polycyclic compound or an unsaturated monocyclic compound having a polar substituent on a ring can be used. Ketone solvents such as acetone, 2-butanone, 2-pentanone, 3-pentanone, 4-methyl-3-pentanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, diethyl ether, methyl-tert-butyl ether, There are ether solvents such as tetrahydrofuran, 1,4-dioxane, and ethylene glycol dimethyl ether.

The amount of the solvent to be used is generally 50 to 95% by weight, preferably 60 to 95% by weight, based on the whole reaction system (total weight of unsaturated monocyclic compound, unsaturated polycyclic compound, metal carbene complex catalyst and solvent). It is about 90% by weight. When a solvent is used, the decomposition reaction tends to proceed if the metal carbene complex catalyst is left in a solution state for a long time in a heated state. Therefore, a powdery metal carbene complex catalyst is added after dissolving the unsaturated monocyclic compound in the solvent. Alternatively, it is preferable to add a small amount of a metal carbene complex catalyst (solution) dissolved in the same solvent.

Following the step (ii), a metathesis polymerization reaction can be terminated by adding a reaction terminator such as vinyl acetate as described above (step (iii)).

Further, as described above, a carbon-carbon double bond exists in the molecular chain of the copolymer obtained here as shown by the above formulas (3) and (4). When this is exposed to an oxygen atmosphere for a long period of time, an oxidation reaction occurs and its performance changes. At high temperatures, addition reactions with other molecules, cross-linking reactions, and the like occur, and the physical properties change. In order to avoid such a reaction, it is preferable that the obtained reaction product is further subjected to a hydrogenation reaction to saturate the unsaturated bonds 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 (edited by The Chemical Society of Japan, New Experimental Chemistry, Oxidation and Reduction, Maruzen Publishing (1977), Nishimura,
Takagi, Catalytic hydrogenation application to organic synthesis, see Tokyo Chemical Dojin (1987), etc.).

After completion of the reaction, the product is taken out of the reaction vessel to obtain the desired block copolymer. If necessary, the obtained block copolymer is washed with water, distilled,
Using a known method such as reprecipitation, the catalyst, the solvent and the like can be removed and purified.

According to the above-mentioned production method, one of the blocks of the copolymer is a molecular chain (m) in which the molecular species (A) having an unsubstituted or substituted methylene group in the main chain are connected in m chains.
A; -AAA ... AAA-; Block A), and the other blocks are molecular species (B) having a cyclocyclic structure in the main chain.
Are n-chain molecular chains (nB; -BBB ... BBB
-A block copolymer consisting of block B) and having, at one end of the copolymer molecule, a residue other than the catalytically active site derived from the metal carbene complex catalyst (C) bonded thereto.

In some cases, a copolymer having a catalytically active site derived from the metal carbene complex catalyst (C) bonded to the other end of the copolymer molecule is obtained.

The degree of dispersion of the molecular weight distribution of the above block copolymer is usually 1.0 or more and 2.5 or less (preferably 1.
0 to 2.0). Here, the degree of dispersion of the molecular weight distribution is a value calculated by the ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn).

In the above-mentioned production method, if the starting monomer is selected, a non-polar and flexible molecular chain in which the molecular species (A) having a methylene group substituted or unsubstituted by a non-polar group in the main chain is connected in m chains. (MA, that is, -AAA ... AAA-)
A cycloalkane derivative, a cycloalkene derivative, an oxacycloalkane derivative, an oxacycloalkene derivative, a thiacycloalkane derivative or a thiacycloalkene derivative, wherein the main chain contains a cyclo ring structure thereof, and a polar substituent on the cyclo ring. Is a polar and rigid molecular chain (nB, ie, -B
A block copolymer comprising BB ... BBB-)
The degree of dispersion of the molecular weight distribution of the block copolymer is 1.0 to
A block copolymer having a homogeneity of 2.5 (preferably 1.0 or more and 2.0 or less) is obtained. These include modified block copolymers, ie molecular chain mA-molecular chain nB
-It is also possible to obtain a block copolymer such as a molecular chain mA (triblock copolymer).

The number of repetitions m of the molecular species (A) and the number of repetitions n of the molecular species (B) of such a block copolymer (diblock copolymer) are basically based on the raw materials (monomer A,
It depends on the amount of monomer B and catalyst C) used. Normally,
5 to 5000 (preferably, 10 to 100
0). If it is less than 5, it is difficult to exhibit the properties 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. In addition, the molecular chain mA
It is also difficult to exhibit the non-polarity and the polarity of the molecular chain nB, respectively. On the other hand, if it exceeds 5000, the synthesis reaction takes a long time. The ratio (m / n) between m and n of the number of repetitions is a number balanced with each other, and is usually 9
5/5 to 5/95 (preferably 90/10 to 10/9)
0). Then, it is well compatible with other components by the action of a surfactant.

In the block copolymer of the present invention, the molecular species (A) preferably has a methylene group which may be substituted by a non-polar organic group (such as an alkyl group) in the main chain. That is, it is a molecular species having a methylene carbon (having sp ³ carbon atoms) in the main chain, and usually does not contain a ring structure in the main chain. As long as a flexible structure can be maintained, some of the carbon atoms constituting the main chain are sp
^It may be ² carbon atoms or sp carbon atoms. Also,
Some of the atoms constituting the main chain may be hetero atoms having a lower electronegativity than carbon atoms (eg, silicon, boron, etc.).

In the block copolymer of the present invention, the molecular species (B) is preferably a molecular species having in its main chain a ring substituted with a polar group. Such a molecular species (B) includes a saturated or unsaturated alicyclic compound substituted with a polar group,
Examples include an aromatic compound substituted with a polar group, a heterocyclic compound substituted with a polar group, and an unsubstituted heterocyclic compound containing a heteroatom having a higher electronegativity than carbon.

The non-polarity of each of the molecular chains mA and nB
As for the polarity, an appropriate raw material monomer can be selected using the organic conceptual diagram as a guide. The organic conceptual diagram is an effective method for predicting various physicochemical properties from the chemical structure of an organic compound (see Yoshio Koda, Organic Conceptual Diagram-Basics and Applications, Sankyo Publishing (1984)). Organic value of methylene group is 2
0 (its inorganic value is 0) and the inorganic value of the hydroxyl group is 10
Assuming that 0 (the organic value is 0), the inorganic value and the organic value of the other substituent are determined, and the inorganic value and the organic value of the organic compound are calculated. Organic compounds having large inorganic values have high polarity, and organic compounds having large organic values have low polarity.

When the organic conceptual diagram is used as a guide, the ratio of inorganic to organic (inorganic / organic) of the molecular species (A) of the block copolymer of the present invention is usually 0 to 0.3 ( It is preferably 0 to 0.25, and more preferably 0 to 0.2).
When the molecular species (A) is methylene, the ratio of inorganicity to organicity is 0, which means that the polymethylene chain of the molecular chain mA has nonpolar and flexible properties.

For the molecular chain (nB), the polar substituent on the cyclo ring is represented by a “substituent constant based on the polar group effect” σ separated from the Hammett's substituent constant σ.
I as a guideline (M. Chart
on, Prog. Phys. Org. Chem. , 1
3, 119-251 (1981)). Assuming that the hydrogen atom is 0, σI has a larger value as the polarity of the substituent is higher.
ΣI of polar substituent on cyclo ring in molecular chain (nB)
Is usually +0.05 or more and +0.80 or less (preferably +
0.10 or more and +0.80 or less, more preferably +0.1
0 or more and 0.70 or less).

The ratio of inorganic to organic on the organic conceptual diagram of the molecular chain (nB) (inorganic / organic) is usually 0.4
Or more and 10.0 or less (preferably 0.45 or more and 7.5 or less, more preferably 0.5 or more and 5.0 or less).

Examples of the polar substituent on the cyclo ring in the molecular chain (nB) include a carbonyl group, a cyano group, an isocyano group, a nitro group, a siloxy group, and a group having 2 to 2 carbon atoms.
20 alkoxycarbonyl groups, alkylcarbonyloxy groups having 2 to 20 carbon atoms, amino groups, amide groups, formyl groups, hydroxyl groups, hydroxyalkyl groups having 1 to 20 carbon atoms, alkoxyalkyl groups having 1 to 20 carbon atoms, carbon number 1
An acyloxyalkyl group having from 20 to 20 carbon atoms, a cyanoalkyl group having from 2 to 20 carbon atoms, an alkoxy group having from 1 to 20 carbon atoms, an alkylthio group having from 1 to 20 carbon atoms, an alkylsulfinyl group having from 1 to 20 carbon atoms, 20 alkylsulfonyl groups, alkyl seleno groups having 1 to 20 carbon atoms, 1 to 2 carbon atoms
An alkylseleninyl group of 0, an alkylselenonyl group having 1 to 20 carbon atoms, a -CO-O-CO- group (acid anhydride), a -CO-O- group (lactone), and the like. Also,
—CO—NR ⁵ —CO— group (imide) or —CO—NR ⁵ —
There are also groups (lactams). Here, R ⁵ is a hydrogen atom,
It is an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms. In the case of an imide, R ⁵ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or It is an aryl group having 6 to 12 carbon atoms.

The application of the obtained block copolymer is as follows: a curable compound and a curing agent are added thereto, and if necessary, an appropriate amount of a base resin and other additives are added. can do. The adhesive can be in various forms (film, sheet, tape, liquid, paste, etc.) depending on the application. In addition, when preparing the adhesive for circuit connection, each compounding ratio is about 100 parts by weight of the curing agent to 100 parts by weight of the curable compound.
Parts by weight (if microencapsulated is used,
The amount of the block copolymer is about 5 to 500 parts by weight.

I) Curable Compound A curable compound is a substance having a functional group that can be polymerized by a curing agent (described below), and may be a monomer or an oligomer. Specifically, there are an ionic polymerizable epoxy compound, a radical polymerizable acrylate, and a methacrylate compound.

Ii) Curing agent The curing agent is a compound that initiates the polymerization of the above-mentioned curable compound. Usually, a curing agent that generates polymerization active species by heating or irradiation with energy rays is used. Examples of such a curing agent include radical polymerization that generates radicals by heating ionic polymerizable monomers such as imidazole derivatives (including microencapsulated ones) and sulfonium salts, organic peroxides, and azo compounds. Sex monomers.

Iii) Base resin As the base resin, a resin having a high film-forming ability, excellent stress relaxation during curing, and high adhesiveness can be used. Examples of such a resin include a phenoxy resin having a hydroxyl group in the molecule and having a molecular weight of 10,000 or more.

Iv) Other additives Conductive particles can be added and dispersed for the purpose of absorbing the height and variation of the circuit electrode and for the purpose of positively imparting anisotropic conductivity. Further, for the purpose of improving connection reliability and the like, a coupling agent, a filler, an antioxidant, and the like can be added.

[0069]

EXAMPLES The present invention will be described more specifically with reference to the following examples. Example 1 Synthesis of poly (cyclooctene) -block-poly (endo-5-norbornene-2,3-dicarboxylate): A / B of charged monomer is 50/50.
(Molar ratio)

Embedded image

A 500 ml reaction vessel was replaced with nitrogen, and 90 ml of tetrahydrofuran (THF, manufactured by Wako Pure Chemical Industries) and 11 g of cyclooctene (manufactured by Tokyo Chemical Industry) (0.10 mol)
l) was added and the reaction vessel was heated to 60 ° C. in a nitrogen atmosphere. There, 0.27 g (0.33 mmol) of a ruthenium carbene complex of the formula (7) (manufactured by Boulder Science) was added.
l) was added and the mixture was stirred at 60 ° C for 1 hour (reaction (i)).
A small amount of the reaction solution was withdrawn from the reaction system, and vinyl acetate (manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto to stop the reaction.
A sample for C measurement was used. Then, endo was added to the reaction solution.
Dimethyl-5-norbornene-2,3-dicarboxylate (endo-DME, manufactured by Lancaster) 21 g (0.10 mo
l) was added and the mixture was stirred at 60 ° C. for 4 hours in a nitrogen atmosphere (reaction (ii)). Thereafter, a small amount of the reaction solution was withdrawn from the reaction system, vinyl acetate was added thereto, and the reaction was stopped to obtain a sample for GPC measurement. 6.0 ml (66 mmol) of vinyl acetate was added to the reaction solution in the reaction vessel, and the reaction vessel was cooled to room temperature while stirring. The product is THF2
The mixture was diluted with 00 ml and poured into 1 L of methanol (manufactured by Wako Pure Chemical Industries). The resulting precipitate was collected by filtration and dried under reduced pressure to obtain 28 g of a colorless fibrous substance (isolation yield: 90%).

FIG. 1 shows the results of tracking the polymerization reaction by GPC. GPC measurement conditions are as follows: Column: TSKgelGM
Two HXL-L (manufactured by Tosoh Corporation), eluent: THF,
Flow rate: 1 ml / min), Column temperature: room temperature. In FIG. 1, a shows a chart 1 hour after the start of cyclooctene polymerization (that is, after the reaction (i)), and b shows an en
4 shows a chart after 4 hours from the addition of dimethyl do-5-norbornene-2,3-dicarboxylate (that is, after the reaction (ii)).

After the addition of dimethyl endo-5-norbornene-2,3-dicarboxylate, the molecular weight of the reaction product shifted to a higher molecular weight side with the lapse of time while maintaining the peak shape after cyclooctene polymerization. It was determined that a block copolymer had been formed. The number average molecular weight of the peak (in terms of polystyrene) was 4 immediately after cyclooctene polymerization.
5,000 to endo-5-norbornene-2,3
-92,000 after the addition of dimethyl dicarboxylate. The number average molecular weight of the isolated polymer was 103,0
00, molecular weight distribution was 1.91.

FIG. 2 shows the ¹ H-NMR chart of the obtained polymer. The measurement of the ¹ H-NMR spectrum is performed by Br
In ukerAC-250, solvent: is chloroform -d _1. The figure shows a peak attributable to the proton of the methylene chain (ha in the structural formula of FIG. 2) near δ1.3 and a proton derived from the methyl ester (Hb in the structural formula of FIG. 2) near δ3.6. The integration ratio was 8: 6, indicating that the ratio of the poly (cyclooctene) chain to the poly (endo-5-norbornene-2,3-dicarboxylate) chain was 1: 1. This corresponded to the charging ratio of both monomers.

The resulting poly (cyclooctene) -blo
ck-Poly (endo-5-norbornene-2,3-dicarboxylate) has an inorganic / organic value of 0.01 on the organic conceptual diagram of the cyclooctene ring-opening polymer chain, and methoxycarbonyl on the cyclohexane ring. The substituent constant σI based on the polar group effect of the group is +0.32. Therefore, in each block of the block copolymer, the difference between the hard segment and the soft segment is remarkable, and the difference between the polarity and the non-polarity is also remarkable.

Example 2 A / B of charged monomer was 80/2
0 (molar ratio) In the same manner as in Example 1 except that the amount of cyclooctene used was 70 g (640 mmol) and the amount of endo-5-norbornene-2,3-dimethyl ester was 34 g (160 mmol) (formula ( The amount of the ruthenium carbene complex used in 7) was 0.33 mmol) to obtain a polymer. The yield was 85%, the Mn in terms of standard polystyrene was 75,000,
The degree of dispersion of the molecular weight distribution was 1.6. Example 1
As a result, the molar ratio of each raw material component was calculated, and as a result, the molar ratio of cyclooctene / endo-DME in the polymer was 78:22.

Example 3 A / B of charged monomer was 50/5
A large amount of catalyst was used at 0 (molar ratio). The amount of the ruthenium carbene complex of the formula (7) was determined in Example 1.
A polymer was obtained in the same manner as in Example 1 except that the amount was 3.3 mmol, which was 10 times the amount of. The yield was 90%, the Mn in terms of standard polystyrene was 33,000, and the degree of dispersion of the molecular weight distribution was 1.9. The molar ratio of each raw material component was calculated in the same manner as in Example 1, and as a result, cyclooctene / endo in the polymer was obtained.
The molar ratio of -DME was 53:47.

Example 4 A / B of charged monomer was 80/2
Use a large amount of catalyst at 0 (molar ratio) 10 g (13 mmol) of ruthenium carbene complex
A polymer was obtained in the same manner as in Example 1 except that l) was used. The yield was 88%, and Mn in terms of standard polystyrene was 2
The molecular weight distribution was 4,000, and the degree of dispersion was 1.9. The molar ratio of each raw material component was calculated in the same manner as in Example 1. As a result, the molar ratio of cyclooctene / endo-DME in the polymer was 7%.
9:21.

Example 5 Preparation of film-like adhesive for circuit connection 20 g of PKHC (phenoxy resin, trade name of Union Carbide Co., Ltd.) and Epicoat YL-983U (bisphenol F liquid epoxy resin, Yuka Shell Epoxy Co., Ltd.) (Product name) 30 g and 20 g of the block copolymer (number average molecular weight 103,000, molecular weight distribution 1.91) prepared in Example 1 were weighed, and a mixed solvent of toluene / ethyl acetate = 50/50 (weight ratio) was used. Into a solution having a solid content of 40%. In addition, NOVACURE HX-394
1HP (latent curing agent, trade name, manufactured by Asahi Ciba Co., Ltd.) 30
and 1.5 g of an epoxy silane compound (A-187, trade name of Nippon Unicar Co., Ltd.) 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 the particles having polystyrene as a core), and a 0.02 μm thick layer was formed outside the nickel layer. 3% by volume (based on the solid content) was dispersed and mixed, and this mixed solution was applied to an 80 μm-thick fluororesin film using a coating device, and heated at 70 ° C. for 10 minutes. By drying, the thickness is 25 μm on the fluororesin film.
A film-like adhesive for circuit connection was obtained.

Example 6 Preparation of a circuit connector A circuit width of 50 μm, a pitch of 100 μm and a film-like adhesive (25 μm in thickness) for circuit connection, one surface of which was covered with a fluororesin film obtained in Example 5, were used. 18μ thickness
circuit board (FP) having 500 copper circuits
C) and glass having a thin layer of indium oxide (ITO) of 0.2 μm (thickness: 1.1 mm, surface resistance: 20 ohms)
m) was heated and pressurized at 180 ° C. and 4 MPa for 20 seconds and connected over a width of 2 mm. At this time, the IT
On the O-glass, the adhesive surface of the film-like circuit connecting material is 70
℃, 0.5MPa for 5 seconds after heating and temporary connection,
The fluororesin film was peeled off and connected to another FPC, which was an adherend, to form a connector. When the resistance value between the adjacent circuits of the obtained connection body was measured, the resistance between the adjacent circuits was 1
The average of 50 points was 2.7 ohm, indicating good connection characteristics. In addition, the adhesive strength of this connection body was measured according to JIS-Z02.
When measured by a 90-degree peeling method according to No. 37, the adhesive strength was 800 N / m, indicating a sufficient adhesive strength. The adhesive strength was measured by using Tensilon UTM-4 manufactured by Toyo Baldwin Co., Ltd. (peeling speed: 50 mm / min, 25 ° C.).

Example 7 Poly (cyclooctene) -bl
ock-poly (endo-5-norbornene-2,3-
Synthesis of dimethyl dicarboxylate): Using a ruthenium carbene complex catalyst of the formula (16) Instead of the ruthenium carbene complex of the formula (7), a compound of the formula (1)
0.28 g (0.33 m) of the complex 6) (manufactured by Simetech)
mol)) to obtain a polymer in the same manner as in Example 1. The yield was 91%, the Mn in terms of standard polystyrene was 68,000, and the polydispersity of the molecular weight distribution was 1.6.
The molar ratio of each raw material component was calculated in the same manner as in Example 1. As a result, the molar ratio of cyclooctene / endo-5-norbornene-2,3-dicarboxylate in the polymer was 4%.
5:55.

[0081]

The block copolymer of the present invention is a novel block copolymer. Further, the block copolymer of the present invention has low elasticity, high strength, low stress, high adhesiveness, moisture resistance, heat resistance, film forming ability, and excellent compatibility with other components. Therefore, it can be used as an adhesive material for electronic materials such as semiconductor packages, a compatibilizer, a flexibilizer, a nonionic polymer surfactant, and the like. According to the production method of the present invention, the block copolymer of the present invention can be easily produced. INDUSTRIAL APPLICABILITY The adhesive for circuit connection of the present invention is applied as a circuit connection for electric / electronic parts such as semiconductor packages, and exhibits good connection characteristics and adhesive strength.

[Brief description of the drawings]

FIG. 1 is a GPC chart of a product.

FIG. 2 is the ¹ H-NMR spectrum of the product.

[Explanation of symbols]

a: 1 hour after the start of cyclooctene polymerization (endo-5-
(Just before the addition of dimethyl norbornene-2,3-dicarboxylate) b: After 4 hours from the addition of dimethyl endo-5-norbornene-2,3-dicarboxylate

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Toshihiko Takasaki 48 Wadai, Tsukuba, Ibaraki Prefecture Within Hitachi Chemical Co., Ltd. In-house (72) Inventor Hiromasa Kawai 48 Wadai, Tsukuba-shi, Ibaraki Prefecture F-term in Hitachi Chemical Co., Ltd. GA32 NA20 QA01

Claims (11)

[Claims] 1. One block is composed 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, and the other block is a cyclocyclic compound. A block copolymer comprising a molecular chain (nB) in which n molecular species (B) having a structure in the main chain are connected in a chain, and one end of the copolymer molecule has a metal carbene complex catalyst ( A block copolymer to which a residue other than the catalytically active site derived from C) is bonded. 2. The block copolymer according to claim 1, wherein a catalyst active site derived from a metal carbene complex catalyst (C) is further bonded to the other end of the copolymer molecule. Polymer. 3. The block copolymer according to claim 1, wherein the degree of dispersion of the molecular weight distribution of the copolymer (weight average molecular weight / weight average molecular weight)
Block copolymer having a number average molecular weight of 1.0 or more and 2.5 or less. 4. The block copolymer according to claim 1, wherein the one block comprises m molecular species (A) having a methylene group substituted or unsubstituted by a nonpolar group in a main chain thereof. The other block is composed of a continuous nonpolar and flexible molecular chain (mA), and the other block includes a cyclocyclic structure in the main chain, and n molecular species (B) having a polar substituent on the cyclocyclic ring are connected in a chain. A block copolymer composed of polar and rigid molecular chains (nB). 5. The block copolymer according to claim 4, wherein the molecular species (A) has a ratio of inorganic to organic on the organic conceptual diagram of from 0 to 0.3, and the molecular species (B) is cycloalkyl. The polar substituent on the ring has a substituent constant (σI) of 0.05 or more and 0.80 or more.
A block copolymer having the following groups. 6. A non-polar and flexible molecular chain (mA), wherein m molecular species (A) having an unsubstituted or non-polar group-substituted methylene group in the main chain are connected in a chain, and a cycloalkane derivative; Cycloalkene derivatives, oxacycloalkane derivatives, oxacycloalkene derivatives,
A polar and rigid molecular chain in which a cyclocyclic structure of either a thiacycloalkane derivative or a thiacycloalkene derivative is contained in a main chain, and n molecular species (B) having a polar substituent on the cyclo ring are connected in a chain. (NB). 7. The block copolymer according to claim 6, wherein the molecular species (A) has a ratio of inorganic to organic in the organic conceptual diagram of 0 or more and 0.3 or less, and the molecular species (B) is cycloalkyl. The polar substituent on the ring has a substituent constant (σI) of 0.05 or more and 0.80 or more.
A block copolymer having the following groups. 8. The method for producing a block copolymer according to claim 1, comprising the following steps (i) and (ii). (I) First, a step of mixing and reacting the unsubstituted or substituted unsaturated monocyclic compound (A) capable of ring-opening metathesis polymerization with the entire amount of the required metal carbene complex catalyst (C). (Ii) Subsequently, a step of adding an unsaturated polycyclic compound (B) capable of ring-opening metathesis polymerization and having a polar substituent on a ring, and reacting the compound. 9. The method according to claim 8, wherein a reaction terminator is further added after the reaction to terminate the polymerization reaction and to remove a catalyst active site derived from the catalyst (C) bonded to one end of the polymer. A method for producing a block copolymer to which is added. 10. A method for producing a block copolymer according to claim 9, wherein a hydrogenation reaction step is further added after said reaction. 11. An adhesive for circuit connection, comprising the block copolymer according to claim 1.