JPS61136510A - Production of impact-resistant resin - Google Patents

Abstract

PURPOSE:To obtain the titled resin which can give a molding excellent in weather resistance, surface gloss, hardness, etc., by adding acrylonitrile, etc., to a specified polyorganosiloxane to allow the former to permeate and diffuse into the latter and subjecting the mixture to graft polymerization so that the produced resin may satisfy the given requirement. CONSTITUTION:Polyorganosiloxane (A) is obtained by adding 0.001-10pts.wt. organosiloxane graft crosslinking agent having a unit of formula I (wherein R<2> is H or CH3, R<1> is R<2>, C2H5 or phenyl, n is 0-2 and p is 1-6) to 100pts.wt. organosiloxane such as hexamethyltricyclosiloxane and polymerizing the mixture. 30-99wt% vinyl monomer (B) comprising 20-35wt% acrylonitrile and 80-65wt% styrene is added to component A and allowed to penetrate and diffuse fully thereinto. After a radical polymerization initiator is added, the mixture is subjected to graft polymerization so that the obtained resin may satisfy the requirement of formula II [wherein IZ is a value as determined according to ASTM-D-256-56 (at 23 deg.C with a 1/4 in. notch) and MF is a value as determined according to ASTM-D-1238 (5kg load, 200 deg.C)].

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a polymer-grated polyorganone loxane-based graft copolymer having high impact absorption ability.

In general, impact-resistant resins are formed from a rubber layer and a matrix layer, and the rubber layer has a glass transition temperature (
It is said that using a resin with a low Tg (hereinafter abbreviated as Tg) is advantageous in absorbing impact energy. This means that compared to an impact-resistant resin using polybutyl acrylate resin with a Tg of -55°C, T and H are -80°C.
It is clear from the fact that the resin using polybutadiene resin as rubber, that is, ABS resin, has better impact resistance even though the rubber content is the same. Accordingly, if polydimethylsiloxane whose temperature is -123°C can be used as a rubber source for impact-resistant resin, AB
It is thought that a resin that is more immersed than S resin can be produced.

However, polyorganonoloxane generally has poor reactivity with vinyl monomers, making it difficult to form chemical bonds. Several methods have been disclosed for forming bonds between these image components, but these methods have not always been satisfactory. For example, U.S. Pat. No. 5,898,300 discloses that an emulsion of polydimethylsiloxane/polymer containing vinyl A70 xane or allylsiloxane,
It has been reported that impact strength is improved by polymerizing vinyl monomers to form graft polymers.

A method is described that uses siloxanes to further improve impact strength. In other words, the impact strength is increased (changed) due to the mercapto group content in the boridimethylnoroxane-mercabutoglobylsiloxane copolymer, and the presence of the graft polymer via the mercapto group improves the impact properties. Show (・ru.

However, these methods do not describe the fluidity, surface hardness, and surface gloss of the polymer, which determine its effectiveness as a molding material, and its suitability as a molding material is unclear.

The present inventors investigated this dynamic impact-resistant resin, and found that an impact-resistant resin using a polymer graft polyorganone loxane-based draft copolymer obtained by using a special graft polymerization method: It has been found that fluidity is improved without reducing impact resistance and surface hardness. It has also been found that this effect becomes even more pronounced when Acryloki/Organosiloxane or Methacryloxy/Organo/Loxa/ is used as a grafting agent for polyorganonoloxane.

In the present invention, acrylonitrile and styrene are added to a polyorganonoloxane obtained by adding a graft cross-agent to organosiloxane and polymerized, and the graft polymerization is then carried out by adding a radical polymerization initiator. Formula condition IZ X (MF)'/'≧20 (IZ: 1/4 based on ASTM-D-256-56
Inch notch 23℃, MF: ASTM-D-12
This is a method for producing a graft copolymer, characterized in that the method is carried out so as to satisfy the following values (at 200° C. and a load of 51\9, based on No. 38).

The present invention further provides that the graft copolymer obtained in this way is subjected to the following conditions for the interlayer mixture: tz X (MF
)'/2220 (Iz: Based on ASTM-D-256-56 (1/
23℃ with 4 inch notch, MF: ASTM-D-1
This is a method for producing an impact-resistant resin, which is characterized by mixing an acrylonitrile-styrene copolymer as a matrix so as to satisfy the value at 200° C. and 5 kg load based on 238.

The flowability of impact-resistant resins is determined to a large extent by the matrix resin for a given rubber content;
Improving fluidity reduces impact resistance. This relationship is observed regardless of the rubber content.

When performing graft polymerization of acrylonitrile-styrene copolymerization onto polydimethylsiloxane, 7.1) Diffusion of lonitrile and styrene monomers into polydimethylnoroxane is slow, so if ordinary emulsion polymerization or dropwise polymerization is performed, The grafting rate decreases and the graft chain length increases. For this reason, the fluidity of the polymer after completion of polymerization is inhibited, and only a product with poor moldability can be obtained. On the other hand, according to the method of the present invention, the acrylonitrile/styrene mixed monomer is diffused into polydimethylsiloxane, and after sufficient diffusion, a radical polymerization initiator is added to perform graft polymerization, so that the grafting rate is improved. In addition, the length of the graft chain can be shortened.

The grafting cross-agent is particularly suitable for the general formula (where R' is a hydrogen atom, a methyl group, an ethyl group, a propyl group, or a phenyl group, R2 is a hydrogen atom or a methyl group, n is 0, 1 or 2, and p is 1-- Acryloxy or methacryloxyorganosiloxane having a unit represented by the general formula %) (in which R1 and n have the abovementioned meanings) or a vinylorganosiloxane having a unit represented by the general formula It is preferable to use a mercaptoorganosiloxane having units of the formula % (in which R', n and p have the meanings given above). When acryloxy or methacryloxyorganosiloxane is used, the grafting ratio of the graft polymer increases, making it easier to balance impact resistance and fluidity.

When producing the polymer of the present invention, first, organo7
97ft of polyorganon was produced by adding a grafting agent to xane and condensing it. As organozoloxa/, pe/tacyclosiloxane, dodecamethylhexacyclosiloxane, trimethyltriphenyltricyclosiloxane, etc. are used.

The amount of graft cross-agent added is organosiloxane 100
0.001 to 10 parts by weight, preferably 0
．． It is 1 to 10 parts by weight. Addition amount of graft cross-agent is 0
．． If the amount is less than 0.001 parts by weight, the grafting ratio will be too small to achieve the desired grafting effect. Addition amount is 10
If the amount is more than 1 part by weight, the condensation with the organosiloxane will be insufficient and a uniform polymer will not be obtained.

Polyorganosiloxane is disclosed in U.S. Patent No. 2,891,920.
No. 6294725, etc. (・
It is preferable to produce by a method in which the organosiloxane and the graft cross-agent are shear-mixed using, for example, a homogenizer in the presence of an emulsifier such as an alkylbenzenesulfonic acid. Alkylbenzenesulfonic acid is suitable because it acts as an emulsifier for polyorganosiloxane and also serves as a polymerization initiator.

In the emulsion polymerization of organosiloxane, the polyorganosiloxane 7 may contain a trifunctional or 4'g functional silicon atom. These polyfunctional silicon atoms act as so-called crosslinking agents, and crosslinked polyorganosiloxanes using them are effective when used as a rubber source for impact-resistant resins. Specific examples include trifunctional crosslinking agents such as methyltrimethoxysilane, phenyltrimethoxysilane, and ethyltriethoxysilane, and tetrafunctional crosslinking agents such as tetraethoxysilane. Using 0.1 to 10 parts by weight of these to 100 parts by weight of the polyorganosiloxane polymer described above, an emulsion is prepared. When the unit weight is saturated at 25° C. in a toluene solvent, the weight ratio of toluene absorbed by the polyorganosiloxane is adjusted to 5.0 to 15.0.

The degree of swelling is measured as follows. The prepared polyorganosiloxane latex is added to about 6 to 5 times the amount of inpropyl alcohol with stirring, and the emulsion is broken and coagulated to obtain a siloxane polymer.

After washing the polymer thus obtained with water, it was heated to 80°C for 1
Dry under reduced pressure for 0 hours. After drying, approximately 11 polymers were accurately weighed and weighed approximately 301°! immersed in toluene and heated at 25°C for 10
The polymer was left to stand for 0 hours, and the polymer was swollen with toluene. Next, the remaining toluene is separated and removed by decantation, weighed accurately, and then dried under reduced pressure at 80° C. for 16 hours, the absorbed toluene is removed by evaporation, and weighed accurately again. The swelling degree is calculated by the following formula.

The polyorganosiloxane then contains 65-80% by weight of styrene and 35-20% by weight of acrylonitrile.
Graft polymerize the r vinyl monomer. The ratio of the vinyl monomer to the polyorganosiloxane is 1 to 70% by weight, preferably 10 to 60% by weight, based on the total amount of the polyorganosiloxane.

In the graft polymerization reaction (Row 5), first, a vinyl heptanomer is added to the polyorganosiloxane latex, and the vinyl heptanomer is diffused in the polyorganone fuxane particles. This operation must be carried out in the absence of a radical polymerization initiator. In order to diffuse the vinyl monomer, it is preferable to heat and stir. Stirring can keep the vinyl monomer in the form of small oil droplets, increasing the surface area and facilitating diffusion into the polyorganosiloxane. The time required for diffusion may be short at high temperatures, for example, 10 to 300 minutes when heated to 75°C. However, heating above 90° C. is not preferable because water evaporates.

The permeation and diffusion of heavy vinyl monomer in polyorganone cuxane was confirmed by adding polyorganosoloxa/ to a mixed vinyl monomer consisting of 25% by weight of acrylonitrile and 75% by weight of styrene, and measuring the change in swelling degree over time. You can check it from the trap. That is, the polyorganosoroxane latex that had completed polymerization was reprecipitated by adding it to methanol, and the purified polyorgano 70xane was immersed in the acrylonitrile-styrene mixed vinyl monomer of the above composition heated to 75°C, and its degree of swelling was determined. Measure changes over time. If immersed for 10 minutes or more, no change in swelling degree over time will be observed. This indicates that the vinyl monomer penetrates and diffuses into the polyorganosiloxane.

After completion of the diffusion, a radical polymerization initiator is added to carry out graft polymerization.

The vinyl monomer can be graft-polymerized onto the polyorganosiloxane by a conventional radical polymerization method. Various radical polymerization initiators are used for graft polymerization, but these initiators need to be added before graft polymerization. Depending on the type of radical polymerization initiator, it is necessary to neutralize the polyorganosoroxane latex acidified with alkylbenzenesulfonic acid to neutrality with an alkali. As the alkali, caustic soda, caustic potash, sodium carbonate, sodium bicarbonate, triethanolamine, triethylamine, etc. are used.

Examples of the radical polymerization initiator used in the present invention include di-tertiary butyl peroxide, dicumyl peroxide, tertiary butyl perphthalate, tertiary butyl perve/shade, tertiary butyl peracetate, and ditertiary amyl peroxide. oxide, methyl isobutyl ketone peroxide, lauroyl peroxide, cyclohexanone peroxide, 2,5-dimethyl-2,5-ditertiary butyl peroxyhexane, tertiary butyl peroctanoate, tertiary butyl peryne butyrate, Organic peroxides such as tertiary butyl peroxyisopropyl carbonate and diisopropyl peroxydicarbonate, dimethyl-2
, 2'-azobisisobutylene), 1.1'-azobiscyclohexanecarbonitrile, 2-phenyl7so2
．． Azo compounds such as 4-dimethyl-4-methoxyvaleronitrile, 2-carbamoylazoisobutyronitrile, 2,2'-azohis-2,4-dimethylvaleronitrile, 2°2'-azobisisobutyronitrile, Hydroperoxide-ferrous sulfate-ylucose-sodium birophosphate, hydroberoquindo-ferrous sulfate-dextrose-sodium birophosphate-sodium phosphate, hydroperoxide-ferrous sulfate-iron-sodium birophosphate-phosphoric acid Examples include redox initiators such as sodium, hydroperoxide-ferrous sulfate-formaldehyde sodium sulfoquinrad-ethylenediamine acetate, persulfate-hexacyanoferrous (Ill potassium, persulfate-sodium thiosulfate-copper sulfate) Hydroperoxide temperature: Cumene hydroperoxide, tertiary butyl hydroperoxide, diinoprobyl benzene hydroperoxide, p-menthane hydroperoquinde, Ll, 5.3
Examples of persulfates include potassium persulfate and ammonium persulfate. Persulfates can also be used alone.

During graft polymerization, the graft vinyl monomer is divided, and the first half is used as a normal graft polymer generation part, and the second half is added with a small amount of alkyl mercaptans to generate a relatively low molecular weight free polymer that does not participate in grafting. Generally, a so-called two-stage grafting method is used to improve the fluidity of the grafted polymer. The graft vinyl monomer is not used separately, but the entire amount is used as the graft polymer generation portion. In this case, acrylonitrile-styrene copolymer obtained by separate polymerization,
The resulting resin mixture has the following formula (Iz: ASTM-
Based on D7256-56 (23℃ with 1/4 inch notch)
, MP: 200°C based on ASTM-D-1238
,5kl? It is also possible to impart fluidity to the graft polymer by mixing it so as to satisfy the value (value under load) and shaping it for use. The mixing of vinyl monomers with homopolymers can also be applied to polymers produced by two-stage grafting.

The grafting ratio of the graft polymer thus obtained was determined by the following method. Graft polymer latex, approx.
A graft polymer is obtained by adding it to ~5 times the amount of methanol with stirring and coagulating the latex. After washing the polymer thus obtained with water, it was heated to 80°C for 10
Dry under reduced pressure for an hour to remove moisture. Approximately 1g after drying
Accurately weigh out the polymer and add about 50 rnl of acetate. This is boiled for about 5 hours at the boiling point of acetone, so that the acetone-soluble graft polymer not bonded to the polyorganosiloxane is dissolved in the acetone. After cooling, about 1
Centrifugation is performed at 10,000 rpm for 1 hour, and the polymer bonded to the polyorganosiloxane and the acetone-soluble polymer are separated by decantation. Acetone was further added to the polymer bound to polyorganonoloxane, and the polymer was washed by repeating centrifugation and decantation in the same manner, and then dried under reduced pressure at 800G for 10 hours.
Determine the weight of the acetone extraction residue. The grafting rate is calculated using the following formula.

(7 weights of polyorganosiloxa) The obtained graft polymer latex is coagulated by a normal salt coagulation method, and the obtained powder is washed with water, dried, and shaped using an extruder to form pellets.

At this time, when a matrix resin obtained by bulk polymerization, suspension polymerization, emulsion polymerization, etc. is added and extruded to form a molded product, the physical properties of the resin such as fluidity, surface gloss, surface hardness, etc. It can be improved. Generally when using impact resistant resin.

The appropriate range of the grafting ratio of the polymer is 20 to 100% based on the rubber polymer. If the grafting ratio is lower than this, affinity between the matrix and the rubber cannot be ensured. Moreover, if it is higher than this, the fluidity of the resin will be impaired. Therefore, while maintaining high grafting efficiency (grafting rate of 20%),
By setting the amount to 100%, it is possible to reduce the amount of 7-ribolymer generated during graft polymerization, and it is possible to produce a polyorganosiloxane copolymer with a high rubber content. However, if you try to polymerize all of the matrix resin following kraft polymerization, the polymerization will occur in the presence of rubber, making it difficult to adjust the polymer chain length, copolymerization ratio, etc., resulting in a polymer with low fluidity and surface hardness. I end up. Therefore, during graft polymerization, it is preferable to have a structure that has fluidity to the extent that it can be made compatible with the matrix resin, and to add it when shaping the remaining matrix resin.

In addition, fillers, heat stabilizers, ultraviolet absorbers,
Additives such as lubricants can also be added. The pelletized polyurethane polymer is processed and molded by conventional means such as compression molding and injection molding.

Molded articles made of the polymer of the present invention and resin compositions containing the same can generally have high impact strength with a low polyorganosiloxane content, and have good weather resistance, good surface gloss, good fluidity, and good It exhibits excellent properties such as high surface hardness. In other words, 1z
When (MF)1/2t is calculated, this value becomes 20 or more.

The impact strength of the molded products in the following examples is ASTM-D-2.
Notched test piece according to 5-56 (notches are 45° and 0
．． 1 inch deep) were made by injection molding and measured by Izod (Iz) impact testing at 25°C. In addition, the glossiness of the molded product was expressed as a value (ch) based on ASTM-D-523-62T (x), where the gloss of the glass surface was taken as 100.

The fluidity of the molded product is shown by the melt 70-Leh (MF) method, and is measured at 200°C and 5 kg according to the ASTM-D-1238 standard.
Measured by load. The surface hardness of the molded product was determined by the Rockwell method and determined by I11 based on ASTM-D-785.

Reduced viscosity of acrylonitrile-styrene copolymer (ηs
p/C) was measured at 25°C in acetone solvent, and dIl
/, expressed in units of li'.

Example 1 1.0 parts by weight of ethyl orno/licade, 0.75 parts by weight of r-methacryloxyglobildimethoxymethylsilane and 99 parts by weight of octamethyltetracyclosiloxane were mixed, and this was mixed with 1.0 parts by weight of dodecylbenzenesulfonic acid. was dissolved in 300 parts by weight of distilled water, pre-stirred with a homomixer, and then mixed with 250 parts of distilled water with a homogenizer.
It was emulsified and dispersed by passing it through twice at a pressure of kg/crrt'.

This mixed solution was prepared using a condenser, a nitrogen inlet, and a stirring blade. The mixture was transferred to a parallel flask and heated at 90° C. for 6 hours while stirring and mixing to complete polymerization of polydimethylsiloxane. The polymerization rate of the obtained polyorganosiloxane was 91.61%, the degree of swelling was 96, and the particle size of the polyorganosiloxane polymer measured by turbidity method was 0.13μ.

This polyorganosiloxane latex was neutralized to a pH of 8 with an aqueous sodium carbonate solution. 690 parts by weight of distilled water was added thereto, and the mixture was transferred to a separable flask equipped with a dropping bottle, a condenser, a nitrogen inlet, and a stirring blade, and the temperature was raised to 75° C. while flowing nitrogen. Next, as the first stage graft polymerization, a mixed monomer of 41.7 parts by weight of acrylonitrile and 124.9 parts by weight of styrene was added at once during stirring, and stirring was continued for 30 minutes to perform permeation and diffusion. No polymerization of the graft monomer was observed.Next, 1.5 parts by weight of potassium persulfate was dissolved in 10 parts by weight of water and added.After adding potassium persulfate, the polymerization reaction was carried out for 2 hours, and the polymerization was substantially completed. Thereafter, as a second-stage graft polymerization, a monomer mixture of 16.7 parts of acrylonitrile, 50 parts of styrene, and 0.2 parts of n-octylmercaptan was slowly added over 1 hour using a dropping bottle.

After the completion of the dropwise addition of the nanatsumer, the polymerization reaction was carried out for 2 hours, and after the polymerization was substantially completed, the mixture was cooled.

The particle size of the obtained polymer latex was 0.50 μ. Add this latex to 15 parts by weight of Cac]4.
The polymer was separated by pouring into hot water in which 2H20 was dissolved and salting out and coagulating. After thoroughly washing with water, it was dried at 80° C. for 16 hours to obtain a polyorgano 70 xane graft polymer. The graft ratio of the obtained graft polymer was 88
．． It was 6%. Also, the polymerization rate of the graft monomer is 99%.
It was 8%.

A copolymer obtained by polymerizing 50% by weight of this graft polymer powder with acrylonitrile and styrene monomers at a monomer charge ratio of 25:75 (lsp/c is 0.65 dl/g
) and 50% by weight, and heated and shaped at 220°C using a single screw extruder with L/D==25 to obtain pellets. kg·cWL/cIrL, and the glossiness of the flat plate was 90%. In addition, the melt flow value measured at 200℃ and 5 kg load was 0.9.9/10 minutes,
The surface hardness of the molded plate was 104 on the R scale. Therefore, the product of the Izod value and the square root of the MF value is 62°6
Met.

Example 2 Using the acrylonitrile-styrene graft polyorganosiloxane polymer obtained in Example 1, ηs p / C of the acrylonitrile-styrene copolymer to be mixed
Polymers were produced by varying the That is, the grafted polyorganosiloxane polymer and the acrylonitrile Φ styrene copolymer were mixed in an amount of 50% by weight and shaped and molded in the same manner as in Example 1 to determine the physical properties and obtain the results shown in Table 1. It is known that as the +ysp/C value of the acrylonitrile-styrene copolymer of the blend polymer increases, that is, as the degree of polymerization increases, the Izod value increases and the MF value, which indicates the fluidity of the polymer, decreases. Here, the product of the Izot value and the MF value is a value of 20 or more,
It is known to be a good impact resistant resin.

Table 1 Example 3 Acrylonitrile/styrene grafted polyorganosiloxane polymer and acrylonitrile/styrene copolymer obtained in Example 1 (ηsp/C is 0.65 dl/
i), shaping by changing the mixing ratio of acrylonitrile-styrene copolymer to the graft polymer powder,
Molding was performed, and the physical properties of the molded product were determined, and the results shown in Table 2 were obtained. Although the Izod value improves as the grafted polyorganosiloxane content increases, the rubber content 2
0% by weight or more (graft polyorganosiloxane ratio 6
6.7% or more), no improvement in Izot value was observed. Conversely, the MF value and surface hardness decreased with increasing rubber content.

Table 2 Example 4 Using the polyorgano 70 xane latex prepared in Example 1, neutralize it with an aqueous sodium carbonate solution to bring the pH to 8, add 190 parts by weight of distilled water, and remove the dropping bottle, condenser, nitrogen inlet, and stirring blade. The mixture was transferred to a separable flask and heated to 75° C. while flowing nitrogen. Next, a mixed solution of 25 parts by weight of acrylonitrile and 75 parts by weight of styrene was added at once while stirring, and the mixture was stirred for 60 minutes. Thereafter, 0.75 parts by weight of potassium persulfate was dissolved in 10 parts by weight of water and added. After adding potassium persulfate, the polymerization reaction was carried out for 2 hours, and after the polymerization was substantially completed, the mixture was cooled.
The polymer was recovered by the same operation as in Example 1.

The graft ratio of the obtained polymer was 3.4'Q. Moreover, the polymerization rate of the graft monomer was 997%. A copolymer obtained by polymerizing 60% by weight of this graft polymer powder with a monomer charging ratio of acrylonitrile and styrene of 25:75 (ηsp/C is o, 65aA!/L)
70% by weight, and the molded resin was shaped and extruded in the same manner as in Example 1, and the physical properties of the obtained molded resin were evaluated. the result,
Izotsu impact value is 28. OKE7・cm/cr
n, the gloss level of the flat plate is 87% and 200°C5! /
The MF value measured under load was 0.6 J/10 minutes, and the surface hardness of the molded plate was 101 on the R scale. Therefore, the product of the Izod value and the square root of the MF value was 21.7.

Example 5 During polymerization of polyorganosiloxane, 0.75 parts by weight of tetravinyltetramethyltetrancrosiloxane or 0.75 parts by weight of r-mercaptopropyldimethoxymethylsilane was used instead of r-methacryloxypropyldimethoxymethylsilane. Polydimethylsiloxane was produced in the same manner as in Example 1, and then acrylonitrile and styrene were graft-polymerized. Furthermore, the acrylonitrile-styrene copolymer used in Example 1 was blended in the same manner, and the resulting resin composition was extruded and molded.

Extrusion, molding, etc. were carried out in the same manner as in Example 1. Table 6 shows the grafting rate, grafting efficiency, and physical properties of the molded product of the obtained polymer.

Table 3 Comparative Example 1 Grafted polydimethylsiloxane was produced by the method described in US Pat. No. 3,898,500. Dodecylbenzene sulfo/1l 160.9 is dissolved in water 2000.9, and mixed polydimethylsiloxane cyclic body 1 is added to this solution.
122g, mixed polymethylvinylsiloxane cyclics 71
After adding 725 g of p and tetraethoxysila and premixing, the mixture was passed through a homogenizer 6 times at 250 9/crlL2. The emulsion thus obtained was transferred to a separable flask equipped with a condenser, a nitrogen inlet, and a stirring blade, and heated at 90°C for 3 hours while stirring. The emulsion was cooled to room temperature, stored in a freezer at 0 to 5°C for 100 hours, and then adjusted to pH 7.5 with sodium carbonate. The polymerization rate of the obtained polyorganosiloxane was 90.5%, the swelling degree was 10.6, and the polyorganosiloxane/
The particle size of the polymer was 0.14μ.

Transfer 148 g of this polyorgano 70 xane latex to a separable flask equipped with a dropping bottle, a condenser, a nitrogen inlet, and a stirring blade. Perokinodo t7,9. , n-dodecyl mercaptan 0.6 g and ferrous sulfate heptahydrate 0.24.9
added. This mixture was heated to 65°C under a nitrogen stream,
A mixture of 165 g of styrene and 759 g of acrylonitrile was continuously added dropwise over 6 hours. After dropping, the state was maintained for 2 hours, and the polymerization was completed when it was confirmed that 98% or more of styrene and acrylonitrile had been polymerized. The obtained latex was coagulated with a hot aqueous solution of calcium chloride, washed, dried, shaped and molded, and the physical properties of the molded resin were evaluated. As a result, the Izod impact value is 61 k
g・α/α. However, the gloss level of the flat plate is low at 75%, 200℃, 5kl? The MF value measured under load is 0. (
71.1i1710 minutes and had almost no fluidity. Further, the surface hardness was 96 on the R scale, and the product of the Izod value and the square root of the MF value was 6°1, which was unbalanced as an impact-resistant molding material.

Comparative Example 2 A graft polymer was obtained in the same manner as in Comparative Example 1, except that 21 g of acrylonitrile and 66 g of styrene were used as graft monomers.

50% by weight of this graft polymer powder and acryloni
- Monomer charge ratio of IJ and styrene: 25:7
The copolymer obtained by polymerizing step 5 (ηsp/C is 0.6 dl
l/jj ) 50% by weight, and shaped and molded in the same manner as in Example 1, and the physical properties were evaluated. The Izod impact value was 23 ky-on/an. Also 200℃, 5
The MF value measured with ky load is 0.08! j/10 minutes, and had almost low fluidity. Therefore, the product of the Izod value and the square root of the MF value was 7.55, which was unbalanced as an impact-resistant molding material.

Comparative Example 3 Based on the description in U.S. Pat. No. 4,071,577, mercaptone loxane was used as a graft cross-agent, and other methods such as the method for producing polydimethylronoxane latex and the method for grafting acrylonitrile-styrene copolymer were described in the U.S. patent. A grafted polydimethylsiloxane was produced according to the description in No. 6,898,300.

That is, as a raw material for producing polydimethylronoxane latex, 71 g of cyclic mercagutopropyl methylsiloxane was used in place of the mixed polymethylvinylsiloxane ρ ring, and the other operations were the same as in Comparative Example 1, and the resulting molded resin was Physical properties were evaluated. As a result, the Izod impact value was 51 υ·an/cm. However, the gloss of the flat plate is as low as 79%, and the MF value measured at 200°C and a 5 kg load is 0.02 fI710 min, showing almost no fluidity, and the product of the Izod value and the square root of the MF value is 7.2.
Therefore, it was unsuitable as an impact-resistant resin.

Comparative Example 4 Polyorganosiloxane latex 14 obtained in Comparative Example 6
8J and acrylonitrile 21! as the grafting monomer! A graft polymer was obtained by the same method as in Comparative Example 3 except that i and styrene 6Sj9 were used.

This graft polymer powder 50% by weight and the monomer charge ratio of acrylonitrile and styrene were 25:75.
Copolymer obtained by polymerization (ηsp/C is o, 6d//g
)so weight % was mixed, shaped and molded in the same manner as in Example 1, and the physical properties were evaluated. Izot impact value is 48 euroc
It was rn/crn. Further, the MF value measured at 200° C. and 5 ki/load was O, C10, p/fO, indicating almost low fluidity. Therefore, the product of the Izod value and the square root of the MF value was 15.57, which was unbalanced as an impact-resistant molding material.

Claims (1)

[Claims] 1. After adding acrylonitrile and styrene to a polyorganosiloxane obtained by adding a grafting agent to an organosiloxane and polymerizing the same, and allowing the mixture to permeate and diffuse,
Graft polymerization was carried out by adding a radical polymerization initiator under the following conditions: Iz×(MF)^1^/^2≧20 (Iz: 23°C with 1/4 inch notch based on ASTM-D-256-56, MF : A method for producing a graft copolymer, characterized in that the method is carried out so as to satisfy the following values (at 200° C. and 5 kg load based on ASTM-D-1238). 2. After adding acrylonitrile and styrene to the polyorganosiloxane obtained by adding a grafting agent to the organosiloxane and polymerizing it and allowing it to permeate and diffuse,
A graft copolymer obtained by adding a radical polymerization initiator and performing graft polymerization, and a resin mixture obtained under the following formula conditions Iz×(MF)^1^/^2≧20 (Iz: ASTM-D Acrylonitrile-styrene copolymer must be mixed as a matrix to satisfy the following values: 23°C with 1/4 inch notch based on -256-56, MF: 200°C, 5 kg load based on ASTM-D-1238). A method for producing impact-resistant resin, characterized by: 3. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^1 is a hydrogen atom, methyl group, ethyl group, propyl group, or phenyl group, R^2 is a hydrogen atom or a methyl group,
Claim 1 or 2, characterized in that an organosiloxane graft cross-agent having a unit represented by n is 0, 1 or 2, and p is a number from 1 to 6 is used.
The method described in section.