JPH02279729A - Production of modified polystyrene resin and impact-resistant polystyrene resin composition - Google Patents

Abstract

PURPOSE:To obtain a modified polystyrene resin improved in mold release, abrasion resistance, lubricity, impact resistance, etc., by reacting a maleic anhydride-modified PS elastomer with a reactive polysiloxane. CONSTITUTION:A styrene/butadiene block copolymer of a polystyrene segment content of 15 to 60wt.% is dissolved in an inert hydrogen diluent and hydrogenated in the presence of an insoluble hydrogenation catalyst. 0.02 to 20wt.% maleic anhydride is added to the reaction system and melt-kneaded at 250 deg.C or below to obtain maleic anhydride-modified polystyrene elastomer, which is reacted with 0.05 to 70wt.% polysiloxane having a reactive group and a weight-average mol.wt. of 1000 to 100000 to obtain a modified polystyrene resin. This resin is reacted with polystyrene or a styrene copolymer resin to obtain an impact- resistant polystyrene resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a polystyrene resin modified by grafting polysiloxane and a composition thereof.

[Conventional technology]

Polystyrene resin is hard, has excellent high-frequency electrical insulation, and is resistant to acids and alkalis.
Since it becomes a viscous liquid at about 30°C, injection molding is easy. On the other hand, in addition to having the disadvantage of being brittle, the molded product has insufficient sliding properties such as lubricity on the surface, so there are problems with mold releasability, wear resistance, and lubricity during molding.

Among the above-mentioned drawbacks of conventional polystyrene-based resins, high-impact polystyrene and ABS
It has been improved through the development of resin, ASA resin, etc.
Sliding properties have been improved by the following methods.

1) Spraying silicone oil such as polydimethylsiloxane onto a mold during molding, 2) Blending silicone oil such as polydimethylsiloxane, 3) Blending an olefin compound with styrene and polydimethylsiloxane chains. 4) A blend of a copolymer of styrene and an olefin compound having a polydimethylsiloxane chain with another styrenic resin that does not have a polysiloxane chain as a constituent unit; 5) A copolymer with a polystyrene unit and a polysiloxane unit. Block copolymerization, 6) Blending of a block copolymer having a polystyrene unit and a polysiloxane unit with a styrenic resin having other polysiloxane chains as constituent units, 7) Styrene monomer to the holJ siloxane chain 8) Blending of a copolymer in which a styrene monomer is grafted to a polysiloxane chain and a styrenic resin that does not have other polysiloxane chains as a constituent unit [Problem to be solved by the invention] Prior art The method of spraying silicone oil onto the mold inside the mold leaves the oil sprayed as a mold release agent on the surface of the product, and is inefficient as it requires frequent spraying of the mold release agent onto the mold. In addition to these drawbacks, it is not useful for improving sliding properties.

Polystyrene-based resins modified by blending silicone oil tend to have poor compatibility with the resin, so the silicone oil tends to separate during molding or mixing, easily bleeds out, does not mix uniformly, and has a poor appearance. Problems may occur, such as significant damage to the surface, easy formation of flakes, and deterioration of physical properties, especially a decrease in impact strength.

A copolymer of styrene and an olefin compound having a polydimethylsiloxane chain is produced by Yuhsuke Kawakami.
, R.A., N., Murthy and YuyaYamas.
lxfta Paper by K (Die Makromole
kulareChemie Volume 185, page 9 (1
It is possible to synthesize it by radical copolymerization, anionic copolymerization, etc., including the method described in 984)), but the degree of polymerization and yield are insufficient with the current method.
Furthermore, a large amount of homopolystyrene is produced as a by-product, which is difficult to remove and is difficult to produce industrially. Therefore, it is also difficult to blend this type of copolymer with other resins.

Method for synthesizing block copolymers having polystyrene segments and polysiloxane segments J, C, 5aan
, D. J., Gardon and 8. Lindsay
Paper by K (Macromolecules Vol. 3, p. 1 (19'10)), A. Marat and Y.
, a paper by Ga1lot (Die Makromol
ekulare Chemie Vol. 176, p. 1641 (1975)), J., G., Zillox, J.
J.L. Roovers and 8. Paper by Bywater (Macromolecules Vol. 8, 5'73)
D, 8. Bro
vrn, K.U., Fulcher and R.E.W.
Etton's paper (Journal of Pol
ymer Science Polymer Letter
r Edition Volume 8, page 659 (1970)
), paper by J.W. Dean (Journal
of Polymer 5science Polymer
rLetter Editor 1 on Volume 8 6 Muff Page (19'70)), Paper by D, J, fegrant IIC (Journal of PolymerSci
ence B Volume 8, Page 195 (197o)), H
, G. Kim (Macromolecule
a, Volume 5, page 594 (1972)), C, Pr1c
e, A, G.

The paper by Warson and M.T.Chov (Po.
lymar Vol. 13, p. 333 (1972)), F
, R. Jones (European Po1
y, marJournal Vol. 10, page 249 (19
74)) with bifunctional initiators such as sodium naphthalene and lithium naphthalene, as described in P. Bajaj, S., Varshney.
and a paper by A. Misra (Journal
of PolymerScience Polymer
Chemistry Bddition Volume 18 29
It can be obtained by the method of anionically polymerizing styrene using lithium biphenyl as an initiator as described on page 5 (1980), and then polymerizing hexamethylcyclotrisiloxane or octamethylcyclotetrasiloxane, but it requires a special reaction. In addition to requiring equipment, it has drawbacks such as requiring a long reaction time.In addition, it is difficult to maintain appropriate reaction conditions, making it difficult to adjust the molecular weight of each polystyrene segment and polysiloxane segment, and the molecular weight of the final product. The types of polymers that can be synthesized are limited, and it is difficult to obtain products with the desired composition, and therefore it is also difficult to blend this type of copolymer with other resins. In addition, this type of block copolymer is A, 5kou
Condensation of polystyrene modified with silanol at both ends and polysiloxane having a chlorinated functional group at both ends, as described in the paper by Macromolecules Vol. 4, page 268 (19'21). It can also be obtained by reaction, but this method not only produces different numbers of segments, but also involves adjusting the molecular weight of each polystyrene segment and polysiloxane segment.
It is difficult to adjust the molecular weight of the final product, the types of polymers that can be synthesized are limited, and it is difficult to obtain products with the desired composition.
Therefore, it is also difficult to blend this type of copolymer with other resins.

The graft copolymer of styrene onto polysiloxane chains is
This copolymer itself has the potential to be a material with good mold releasability, wear resistance, and lubricity during molding, but the conventional method for synthesizing this graft copolymer is that of P, Bajaj SD,
Paper by C.Gupta and K.Varshung (Polymer Engineering
5science, Vol. 23, p. 825 (1983)) and papers by J.A., Barry and K., uunaay (Journal of Membrance
5science Vol. 13, p. 175 (1983)), styrene can be removed from the vinyl group of polydimethylsiloxane-polymethyl and nylsiloxane block copolymer or methylvinylsiloxane-dimethylsiloxane copolymer by radical or aoq. is obtained by graft copolymerization, which is polymerized by irradiation, but this also involves a crosslinking reaction, and it is difficult to maintain appropriate reaction conditions, so it is necessary to adjust the molecular weight of each polystyrene unit and polysiloxane unit, and the molecular weight of the final product. It is difficult to adjust, it is difficult to obtain a product with the desired composition, and the resulting graft copolymer has a molecular structure in which styrene is grafted onto polysiloxane chains.
When blended with styrenic resins that do not have other polysiloxane chains as constituent units, there are disadvantages such as problems with compatibility and a decrease in impact strength. , the expected effects on abrasion resistance, impact resistance, etc. have not been achieved.

The present inventors focused on the above problems of surface properties and impact strength of polystyrene resin, and as a result of intensive research into modification of polystyrene resin, the present invention was developed.

That is, an object of the present invention is to solve the above-mentioned problems and provide a polystyrene resin with improved mold releasability, abrasion resistance, lubricity, impact resistance, etc. during molding.

[Means to solve the problem]

The method for producing a modified polystyrene resin of the present invention is characterized by reacting a polystyrene elastomer modified with maleic anhydride (hereinafter abbreviated as modified polystyrene elastomer) with a polysiloxane having a reactive group. .

In the modified polystyrene elastomer used in the method for producing a modified polystyrene resin of the present invention, the polybutadiene segment of the styrene-butadiene block copolymer (containing one or more polystyrene segments and one or more polybutadiene segments) selectively It is hydrogenated and graft-modified with maleic anhydride.

The first method for producing the impact-resistant polystyrene resin composition of the present invention is characterized by mixing the modified polystyrene resin of the present invention and polystyrene or styrene copolymer resin.

The second method for producing the composition of the present invention is characterized by reacting a modified polystyrene elastomer with a polysiloxane having a reactive group in the presence of polystyrene or a styrene copolymer resin.

The styrene-butadiene block copolymer of the present invention preferably has polystyrene segments in a range of 15 to 60% by weight, more preferably 20% by weight.
~50% by weight. When the proportion of polystyrene segments is less than 15% by weight, in the second method for producing the composition of the present invention, the reaction product of the modified polystyrene elastomer and the polysiloxane having a reactive group and the polystyrene or styrene copolymer Problems such as decreased compatibility with the resin and failure of the reaction to proceed smoothly occur, and if the weight exceeds 60%, the melting temperature increases when reacting the modified polystyrene elastomer with the polysiloxane having a reactive group. Otherwise, it may have an unfavorable effect on moldability or the final product, such as a decrease in dispersibility.

The modified polystyrene elastomer in the present invention is obtained by selectively hydrogenating the polybutadiene segment of a styrene-butadiene block copolymer and further graft-modifying it with maleic anhydride. More specifically, the proportion of unsaturated bonds remaining without being hydrogenated in the polybutadiene segment is 20% or less, preferably 10% or less, and more preferably 5 or less. If the degree of unsaturation exceeds 20%, heat resistance, heat aging resistance, and weather resistance will deteriorate, which is not preferable.

Furthermore, if 10% or more of the polystyrene segment is hydrogenated, the mechanical strength and impact resistance of the composition of the present invention tend to decrease.

The content of maleic anhydride in the modified polystyrene elastomer of the present invention is in the range of 0.02 to 20% by weight,
A preferred range is 0.1 to 10% by weight, and a particularly preferred range is 0.2 to 5% by weight. If the content of maleic anhydride units is less than 0.02% by weight, it becomes difficult to react the maleic anhydride units of the modified polystyrene elastomer with the reactive polysiloxane. In addition, if the weight exceeds 20%, unreacted acid anhydride groups will eliminate the modifying function of the polysiloxane chain, reducing the sliding properties such as the lubricity of the surface of the molded product, and improving the mold release property and wear resistance during molding. There is a risk of adverse effects on sex and lubricity.

A specific example of the styrene-butadiene block copolymer used in the production method of the present invention is disclosed in U.S. Patent No. 42196.
No. 21, No. 3251905, No. 339020'7
and Japanese Patent Publication No. 45-29669. These publications disclose block copolymers each consisting of one polystyrene segment and one polybutadiene segment, which are produced by sequential addition of monomers, increased addition of monomers, or coupling reaction.

Also, Japanese Patent Publication No. 5B-10413, Special Publication No. 53-1
No. 5958, Japanese Patent Publication No. 41-8782, Japanese Patent Application Publication No. 94584-1984, U.S. Patent Specification No. 325190
No. 5, Publication No. 3639521. These publications disclose multi-block copolymers containing tapered copolymer blocks produced by copolymerizing a mixture of butadiene and styrene by taking advantage of differences in copolymerization reaction rates.

Methods for hydrogenating styrene-butadiene block copolymers are described in US Pat. No. 3,113,986 and Japanese Patent Publication No. 59-37294. That is, the styrene-butadiene block copolymer or multi-block copolymer obtained by the above method is dissolved in an inert hydrogen diluent such as cyclohexane, and a hydrogenation reaction is carried out in the presence of a soluble hydrogenation catalyst.

Known methods for graft modification with maleic anhydride are disclosed, for example, in JP-A-61-76518 and JP-A-62-2.
It is described in Japanese Patent Application Laid-open No. 50018, Japanese Patent Application Laid-Open No. 1986-9211, etc.

For example, in the presence of a radical generator, maleic anhydride is grafted onto maleic anhydride and a block copolymer or multiblock copolymer which has been subjected to the above hydrogenation treatment by melt mixing.

The reactive polysiloxane in the present invention has an amine group-containing substituent at one or both ends, and has a weight average molecular weight of 1,000 to 100,000, preferably 5,000.
~50,000 is good. If the weight average molecular weight is less than 1,000, three-dimensionalization will occur during the reaction with the modified polystyrene elastomer, which will have unfavorable effects on moldability and final products such as increased melting temperature or decreased dispersibility. . Furthermore, if the weight average molecular weight of the reactive polysiloxane is 100,000 or more, there is a risk that the reactivity with the modified polystyrene elastomer may decrease.

The above weight average molecular weight can be measured by gel permeation chromatography. In addition, if the reactive polysiloxane has an amino group-containing substituent at one or both ends, I! Although any manufacturing method may be used, those having a skeleton of living polymerized polysiloxane are particularly preferred from the viewpoint of ease of controlling the degree of polymerization and molecular weight distribution. Such reactive polysiloxanes can be produced by living polymerizing hexamethylcyclotrisiloxane in the presence of a lithium catalyst using trimethylsilanol or both-terminated silanol dimethylsiloxane oligomers as an initiator, and then reacting it with dimethylchlorosilane. A 5i-1 (bond) is introduced at the terminal end, and one or both ends are made into an amino group by a hydrosilylation reaction.

The method for producing a modified polystyrene resin of the present invention involves reacting a modified polystyrene elastomer with a reactive polysiloxane having an amino group at the end by a solution method or a melt method. In this reaction, the addition ratio of the reactive polysiloxane to the modified polystyrene elastomer is 0.05.
It is preferably 70% by weight. If it is less than 0.05% by weight, the surface lubricity and wear resistance of the molded product made of the modified polystyrene resin will be insufficient, and if it exceeds 70% by weight, the modified polystyrene resin will become grease-like or the resin will not be used. There is a risk of producing undesirable effects such as a decrease in the compatibility of the molded product, occurrence of bleeding, and deterioration of physical properties. When producing the modified polystyrene resin of the present invention by a solution method, the above modified polystyrene elastomer and a reactive polysiloxane containing an amino substituent at one or both ends are stirred in a common solvent and the solvent is removed. Only by doing K, you can obtain the object. Examples of the solvent used in this case include diimpropyl ether, diimpropyl ether, dioxane,
Linear or cyclic ethers such as tetrahydro-7rane, aliphatic or aromatic ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, cyclohexanone, etc., esters such as ethyl acetate, isobutyl acetate, n-butyl acetate, etc. and aromatic hydrocarbons such as toluene and xylene. Even if the solvent is not exemplified here, as long as it is a common solvent for the modified polystyrene elastomer and the reactive polysiloxane having an amino group at one or both ends, as long as there is no problem in terms of safety and health. You can use anything. Further, there is no problem in using K as a mixed solvent of two or more types.

Further, although room temperature is sufficient for the reaction temperature, there is no problem in raising the temperature to a temperature at which the solvent boils.

A first method for producing the impact-resistant polystyrene resin composition of the present invention is a method in which the modified polystyrene resin of the present invention and polystyrene or styrene copolymer resin are blended by a melting method. - It is possible to blend using a melt mixer used in the field of general synthetic resins, such as an extruder, and in this case, the kneading temperature is 250°C or less, preferably 150 to 230°C.

At temperatures exceeding 250°C, the stability of the modified polystyrene resin may also be impaired. In addition, various additives such as heat stabilizers, ultraviolet absorbers, lubricants, colorants, or antistatic agents, or various fillers such as talc, glass fibers, etc. can be optionally added during formulation.

The second method for producing the composition of the present invention is a method in which the production of a modified polystyrene resin and the blending with a styrene polymer are carried out simultaneously, and the reaction is performed with a modified polystyrene elastomer having an amino group at one or both ends. A method such as mixing a polysiloxane and a polystyrene or a styrene copolymer resin, melting and reacting the mixture, or making a solution of these in a common solvent and reacting with heating, and then removing the solvent. Similar to the first method, various additives can be added at this time.

The polystyrene used in the method for producing the impact-resistant polystyrene resin composition of the present invention includes polystyrene,
High impact polystyrene can be mentioned. Also, styrene.

Examples of the copolymer resin include acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, ApIJ o nitrile-styrene-acrylic rubber copolymer, acrylonitrile-styrene-EpnM
(Ethylene-propylene-dienter polymer) copolymer, acrylonitrile-chlorinated polyethylene-styrene copolymer, methyl methacrylate-butadiene-styrene 1&, styrene/-butadiene-ethylene-styrene block copolymer, etc. I can do it. Fundamentally, there are no special restrictions as long as the polymer contains styrene as a polymerized unit, but polymers with strong polarity and reactivity, such as acid anhydride groups such as maleic anhydride groups or carboxyl groups in the polymerized unit, are fine. Those with a low content of high groups are preferred. Also 2
There is no problem in using a mixture of styrene-based polymers that exceed the amount of food.

〔Example〕

The present invention will be explained below with reference to Examples.

The physical property values in the examples were measured by the following method after molding the obtained impact-resistant polystyrene resin composition into a test piece using an injection molding machine with a cylinder temperature of 180'C to 200C.

L tensile test, ASTM D63B 2, bending test, ASTM D7903 dynamic friction coefficient,
JIS K'i'218A (Mating material SUB 304
Speed 4 am/5 Load 2 Jc17f Holding time 30 min) 4, Frictional wear amount, JIS K721
8A (Mating material 5US304 Speed 50/S load 1.
02 to 9 f Holding time 100 m1 n) Δnotched Izot impact strength, ASTM D'790 Example 1 Specific gravity 0.91 t/CC, Styrene content 28 weight Maleic anhydride content 2 weight %, Solution viscosity at 25°C 50 parts by weight of a modified polystyrene elastomer block copolymerized as styrene segment-butadiene segment-styrene segment of O00apS (20% solution of luene) was added to 50 parts by weight of a modified polystyrene elastomer of 000apS (20% solution of luene).
50 parts by weight of polydimethylsiloxane having an amino group at one end and having a weight average molecular weight of 5000 as measured by weight part Km solution L by gel permeation chromatography were added, and the mixture was stirred and reacted for 15 hours. Then, the tetrahydro 7-ran was removed under reduced pressure, and the remaining solid was freeze-pulverized and further vacuum-dried to obtain the modified polystyrene resin of the present invention.

Examples 2 to 4 Powdered high impact polystyrene resin having a melt flow index (200°C, 5.00Of) of 3.5 as measured according to ASTM-D1238, Example 1
The modified polystyrene elastomer used in Example 1 and the polydimethylsiloxane having an amino group at one end used in Example 1 were mixed in the composition ratio shown in Table 1, and then mixed in an extruder at a cylinder temperature of 200 to 220°C. An impact-resistant polystyrene resin composition was obtained by extrusion granulation. The physical properties were measured and the results are shown in Table IK.

Example 5 6 parts by weight of the modified polystyrene resin obtained in Example 1 and 94 parts by weight of the same high impact polystyrene resin used in Examples 2 to 4 were heated to a cylinder temperature of 200 to 22%.
Cross-wire extrusion granulation was performed using an extruder set to 0°C to obtain an impact-resistant polystyrene resin composition. The physical properties were measured and the results are shown in Table-1.

Examples 6 to 8 High impact polystyrene resin used in Examples 2 to 4, the same modified polystyrene elastomer as used in Examples 2 to 4, weight average molecular weight 1 O,000, containing amine groups at both ends The reactive polysiloxane of the following formula and the polydimethylsiloxane having the same terminal amino group as in Examples 2 to 2 were mixed, and then the cylinder temperature was raised to 20°C.
An impact-resistant polystyrene resin composition was obtained by kneading and extrusion using an extruder at a temperature of 0 to 220°C. Physical properties are shown in Table-1.

Comparative Example 1 Table 1 shows the physical properties of the high impact polystyrene resin used in Examples 2 to 6.

Comparative Example 2 97 parts by weight of the high-impact polystyrene resin used in Examples 2 to 6 were mixed with 3 parts by weight of a polysiloxane having a weight average molecular weight of 1 and having no reactive groups such as O and OOO, and then the cylinder temperature was raised to 200 to 220. A resin composition was obtained by cross-wire extrusion granulation using an extruder set to ℃. Its physical properties were measured and the results are shown in Table 1ll'.

Comparative Example 3 94 parts by weight of the high-impact polystyrene resin used in Examples 2 to 6, 3 parts by weight of polysiloxane having no reactive groups and having a weight average molecular weight of 10.000, and the modified polystyrene elastomer used in Example i. Mix 3 parts by weight,
Then, cross-wire extrusion granulation was performed using an extruder with a cylinder temperature of 200 to 220°C to obtain a resin composition. Its physical properties were measured and the results are shown in Table-1.

〔Effect of the invention〕

An advantage of the present invention is that it completely solves the unresolved problem of clearly controlling the structure of a modified polystyrene elastomer by reacting a reactive polysiloxane with the modified polystyrene elastomer.

By incorporating the modified styrene resin of the present invention into a conventional polystyrene resin, impact resistance is strengthened, and mold release properties, wear resistance, lubricity, and sliding properties such as surface lubricity of molded products are improved. It has become possible to modify and improve the This is because the modified styrene resin of the present invention is an excellent elastic body and also has excellent compatibility with polystyrene resins.

The modified styrene resin of the present invention can easily control the structure of the polysiloxane part in terms of structure percentage compared to the modification method using conventional technology. It is possible to optimize the ratio of the part to the polysiloxane part, etc., and it is possible to flexibly respond to the variety required by the wide range of uses of styrenic thermoplastic nidistomers.

Polystyrene resin is inexpensive, has excellent hardness, water resistance, and high-frequency electrical insulation, is not attacked by acids or alkalis, and is easy to injection mold, so its uses are very wide. Polystyrene resins can flexibly meet the diversity of requirements when modifying and improving conventional polystyrene resins.

Patent applicant Chisso Co., Ltd. Company agent Patent attorney Yatabu Sasai Katsuhiko Nonaka Procedural amendment (spontaneous) September 18, 1989 To the Commissioner of the Japan Patent Office ``101, Indication of the case 1999 Patent Application No. 10124g Part 2, Title of Invention Process for Manufacturing Modified Polystyrene Resin and Impact Resistant Polystyrene Resin Composition 3, Relationship with the Amendment Case Patent Applicant 3-6 Nakanoshima, Kita-ku, Osaka-shi, Osaka Prefecture No. 32 (530)
(20?) Chisso stock/large company representative Sadao Nogi Former agent Shinjuku 2-8-1 Shinjuku, Shinjuku-ku, Tokyo (160) Shinjuku Seven Building Room 503 (6601) Patent attorney Yatabe Sasai (Tel: 354-1285) ) 6. There is no increase in the number of claims due to the amendment 7. Column 8 of "Claims" and "Detailed Description of the Invention" of the specification subject to the amendment 8. Contents of the amendment (1) Description of the description The full text of the claims shall be amended as attached.

(2) Page 8, line 2 of the specification, [Law J, C, 5
aan j is changed to ``The law is J, C, 5aan J.

(3) Page 11, line 10, “C0” is replaced by “Co”
Changed to

(4) On page 24, line 10, add "butadiene is selectively hydrogenated" after "copolymerized".

(5) In the third line from the bottom of page 24, "the present invention" is changed to "the present invention of the following formula."

(6) Attachment between the second and third lines from the bottom of page 24 9゜ join.

(Page 26, lines 4-6, "Same as Examples 2-4...polydimethylsiloxane" is deleted.

Attached documents (full text of claims) One or more copies Claims (full text) (1) A product characterized by reacting a polystyrene elastomer modified with maleic anhydride with a polysiloxane having a reactive group. A method for producing modified polystyrene resin.

(2) In the polystyrene-based elastomer modified with maleic anhydride, the polybutadiene segments of the styrene-butadiene block copolymer (in which one or more polystyrene segments and one or more polybutadiene segments each) are selectively hydrogenated. The method for producing a modified polystyrene resin according to claim 1, wherein the modified polystyrene resin is added and graft-modified with maleic anhydride.

(3) The method for producing a modified polystyrene resin according to claim (2), wherein the polystyrene segment is a styrene-butadiene block copolymer containing 15 to 60 i1i%.

(4) The method for producing a modified polystyrene resin according to claim (1), (2) or (3), wherein the maleic anhydride unit contains 20 or less units by weight.

(5) The polysiloxane having a reactive group has an amino group at one end and has a weight average molecular weight of 1. O() O~100
．． 000 polysiloxane, the method for producing a modified polystyrene resin according to claims (1) to (4).

(6) Polysiloxane having reactive groups has amine groups at both ends and has a weight average molecular weight of 1,000 to 100.0
00 polysiloxane, the method for producing a modified polystyrene resin according to claims (1) to (4).

(7) A method for producing an impact-resistant polystyrene resin composition, which comprises mixing the modified styrenic resin according to any one of items 1 to 6 with polystyrene or a styrene copolymer resin. .

(8) A method for producing an impact-resistant polystyrene resin composition in which a polystyrene elastomer modified with maleic anhydride and a polysiloxane having a reactive group are copolymerized with polystyrene or styrene.

(9) In the polystyrene-based elastomer modified with maleic anhydride, the butadiene polymerized segment of the styrene-butadiene block copolymer (in which one or more polystyrene segments and one or more polybutadiene segments each) is selectively hydrogenated. Claim (7) or (8), which is obtained by graft-modifying with maleic anhydride
) A method for producing an impact-resistant polystyrene resin composition.

The method for producing an impact-resistant polystyrene resin composition according to claim 9, wherein the Ql polystyrene segment is a styrene-butadiene block copolymer containing 15 to 60% by weight.

A method for producing a high-impact polystyrene resin composition according to claim (8), (9) or Sec., wherein the maleic anhydride unit contains 20 or less weight units.

(1) Polysiloxane having a reactive group has an amine group at one end and has a weight average molecular weight of i, o o o~i
oo, ooo polysiloxane (manufacturability of the impact-resistant polystyrene resin composition as described in αB).

0 Polysiloxane having reactive groups has amino groups at both ends and has a weight average molecular weight of 1,000 to 100.00
Claims (7) to 17J, which is a polysiloxane of 0
The impact-resistant polystyrene resin composition described.

that's all

Claims (13)

[Claims] (1) A method for producing a modified polystyrene resin, which comprises reacting a polystyrene elastomer modified with maleic anhydride with a polysiloxane having a reactive group. (2) Polystyrene-based elastomers modified with maleic anhydride are produced by selectively hydrogenating the polybutadiene segments of a styrene-butadiene block copolymer (in which one or more polystyrene segments and one or more polybutadiene segments each). The method for producing a modified polystyrene resin according to claim 1, wherein the modified polystyrene resin is graft-modified with an acid. (3) The method for producing a modified polystyrene resin according to claim (2), wherein the polystyrene segment is a styrene-butadiene block copolymer containing 15 to 60% by weight. (4) The method for producing a modified polystyrene resin according to claim (1), (2) or (3), which contains 20% by weight or less of maleic anhydride units. (5) Polysiloxane having a reactive group has an amino group at one end and has a weight average molecular weight of 1,000 to 100,00
0 polysiloxane.
4) The method for producing a modified polystyrene resin. (6) Polysiloxane having reactive groups has amino groups at both ends and has a weight average molecular weight of 1,000 to 10,00
0 polysiloxane.
4) Method for producing the modified polystyrene resin described above. (7) A method for producing an impact-resistant polystyrene resin composition, which comprises mixing the modified styrenic resin according to any one of items 1 to 6 with polystyrene or a styrene copolymer resin. . (8) An impact-resistant polystyrene resin composition characterized by simultaneously reacting a polystyrene elastomer modified with maleic anhydride, a polysiloxane having a reactive group, and a polystyrene or styrene copolymer resin. Manufacturing method. (9) Polystyrene-based elastomers modified with maleic anhydride are produced by selectively hydrogenating the butadiene polymerized segments of a styrene-butadiene block copolymer (in which one or more polystyrene segments and one or more polybutadiene segments each). Claim (7) or (8) wherein the product is graft-modified with maleic acid.
) A method for producing an impact-resistant polystyrene resin composition. (10) The method for producing an impact-resistant polystyrene resin composition according to claim (9), wherein the polystyrene segment is a styrene-butadiene block copolymer containing 15 to 60% by weight. (11) The method for producing an impact-resistant polystyrene resin composition according to claim (7), (8), (9) or (10), which contains 20% by weight or less of maleic anhydride units. (12) Polysiloxane having a reactive group has an amino group at one end and has a weight average molecular weight of 1,000 to 100,0
Claims (7) to (11) which are polysiloxanes of No. 00
) A method for producing the impact-resistant polystyrene resin composition. (13) Polysiloxane having reactive groups has amino groups at both ends and has a weight average molecular weight of 1,000 to 10,0
Claims (7) to (12) which are polysiloxanes of No. 00
) The impact-resistant polystyrene resin composition described.