JPS59202212A - Thermoplastic resin and its production - Google Patents

Abstract

PURPOSE:To obtain the titled resin low in gloss and excellent in thermal and mechanical properties, by copolymerizing an aromatic vinyl monomer with a vinyl cyanide monomer in the presence of a specified monomer and a polybutadiene elastomer latex. CONSTITUTION:A closed vessel is charged with a polymerizable vinyl group- containing monomer having a solubility parameter of 8.0-8.9 (Cal/cm<31/2> and being liquid at 20-60 deg.C (e.g., alpha-methylstyrene) and a latex of an elastomer containing 50wt% or above polybutadiene, and the mixture is aged at 30-70 deg.C for 30min or above in an inert gas atmosphere to cause morphological changes among elastomer latex particles. An aromatic vinyl monomer, a vinyl cyanide monomer and, optionally, a monomer copolymerizable therewith are added to the above produced latex, and the graft copolymerization is effected to obtain a thermoplastic resin having a weight fraction of the elastomer component of 0.05-0.5.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a thermal 111' plastic resin which has much lower gloss and better thermal and mechanical properties than FLT, BBS-based resins, and a method for producing the same. , and nuclear heat iJT
t. The present invention relates to a method for producing an essential component of a singing resin.

ABS resins are used in a variety of applications because of their excellent moldability, impact resistance, rigidity, and good surface gloss. However, depending on the application, not all of these physical properties are necessarily required; for example, when used for the interior and exterior of automobiles, it is necessary to reduce the gloss of the surface of the molded product without reducing other physical properties. It is desirable to have an ABS resin that has been modified to have a matte state.

Conventionally, as a method of modifying ABS resin to make it matte, a method of adding organic fillers to ABS resin (Japanese Patent Publication No. 48
No. 383) is known, but it has a low matting effect and has the drawback of reducing the impact resistance and moldability of ABS resin.

On the other hand, there is a method in which an elastomer component is added after polymerizing the BS resin (Japanese Patent Publication No. 44-25897).

JP-A No. 54-142259), this method provides a matte effect without reducing the moldability of the ABS resin, but it also reduces the heat resistance and rigidity and causes damage to the area around the gate of the injection molded product. There is a drawback that silpal-like marks occur due to poor dispersion of the elastomer component, resulting in poor appearance.

Inventor-'! In view of such conventional technology, J
It is an object of the present invention to provide other resins that have good heat resistance, impact resistance, moldability, and rigidity equivalent to #irJ resins, and have a matte surface and good appearance. As a result of intensive research aimed at
Grafting the body with vinyl cyanide monomer, etc.! (When polymerizing, 117 Tokden's polymerizable monomer that swells polybutadiene well is charged together with the elastomer latex, aged, and then subjected to a copolymerization reaction. The present invention was completed based on the finding that the thermal ij]/1v resin contained as a component not only impedes on the above-mentioned thermal and mechanical properties, but also has a good matte surface. be.

That is, the present invention has a solubility parameter of 80 to 8,9 (
cal/cn? ') ', temperature 20~
At 60C, 11Φ or two or more of the monomers having a polymerizable vinyl group in the form of LF are mixed together with an elastomer latex containing polybutadiene as the main component, and then cyanated with the aromatic vinyl monomer. A method for producing a graft copolymer characterized by copolymerizing a vinyl monomer or an aromatic vinyl monomer with a vinyl cyanide monomer and a monomer copolymerizable therewith, and the solubility parameter is s, o-'s, 9 (caVyi3)
One or more monomers having vinyl groups that are liquid and polymerizable at a temperature of 20 to 60°C are added together with an elastomer latex containing polybutadiene as a main component at the initial stage of polymerization, and aging is then carried out. to cause a morphological change between the elastomer latex particles, and furthermore, the aromatic vinyl monomer and cyanide vinyl monomer,
Alternatively, an aromatic vinyl monomer, a sia/1-hibinyl monomer, and a monomer copolymerizable with these monomers are added, and these monomers are graft copolymerized to an elastomer with the same morphology change. a copolymer of an aromatic vinyl monomer and a vinyl cyanide monomer, or an aromatic vinyl monomer and a vinyl cyanide monomer, and the amount of fljl that can be co-merged with these A thermoplastic resin, which is a composition consisting of a body copolymer B, characterized in that the weight fraction of the elastomer component in the composition is 0.05 to 0.05;
Furthermore, the graft copolymer, and the copolymer B,
A method for producing a thermoplastic resin characterized by blending the elastomer component in a weight fraction of 0.05 to 0.05 with respect to the total amount of graft copolymer A and copolymer B. be.

The present invention will be explained in detail below.

In the graft copolymer A produced by the method of the present invention, a monomer containing a polymerizable vinyl group that makes polybutadiene swell well is charged together with an elastomer latex whose main component is polybutadiene in a closed container such as an autoflenib. After sufficiently purging with nitrogen gas while stirring and aging for a predetermined period of time to cause a morphological change between particles of the elastomer latex, the aromatic vinyl '4FM' form and the anionized vinyl monomer are added as needed. 1.6 Copolymerization with these monomers Each monomer to which an ET capable monomer is added is copolymerized with the elastomer that has undergone the above-mentioned morphology change.

When the graft copolymer A is used as a dispersed phase of a thermoplastic resin composition, a stable composition having excellent compatibility with various resins used as continuous phases can be obtained.

Examples of elastomers containing polybutadiene as a main component include polybutadiene, styrene-butadiene copolymer, butadiene/-axlonitrile co-M (combination), styrene-butadiene-methyl methacrylate copolymer, butadiene-methyl methacrylate copolymer, butadiene- Examples include acrylic ester copolymers.Here, an elastomer containing polybutadiene as a main component is one in which polybutadiene is contained in the elastomer in an amount of 50% by weight or more, preferably 8% by weight.
It means that the content is 0 weight or more. In this case, an elastomer with a polybutadiene content of 50% by weight or more may be used as is, or an elastomer latex with a polybutadiene content of less than 50% by weight may be blended with an elastomer latex containing 50% by weight or more of polybutadiene.

A monomer (hereinafter referred to as "monomer") having a small, θ vinyl group has a solubility parameter of 80 to 89 (c a J
, ")/2, and a liquid intermediate is used at a temperature of 20 to 60°C, and it is preferable to use one with a small difference in solubility parameter from the elastomer whose main component is polybutadiene.
~8.9 (c:alz6 units) If it is outside the range of (a), the compatibility with polybutane, which is the main component of the elastomer latex, will be poor and the aging will be extremely long.j1. j, - time is required, or the polybutadiene does not swell even after aging, making it unsuitable for practical use. Here, the solubility paramelter may be determined by calculation or actual measurement, but it is more conveniently determined by "Pol
ymer Handbook” 2nd, Ecl,
, Jolln Wiley & 5ons, N
ew York (1975) may be used.

Specifically, monomer C is α-methylstyrene.

Methyl methacrylate, inbutyl acrylate.

Ethyl methacrylate, butyl methacrylate.

One or more intermediates selected from 11-butyl acrylate, ethyl acrylate, etc. are used.

The monomer C is charged together with an elastomer latex containing polybutadiene as a main component and aged to cause a change in morphology between the elastomer latex particles. Although it varies depending on the solubility parameter value, usually 30 minutes at 30°C to 70°C is sufficient, and preferably 45 to 120 minutes at 50°C. -8, (.8.
In the case of boiled α-methylstyrene, 60 minutes at 50°C is more preferable.

If the aging time is short or the aging temperature is low, sufficient morphological changes cannot be caused in the elastomer phase, and the resulting graft copolymer A is blended with the copolymer forming the continuous phase to form ABS. □If the aging temperature exceeds 70°C, thermal deterioration will occur in the elastomer phase, and if a kBs-based resin composition is used, the impact resistance will be low. It's not practical.

Furthermore, after aging, an aromatic vinyl monomer and a vinyl cyanide monomer, or an aromatic vinyl monomer and a vinyl cyanide monomer, and a monomer copolymerizable with these are added continuously or sequentially. Graft copolymerization is carried out in a conventional manner.

The aromatic vinyl monomer (hereinafter referred to as monomer) is one or more of intermediate C and a monomer capable of radical copolymerization with vinyl cyanide monomer. Specific examples thereof include styrene, α-methylstyrene, ρ-methylstyrene, 1:゛-ternarybutylsterene, chlorinated styrene, dimethylstyrene, and the like.

As the cyanide-1-hibinyl monomer (hereinafter referred to as monomer E), one or more monomers having radical copolymerization ability with monomer C and/or monomer R are used. Specific examples thereof include ac-90 nitrile, methacrylonitrile, chloroacrylonitrile, and the like.

The usage ratio of each monomer of monomers C, D, and E is monomer 010
~80% by weight, monomer D15-85% by weight, monomer 85
~75% by weight, preferably monomer 025-45%, monomer D25-45%, monomer E20-40
In the range of 10% by weight, 10 monomers, 10 monomers, and 10 monomers E.
It is desirable to have a composition that provides zero vehicle weight.

In addition, the monomer C may be the same as the monomer R,
The monomer C may have two compositions, and may be a mixture of the above monomers. In this case, the solubility parameter δΣ of monomer C is calculated as follows.

Let n be the number of components in monomer C, and let the solubility parameter of each component be δ1. δ2...δ. , the weight fraction is W,
, W2. ...If it is a breast, δΣ=Σδkwk 1 (=1 In addition, in the graft copolymerization reaction, in addition to the above monomer E, monomer C7 monomer or @i-mer E can be copolymerized. One or more monomers selected from monomers (hereinafter referred to as monomer F) can be used.The graft co-market obtained using monomer F is used as a dispersed phase, In a thermoplastic resin composition obtained using a styrene-acrylonitrile copolymer resin (As resin) as a continuous phase, the amount of monomer F to be added and the total amount of monomer E (weight group "
) is preferably less.

Specific examples of monomer D' include one or a mixture of two or more selected from maleimide, N-argyl or aryl substituted maleimide, maleic anhydride, methacrylic ester, acrylic ester, etc. Among these, N-phenylmaleimide and/or methyl methacrylate are particularly preferred in terms of heat resistance.

Each monomer mentioned above C+D+E or C+D+E +
Graft copolymer A obtained from an elastomer containing F and polybutadiene as main components exhibits excellent thermal and mechanical properties and a matte surface when used alone or in the form of a composition with other copolymers. It can be used as a thermoplastic resin.

When graft copolymer A is used alone as a thermoplastic resin, the elastomer component of the elastomer latex mainly composed of polybutadiene that has been aged to cause a morphological change between particles forms a dispersed phase in the resin, It exhibits a form in which monomers C+D+E or C+D+E+F acid component form a continuous phase. The content of the elastomer in the thermoplastic resin is preferably in the range of 5 to 60% by weight, and if it is less than 5% by weight, the gloss of the resin will increase and the impact strength will decrease significantly. Moreover, if it exceeds 60%, the moldability will be extremely poor and it will not be suitable for practical use.

On the other hand, when graft copolymer A is blended with another copolymer B and used in the form of a thermoplastic resin composition, the graft copolymer A forms a dispersed phase and the copolymer B forms a continuous phase. .

The composition of each monomer and elastomer in graft copolymer A is such that the graft chains and grafting efficiency ((rerafted monomer (polymerized monomer) It can be set arbitrarily within a range that maintains compatibility with other resins to be formed, but specifically, each monomer, etc. is added to 100 parts by weight (in terms of dry weight) of an elastomer whose main component is borifutadiene. The total weight of
It is preferably within the range of 150 parts by weight. In the thermoplastic resin composition, for the graft copolymer A forming the dispersed phase, any copolymer B forming the continuous phase can be used as long as it is compatible with the graft copolymer A. However, specific examples include styrene-acrylonitrile copolymer, sterene-methacrylonitrile copolymer, styrene-acrylonitrile-methacrylic acid ester copolymer, styrene-α-methylstyrene-
Acrylonitrile copolymer 2, styrene-α-methersterene-methacrylonyl 11 copolymer, styrene-α-
Methylstyrene-acrylonitrile-methacrylic acid ester copolymer.

α-methylstyrene-acrylonitrile copolymer.

α-methylsterene-methacrylonitrile copolymer, α
-Methylstyrene-acrylonitrile-methacrylic acid ester copolymer, styrene-1]-methylstyrene-acrylonitrile copolymer, styrene-p-methylstyrene-methacrylic acid ester copolymer1. - Methylstyrene-acrylonitrile copolymer, p-methylstyrene-methacrylonitrile copolymer, chlorostyrene-acrylonitrile copolymer, styrene-acrylonitrile-methacrylic acid ester-maninic anhydride copolymer.

Styrene-acrylonitrile maleic anhydride copolymer,
Styrene-methacrylonitrile-maleic anhydride copolymer, α-methylstyrene-acrylonitrile-maleic anhydride copolymer, styrene-acrylonitrile-maleimide copolymer, sterene-methacrylonitrile-maleimide copolymer, Stesyn-Ac90 nitrile N-alkyl or arylmaleimide, sterene-methacrylonitrile-N-alkyl or arylmaleimide copolymer.

α-methylstyrene-acrylonitrile-maleimide copolymer, α-methylsterene-methacrylonitrile-maleimide copolymer, α-methylstyrene-acrylonitrile-N-argyl or arylmaleimide copolymer,
α-methylsterennotacrylonitrile-N-alkyl or arylmaleimide copolymer estyrene-α-methylstyrene-acrylonitrile-maleimide-methacrylate/l/Acid: r-nutyl copolymer, styrene-α-methylnutylene-methacrylate Ronitrile-maleimide-methacrylic acid ester copolymer, styrene-α-methylstyrene-acrylonitrile-N-7/lz-kyl or acylmaleimide-methacrylic acid ester copolymer, styrene-α-methylstyrene-methacrylonitrile-N
- Styrene derivatives and acrylonitrile derivatives represented by alkyl or aryl maleimide-methacrylic acid ester copolymers.

A copolymer containing at least a styrene derivative and an acrylonitrile derivative in its composition, using monomers selected from methacrylic acid esters and maleimide derivatives, or a blend of two or more thereof. is preferred. Further, as the continuous phase resin, other resins such as polycarbonate shields can be blended with the above-mentioned copolymers and the like. ABS with sufficient mechanical and thermal properties, no defects in molded appearance, and excellent gloss and low gloss.
In order to obtain the thermoplastic resin of the system, heat 1 obtained by blending the resin of the continuous phase and the graft copolymer A is used.
- It is necessary to keep the weight fraction of the elastomer component in the Tffi resin composition in the range of 0.05 to 0.5.
If it is less than 5, the gloss of the resin will increase and the impact strength will decrease significantly.

Next, the morphological change that occurs between the elastomer latex particles of the graft copolymer A in the present invention will be explained based on the morphological change of the elastomer phase in the thermoplastic resin. Figure 1 shows the elastomers of a conventional ABS resin with high gloss, and Figure 2 shows the elastomers of an ABS resin with extremely low gloss using uninvented graft copolymer A as a dispersed phase (corresponding to Example 2 described below). A transmission electron micrograph taken after staining the phase with osmic acid is shown.

The morphology of the elastomer phase of conventional high-gloss ABS resins is shown in Figure 1, where island-shaped elastomer particles containing small particle sizes are uniformly distributed in the continuous phase, which is observed as white without being dyed in the drawing. Dispersed (in the drawing, it is stained and observed as black). On the other hand, A with extremely low gloss
In BSS resin, as shown in Figure 2, some elastomer particles are pseudopod-like and fused and aggregated, and some are H-like and aggregate. Some elastomer bills deform and become ameba-like,
It has a melted, grainy appearance. These two people
As is clear from the J ratio, the morphological change in the present invention means that the morphology of the elastomer particles of the ABS resin, which originally has high gloss (Fig. 1), undergoes a change as shown in Fig. 2 above.

What is characteristic is that the uniform dispersion of small-sized particles seen in Figure 1 is no longer seen in Figure 2, where the morphology has changed, due to fusion and fibrillation, and that the uniform dispersion seen in Figure The spherical elastomer particles shown in FIG. 2 are deformed and take on various shapes. These morphological changes are more clearly observed in small particles with a particle size of 200 m/1 or less (Figures 1 and 2 are typical examples), but in the case of so-called medium particles with a particle size exceeding 200 m/1. Diameter, 5007
Similar morphological changes are also observed in so-called large particle sizes exceeding 71μ.

Desired thermoplastic resins or compositions of the thermoplastic resin of the present invention can be obtained by arbitrarily combining monomers and copolymers of the above-mentioned groups. Among them, ABS resin, super heat-resistant ABS resin is preferred.

As explained above, in the present invention, a monomer that can sufficiently swell the elastomer is charged into the elastomer latex together with the elastomer latex, the elastomer is appropriately aggregated and fused by aging, and then the monomer is continuously added. , or by sequentially adding the monomers charged in the handle part, graft copolymerization is carried out and completed, which is an extremely simple operation, and when used as a dispersed phase, the gloss can be significantly lowered. It is possible to obtain a graft copolymer resin or composition that exhibits a different morphology.

The obtained thermoplastic resin has excellent mechanical strength, heat resistance, and moldability, and has a matte appearance with low surface gloss.
Moreover, it has a good appearance without producing silver-like marks during molding.

Therefore, taking advantage of its properties, the thermoplastic resin of the present invention can be used alone or with the addition of weather and/or light resistance agents for the interior and exterior of automobiles, the exterior of motorcycles, the interior of aircraft or ships, daily necessities, etc. However, its industrial value is a dog.

Next, the present invention will be further comprehensively explained with reference to Examples and Comparative Examples.

Implementation [9th 1-18) Support comparative examples 1-5...Example 1-
The preparation composition for graft polymerization of the graft co-vehicle body A used in No. 18 is shown in Table 1, the aging time is 1 hour (1,1), and the internal temperature (TI) of the polymer chains at that time.

Time at which monomers should be added continuously or sequentially (t2)
.

and the isothermal temperature (T2) of the polymer chain in 1)-1, the time from the end of continuous or sequential addition of monomers to the end of polymerization (t,), and the isothermal temperature of the polymer chain at that time (T2), T3) is shown in Table 2.

Elastomer latex containing polybutadiene as a main component listed in Table 1 (particle size: OO~500mlt).

Distilled water, potassium rosinate, and monomer C are charged into a sootclave with the composition shown in Table 1, and the mixture is sufficiently purged with nitrogen while stirring, and stirred for a predetermined time (tl) at the predetermined aging temperature (T1) listed in Table 2. . After that, the internal temperature was set to T2 shown in Table 2,
When the internal temperature reaches T2, add sodium formaldehyde sulfoxylate and tetrasodium ethylenediaminetetraacetate (EDTA・4Na).

Ferrous sulfate was added in the amount shown in Table 1, and a mixed solution of monomer, E or monomer, E and F1 diisobutylene hydroperoxide, and n-dodecyl mercaptan was prepared as shown in Table 1. were added continuously or sequentially over the time (t2) listed in Table 2 while maintaining the internal temperature at the temperature (T2) listed in Table 2. After the addition is complete, the internal temperature is set to the temperature (T3) listed in Table 2, and the polymerization is completed at that temperature for the time (t3) listed in Table 2 to form the copolymer a-o.
I got it.

After completion of polymerization, salt out the latex with magnesium chloride,
The obtained graft copolymer was isolated by filtration and drying. Table 3 shows the conversion rate of the monomers used in the copolymerization, the composition of the obtained graft copolymer A, and the graft efficiency.

Preparation of graft copolymers used in Comparative Examples 1, 2, and 5) Graft copolymers 11 and 11 were prepared by changing the conditions in the same manner as in the production of graft copolymers used in Examples 1 to 18.
<Combined P to Q and S were obtained. graft copolymer p,
Table 4 shows the graft composition of Q and S at the Japan Automobile Agency. The polymerization operation was carried out under the conditions shown in Table 5 in the same manner as described in Example 1raJ. After the vehicle chassis was completed, the graft copolymer was prepared in the same manner as described in Example (here). The composition of the graft-effect dog is shown in -A6.

...The thermoplastic resin composition graft copolymers a to Q and S are 12 parts of 2.6 parts per 100 parts of the elastomer component in the graft copolymer.
Di-t-butyl 4-methylphenol was added to IILI, and resins forming a continuous phase were blended with the resin compositions shown in Examples 1 to 18 and Comparative Examples 1 to 3 and 5 in Table 7 using a Henschel mixer. The mixture was melt mixed using an extruder to obtain a pelletized thermoplastic resin composition. The removed continuous phase-forming resins were all resins with average molecular chain lengths in the range of 2,000 to 3,300 as determined by gel permeation chromatography.

The thus obtained thermoplastic resin composition was molded into a test piece according to JIS method by injection molding, and its mechanical properties and thermal properties were measured according to JIS method. Further, the determination of silver-like marks was based on visual observation.

The results are shown in Table 8.

Comparative Example 4 Polybutadiene latex (particle size 300 mp, solid content 4
30 parts (in terms of dry weight), 150 parts by volume of distilled water, and 06 parts by weight of potassium rosinate are placed in an autoclave, and the autoclave is sufficiently purged with nitrogen while stirring and the temperature is raised. Internal temperature 50℃
At the time, 05 parts by weight of sodium formaldehyde sulfoxylate, 2 parts by weight of EDTA-4NaO, 0.02 parts by weight of ferrous sulfate, 20 parts by weight of acrylonitrile and 50 parts by weight of Stereph were added with diisobutylene hydroper. Oxide 0. 1. Add 0.5 parts of Isjly and 0.5 parts of n-dodecyl mercaptan and 11 parts of n-dodecyl mercaptan and maintain the internal temperature at 50°C. ! The 14-merion was completed to obtain a graft copolymer.

100 copies of the craft (converted to dry car volume) have an average diameter of 2
15 parts of 50 mp styrene-butadiene copolymer latex was added in terms of dry car weight, and after stirring, the latex was salted out with magnesium chloride, filtered, and 1:! 13"
i, I fat solids were obtained. This is referred to as a graft copolymer R. 50 parts of styrene-acrylonitrile (weight average molecular chain length analyzed by gel permeation talomadography method: 2600 A) was blended with 50 parts of this resin solid content, and the mixture was melt-kneaded using an extruder to obtain a pellet-like resin composition. Ta. Don't do it like this! The resin composition is made by injection molding.
A test piece conforming to the IS method was molded and evaluated according to the JIS method.

In addition, the determination of silver-like barbs was based on visual inspection. Table 8 shows the results.
Shown below.

The JIS method for each measurement is shown in (2) and (2).

1) Tensile strength: JISK 687] 2) Izot (Φi impact strength', JISK-68713) Heat deformation temperature: JIS K-72074) Gloss JIS;
8741 (angle 60°) and below.2.As shown in Examples 1 to 18, if the solubility parameter of the monomer having a polymerizable vinyl group is within the range of 80 to 8.9 (cal/ni'), (Low gloss, good mechanical properties,
A thermoplastic resin having heat resistance and a molded outer envelope 1 can be obtained, but if it deviates from the cylinder 111], for example, as shown in Comparative Example 1.2, the gloss value and H1 mechanical properties decrease 2, etc., making it difficult to put into practical use. Don't be violent.

The elastomer content as a matte ABS resin (with respect to Examples 1 to 18, if the weight fraction is within the range of 005 to 05, the elastomer content is extremely low and the elastomer content is extremely low in terms of other physical properties. While achieving good thermoplasticity + i'iJ resin, if it deviates from this range, as seen for example in Comparative Example 3, an increase in gloss value or a decrease in mechanical properties will occur, making it impractical. .

The matte ABS resins (Examples 1 to 18) obtained by the method of the present invention were
It clearly has significantly lower gloss than the S resin, and is particularly superior in mechanical properties and molded envelope compared to the conventional matting method (Comparative Example 4).

Examples 19.20 and Comparative Example 6 - Thermoplastic resin graft copolymers m and n consisting only of kraft copolymer A 1. 12 parts of 2,6-di-t-butylmethylphenol was added to 100 parts of the elastomer component, and pelletized using an extruder. was measured. The results are shown in Table 9.O Table 9 Kraft copolymer n with a high elanodomer content was unique to flow and support [poor quality, less pellet discharge layer than extruder, burnt resin, pellets worth evaluating physical properties] was not obtained.

As shown in Example 19.20, even if the kraft copolymer A alone has an elastomer content of ia LIJ, it becomes matte.

[Brief explanation of drawings]

FIG. 1 shows an electron micrograph of a conventional ABS resin, and FIG. 2 shows an electron micrograph of the ABS resin of the present invention. In both cases, the magnification is 15,000 times. Applicant: Denki Kagaku Kogyo Co., Ltd. Agent Yutaka 1
) Yoshio

Claims (1)

[Claims] 1) Solubility: rammeter of 8° to 8. (・aycm
”) One or two monomers which are in the range of (a) and which form a polymerizable vinyl group in a liquid state at a temperature of 20 to 60°C,
The upper layer is mixed with an elastomer latex containing polybutadiene as the main component and aged. A method for producing a graft co-!1'! combination characterized by copolymerizing copolymerizable monomers. 2) Solubility Wr degree parameter is 8" to 89 (Cal/C
iz") in the range of A, 11'1□14 degrees 20-60
One or more monomers that are liquid at °C and have a polymerizable vinyl group are charged together with an elastomer latex containing polybutadiene as a main component at the initial stage of polymerization, and then aged to cause a morphological change between the elastomer latex particles. and further add an aromatic vinyl monomer and a vinyl cyanide monomer, or an aromatic vinyl monomer and a vinyl cyanide monomer, and a monomer copolymerizable with these to cause a morphological change. A graft copolymer A obtained by graft copolymerizing these monomers to a elastomer obtained by grafting, a copolymer of an aromatic vinyl monomer and a vinyl cyanide monomer, or an aromatic vinyl intermediater. A composition consisting of a copolymer B of a cyan[hibinyl intermediate and a monomer copolymerizable with these, characterized in that the weight fraction of the elastomer component in the composition is 005 to 05. thermoplastic resin. 3. Solubility 7. 1# or 2 or more monomers that are in the range of 1.J -9-,5"&.~89(.Tsu□), are liquid at a temperature of 20 to 60°C, and have a polymerizable vinyl group. is added together with an elastomer latex mainly composed of polybutadiene at the initial stage of polymerization, and aged to cause a change in morphology between the elastomer latex particles. (Aromatic vinyl intermediates, vinyl cyanide monomers, and monomers that can be co-combined with these monomers are added to the elastomer to cause a morphological change.)
A copolymer of an aromatic vinyl monomer and a sia/(hyhinyl) monomer, or a copolymer of an aromatic vinyl monomer and a cyanide copolymer obtained by graft copolymerization of the Copolymer B of vinyl monomers and intermediates copolymerizable with these is prepared such that the weight fraction of the elastomer component is 0.05 to 0.05 with respect to the total amount of graft copolymer A and copolymer B. 1. A method for producing a thermoplastic resin, which comprises blending the thermoplastic resin in such a manner as to achieve the following.