JPH06256417A - Compatibilizer for resin, and resin composition - Google Patents

Abstract

PURPOSE:To obtain a compatibilizer which has a good dispersant activity and gives, when mixed into a resin blend, a blend having sufficient impact resistance and processibility. CONSTITUTION:This compatibilizer comprises an epoxy-modified block copolymer comprising a polymer block consisting mainly of arom. vinyl compd. units and a polymer block consisting mainly of conjugated diene compd. units of which double bonds at unsatd. carbonatcms have been epoxidized. The compatibilizer enables two resins to be blended with each other without detriement to the physical properties such as impact resistance.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a compatibilizer for resins and a resin composition.

[0002]

2. Description of the Related Art Resin modification has been actively investigated by polymer blends which blend polymers having different properties. It is also well known that in polymer blends, the various properties of the polymer material obtained by the compatibility of the polymers to be blended are affected.
A method of using a styrene-based thermoplastic elastomer as a compatibilizing agent in order to improve the compatibility has been proposed (for example, JP-A-47-11486 and JP-A-50-).
75651, JP-A-56-100840, etc.).

[0003]

However, the conventional ones have problems such as poor dispersion effect, insufficient impact resistance and workability.

[0004]

The present inventors have arrived at the present invention as a result of studies to solve the above problems. That is, the present invention provides "conjugation of a block copolymer comprising a polymer block (A) mainly containing a vinyl aromatic compound and a polymer block (B) mainly containing a conjugated diene compound in the same molecule. "Compatibilizer for resin consisting of epoxy-modified block polymer in which double bond of unsaturated carbon of diene compound is epoxidized", "polymer block mainly containing vinyl aromatic compound in the same molecule, and conjugated diene compound" Resins composed of epoxy-modified block polymers obtained by epoxidizing unsaturated carbon double bonds of conjugated diene compounds of partially hydrogenated block polymers obtained by partially hydrogenating a block polymer composed of a polymer block mainly composed of Compatibilizer "
And "a resin composition containing the above-mentioned resin compatibilizer".

Examples of the vinyl aromatic compound which constitutes the block polymer used in the present invention include styrene and α
-Methylstyrene, vinyltoluene, p-tertiary butylstyrene, divinylbenzene, p-methylstyrene,
1 or 2 of 1,1-diphenylstyrene
One or more kinds can be selected, and styrene is preferable. Examples of the conjugated diene compound include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,
One or more of 3-butadiene, piperylene, 3-butyl-1,3-octadiene, phenyl-1,3-butadiene, etc. are selected, among which butadiene,
Isoprene and combinations thereof are preferred. The block copolymer referred to herein is a block copolymer composed of a polymer block A containing a vinyl aromatic compound as a main component and a polymer block B containing a conjugated diene compound as a main component. The copolymerization ratio of the conjugated diene compound is 5/95 to 70/30, especially 10/90 to 60/4
A polymerization ratio of 0 is preferred. The number average molecular weight of the block copolymer used in the present invention is 5,000 to 600,000,
It is preferably in the range of 10,000 to 500,000, and the molecular weight distribution [weight average molecular weight (Mw) and number average molecular weight (M
The ratio with (n) (Mw / Mn)]) is 10 or less. The molecular structure of the block polymer may be linear, branched, radial or any combination thereof.

For example, A-B-A, B-A-B-A,
(A-B-) ₄ is a vinyl aromatic compound-conjugated diene compound block polymer having a structure such as Si and A-B-A-B-A. Further, the unsaturated bond of the conjugated diene compound of the block polymer may be partially hydrogenated.

As the method for producing the block polymer used in the present invention, any method can be used as long as it has the above-mentioned structure. For example, Japanese Patent Publication No. 40-2
No. 3798, Japanese Patent Publication No. 43-17979, Japanese Patent Publication No. 46-
A vinyl aromatic compound-conjugated diene compound block copolymer can be synthesized in an inert solvent using a lithium catalyst or the like by the method described in JP-A-32415 and JP-B-56-28925. Furthermore, Japanese Examined Japanese Patent Publication No. 42-87
A portion to be hydrogenated in the presence of a hydrogenation catalyst in an inert solvent by the method described in JP-A-04, JP-B-43-6636, or JP-A-59-133203, and used for the present invention. It is possible to synthesize a block copolymer that has been hydrogenated.

In the present invention, the epoxy-modified block copolymer used in the present invention is obtained by epoxidizing the above block copolymer.

The epoxy-modified block copolymer in the present invention can be obtained by reacting the above block copolymer with an epoxidizing agent such as hydroperoxides and peracids in an inert solvent.

Examples of peracids include formic acid, peracetic acid, perbenzoic acid, trifluoroperacetic acid and the like. Of these, peracetic acid is industrially produced in large quantities and is available at low cost.
It is also a preferred epoxidizing agent because of its high stability. Hydroperoxides include hydrogen peroxide, tertiary butyl hydroperoxide, cumene peroxide and the like.

In the epoxidation, a catalyst can be used if necessary.

For example, in the case of peracid, an alkali such as sodium carbonate or an acid such as sulfuric acid can be used as a catalyst. In the case of hydroperoxides, a catalytic effect can be obtained by using a mixture of tungstic acid and caustic soda with hydrogen peroxide, an organic acid with hydrogen peroxide, or molybdenum hexacarbonyl with tertiary butyl hydroperoxide. You can

There is no strict regulation on the amount of epoxidizing agent, the optimum amount in each case is variable, such as the particular epoxidizing agent used, the desired degree of epoxidation, the particular block copolymer used, etc. Determined by factors.

The inert solvent can be used for the purpose of decreasing the viscosity of the raw material and stabilizing it by diluting the epoxidizing agent. In the case of peracetic acid, aromatic compounds, ethers, esters and the like can be used. Can be used. Particularly preferred solvents are hexane, cyclohexane, toluene, benzene, ethyl acetate, carbon tetrachloride, chloroform. There are no strict restrictions on the epoxidation reaction conditions. The reaction temperature range that can be used depends on the reactivity of the epoxidizing agent used. For example, peracetic acid is preferably 0 to 70 ° C., the reaction is slow below 0 ° C., and the decomposition of peracetic acid occurs above 70 ° C. Also, tertiary butyl hydroperoxide, which is an example of hydroperoxide
In the molybdenum dioxide diacetylacetonate system, 20 ° C to 150 ° C is preferable for the same reason. No special manipulation of the reaction mixture is necessary, for example the mixture may be stirred for 2-10 hours. Isolation of the obtained epoxy-modified copolymer by a suitable method, for example, a method of precipitating with a poor solvent, a method of adding the polymer into hot water under stirring and distilling off the solvent, a direct desolvation method, etc. It can be carried out.

(A) is a resin having an affinity with the aromatic vinyl polymer. For example, styrene resin (polystyrene, AS resin, ABS resin, AAS resin, AES resin,
ACS resin, MBS resin, HIPS, styrene-butadiene resin, etc.), aromatic polyethers (polyphenylene ether, etc.), polycarbonate, and mixtures of two or more thereof.

(B) is a resin reactive with an epoxy group. Here, being reactive with an epoxy group means having a residue (eg, carboxylic acid group, hydroxyl group amino group, etc.) or bond (eg, ester bond, amide bond, etc.) that reacts with the epoxy group in the resin. Means polyester (polyethylene terephthalate, polybutylene terephthalate, polycarbonate, etc.), polyamide (6-nylon, 6,6-nylon, 4,6-nylon, 11-nylon, 12 -Nylon, etc.), polyimide, polyamideimide, carboxylic acid-containing polyolefin (ethylene- (meth) acrylic acid copolymer, maleic acid-modified polypropylene, etc.), polyvinyl acetate, ethylene-
Examples thereof include vinyl acetate copolymers and mixtures of two or more thereof. Of these, polyester, polyamide, and carboxylic acid-containing polyolefin, and a mixture of two or more thereof are preferable.

If desired, the composition of the present invention may contain other resins. Other resins include
Thermosetting resin (formaldehyde resin, phenol resin, amino resin, unsaturated polyester, epoxy resin,
Diallyl phthalate resin, silicone resin, thermosetting polyurethane, etc., the following thermoplastic resins such as polyolefin resins (polyethylene, polypropylene, ethylene-α-olefin copolymer, propylene-α-olefin copolymer, Poly-4-methylpentene, polybutene, etc.), polyalkyl (meth) acrylate, polyvinyl chloride, ionomer, polyacetate, polyallyl
, Polysulfone, polyethersulfone, polyphenylene sulfide, elastomers (ethylene propylene rubber, ethylene-acrylic acid ester copolymer, EPD
M, butadiene rubber, styrene- (hydrogenated) conjugated diene elastomer, polyester elastomer, polyamide elastomer, thermoplastic polyurethane and the like).

The resin composition of the present invention has a composition of (a) 5 to 95% and (b) 95 to 5% by weight.
(C) is 0.1 to 50%, and other resins are 0 to 90%.

Whether (a) or (b) exceeds 95% 5
When it is less than%, the remarkable effect of modifying the resin is not exhibited.
If (c) exceeds 50%, the compatibility effect is lowered.
If the content of other resins exceeds 90%,
The resin characteristics based on (a), (b) and (c) are unlikely to appear.

The resin composition of the present invention can be produced by mixing the compatibilizing agent for resin and the resin using various known mixers. Various known mixers are, for example, extruders, brabenders, kneaders, Banbury mixers and the like.

In the resin composition of the present invention, if necessary, various additives such as an antioxidant, a heat stabilizer, an ultraviolet absorber, an inorganic filler such as silica, talc and carbon, a plasticizer and an oil. Softeners such as can be blended and used.

EXAMPLES The present invention will be further described with reference to the following examples, but the present invention is not limited thereto. In the following description, parts and% mean parts by weight and% by weight, respectively.

The characteristics of the molded articles described in the practical examples and comparative examples were evaluated by the following methods.

(1) Epoxy equivalent: The degree of epoxidation of the epoxy modified block polymer in the present invention is calculated by the following formula after titration with hydrobromic acid.

[0025] (2) Impact strength: ASTM D256 with notch, 3.2
mm thickness (3) Heat distortion temperature: ASTM D648 << Example 1 >> A block copolymer of polystyrene-polybutadiene-polystyrene was added to a jacketed reactor equipped with a stirrer, a reflux condenser and a thermometer [Japan Synthetic Rubber Co., Ltd.]. (Product name: TR2000] 300 g and ethyl acetate 1500 g were charged and dissolved. Then 30w of peracetic acid
169 g of a t% ethyl acetate solution was continuously added dropwise, and the mixture was stirred with stirring 4
The epoxidation reaction was carried out at 0 ° C. for 3 hours. The reaction solution was returned to room temperature and taken out of the reactor, a large amount of methanol was added to precipitate the polymer, which was filtered, washed with water and dried to obtain an epoxy-modified polymer. The obtained epoxy modified polymer is referred to as polymer A (epoxy equivalent of the polymer is 470).

Example 2 300 g of polystyrene-polybutadiene-polystyrene block copolymer [Nippon Synthetic Rubber Co., Ltd., trade name: TR2000] in a jacketed reactor equipped with a stirrer, a reflux condenser and a thermometer. ,
1500 g of ethyl acetate was charged and dissolved. Then, 43 g of a 30 wt% ethyl acetate solution of peracetic acid was continuously added dropwise, and an epoxidation reaction was carried out at 40 ° C. for 3 hours while stirring. The reaction solution was returned to room temperature and taken out of the reactor, a large amount of methanol was added to precipitate the polymer, which was filtered, washed with water and dried to obtain an epoxy-modified polymer. The obtained epoxy-modified polymer is referred to as polymer B (epoxy equivalent of the polymer is 182
0).

Example 3 A block reactor of polystyrene-polybutadiene-polystyrene [manufactured by Nippon Synthetic Rubber Co., Ltd., trade name: TR2400] 300 g in a jacketed reactor equipped with a stirrer, a reflux condenser and a thermometer. ,
1500 g of ethyl acetate was charged and dissolved. Then, 113 g of a 30 wt% ethyl acetate solution of peracetic acid was continuously added dropwise,
The epoxidation reaction was carried out at 40 ° C. for 3 hours with stirring. The reaction solution was returned to room temperature and taken out of the reactor, a large amount of methanol was added to precipitate the polymer, which was filtered, washed with water and dried to obtain an epoxy-modified polymer. The obtained epoxy-modified polymer is referred to as polymer C (epoxy equivalent of the polymer is 69
5).

Example 4 A block copolymer of polystyrene-polybutadiene-polystyrene in a jacketed reactor equipped with a stirrer, a reflux condenser and a thermometer [Shell Chemical Co., Ltd., trade name: Califlex D1122].
300 g and 1500 g of cyclohexane were charged and dissolved. Then, 177 g of a 30 wt% ethyl acetate solution of peracetic acid
Was continuously added dropwise, and the epoxidation reaction was carried out at 40 ° C. for 3 hours with stirring. The reaction solution was returned to room temperature and taken out of the reactor, a large amount of methanol was added to precipitate the polymer, which was filtered, washed with water and dried to obtain an epoxy-modified polymer. The obtained epoxy-modified polymer is referred to as polymer D (epoxy equivalent of the polymer is 448).

Example 5 A block copolymer of polystyrene-polyisoprene-polystyrene was added to a jacketed reactor equipped with a stirrer, a reflux condenser, and a thermometer [Shell Chemical Co., Ltd., trade name: Califlex TR111.
1] 300 g and cyclohexane 1500 g were charged and dissolved. Then, a 30 wt% ethyl acetate solution of peracetic acid 222
g was continuously added dropwise, and the epoxidation reaction was carried out at 40 ° C. for 3 hours with stirring. The reaction solution is returned to room temperature and taken out from the reactor, and a large amount of methanol is added to precipitate the polymer,
After separation by filtration, washing with water and drying, an epoxy-modified polymer was obtained. The obtained epoxy-modified polymer is referred to as a polymer E (epoxy equivalent of the polymer is 362).

Example 6 A jacketed reactor equipped with a stirrer, a reflux condenser and a thermometer was used for a polystyrene-butadiene block copolymer [manufactured by Asahi Kasei Co., Ltd., trade name:
Tuftec H-1041] 300 g, cyclohexane 1500
g was added and dissolved. Then, 39 g of a 30 wt% ethyl acetate solution of peracetic acid was continuously added dropwise, and an epoxidation reaction was carried out at 50 ° C. for 3 hours with stirring. The reaction solution was returned to room temperature and taken out of the reactor, a large amount of methanol was added to precipitate the polymer, which was filtered, washed with water and dried to obtain an epoxy-modified polymer. The obtained epoxy-modified polymer is referred to as a polymer F (epoxy equivalent of the polymer is 5340).

Example 7 Polybutylene terephthalate [manufactured by Toray Industries, Inc., trade name 1401-X06, hereinafter PBT
Abbreviated] 60 parts, modified polyphenylene ether [manufactured by Nippon GE Plastics Co., Ltd., trade name Noryl 731]
J, hereinafter abbreviated as modified PPE] 40 parts and 10 parts of the epoxy modified block polymer A were blended using a biaxial extruder to obtain a resin composition of the present invention. This composition was further injection-molded to obtain a test piece. Also, after breaking the test piece in liquid nitrogen, the fracture surface was observed with an electron microscope to measure the dispersed particle size to evaluate the compatibility. The evaluation results are shown in Table 1.

Comparative Example 1 The same operation as in Example 7 was carried out except that the epoxy-modified block copolymer A was not used. The results of the characteristic evaluation are shown in Table 1.

Examples 8 to 18 The same operation as in Example 7 was carried out by changing the combination of the epoxy-modified block copolymer and the resin to be blended to obtain a resin composition of the present invention. The results of the characteristic evaluation are shown in Table 1.

It should be noted that the resins shown in the following tables have PBT and modified P.
Abbreviations other than PE have the following meanings. That is,
PA (nylon: product name UBE nylon 1013, Ube Industries), ABS (ABS resin: product name Sebian 510)
SF, manufactured by Daicel Chemical Industries, PC (polycarbonate)
To: Trade name Panlite L1225, Teijin Kasei), MA
PE (maleic acid-modified polypropylene: trade name Adma-QB010, manufactured by Mitsui Petrochemical Industry).

Comparative Examples 2 to 4 The same operation as in Example 7 was carried out by changing the combination of the epoxy-modified block copolymer and the resin to be blended to obtain a resin composition of the present invention. The results of the characteristic evaluation are shown in Table 1.

Example 19 PA resin (60 parts by weight), ABS (40 parts by weight), and epoxy modified block polymer A (10 parts by weight) were blended using a twin-screw extruder to obtain a resin composition of the present invention. .

This composition was further injection-molded to obtain a test piece. The evaluation results are shown in Table 2.

Comparative Example 5 The same operation as in Example 19 was carried out except that the epoxy modified block copolymer A was not used. The results of the characteristic evaluation are shown in Table 1.

<< Example 20 to Example 35 >> The same operation as in Example 19 was carried out by changing the combination of the compatibilizing agent and the resin to be blended to obtain a resin composition of the present invention. The results of the characteristic evaluation are shown in Table 2.

Comparative Examples 6 to 11 The same operation as in Example 19 was carried out by changing the combination of the compatibilizing agent and the resin to be blended to obtain a resin composition of the present invention. The results of the characteristic evaluation are shown in Table 2.

[0041]

The resin composition of the present invention has the effect that the resins can be blended together without deteriorating the physical properties of the resin such as impact resistance. Conventionally, when modifying a resin with a polymer blend, it is necessary to increase the compatibility of the resins with each other by some method, but the compatibility is not sufficient and the impact resistance is lowered, which results from the polymer blend. In many cases, the modification effect was not exhibited, but the product of the present invention does not have such a phenomenon.

Because of the above effects, the present resin composition is used in various applications such as fluidity improvers, lubricants, paintability improvers, crystallization accelerators, impact resistance improvers and filler dispersants. it can.

Table 1 Epoxy-modified blend resin IS HDT PS Appearance copolymer (a) / (b) Example 7 A (5) modified PPE (40) 12.3 110 to 10 PBT (60) 8 C (5) 10.5 112 〜 1 〇 9 D (5) 10.3 109 〜 1 〇 10 F (5) 11.5 117 〜 1 〇 Comparative Example 1 None 3.2 102 5 〜 10 Delamination Example 11 B (10) Modified PPE (40) 12.5 110 〜 2 〇 PA (60) 12 D (10) 11.3 108 〜 2 〇 13 F (10) 13.2 118 〜 1 〇 Comparative Example 2 None 3.4 100 〜 20 Surface peeling Example 14 B (10) ABS (40) 10.1 70 − 〇 PBT (60) 15 E (10) 9.5 69 − 〇 16 F (10) 15.4 79 − 〇 Comparative Example 3 None 3.5 65 − FM Example 17 C (5) modified PPE (40) 10.6 115 〜 10 MA PP (60) 18 F (5) 12.8 118 ~ 1 ○ Comparative Example 4 None 3.6 105 ~ 10 Surface peeling In Table 1, IS is impact strength (Kg · cm / cm), HDT
Is the heat distortion temperature (° C.), and PS is the dispersed particle size (μm).
The appearance FM indicates "with flow mark".

In the epoxy-modified copolymer and the blend resin, the numerical value in the parentheses () represents parts by weight.

Table 2 Epoxy-modified blend resin IS appearance copolymer (a) / (b) Example 19 A (10) ABS (40) 12.3 〇 PA (60) 20 D (10) 45 〇 21 E (10) 50 ○ Comparative Example 5 None 4.7 Surface peeling Example 22 B (10) modified PPE (40) 59 ○ PC (60) 23 C (10) 45 ○ 24 E (10) 56 ○ Comparative Example 6 None 4.8 FM Example 25 A (10) ABS (40) 9.3 〇 PET (60) 26 C (10) 7.1 〇 27 E (10) 9.0 〇 Comparative Example 7 None 3.2 Lusterless Example 28 C (10) ABS (50) 58 − PC ( 50) 29 E (10) 63- Comparative Example 8 None 35- Example 30 A (10) Modified PPE (40) 10.6 〇 PET (60) 31 E (10) 11.2 〇 Comparative Example 9 None 1.8 Surface exfoliation Example 32 A (10) PA (20) 6.0 ○ PBT (80) 33 E (10) 7.3 ○ Comparative Example 10 None 1.5 Surface peeling Example 34 B (10) PA (20) 10.7 ○ PC (80) 35 E (10) 11.6 Comparative Example 11 None 1.5 Surface peeling In Table 2, IS is impact strength (Kg · cm / cm), HDT
Is the heat distortion temperature (° C.), and PS is the dispersed particle size (μm).
The appearance FM indicates "with flow mark".

In the epoxy-modified copolymer and the blend resin, the numerical value in the parentheses () represents parts by weight. (Below margin)

[Procedure amendment]

[Submission date] April 8, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] Full text

[Correction method] Change

[Correction content]

[Document name] Statement

Title: Compatibilizer for resin and resin composition

[Claims]

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a compatibilizer for resins and the same.
The present invention relates to a resin composition containing a compatibilizer .

[0002]

2. Description of the Related Art Resin modification has been actively investigated by polymer blends which blend polymers having different properties. It is also well known that in polymer blends, the various properties of the polymer material obtained by the compatibility of the polymers to be blended are affected.
A method of using a styrene-based thermoplastic elastomer as a compatibilizing agent in order to improve the compatibility has been proposed (for example, JP-A-47-11486 and JP-A-50-).
75651, JP-A-56-100840, etc.).

[0003]

However, the conventional ones have problems such as poor dispersion effect, insufficient impact resistance and workability.

[0004]

The present inventors have arrived at the present invention as a result of studies to solve the above problems. That is, the present invention provides "conjugation of a block copolymer comprising a polymer block (A) mainly containing a vinyl aromatic compound and a polymer block (B) mainly containing a conjugated diene compound in the same molecule. "Compatibilizer for resin consisting of epoxy-modified block polymer in which double bond of unsaturated carbon of diene compound is epoxidized", "polymer block mainly containing vinyl aromatic compound in the same molecule, and conjugated diene compound" Resins composed of epoxy-modified block polymers obtained by epoxidizing unsaturated carbon double bonds of conjugated diene compounds of partially hydrogenated block polymers obtained by partially hydrogenating a block polymer composed of a polymer block mainly composed of Compatibilizer "
And "a resin composition containing the above-mentioned resin compatibilizer".

Examples of the vinyl aromatic compound which constitutes the block polymer used in the present invention include styrene and α
-Methylstyrene, vinyltoluene, p-tertiary butylstyrene, divinylbenzene, p-methylstyrene,
1 or 2 of 1,1-diphenylstyrene
One or more kinds can be selected, and styrene is preferable. Examples of the conjugated diene compound include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,
One or more of 3-butadiene, piperylene, 3-butyl-1,3-octadiene, phenyl-1,3-butadiene, etc. are selected, among which butadiene,
Isoprene and combinations thereof are preferred. The block copolymer referred to herein is a block copolymer composed of a polymer block A containing a vinyl aromatic compound as a main component and a polymer block B containing a conjugated diene compound as a main component. The copolymerization ratio of the conjugated diene compound is 5/95 to 70/30, especially 10/90 to 60/4
A polymerization ratio of 0 is preferred.

The number average molecular weight of the block copolymer used in the present invention is 5,000 to 600,000, preferably 1.
It is in the range of 0000 to 500,000, and the molecular weight distribution [ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw / Mn)] is 10 or less. The molecular structure of the block polymer may be linear, branched, radial or any combination thereof.

For example, A-B-A, B-A-B-A,
(A-B-) ₄ is a vinyl aromatic compound-conjugated diene compound block polymer having a structure such as Si and A-B-A-B-A. Further, the unsaturated bond of the conjugated diene compound of the block polymer may be partially hydrogenated.

As the method for producing the block polymer used in the present invention, any method can be used as long as it has the above-mentioned structure. For example, Japanese Patent Publication No. 40-2
No. 3798, Japanese Patent Publication No. 43-17979, Japanese Patent Publication No. 46-
A vinyl aromatic compound-conjugated diene compound block copolymer can be synthesized in an inert solvent using a lithium catalyst or the like by the method described in JP-A-32415 and JP-B-56-28925. Furthermore, Japanese Examined Japanese Patent Publication No. 42-87
A portion to be hydrogenated in the presence of a hydrogenation catalyst in an inert solvent by the method described in JP-A-04, JP-B-43-6636, or JP-A-59-133203, and used for the present invention. It is possible to synthesize a block copolymer that has been hydrogenated.

In the present invention, the epoxy-modified block copolymer used in the present invention can be obtained by epoxidizing the above block copolymer.

The epoxy-modified block copolymer in the present invention can be obtained by reacting the above block copolymer with an epoxidizing agent such as hydroperoxides and peracids in an inert solvent.

Examples of peracids include formic acid, peracetic acid, perbenzoic acid and trifluoroperacetic acid. Of these, peracetic acid is industrially produced in large quantities and is available at low cost.
It is also a preferred epoxidizing agent because of its high stability. Hydroperoxides include hydrogen peroxide, tertiary butyl hydroperoxide, cumene peroxide and the like.

In the epoxidation, a catalyst can be used if necessary.

For example, in the case of peracid, an alkali such as sodium carbonate or an acid such as sulfuric acid can be used as a catalyst. In the case of hydroperoxides, a catalytic effect can be obtained by using a mixture of tungstic acid and caustic soda with hydrogen peroxide, an organic acid with hydrogen peroxide, or molybdenum hexacarbonyl with tertiary butyl hydroperoxide. You can

There is no strict regulation on the amount of epoxidizing agent, the optimum amount in each case is variable, such as the particular epoxidizing agent used, the desired degree of epoxidation, the individual block copolymer used, etc. Determined by factors.

The inert solvent can be used for the purpose of decreasing the viscosity of the raw material and stabilizing it by diluting the epoxidizing agent. In the case of peracetic acid, aromatic compounds, ethers, esters and the like can be used. Can be used. Particularly preferred solvents are hexane, cyclohexane, toluene, benzene, ethyl acetate, carbon tetrachloride, chloroform. There are no strict restrictions on the epoxidation reaction conditions. The reaction temperature range that can be used depends on the reactivity of the epoxidizing agent used. For example, peracetic acid is preferably 0 to 70 ° C., the reaction is slow below 0 ° C., and the decomposition of peracetic acid occurs above 70 ° C. Also, tertiary butyl hydroperoxide, which is an example of hydroperoxide
In the molybdenum dioxide diacetylacetonate system, 20 ° C to 150 ° C is preferable for the same reason. No special manipulation of the reaction mixture is necessary, for example the mixture may be stirred for 2-10 hours. Isolation of the obtained epoxy-modified copolymer by a suitable method, for example, a method of precipitating with a poor solvent, a method of adding the polymer into hot water under stirring and distilling off the solvent, a direct desolvation method, etc. It can be carried out.

(A) is a resin having an affinity with the aromatic vinyl polymer. For example, styrene resin (polystyrene, acrylonitrile-styrene copolymer resin, acrylo
Nit Lil - butadiene - styrene copolymer resin, Akurironi
Trilyl -acrylate-styrene copolymer resin, acryloni
Tolyl - ethylene - propylene - styrene copolymer resin, A
Acrylonitrile-styrene copolymer and chlorinated polyethylene
Blend resin with methylmethacrylate-butadien
-Styrene copolymer resin, high impact polystyrene (HI
PS), styrene-butadiene resin, etc.), aromatic polyethers ( modified polyphenylene ether, etc.), polycarbonate
Carbonates and mixtures of two or more of these.

(B) is a resin reactive with an epoxy group. Here, being reactive with an epoxy group means having a residue (eg, carboxylic acid group, hydroxyl group amino group, etc.) or bond (eg, ester bond, amide bond, etc.) that reacts with the epoxy group in the resin. Means polyester (polyethylene terephthalate, polybutylene terephthalate, polycarbonate, etc.), polyamide (6-nylon, 6,6-nylon, 4,6-nylon, 11-nylon, 12 -Nylon, etc.), polyimide, polyamideimide, carboxylic acid-containing polyolefin (ethylene- (meth) acrylic acid copolymer, maleic acid-modified polypropylene, etc.), polyvinyl acetate, ethylene-
Examples thereof include vinyl acetate copolymers and mixtures of two or more thereof. Of these, polyester, polyamide, and carboxylic acid-containing polyolefin, and a mixture of two or more thereof are preferable.

If desired, the composition of the present invention may contain other resins. Other resins include
Thermosetting resin (formaldehyde resin, phenol resin, amino resin, unsaturated polyester, epoxy resin,
Diallyl phthalate resin, silicone resin, thermosetting polyurethane, etc., the following thermoplastic resins such as polyolefin resins (polyethylene, polypropylene, ethylene-α-olefin copolymer, propylene-α-olefin copolymer, Poly-4-methylpentene, polybutene, etc.), polyalkyl (meth) acrylate, polyvinyl chloride, ionomer, polyacetate, polyallyl
, Polysulfone, polyethersulfone, polyphenylene sulfide, elastomers (ethylene propylene rubber, ethylene-acrylic acid ester copolymer, EPD
M, butadiene rubber, styrene- (hydrogenated) conjugated diene elastomer, polyester elastomer, polyamide elastomer, thermoplastic polyurethane and the like).

The composition of the resin composition of the present invention is (a)
Is 5 to 95%, (b) is 95 to 5%, and (c) is (a).
0.1 to 50 parts by weight based on 100 parts by weight of (b)
Parts and other resins are 0 to 90%.

Whether (a) or (b) exceeds 95% 5
When it is less than%, the remarkable effect of modifying the resin is not exhibited.
On the other hand, if (c) exceeds 50% , the compatibility effect is decreased. If the content of other resins exceeds 90%,
The resin characteristics based on (a), (b) and (c) are unlikely to appear.

The resin composition of the present invention can be produced by mixing the compatibilizing agent for resin and the resin using various known mixers. Various known mixers are, for example, extruders, brabenders, kneaders, Banbury mixers and the like.

The resin composition of the present invention may contain various additives, if necessary, such as an antioxidant, a heat stabilizer, an ultraviolet absorber, an inorganic filler such as silica, talc and carbon, a plasticizer and an oil. Softeners such as can be blended and used.

EXAMPLES The present invention will be further described with reference to the following examples, but the present invention is not limited thereto. In the following description, parts and% mean parts by weight and% by weight, respectively.

The characteristics of the molded articles described in the practical examples and comparative examples were evaluated by the following methods.

(1) Epoxy equivalent: The degree of epoxidation of the epoxy modified block polymer in the present invention is calculated by the following formula after titration with hydrobromic acid.

[0026] (2) Impact strength: ASTM D256 with notch, 3.2
mm thickness (3) Heat distortion temperature: ASTM D648 << Example 1 >> A block copolymer of polystyrene-polybutadiene-polystyrene was added to a jacketed reactor equipped with a stirrer, a reflux condenser and a thermometer [Japan Synthetic Rubber Co., Ltd.]. (Product name: TR2000] 300 g and ethyl acetate 1500 g were charged and dissolved. Then 30w of peracetic acid
169 g of a t% ethyl acetate solution was continuously added dropwise, and the mixture was stirred with stirring 4
The epoxidation reaction was carried out at 0 ° C. for 3 hours. The reaction solution was returned to room temperature and taken out of the reactor, a large amount of methanol was added to precipitate the polymer, which was filtered, washed with water and dried to obtain an epoxy-modified polymer. The obtained epoxy modified polymer is referred to as polymer A (epoxy equivalent of the polymer is 470).

Example 2 300 g of a block copolymer of polystyrene-polybutadiene-polystyrene [manufactured by Japan Synthetic Rubber Co., Ltd., trade name: TR2000] in a jacketed reactor equipped with a stirrer, a reflux condenser and a thermometer. ,
1500 g of ethyl acetate was charged and dissolved. Then, 43 g of a 30 wt% ethyl acetate solution of peracetic acid was continuously added dropwise, and an epoxidation reaction was carried out at 40 ° C. for 3 hours while stirring. The reaction solution was returned to room temperature and taken out of the reactor, a large amount of methanol was added to precipitate the polymer, which was filtered, washed with water and dried to obtain an epoxy-modified polymer. The obtained epoxy-modified polymer is referred to as polymer B (epoxy equivalent of the polymer is 182
0).

Example 3 Polystyrene-polybutadiene-polystyrene block copolymer [trade name: TR2400, manufactured by Japan Synthetic Rubber Co., Ltd.] 300 g in a jacketed reactor equipped with a stirrer, a reflux condenser and a thermometer. ,
1500 g of ethyl acetate was charged and dissolved. Then, 113 g of a 30 wt% ethyl acetate solution of peracetic acid was continuously added dropwise,
The epoxidation reaction was carried out at 40 ° C. for 3 hours with stirring. The reaction solution was returned to room temperature and taken out of the reactor, a large amount of methanol was added to precipitate the polymer, which was filtered, washed with water and dried to obtain an epoxy-modified polymer. The obtained epoxy-modified polymer is referred to as polymer C (epoxy equivalent of the polymer is 69
5).

Example 4 A block copolymer of polystyrene-polybutadiene-polystyrene in a jacketed reactor equipped with a stirrer, a reflux condenser and a thermometer [Shell Chemical Co., Ltd., trade name: Califlex D1122].
300 g and 1500 g of cyclohexane were charged and dissolved. Then, 177 g of a 30 wt% ethyl acetate solution of peracetic acid
Was continuously added dropwise, and the epoxidation reaction was carried out at 40 ° C. for 3 hours with stirring. The reaction solution was returned to room temperature and taken out of the reactor, a large amount of methanol was added to precipitate the polymer, which was filtered, washed with water and dried to obtain an epoxy-modified polymer. The obtained epoxy-modified polymer is referred to as polymer D (epoxy equivalent of the polymer is 448).

Example 5 A block copolymer of polystyrene-polyisoprene-polystyrene was added to a jacketed reactor equipped with a stirrer, a reflux condenser, and a thermometer [Shell Chemical Co., Ltd., trade name: Califlex TR111.
1] 300 g and cyclohexane 1500 g were charged and dissolved. Then, a 30 wt% ethyl acetate solution of peracetic acid 222
g was continuously added dropwise, and the epoxidation reaction was carried out at 40 ° C. for 3 hours with stirring. The reaction solution is returned to room temperature and taken out from the reactor, and a large amount of methanol is added to precipitate the polymer,
After separation by filtration, washing with water and drying, an epoxy-modified polymer was obtained. The obtained epoxy-modified polymer is referred to as a polymer E (epoxy equivalent of the polymer is 362).

Example 6 A reactor equipped with a jacket equipped with a stirrer, a reflux condenser and a thermometer was placed in a polystyrene port.
Libutadiene-polystyrene block copolymer part
Polystyrene-butadiene block copolymer that is a hydrogenated product [Asahi Kasei Co., Ltd., trade name: Tuftec H-1041] 30
0 g and 1500 g of cyclohexane were charged and dissolved. Then, 39 g of a 30 wt% ethyl acetate solution of peracetic acid was continuously added dropwise, and an epoxidation reaction was carried out at 50 ° C. for 3 hours with stirring. The reaction solution was returned to room temperature and taken out of the reactor, a large amount of methanol was added to precipitate the polymer, which was filtered, washed with water and dried to obtain an epoxy-modified polymer. The obtained epoxy-modified polymer is referred to as a polymer F (epoxy equivalent of the polymer is 5340).

Example 7 Polybutylene terephthalate [manufactured by Toray Industries, Inc., trade name 1401-X06, hereinafter PBT
Abbreviated] 60 parts, modified polyphenylene ether [manufactured by Nippon GE Plastics Co., Ltd., trade name Noryl 731]
J, hereinafter abbreviated as modified PPE] 40 parts and 10 parts of the epoxy modified block polymer A were blended using a biaxial extruder to obtain a resin composition of the present invention. This composition was further injection-molded to obtain a test piece. Also, after breaking the test piece in liquid nitrogen, the fracture surface was observed with an electron microscope to measure the dispersed particle size to evaluate the compatibility. The evaluation results are shown in Table 1.

Comparative Example 1 The same operation as in Example 7 was carried out except that the epoxy modified block copolymer A was not used. The results of the characteristic evaluation are shown in Table 1.

Examples 8 to 18 The same operation as in Example 7 was carried out by changing the combination of the epoxy-modified block copolymer and the resin to be blended, to obtain a resin composition of the present invention. Combination of resins, epoxy modified block used
Table 1 shows the lock copolymers, their compositions and the resulting characterization results.

It should be noted that the resins shown in the tables below are used for PBT and modified P.
Abbreviations other than PE have the following meanings. That is,
PA (nylon: product name UBE nylon 1013, Ube Industries), ABS ( acrylonitrile-butadiene-styrene )
Ren copolymer resin: trade name Sebian 510SF, manufactured by Daicel Chemical Industries, PC (polycarbonate: trade name Panlite L1225, Teijin Kasei), MA-modified PE (maleic acid-modified polypropylene: trade name Adma-QB010, Mitsui Petrochemical Industry).

Comparative Examples 2 to 4 The same operation as in Example 7 was carried out by changing the combination of the epoxy-modified block copolymer and the resin to be blended to obtain a resin composition for comparison . Combination of resins, epoxy modified block used
Table 1 shows the lock copolymers, their compositions and the resulting characterization results.

Example 19 PA resin (60 parts by weight), ABS (40 parts by weight), and epoxy modified block polymer A (10 parts by weight) were blended using a twin-screw extruder to obtain a resin composition of the present invention. .

This composition was further injection-molded to obtain a test piece. The evaluation results are shown in Table 2.

Comparative Example 5 The same operation as in Example 19 was carried out except that the epoxy modified block copolymer A was not used. The results of the characteristic evaluation are shown in Table 1.

Example 20 to Example 35 The same operation as in Example 19 was carried out by changing the combination of the compatibilizing agent and the resin to be blended to obtain a resin composition of the present invention. Resin combination
And used epoxy modified block copolymers,
Table 2 shows the composition and the obtained characteristic evaluation results.

Comparative Examples 6 to 11 The same operation as in Example 19 was carried out by changing the combination of resins to be blended, and the ratio was changed.
A resin composition for comparison was obtained. Resin combination, used
Epoxy-modified block copolymers, their composition and yield
Table 2 shows the obtained characteristic evaluation results.

[0042]

The resin composition of the present invention has the effect that the resins can be blended together without deteriorating the physical properties of the resin such as impact resistance. Conventionally, when modifying a resin with a polymer blend, it is necessary to increase the compatibility of the resins with each other by some method, but the compatibility is not sufficient and the impact resistance is lowered, which results from the polymer blend. In many cases, the modification effect was not exhibited, but the product of the present invention does not have such a phenomenon.

Because of the above effects, the resin composition is used in various applications such as fluidity improvers, lubricants, paintability improvers, crystallization accelerators, impact resistance improvers and filler-dispersants. it can.

Table 1 Epoxy-modified blend resin IS HDT PS Appearance copolymer (a) / (b) Example 7 A (5) modified PPE (40) 12.3 110 to 10 PBT (60) 8 C (5) 10.5 112 〜 1 〇 9 D (5) 10.3 109 〜 1 〇 10 F (5) 11.5 117 〜 1 〇 Comparative Example 1 None 3.2 102 5 〜 10 Delamination Example 11 B (10) Modified PPE (40) 12.5 110 〜 2 〇 PA (60) 12 D (10) 11.3 108 〜 2 〇 13 F (10) 13.2 118 〜 1 〇 Comparative Example 2 None 3.4 100 〜 20 Surface peeling Example 14 B (10) ABS (40) 10.1 70 − 〇 PBT (60) 15 E (10) 9.5 69 − 〇 16 F (10) 15.4 79 − 〇 Comparative Example 3 None 3.5 65 − FM Example 17 C (5) modified PPE (40) 10.6 115 〜 10 MA PP (60) 18 F (5) 12.8 118 ~ 1 ○ Comparative Example 4 None 3.6 105 ~ 10 Surface peeling In Table 1, IS is impact strength (Kg · cm / cm), HDT
Is the heat distortion temperature (° C.), and PS is the dispersed particle size (μm).
The appearance FM indicates "with flow mark".

In the epoxy-modified copolymer and the blend resin, the numerical value in the parentheses () represents parts by weight.

Table 2 Epoxy-modified blend resin IS Appearance Copolymer (a) / (b) Example 19 A (10) ABS (40) 12.3 〇 PA (60) 20 D (10) 45 〇 21 E (10) 50 ○ Comparative Example 5 None 4.7 Surface peeling Example 22 B (10) modified PPE (40) 59 ○ PC (60) 23 C (10) 45 ○ 24 E (10) 56 ○ Comparative Example 6 None 4.8 FM Example 25 A (10) ABS (40) 9.3 〇 PET (60) 26 C (10) 7.1 〇 27 E (10) 9.0 〇 Comparative Example 7 None 3.2 Lusterless Example 28 C (10) ABS (50) 58 − PC ( 50) 29 E (10) 63- Comparative Example 8 None 35- Example 30 A (10) Modified PPE (40) 10.6 〇 PET (60) 31 E (10) 11.2 〇 Comparative Example 9 None 1.8 Surface exfoliation Example 32 A (10) PA (20) 6.0 ○ PBT (80) 33 E (10) 7.3 ○ Comparative Example 10 None 1.5 Surface peeling Example 34 B (10) PA (20) 10.7 ○ PC (80) 35 E (10) 11.6 Comparative Example 11 None 1.5 Surface peeling In Table 2, IS is impact strength (Kg · cm / cm), HDT
Is the heat distortion temperature (° C.), and PS is the dispersed particle size (μm).
The appearance FM indicates "with flow mark".

In the epoxy-modified copolymer and the blended resin, the numerical value in the parentheses () represents parts by weight. (Below margin)

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08L 63/00 NJN 8830-4J NJY 8830-4J

Claims (6)

[Claims] 1. A conjugated diene compound of a block copolymer comprising a polymer block (A) mainly containing a vinyl aromatic compound and a polymer block (B) mainly containing a conjugated diene compound in the same molecule. Compatibilizer for resins comprising an epoxy-modified block polymer obtained by epoxidizing the unsaturated carbon double bond. 2. A partially hydrogenated block obtained by partially hydrogenating a block polymer composed of a polymer block mainly containing a vinyl aromatic compound and a polymer block mainly containing a conjugated diene compound in the same molecule. A compatibilizing agent for a resin, which comprises an epoxy-modified block polymer obtained by epoxidizing a double bond of an unsaturated carbon of a conjugated diene compound of a polymer. 3. A resin (a) having an affinity with an aromatic vinyl polymer, a resin (b) reactive with an epoxy group, and a compatibilizing agent (c) for a resin according to claim 1 or 2. A resin composition comprising: 4. The resin composition according to claim 3, wherein (a) is at least one selected from the group consisting of polyphenylene ether, polycarbonate, and styrene resin. 5. The resin composition according to claim 3, wherein (b) is one or more selected from the group consisting of polyester, polyamide, and carboxylic acid-containing polyolefin. 6. Amount of (a) is 5 to 95%, (b) is 95 to 5%, and (c) is based on the total weight of (a), (b) and (c).
The resin composition according to claim 3, 4 or 5, containing 0.1 to 50% of.