JPH05117336A - Production of modified conjugated diene-based resin - Google Patents

Abstract

PURPOSE:To efficiently obtain the subject resin, excellent in mechanical strength, heat resistance, etc., capable of providing cured products having a low thermal expansion coefficient and useful as electrical and electronic materials by adding an N-substituted maleimide' to a specific alkoxide-forming reactional product and carrying out anionic polymerization. CONSTITUTION:(B) An N-substituted maleimide (e.g. N-methylmaleimide) is added to (A) an alkoxide-forming reactional product obtained by subjecting (i) a conjugated diene-based polymer having OH groups in the molecule and 500-50000 number-average molecular weight and (ii) an organosiloxane polymer having carboxyl groups in the molecule and 500-50000 number-average molecular weight at 50-1.5 (preferably 20-2) equiv. ratio of OH/COOH to esterifying reaction and then reacting the residual OH groups of the esterifying reactional product with (iii) an organic alkali metal (preferably n-butyl-lithium, etc.). Reaction is then carried out in an organic solvent such as n-hexane, preferably at -70 to +50 deg.C for 1min to 50hr to afford the objective resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a modified conjugated diene-based resin, and more specifically, it relates an organosiloxane polymer and an N-substituted maleimide polymer to a molecular end and / or a molecular side of the conjugated diene-based polymer. The present invention relates to a method for producing a modified conjugated diene-based resin containing a chain-bonded copolymer. The modified conjugated diene resin obtained by the production method of the present invention,
Since it is used in combination with a thermosetting resin and the cured product has excellent properties, it is effectively applied in a wide range of fields including the field of electric and electronic materials.

[0002]

2. Description of the Related Art In the field of electric and electronic materials, thermosetting resins such as epoxy resins, phenol resins and unsaturated polyester resins have been widely used. For example, as a resin for impregnating a laminated board for a printed wiring board, an epoxy resin, a phenol resin, a polyimide resin, or the like, and a semiconductor element, a diode, a capacitor, a relay, an epoxy resin for sealing electric / electronic parts such as a switch, A low-pressure molding material such as a silicone resin material, a thermosetting or photocurable liquid material such as an epoxy resin material, an acrylic resin material, or a silicon resin material is used.

Further, it is known that a cured product obtained by radically curing a conjugated diene resin represented by a polybutadiene resin is extremely excellent in electrical characteristics, water resistance, moisture resistance and the like. For example, a method for producing a laminate and a molding material using a resin composition comprising a 1,2-polybutadiene resin which is liquid at room temperature and has a number average molecular weight of about 1,000 to 5,000 and a radical polymerization initiator (Japanese Patent Publication No. 47-051952). Gazette, Japanese Patent Publication No. 48-0144
No. 28), the number average molecular weight is 50,000 to 200,000.
A method for producing a laminate using a resin composition comprising a 1,2-polybutadiene resin that is solid at room temperature and a radical polymerization initiator (see Japanese Patent Publication Nos. 58-021925 and 58-021926). , And a curable resin composition comprising a butadiene-vinyl aromatic compound copolymer and a cyanate ester resin composition (see JP-A-61-233060, etc.) and the like.

The present inventors have already proposed a specific copolymer comprising a conjugated diene polymer block and an N-substituted maleimide polymer block, and the copolymer and a thermosetting resin and / or a vinyl monomer. A novel curable resin composition consisting of the following was proposed (JP-A-2-255855,
(See Japanese Patent Application No. 2-165750, Japanese Patent Application No. 2-270443, etc.).

[0005]

In recent years, the miniaturization of electronic devices has made rapid progress, but along with this, high performance and high reliability of electric and electronic parts are required. For example, a substrate (laminated plate) for a printed wiring board used in a high-speed arithmetic circuit or a high-frequency circuit is required to have a material that has excellent dielectric properties such as a low dielectric constant and a low dielectric loss tangent and is flame retardant. Further, as a sealing material for electric / electronic circuit parts, a material having a well-balanced adhesiveness, moisture resistance, heat resistance, thermal shock resistance, electrical characteristics, flame retardancy, etc. is required. In response to these requirements, the laminated board using the general-purpose resin does not satisfy the required dielectric characteristics, and the sealing material also has various required characteristics, particularly both thermal shock resistance and electrical characteristics. There is nothing to be satisfied.

On the other hand, a laminated board using a polybutadiene resin has extremely excellent dielectric properties, but in the method of manufacturing a laminated board using a liquid polybutadiene resin, a prepreg obtained by impregnating a base material and drying it is tacky. Since it has the property, it was difficult to form the laminate. Further, in the method for producing a laminated plate using a solid polybutadiene resin, the solubility in a general-purpose solvent is poor, and the viscosity of the impregnating varnish is extremely high, which also results in extremely poor workability in producing a laminated plate. Furthermore, since the adhesiveness to metal foil such as copper foil is poor in common to both, it is the current situation that it has not been put to practical use industrially.

Further, when a polybutadiene resin is used for electric and electronic parts, it is possible to obtain extremely excellent heat resistance, moisture resistance and electric characteristics, but the contraction rate upon curing is extremely large and the adhesiveness is poor, so that it is liquid. It is not used as a sealing material except for some special purposes. Further, the polybutadiene resin has extremely poor compatibility with other thermosetting fats, and a method using the butadiene-vinyl aromatic compound copolymer has been proposed as a method for improving it, but sufficient compatibility is obtained. Therefore, it is necessary to increase the copolymerization ratio of the vinyl aromatic compound, and in that case, the heat resistance decreases.

On the other hand, according to the method previously proposed by the present inventors, a cured product having extremely excellent mechanical strength, heat resistance, moisture resistance, electrical characteristics and the like can be obtained. However, depending on the composition, the coefficient of thermal expansion is around 10 × 10 ^-5 / ° C, which is slightly larger than that of polyimide resin. There is a problem when it is used as a sealing agent according to the above, or as an impregnating agent for ultra-high density printed wiring boards. The present invention has been made in view of such circumstances, in order to obtain a curable resin composition having excellent mechanical strength, heat resistance, moisture resistance, thermal shock resistance, electrical characteristics, and the like, and a small thermal expansion coefficient. It is an object to provide a method for producing a modified conjugated diene resin.

[0009]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve the above object, and as a result, a conjugated diene polymer having a hydroxyl group in the molecule and an organosiloxane polymer having a carboxyl group in the molecule. And an esterification reaction are carried out at a specific equivalent ratio, and then the residual hydroxyl group in the reaction product is alkoxided with an organic alkali metal, and then an N-substituted maleimide is added to perform polymerization by an anionic polymerization method. The resulting specific modified conjugated diene-based resin has a mechanical strength when blended with a curable resin,
The present invention has been completed by finding that a cured product having excellent heat resistance, moisture resistance, electrical characteristics, and the like and having a small coefficient of thermal expansion can be obtained.

The present invention has a conjugated diene polymer (a) having a hydroxyl group in the molecule and a number average molecular weight of 500 to 50,000 and a carboxyl group in the molecule, and a number average molecular weight of 500 to 500. The organosiloxane polymer (b) of 50,000 is subjected to an esterification reaction at a ratio of OH / COOH = 50 to 1.5 (equivalent ratio), and then the residual hydroxyl group of the esterification reaction product and the organic alkali metal (c ) To the alkoxide reaction product (d) obtained by reacting
A method for producing a modified conjugated diene resin, which is characterized in that the substituted maleimide (e) is added and anionic polymerization is performed. Hereinafter, the present invention will be described in detail.

The conjugated diene polymer (a) used in the present invention is a conjugated diene polymer and / or a copolymer composed of a conjugated diene and a vinyl monomer, and has a number average molecular weight of 500 in the molecule and a hydroxyl group. ~ 50,000. Further, a polymer obtained by hydrogenating a part or all of the conjugated diene unit in the polymer can also be used in the present invention. As the conjugated diene, a conjugated diene having 4 to 12 carbon atoms is generally used, and examples thereof include 1,3-butadiene, isoprene, and
2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3
-Hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, etc. are mentioned, and they are used by 1 type (s) or 2 or more types.

As the vinyl monomer, vinyl fragrance such as styrene, o-methylstyrene, p-methylstyrene, α-methylstyrene, p-tert-butylstyrene, vinylnaphthalene, divinylbenzene and 1,1-diphenylethylene. Group compounds; (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate; 2-hydroxyethyl methacrylate and the like having a hydroxyl group in the molecule (meth) Acrylates; acrylonitrile and the like can be mentioned, and they are used in one kind or two or more kinds.

The conjugated diene-based copolymer used in the present invention is
The conjugated diene or the conjugated diene and the vinyl monomer, a known anion using an alkali metal such as lithium or sodium or butyllithium, lithium biphenyl, sodium naphthalene, an organic alkali metal such as α-methylstyrene sodium dianion as a polymerization initiator. After polymerized by the polymerization method, a conjugated diene polymer having a hydroxyl group at the molecular end is produced by treating with a cyclic ether compound such as ethylene oxide or propylene oxide. As a commercial product manufactured by this method, NIS
SO PBG-1000, Same-2000, Same-300
0, and as hydrogenated products thereof, NISSOPBGI-
Examples thereof include 1000, -2000, and -3000 (all manufactured by Nippon Soda Co., Ltd.).

Compounds having a hydroxyl group in the molecule such as hydrogen peroxide, azobis-4-cyanopentanol, azobisisobutyronitrile, azobis-2, and the above conjugated diene or the conjugated diene and a vinyl monomer are used. A conjugated diene polymer having a hydroxyl group in the molecule is produced by polymerization by radical polymerization using a combined system of an azo compound such as 4-dimethylvaleonitrile and a hydroxyl group-containing mercaptan such as mercaptoethanol. .. As a commercial product manufactured by this method, PolybdR-15HT,
The same R-45HT and Epol (all manufactured by Idemitsu Atchem Co., Ltd.) are exemplified as hydrogenated products.

The organosiloxane polymer (b) used in the present invention is a polymer having a dimethylsiloxane unit as a basic repeating unit and having a carboxyl group at the terminal and / or side chain in this molecule, and further, in the repeating unit. It may have a structure in which a part of the methyl group is substituted with an alkyl group having 2 to 20 carbon atoms, a cycloalkyl group, a vinyl group, an aryl group, an aralkyl group or a polyoxyalkylene group. Examples of commercially available products include SF-8418 and BY16-750 (both manufactured by Toray Dow Corning Silicone Co., Ltd.).

The esterification reaction between the conjugated diene polymer (a) having a hydroxyl group in the molecule and the organosiloxane polymer (b) having a carboxyl group in the molecule is OH /
COOH = 50 to 1.5 (equivalent ratio), preferably 20 to 2
50 to 250 in the presence or absence of a solvent at a ratio of
It is performed at a temperature of 1 to 20 hours. An esterification catalyst is used if necessary. When the OH / COOH ratio exceeds 50, the effect of lowering the coefficient of thermal expansion is not sufficient when the curable resin composition is prepared, while when it is less than 1.5, thickening to gelation occurs during the esterification reaction, which is preferable. Absent.

Examples of the reaction solvent include aromatic hydrocarbon solvents such as benzene and toluene; alicyclic hydrocarbon solvents such as cyclohexane and methylcyclohexane; ether solvents such as dioxane, anisole and ethylene glycol dimethyl ether; methyl ethyl ketone and methyl. Ketone solvents such as isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; chlorine solvents such as carbon tetrachloride and monochlorobenzene; dimethylformamide and the like can be used.

As the esterification catalyst, commonly used known tetrabutyl titanate, tetrabutyl zirconate, tetraphenyl tin, zinc acetate, stannous oxalate,
Sulfuric acid, p-toluenesulfonic acid, etc. are used.

The atmosphere of the reaction system may be air or an inert gas such as nitrogen or argon. If necessary, a thermal polymerization inhibitor such as alkylphenol, catechol or hydroquinone may be used. Good.

The esterification reaction product having an excess of hydroxyl groups obtained by the above-mentioned method is first treated with a solvent, an esterification catalyst, water, etc. which inhibit anionic polymerization from the reaction system under reduced pressure, extraction, etc. After removing by using the organic alkali metal (c) under the inert gas atmosphere,
The alkoxidation reaction is usually performed in an organic solvent at a temperature of −100 to + 100 ° C., preferably −70 to + 50 ° C. for 1 second to 5 hours, preferably 1 minute to 3 hours to give an alkoxide-conjugated conjugated diene-based polymer. An esterification reaction product of the combined product and the organosiloxane polymer is obtained.

Examples of the organic alkali metal (c) include ethyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, ethyl sodium, butadienyl dilithium, butadienyl disodium, lithium biphenyl, lithium naphthalene. , Lithium triphenyl, lithium fluorene, sodium biphenyl, sodium naphthalene, sodium triphenyl,
Examples thereof include sodium fluorene and α-methylstyrene sodium dianion, and preferably an alkyllithium compound such as n-butyllithium and sec-butyllithium is used.

Examples of the organic solvent include aliphatic hydrocarbons such as n-hexane and n-heptane; alicyclic hydrocarbons such as cyclohexane and cyclopentane; aromatic hydrocarbons such as benzene and toluene; tetrahydrofuran and dioxane. , Ethers such as anisole; acetals such as methylal and dimethoxyethane; amines such as trimethylamine and N-methylmorpholine, which are used in one or a mixture of two or more organic solvents used in usual anionic polymerization. It

The anionic copolymerization reaction of the alkoxide product (d) obtained by the alkoxide reaction with the N-substituted maleimide (e) is carried out in the above-exemplified organic solvent at a reaction temperature of −100 to + 100 ° C. Preferably at a temperature of −70 to + 50 ° C. for 1 minute to 100 hours,
The modified conjugated diene resin of the present invention is obtained by carrying out the reaction for preferably 1 to 50 hours.

The N-substituted maleimide is represented by the following general formula [1],

[0025]

[Chemical 1] (Here, R represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group or a substituted aryl group).

Specific examples of the N-substituted maleimide include N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, Nn-hexylmaleimide, N-cyclohexylmaleimide, N- Phenylmaleimide, N- (1-
Naphthyl) maleimide, N-benzylmaleimide, N-
(2-fluorenyl) maleimide, N-1- (4-acetoxynaphthyl) maleimide, N-2-methylphenylmaleimide and the like are mentioned, and these monomers are used alone or in combination of two or more.

The modified conjugated diene resin thus obtained depends on the esterification ratio (OH / COOH) of the conjugated diene polymer and the organosiloxane polymer,
A terpolymer mainly consisting of a conjugated diene polymer block, an organosiloxane polymer block and an N-substituted maleimide polymer block, and a ternary copolymer consisting of a conjugated diene polymer block and an N-substituted maleimide polymer block It is presumed to consist of a mixture with the original copolymer. In the modified conjugated diene resin, the conjugated diene polymer block: X and the organosiloxane polymer block: Y
There is no particular limitation on the constitutional ratio (weight basis) of N and N-substituted maleimide polymer block: Z, but 1/99 ≦ Y / X +
Y + Z ≦ 50/50 is preferable, and 10/90 ≦ Z
/ X + Y + Z ≦ 80/20 is preferable.

By the above-mentioned production method, the desired modified conjugated diene resin can be obtained very easily and efficiently.
The modified conjugated diene resin is excellent in mechanical strength, heat resistance, moisture resistance, thermal shock resistance, electrical characteristics, and the like, and has a small coefficient of thermal expansion when used by being mixed with a thermosetting resin, a curing catalyst and the like. A cured product is obtained, and it is expected to be applied to a wide range of fields including the field of electric and electronic materials.

[0029]

EXAMPLES The method for producing the modified conjugated diene resin of the present invention will be described in more detail with reference to examples and application examples. However,
The present invention is not limited to these examples. In addition, "part" and "%" in the examples are based on weight unless otherwise specified.

Example 1 A commercially available hydroxyl group-containing 1, 1
2-polybutadiene (hydroxyl value 71.0, trade name NIS
SO PBG-1000, manufactured by Nippon Soda Co., Ltd. 100
g, a commercially available dimethylpolysiloxane having a carboxyl group (acid value 80.1, trade name BY16-750, Toray.
Dow Corning Silicone Co., Ltd.) 6g (OH / C
OOH (equivalent ratio) = 14.7) and 0.1 g of hydroquinone as a polymerization inhibitor were charged, and the esterification reaction was carried out at 190 to 200 ° C. for 8 hours while removing water generated as a by-product to the outside of the system with stirring. The temperature was lowered to 140 to 150 ° C., xylene was added to remove residual water azeotropically under reduced pressure, and an esterification reaction product having an acid value of 0.05 or less and a hydroxyl value of 62.5 (hereinafter referred to as an intermediate) Got Obtained intermediate 50
425 g of tetrahydrofuran (hereinafter referred to as THF)
Was dissolved in, and 50.1 mmol of n-butyllithium was added dropwise while stirring at 0 ° C under a nitrogen atmosphere to carry out an alkoxide reaction. Then, the temperature of the reaction system
110 g of a solution prepared by dissolving 16.7 g of N-phenylmaleimide (hereinafter referred to as PMI) in THF was added dropwise to the mixture at 50 ° C. over 1 hour, and the mixture was kept for 3 hours, and then a hydrochloric acid-methanol solution was added. The polymerization reaction was stopped. Next, water was added to the polymerization reaction liquid to separate the liquid, and the solvent was distilled off from the organic layer under reduced pressure to obtain a brown elastomer-like modified conjugated diene resin (Sample A-1). Polymerization yield is 9
It was 9.0%.

Example 2 In a reaction vessel sealed with nitrogen, a commercially available hydroxyl group-containing 1,
2-polybutadiene (hydroxyl number 33.7, trade name NIS
SO PBG-3000, manufactured by Nippon Soda Co., Ltd. 100
g, 15 g of dimethylpolysilosan having the above-mentioned carboxyl group (OH / COOH (equivalent ratio) = 2.8) and 0.1 g of hydroquinone were charged, and esterification reaction was carried out in the same manner as in Example 1 to obtain an acid value of 0.05 or less , Hydroxyl value 18.8
Was obtained. 50 g of the obtained intermediate was added to THF425
It was dissolved in g, and 15.1 mmol of n-butyllithium was added dropwise while stirring at 0 ° C. under a nitrogen atmosphere to carry out an alkoxide reaction. Then, PMI 25g
Polymerization reaction and post-treatment were carried out in the same manner as in Example 1 except that 160 g of the solution dissolved in HF was used to obtain a brown elastomer-like modified conjugated diene resin (Sample A-2). The polymerization yield was 98.8%.

Example 3 A commercially available diene-α-methylstyrene copolymer having a hydroxyl group (butadiene content = 50%, hydroxyl value 50.5, trade name NISSOPBS) was placed in a reaction vessel sealed with nitrogen.
G-2050, manufactured by Nippon Soda Co., Ltd., 100 g, and dimethylpolysiloxane having a carboxyl group, 20 g (O).
H / COOH (equivalent ratio) = 3.1), hydroquinone 0.1 g, and p-toluenesulfonic acid 0.2 g as an esterification catalyst were dissolved in xylene 240 g, and by-produced water was removed to the outside of the system with stirring. However, the xylene reflux state (14
After the esterification reaction at 0 to 145 ° C. for 2 hours, the reaction solution is washed with water, and then xylene is removed from the organic layer to give an intermediate having an acid value of 0.05 or less and a hydroxyl value of 28.7. Obtained. 50 g of the obtained intermediate was dissolved in 425 g of THF, and n-
22.9 mmol of butyl lithium was added dropwise to carry out an alkoxide reaction. Then, the temperature of the reaction system was set to -40 ° C, and while stirring, o-methylphenylmaleimide 2
160 g of a solution prepared by dissolving 5 g in THF was added dropwise over 1 hour, and the solution was kept for 3 hours, and then a hydrochloric acid-methanol solution was added to terminate the polymerization reaction. Then, the polymerization reaction liquid is poured into a large amount of methanol to precipitate a polymer, and the polymer is filtered,
After washing, it was dried at 60 ° C. for 5 hours to obtain a yellow-white powdery modified conjugated diene resin (Sample A-3). Polymerization yield is 9
It was 8.5%.

Example 4 In a reaction vessel sealed with nitrogen, commercially available hydroxyl-containing 1,
4-polybutadiene (hydroxyl value 45.5, trade name Pol
ybd R45HT, Idemitsu Atchem Co., Ltd. 100
g, esterification reaction and post-treatment were carried out in the same manner as in Example 3 except that 10 g of dimethylpolysiloxane having a carboxyl basis (OH / COH (equivalent ratio) = 5.7) was used, and an acid value of 0.05 or less, An intermediate having a hydroxyl value of 34.1 was obtained. 50 g of the obtained intermediate was dissolved in 425 g of THF,
While stirring under a nitrogen atmosphere, n-butyllithium 2
An alkoxide reaction was carried out by dropping 7.3 mmol. Next, a solution 33 in which 50 g of PMI is dissolved in THF
Polymerization reaction and post-treatment were performed in the same manner as in Example 3 except that 0 g was used, and a yellow-white powdered modified conjugated diene resin (Sample A
-4) was obtained. The polymerization yield was 99.0%.

Example 5 In a reaction vessel sealed with nitrogen, 50 g of 1,2-polybutadiene (PBG-3000), 50 g of 1,4-polybutadiene (Polybd R45HT), and 10 g of dimethylpolysiloxane (OH / COOH (equivalent ratio) )
= 4.9), an esterification reaction and post-treatment were carried out in the same manner as in Example 3 to obtain an intermediate having an acid value of 0.05 or less and a hydroxyl value of 28.7. 50 g of the obtained intermediate is TH
The solution was dissolved in F425 g, and 22.9 mmol of n-butyllithium was added dropwise with stirring at 0 ° C under a nitrogen atmosphere to carry out an alkoxide reaction. Then PMI1
Polymerization reaction and post-treatment were performed in the same manner as in Example 1 except that 80 g of a solution prepared by dissolving 2.5 g in THF was used to obtain a brown elastomer-like modified conjugated diene resin (Sample A-5). The polymerization yield was 99.8%. The properties of the modified conjugated diene-based resins of Samples A-1 to A-5 obtained by the above method are shown in Table 1.

[0035]

[Table 1]

Application Example 1 (Sample A of the modified conjugated diene resin prepared in Example 5)
-5) 50 parts, 30 parts of polyphenylene methylene bismaleimide (trade name Bismaleimide M20, manufactured by Mitsui Toatsu Chemicals, Inc.) as a curable resin and 20 parts of triallyl isocyanurate, 1 part of curing accelerator dicumyl peroxide,
250 parts of crystalline silica powder surface-treated with a silane coupling agent as a filler was kneaded at a temperature of 100 to 110 ° C., then cooled and pulverized to prepare a granular curable resin composition. Prepared sample is 170 ℃ × 30kg /
Compression molding was carried out under the condition of cm ² × 3 minutes, and the obtained molded product was post-cured at 250 ° C. for 2 hours.

The obtained molded product had the following characteristics. Bending strength: 11.8 kg / cm ² (20 ° C.) 9.5 kg / cm ² (200 ° C.) Dielectric constant: 3.2 (1 MHZ, 2
0 ° C) Water absorption: 0.1% (holding in boiling water for 2 hours) Heat loss: 0.1% (180 ° C x 2
Hold for 4 hours) Thermal expansion coefficient: 1.7 × 10 ^-5 / ° C

Application Example 2 Modified conjugated diene resin prepared in Example 2 (Sample A-
2) 40 parts, polyphenylene methylene bismaleimide (described above) 20 parts, epoxy resin (trade name YD-128,
30 parts by Tohto Kasei Co., Ltd., 10 parts triallyl isocyanurate, and 25 parts of methylhexahydrophthalic anhydride as a curing agent for epoxy resin are heated and dissolved to form a uniform solution, and then a curing accelerator dicumyl peroxide. (Previous) 1
And 0.3 part of benzyldimethylamine were added to prepare a light brown transparent liquid curable resin composition. The prepared curable resin composition for casting is heated at 110 ° C for 3 hours and further at 150 ° C.
It was cured for 3 hours at + 200 ° C. for 3 hours.

The cured product of the obtained casting resin had the following characteristics. Curing shrinkage rate (Vs): 1.5% Vs = (solid specific gravity-liquid specific gravity) / solid specific gravity × 100 Bending strength: 9.8 kg / cm ² (20
℃) 7.5 kg / cm ² (150 ℃) Dielectric constant: 2.8 (1 MH
z, 20 ° C.) Thermal expansion coefficient: 5.1 × 10 ⁻⁵ / ° C. Thermal shock resistance: 120 ° C. to −30 ° C. × 10 cycles or more Using a 30 g test resin in a 100 ml poly cup, a spring having an outer diameter of 40 mmΦ. After embedding a washer and curing by heating, 120 ° C. × 1 hour to −30 ° C. × 1 hour was set as one cycle, and repeated tests were conducted until a crack was formed.

[0040]

Industrial Applicability According to the production method of the present invention, a copolymer obtained by extremely easily and efficiently binding an organosiloxane polymer and an N-substituted maleimide polymer to a molecular end and / or a molecular side chain of a conjugated diene polymer is obtained. A modified conjugated diene-based resin containing the same can be produced. The modified conjugated diene-based resin obtained by the production method is used by being mixed with a thermosetting resin, and the cured product is excellent in mechanical strength, heat resistance, moisture resistance, thermal shock resistance, electrical characteristics, and the like, and It has the characteristic of a small coefficient of thermal expansion. Therefore, it is effectively applied in a wide range of fields including the electric and electronic material field, and its industrial utility is extremely large.

[0041]

[Brief description of drawings]

The IR absorption spectrum of the modified conjugated diene resin sample A-2 obtained by the modified conjugated diene resin production method of the present invention is shown in FIG.

FIG. 1 is an IR absorption spectrum diagram of Sample A-2. (Below margin)

Claims (1)

[Claims] 1. A conjugated diene polymer (a) having a hydroxyl group in the molecule and a number average molecular weight of 500 to 50,000 and a carboxyl group in the molecule, and having a number average molecular weight of 500 to 5
And the organosiloxane polymer (b), which is 0,000,
Alkoxide reaction product obtained by causing esterification reaction at a ratio of H / COOH = 50 to 1.5 (equivalent ratio), and then reacting the residual hydroxyl group of the esterification reaction product with an organic alkali metal (c). A method for producing a modified conjugated diene-based resin, which comprises adding N-substituted maleimide (e) to (d) and performing anionic polymerization.