JP3434554B2 - Compatibilizer for resin and resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition containing a compatibilizing agent for resins.

[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 is directed to " having an affinity with an aromatic vinyl-based polymer.
Resin (a), resin (b) that is reactive with epoxy groups
And an unsaturated carbon of a conjugated diene compound of a block copolymer composed of 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. Double bond in an inert solvent
Epoxidation of hydroperoxides and peracids with
Containing a compatibilizer (c) for resin, which comprises an epoxy-modified block polymer epoxidized by reacting with an agent
A resin composition comprising: And "Aromatic vinyl
Resin (a), which has an affinity for polymer
A responsive resin (b) and a block copolymer composed of 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. The unsaturated carbon double bond of the conjugated diene compound of the partially hydrogenated partially hydrogenated block polymer is treated with hydroperoxides and peracids in an inert solvent.
A compatibilizer for resins consisting of an epoxy-modified block polymer epoxidized by reacting with any epoxidizing agent
A resin composition comprising (c). It is.

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 tert-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 invention is not limited thereto. In the following description, parts and%
It means 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: Degree of epoxidation of the epoxy-modified block polymer in the present invention (epoxy
Equivalent) is calculated by the following formula after titration with 0.1 N hydrobromic acid.

[0026]

[Chemical 1] (2) Impact strength: ASTM D256 with notch, 3.2
mm thickness (3) Heat distortion temperature: ASTM D648 << Example 1 >> Block copolymer of polystyrene-polybutadiene-polystyrene [Japan Synthetic Rubber Co., Ltd.] in a jacketed reactor equipped with a stirrer, reflux condenser and thermometer. (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 Polystyrene-polybutadiene-polystyrene block copolymer [manufactured by Nippon Synthetic Rubber Co., Ltd., trade name: TR2000] 300 g in a jacketed reactor equipped with a stirrer, a reflux condenser and a thermometer. Then, 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 1820).

Example 3 A block copolymer 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. Then, 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, 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 C (epoxy equivalent of the polymer is 695).

Example 4 A block reactor of polystyrene-polybutadiene-polystyrene was added to a jacketed reactor equipped with a stirrer, a reflux condenser and a thermometer [Shell Chemical Co., Ltd., trade name:
300 g of Califlex D1122 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 mixture was stirred at 40
The epoxidation reaction was carried out at ℃ 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 D (epoxy equivalent of the polymer is 448).

Example 5 A block reactor 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:
300 g of Califlex TR1111] and 1500 g of cyclohexane were charged and dissolved. Then, 222 g of a 30% by weight ethyl acetate solution of peracetic acid was continuously added dropwise, and the mixture was stirred under 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 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 placed in a polystyrene-polybutadiene-polystyrene mixture.
Polystyrene-butadiene block copolymer [Asahi Kasei Co., Ltd., trade name: Tuftec H-1041], which is a partially hydrogenated block copolymer of ethylene, cyclohexane 15
00 g was charged and dissolved. Then, 39 g of a 30 wt% ethyl acetate solution of peracetic acid was continuously added dropwise, and the mixture was stirred at 50 ° C. for 3 hours.
The epoxidation reaction was carried out for a time. 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 F.
(Epoxy equivalent of polymer is 5340).

Example 7 Polybutylene terephthalate [manufactured by Toray Industries, Inc., trade name 1]
401-X06, hereinafter abbreviated as PBT] 60 parts, modified polyphenylene ether [manufactured by Nippon GE Plastics Co., Ltd., trade name Noryl 731J, hereinafter abbreviated as modified PPE] 40 parts, 10 parts of epoxy modified block polymer A The resin composition of the present invention was obtained by blending using an axial extruder. 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 performed 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. Resin combination and usage
Used epoxy modified block copolymers, their composition and
Table 1 shows the obtained characteristic evaluation 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 . Resin combination and usage
Used epoxy modified block copolymers, their composition and
Table 1 shows the obtained characteristic evaluation 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.

Examples 20 to 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, epoxy modified block used
Table 2 shows the copolymers, their composition and the obtained characterization results.

Comparative Examples 6 to 11 The same operation as in Example 19 was carried out by changing the combination of the resins to be blended to obtain a resin composition for comparison . Resin assembly
Epoxy modified block copolymer used together, it
Table 2 shows the composition of these materials and 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)

Claims (6)

(57) [Claims] 1. A tree having an affinity with an aromatic vinyl polymer.
A resin (a), a resin (b) reactive with an epoxy group, and a polymer block (A) mainly containing a vinyl aromatic compound and a conjugated diene compound mainly in the same molecule. The double bond of the unsaturated carbon of the conjugated diene compound of the block copolymer consisting of the polymer block (B) is made high in an inert solvent.
Do not react with dropper oxides, epoxidizing agents such as peracids, etc.
To contain epoxidized epoxy-modified block comprising a polymer resin for compatibilizer (c) by response
A resin composition comprising: 2. A tree having an affinity with an aromatic vinyl polymer.
A resin (a), a resin (b) reactive with an epoxy group, and a polymer block (A) mainly containing a vinyl aromatic compound and a conjugated diene compound mainly in the same molecule. The double bond of the unsaturated carbon of the conjugated diene compound of the partially hydrogenated block polymer obtained by partially hydrogenating the block copolymer consisting of the polymer block (B) is treated with hydroperoxide in an inert solvent.
-React with epoxidizing agents such as oxides and peracids
It is characterized by containing a compatibilizing agent for resin (c) consisting of an epoxy-modified block polymer epoxidized by
And a resin composition. Wherein (a) is polyphenylene - ether, polycarbonate - Bonnet - DOO, and the resin composition according to claim 1 or 2, wherein at least one selected from the group consisting of styrene resin. 4. The resin composition according to claim 1, wherein (b) is at least one selected from the group consisting of polyester, polyamide, and carboxylic acid-containing polyolefin. 5. (a) 5 to 95%, (b) 95 to 5
%, The total amount the resin composition of claim 1 wherein the 0.1 to 50 parts by weight per 100 parts by weight of the (c) (a) and (b). 6. A combination of (a) and (b) is modified polyphenylene ether and polybutylene terephthalate, modified polyphenylene ether and polyamide, acrylonitrile-butadiene-styrene copolymer and polybutylene terephthalate. Modified polyphenylene ether and maleic anhydride modified polypropylene, acrylonitrile-butadiene-
Styrene copolymer and polyamide, modified polyphenylene ether and polycarbonate, acrylonitrile-butadiene-styrene copolymer and polyethylene terephthalate
, Acrylonitrile-butadiene-styrene copolymer and polycarbonate, modified polyphenylene ether and polyethylene terephthalate, acrylonitrile-butadiene-styrene copolymer and polybutylene terephthalate or polycarbonate 3. The resin composition according to claim 1, which is one of: