POLYORGANOSILOXANE-CONTAINING POLYMER, COMPOSITION, AND MOLDED ARTICLE

Abstract

Provided is a polyorganosiloxane-containing polymer which makes it possible to obtain a molded product exhibiting excellent flame retardance without significantly degrading the impact resistance characteristics in a case where the polyorganosiloxane-containing polymer is added to a resin. The polyorganosiloxane-containing polymer according to the present invention contains alkali metal atoms of 100 ppm by mass or more and has a mass average particle diameter Dw of 350 nm or more.

Claims

1. A polyorganosiloxane-containing polymer comprising: 100 ppm by mass or more of an alkali metal atom, wherein a mass average particle diameter Dw is 350 nm or more.

2. The polyorganosiloxane-containing polymer according to claim 1, wherein the mass average particle diameter Dw is 1,000 nm or less.

3. The polyorganosiloxane-containing polymer according to claim 1, wherein the polyorganosiloxane-containing polymer is a polymer having a composite body and a graft part, the composite body comprises a polyorganosiloxane and a first vinyl polymer, and the graft part comprises a second vinyl polymer.

4. The polyorganosiloxane-containing polymer according to claim 3, wherein a proportion of the graft part in 100% by mass of the polyorganosiloxane-containing polymer is 5% by mass or more and 20% by mass or less.

5. The polyorganosiloxane-containing polymer according to claim 3, wherein the first vinyl polymer comprises a constitutional unit derived from a (meth)acrylate monomer.

6. The polyorganosiloxane-containing polymer according to claim 3, wherein the second vinyl polymer comprises a constitutional unit derived from a (meth)acrylate monomer.

7. The polyorganosiloxane-containing polymer according to claim 3, wherein the polyorganosiloxane comprises a constitutional unit derived from a siloxane-based crosslinking agent, and a proportion of the constitutional unit derived from the siloxane-based crosslinking agent in 100% by mass of the polyorganosiloxane is 3% by mass or less.

8. The polyorganosiloxane-containing polymer according to claim 1, wherein a proportion of a polyorganosiloxane in 100% by mass of the polyorganosiloxane-containing polymer is 70% by mass or more and 98% by mass or less.

9. The polyorganosiloxane-containing polymer according to claim 1, wherein the alkali metal atom is a sodium atom.

10. The polyorganosiloxane-containing polymer according to claim 1, wherein the polyorganosiloxane-containing polymer is in a powder state.

11. A composition comprising: the polyorganosiloxane-containing polymer according to claim 1; and a thermoplastic resin.

12. A molded product comprising: the polyorganosiloxane-containing polymer according to claim 1; and a thermoplastic resin.

Description

EXAMPLES

[0215] The present invention will be specifically described below with reference to Examples and Comparative Examples. Prior to Examples, various evaluation methods and Production Examples 1-1 to 1-6 of latexes of polyorganosiloxanes will be described. Examples 1-1 to 1-6 and Comparative Examples 1-1 to 1-7 are examples relating to the production and evaluation of graft copolymers, and Examples 2-1 to 2-9 and Comparative Examples 2-1 to 2-8 are examples relating to the production and evaluation of thermoplastic resin compositions. In Production Examples and Examples, part, %, and ppm mean part by mass, % by mass, and ppm by mass unless otherwise specified.

[0216] <Solid Content>

[0217] A latex of a polyorganosiloxane having a mass w1 is dried with a hot air dryer at 180 C. for 30 minutes, a mass w2 of a residue after the drying is measured, and the solid content [%] is calculated according to the following expression.

Solid content [%]=w2/w1100

[0218] <Particle Diameter>

[0219] The polyorganosiloxane (A1) latex or the polymer (C) latex) was diluted with deionized water to a concentration of solid contents of about 3% and used as a specimen, and using a CHDF 2000 type particle size distribution meter manufactured by MATEC Applied Sciences in the United States, the number average particle diameter Dn and the mass average particle diameter Dw were measured using the following conditions. [0220] Cartridge: A dedicated particle separation capillary type cartridge (product name; C-202), [0221] Carrier liquid: A dedicated carrier liquid (product name; 2XGR500), [0222] Liquidity of carrier liquid: neutral, [0223] How rate of carrier liquid: 1.4 mL/min, [0224] Pressure of carrier liquid: 4,000 psi (2,600 kPa), [0225] Measurement temperature: 35 C., [0226] Using amount of specimen: 0.1 mL.

[0227] <Amount of Residual Metal>

[0228] The amount of the residual metal was quantified with an ICP luminescence analyzer (iCAP7400 Duo, manufactured by Thermo Fisher Scientific, Inc.) by using, as a test solution, a solution obtained by weighing approximately 0.25 g of a specimen, adding 8 mL of nitric acid and 2 mL of hydrogen fluoride water thereto, carrying out a decomposition treatment with a microwave (wet-type decomposition), and the volume was adjusted to 50 mL with distilled water.

[0229] <Thermal Decomposability>

[0230] The graft copolymer was subjected to thermal gravimetric analysis using TG/DTA6200 (manufactured by Seiko Instruments, Inc.), and the thermal decomposability was evaluated by the following method.

[0231] Under the condition of a nitrogen flow rate of 200 mL/min, the residual amount at each temperature in a case where the specimen temperature was raised to 550 C. at 10 C./min was calculated by Expression (1). The one in which the residual amount reached 1% or less at the end of the test was evaluated as A, and the one in which the residual amount did not reach 1% or less was evaluated as B. For a sample having the thermal decomposability A, the thermal decomposability was calculated by Expression (2). The smaller the value calculated by (2), the shorter the time required from the start to the end of thermal decomposition, and the more excellent the thermal decomposability.

Residual amount (%)=mass (g) after holding/mass (g) of charging Expression (1)

Thermal decomposability ( C.)=((temperature at moment when residual amount is 70%)(temperature at moment when the residual amount is 1%)Expression (2)

Production Method for Polymer

Production Example 1-1: Production of Polyorganosiloxane Latex (S-1)

[0232] 2 parts of -methacryloyloxypropyldimethoxymethylsilane (DSMA) and 98 parts of octamethylcyclotetrasiloxane (manufactured by Momentive Performance Materials Japan LLC, product name: TSF404) were mixed to obtain 100 parts of an organosiloxane mixture. An aqueous solution obtained by dissolving 1 part of sodium dodecylbenzenesulfonate (DBSNa) in 150 parts of deionized water was added to the organosiloxane mixture, and the resultant mixture was stirred at 10,000 rpm for 5 minutes with a homogenization mixer and then allowed to pass through a homogenizer two times at a pressure of 20 MPa to obtain a stable premixed emulsion.

[0233] After placing the obtained emulsion in a separable flask having a capacity of 5 liters, equipped with a cooling condenser, the emulsion was heated to 80 C., and a mixture of 0.20 parts of sulfuric acid and 49.8 parts of distilled water was continuously added over 3 minutes. After the polymerization reaction was carried out by maintaining for 7 hours a state of being heated to 80 C., cooling was carried out to room temperature (25 C.), and the obtained reactant was held at room temperature for 6 hours. A 5% aqueous sodium hydroxide solution was added to the obtained reactant, and the reaction solution was neutralized to a pH of 7.0 to obtain a polyorganosiloxane latex (S-1).

[0234] The solid content of the polyorganosiloxane latex (S-1) was 30.2% by mass. The number average particle diameter (Dn) was 384 nm, the mass average particle diameter (Dw) was 403 nm, and Dw/Dn was 1.05.

Production Example 1-2: Production of Polyorganosiloxane Latex (S-2)

[0235] The same operation as in Production Example 1-1 was carried out to obtain a polyorganosiloxane latex (S-2), except that the formulation of the organosiloxane mixture was changed to the formulation shown in Table 1.

[0236] The solid content of the polyorganosiloxane latex (S-2) was 30.4% by mass. The number average particle diameter (Dn) was 384 nm, the mass average particle diameter (Dw) was 403 nm, and Dw/Dn was 1.05.

Production Example 1-3: Production of Polyorganosiloxane Latex (S-3)

[0237] The same operation as in Production Example 1-1 was carried out to obtain a polyorganosiloxane latex (S-3), except that the formulation of the organosiloxane mixture was changed to the formulation shown in Table 1.

[0238] The solid content of the polyorganosiloxane latex (S-3) was 30.6% by mass. The number average particle diameter (Dn) was 384 nm, the mass average particle diameter (Dw) was 403 nm, and Dw/Dn was 1.05.

Production Example 1-4: Production of Polyorganosiloxane Latex (S-4)

[0239] The same operation as in Production Example 1-1 was carried out to obtain a polyorganosiloxane latex (S-4), except that the formulation of the organosiloxane mixture was changed to the formulation shown in Table 1.

[0240] The solid content of the polyorganosiloxane latex (S-4) was 30.8% by mass. The number average particle diameter (Dn) was 384 nm, the mass average particle diameter (Dw) was 403 nm, and Dw/Dn was 1.05.

Production Example 1-5: Production of Polyorganosiloxane Latex (S-5)

[0241] 0.5 parts of -methacryloyloxypropyldimethoxymethylsilane (DSMA), 2 parts of tetraethoxysilane (TEOS), and 97.5 parts of octamethylcyclotetrasiloxane (manufactured by Shin-Etsu Silicone Co. Ltd., product name: DMC, a mixture of a 3- to 6-membered cyclic organosiloxanes) were mixed to obtain 100 parts of an organosiloxane mixture. An aqueous solution obtained by dissolving 0.68 parts of sodium dodecylbenzenesulfonate (DBSNa) and 0.68 parts of dodecylbenzenesulfonic acid (DBSH) in 150 parts of deionized water was added to the organosiloxane mixture, and the resultant mixture was stirred at 10,000 rpm for 5 minutes with a homogenization mixer and then allowed to pass through a homogenizer two times at a pressure of 20 MPa to obtain a stable premixed emulsion.

[0242] After placing the obtained emulsion in a separable flask having a capacity of 5 liters, equipped with a cooling condenser, the emulsion was heated to 80 C., maintained for 5 hours to carry out a polymerization reaction, and then cooled to room temperature (25 C.), and the obtained reactant was held at room temperature for 6 hours A 5% aqueous sodium hydroxide solution was added to the obtained reactant, and the reaction solution was neutralized to a pH of 7.0 to obtain a polyorganosiloxane latex (S-5).

[0243] The solid content of the polyorganosiloxane latex (S-5) was 33.0% by mass. The number average particle diameter (Dn) was 64 nm, the mass average particle diameter (Dw) was 248 nm, and Dw/Dn was 3.88.

Production Example 1-6: Production of Polyorganosiloxane Latex (S-6)

[0244] The same operation as in Production Example 1-1 was carried out to obtain a polyorganosiloxane latex (S-6), except that the formulation of the organosiloxane mixture was changed to the formulation shown in Table 1 and the amount of sodium dodecylbenzenesulfonate (DBSNa) was increased to 1.5 parts.

[0245] The solid content of the polyorganosiloxane latex (S-6) was 30.8% by mass. The number average particle diameter (Dn) was 38 nm, the mass average particle diameter (Dw) was 276 nm, and Dw/Dn was 7.26.

[0246] The components of Production Examples 1-1 to 1-6 are shown in Table 1.

[0247] The abbreviations in Table 1 are as follows. [0248] TSF404: Octamethylcyclotetrasiloxane [0249] DMC: A mixture of 3- to 6-membered cyclic organosiloxanes [0250] DSMA: -methacryloyloxypropyldimethoxymethylsilane [0251] TEOS: Tetraethoxysilane

TABLE-US-00001 TABLE 1 Production Example 1-1 1-2 1-3 1-4 1-5 1-6 Polyorganosiloxane S-1 S-2 S-3 S-4 S-5 S-6 TSF404 [Part] 98 97 96 95 96 DMC [Part] 97.5 DSMA [Part] 2 2 2 2 0.5 2 TEOS [Part] 1 2 3 2 2 Proportion of constitutional [% by 0 1 2 3 2 2 unit derived from siloxane-based mass] crosslinking agent in 100% by mass of polyorganosiloxane

Example 1-1

[0252] parts (10.0 parts in terms of polymer) of the polyorganosiloxane latex (S-1) obtained in Production Example 1-1 was collected in a separable flask having a capacity of 5 liters, and 8.82 parts of butyl acrylate (BA), 0.18 parts of allyl methacrylate (AMA), and 0.16 parts of cumene hydroperoxide (CB) were added thereto, and stirring was continued at room temperature for 1 hour to impregnate the polyorganosiloxane.

[0253] The atmosphere in the flask was substituted with nitrogen by allowing a nitrogen stream to pass through, and the liquid temperature was raised to 50 C. At a moment when the liquid temperature reached 50 C., an aqueous solution obtained by dissolving 0.001 parts of ferrous sulfate (Fe), 0.003 parts of disodium ethylenediaminetetraacetic acid (EDTA), and 0.24 parts of sodium formaldehyde sulfoxylate (SFS) in 10 parts by mass of deionized water was added thereto start a radical polymerization. After the completion of the dropwise addition, a state of a liquid temperature of 65 C. was maintained for 1 hour in order to complete the polymerization of the acrylate component, whereby a latex of a composite rubber of the polyorganosiloxane and the poly-n-butyl acrylate.

[0254] The liquid temperature of the obtained latex of the composite rubber was set to a mixed liquid of 11.0 parts of methyl methacrylate (MMA) and 0.24 parts of cumene hydroperoxide (CB) was added dropwise to the latex over 1 hour, and then the graft polymerization reaction was started. After the completion of the dropwise addition, the temperature was maintained at a temperature of 65 C. for 1 hour and then cooled to room temperature to obtain a latex of a polyorganosiloxane-containing graft copolymer (G-1).

[0255] 500 parts of an aqueous solution having a calcium acetate concentration of 1% by mass was heated to 85 C., and 340 parts of the latex of the graft copolymer (G-1) was gradually added dropwise thereto and solidified while stirring. The obtained graft copolymer (G-1) was filtered, washed, dehydrated, and then dried to obtain a graft copolymer (G-1).

[0256] 10 parts of the obtained graft copolymer (G-1) was added to 141 parts of deionized water, stirring was carried out for 3 minutes, and then 10 parts of a 10% by mass aqueous sodium chloride solution was added thereto, followed by stirring for 3 minutes. A graft copolymer (A-1) was filtered, washed, dehydrated, and then dried to obtain a sodium-containing powder (A-1) of the graft copolymer.

[0257] The mass average particle diameter, amount of alkali metal, and thermal decomposability of the obtained powder (A-1) of the graft copolymer were measured according to the above-described method. The obtained results are shown in Table 2.

Examples 1-2 to 1-4

[0258] Polyorganosiloxane-containing graft copolymers (G-2 to G-4) were produced in the same manner as in Example 1-1 except that the formulation of each raw material used in Example 1-1 was changed under the conditions shown in Table 2, and further, powders (A-2 to A-4) of the graft copolymers were obtained, and the same measurement was carried out. The obtained results are shown in Table 2.

Example 1-5

[0259] A polyorganosiloxane-containing graft copolymer (G-1) was produced in the same manner as in Example 1-1, and then a powder (A-5) of a graft copolymers were obtained in the same manner as in Example 1-1, and the same measurement was carried out, except that the amount of the aqueous solution having a sodium chloride concentration of 10% by mass was changed to 20 parts. The obtained results are shown in Table 2.

Example 1-6

[0260] A polyorganosiloxane-containing graft copolymer (G-1) was produced in the same manner as in Example 1-1, and then a powder (A-6) of a graft copolymers were obtained in the same manner as in Example 1-1, and the same measurement was carried out, except that the amount of the aqueous solution having a sodium chloride concentration of 10% by mass was changed to 50 parts. The obtained results are shown in Table 2.

Comparative Example 1-1

[0261] A polyorganosiloxane-containing graft copolymer powder (A-7) was obtained in the same manner as in Example 1-1, and the same measurement was carried out, except that the polyorganosiloxane-containing graft copolymer (G-1) after being obtained was not treated with the sodium chloride solution. The obtained results are shown in Table 2.

Comparative Example 1-2

[0262] A polyorganosiloxane-containing graft copolymer powder (A-8) was obtained in the same manner as in Example 1-2, and the same measurement was carried out, except that the polyorganosiloxane-containing graft copolymer (G-2) after being obtained was not treated with the sodium chloride solution. The obtained results are shown in Table 2.

Comparative Example 1-3

[0263] A polyorganosiloxane-containing graft copolymer powder (A-9) was obtained in the same manner as in Example 1-3, and the same measurement was carried out, except that the polyorganosiloxane-containing graft copolymer (G-3) after being obtained was not treated with the sodium chloride solution. The obtained results are shown in Table 2.

Comparative Examples 1-4

[0264] A polyorganosiloxane-containing graft copolymer powder (A-10) was obtained in the same manner as in Example 1-4, and the same measurement was carried out, except that the polyorganosiloxane-containing graft copolymer (G-4) after being obtained was not treated with the sodium chloride solution. The obtained results are shown in Table 2.

Comparative Example 1-5

[0265] A polyorganosiloxane-containing graft copolymer (G-5) was produced in the same manner as in Example 1-1 except that the formulation of each raw material used in Example 1-1 was changed under the conditions shown in Table 2, and then further, a powder (A-11) of the graft copolymer was obtained, and the same measurement was carried out. The obtained results are shown in Table 2.

Comparative Example 1-6

[0266] After obtaining the polyorganosiloxane-containing graft copolymer (G-5) according to the method described in Comparative Example 1-5, 10 parts of the obtained graft copolymer (G-5) was added to 141 parts of deionized water, stirring was carried out for 3 minutes, and then 10 parts of an aqueous solution containing sodium chloride of a concentration of 10% by mass was added thereto, the resultant mixture was stirred for 3 minutes, filtered, washed, dehydrated, and then dried to obtain a powder (A-12) of the graft copolymer, containing sodium, and the same measurement was carried out. The obtained results are shown in Table 2.

Comparative Example 1-7

[0267] After obtaining the polyorganosiloxane-containing graft copolymer (G-6) in the same manner as in Example 1-1 except that the formulation of each raw material used in Example 1-1 was changed under the conditions shown in Table 2, 10 parts of the obtained graft copolymer (G-6) was added to 141 parts of deionized water, stirring was carried out for 3 minutes, and then 10 parts of an aqueous solution containing sodium chloride of a concentration of 10% by mass was added thereto, the resultant mixture was stirred for 3 minutes, filtered, washed, dehydrated, and then dried to obtain a powder (A-13) of the graft copolymer, containing sodium, and the same measurement was carried out. The obtained results are shown in Table 2.

TABLE-US-00002 TABLE 2 Comparative Example Example 1-1 1-2 1-3 1-4 1-5 1-6 1-1 Graft copolymer (A) A-1 A-2 A-3 A-4 A-5 A-6 A-7 Graft copolymer (G) G-1 G-2 G-3 G-4 G-1 G-1 G-1 Rubber part Polyorganosiloxane (S) Kind S-1 S-2 S-3 S-4 S-1 S-1 S-1 Amount [part] 80.0 80.0 80.0 80.0 80.0 80.0 80.0 Monomer for BA [part] 8.82 8.82 8.82 8.82 8.82 8.82 8.82 composite rubber AMA [part] 0.18 0.18 0.18 0.18 0.18 0.18 0.18 Graft part MMA [part] 11.0 11.0 11.0 11.0 11.0 11.0 11.0 Mass average particle diameter of [nm] 422 409 406 404 422 422 422 graft polymer Amount of residual alkali metal Na [ppm] 260 260 200 210 400 1200 2 K [ppm] <6 <6 <6 <6 <6 <6 <6 Thermal decomposability Determination A A A A A A B [ C.] 25 26 30 31 24 29 Comparative Example 1-2 1-3 1-4 1-5 1-6 1-7 Graft copolymer (A) A-8 A-9 A-10 A-11 A-12 A-13 Graft copolymer (G) G-2 G-3 G-4 G-5 G-5 G-6 Rubber part Polyorganosiloxane (S) Kind S-2 S-3 S-4 S-5 S-5 S-6 Amount [part] 80.0 80.0 80.0 80.0 80.0 80.0 Monomer for BA [part] 8.82 8.82 8.82 8.82 8.82 8.82 composite rubber AMA [part] 0.18 0.18 0.18 0.18 0.18 0.18 Graft part MMA [part] 11.0 11.0 11.0 11.0 11.0 11.0 Mass average particle diameter of [nm] 409 406 404 217 217 298 graft polymer Amount of residual alkali metal Na [ppm] 2 2 2 3 220 1000 K [ppm] <6 <6 <6 <6 <6 <6 Thermal decomposability Determination B B B B A A [ C.] 55 63

[0268] The abbreviations in Table 2 are as follows. [0269] nBA: n-butyl acrylate [0270] AMA: Allyl methacrylate [0271] MMA: Methyl methacrylate [0272] Na: Sodium [0273] K: Potassium

[0274] As compared with the graft polymers according to Comparative Examples 1-1 to 1-7, the graft copolymers according to Examples 1-1 to 1-6 had improved thermal decomposability.

Examples 2-1 to 2-9 and Comparative Examples 2-1 to 2-8

[0275] The polyorganosiloxane-containing polymer powder, the additive, and the thermoplastic resin were blended at a ratio shown in Table 3 to obtain a mixture. This mixture was supplied to a volatilization type twin-screw extruder (manufactured by Ikegai Corp., PCM-30 (product name)) and kneaded to produce a pellet of each resin composition.

[0276] The following one was used as the thermoplastic resin. [0277] PC: A polycarbonate resin (Iupilon S-2000F, manufactured by Mitsubishi Engineering-Plastics Corporation, viscosity average molecular weight: 24,000).

[0278] The following one was used as the additive. [0279] A-3750: Acrylic-modified PTFE (METABLEN A-3750, manufactured by Mitsubishi Chemical Corporation).

[0280] The pellet of the resin composition was subjected to injection molding using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., SE100DU (product name)) to produce a test piece for evaluation.

[0281] Specifications of Test Pieces: [0282] Test piece A: length 80 mmwidth 10 mmthickness 4 mm [0283] Test piece B: length 100 mmwidth 50 mmthickness 2 mm [0284] Test piece C: length 125 mmwidth 13 mmthickness 1.6 mm

[0285] The extrusion conditions and the injection molding conditions are as follows. [0286] Extrusion barrel temperature: 280 C., [0287] Injection cylinder temperature: 280 C., [0288] Metal mold temperature: 60 C.

[0289] A notch of TYPE A in accordance with ISO 179-1 was carved on the test piece A, and the Charpy impact strength was measured. The higher the numerical value of the Charpy impact strength, the higher the impact resistance. The obtained results are shown in Table 3.

[0290] With respect to the test piece B, a flow mark (a pattern seen in a striped shape in the vicinity of the gate of the molded product) appearing in the vicinity of the gate of test piece B is visually observed.

[0291] Determination method: The external appearance of the gate part is visually determined (A: the flow mark is noticeable, B: the flow mark is not noticeable). Table 3 shows the evaluation results.

[0292] Using the test piece C, the total combustion time of the five test pieces and the presence or absence of the drip at the time of ignition were measured according to a vertical combustion test method in accordance with the UL94V test. It is preferable that the shorter the total combustion time is, the higher the flame retardance is, and there is no drip. Table 3 shows the evaluation results.

TABLE-US-00003 TABLE 3 Example 2-1 2-2 2-3 2-4 2-5 2-6 2-7 2-8 2-9 Thermoplastic PC 10 95 93 90 95 95 95 95 95 resin [%] Graft copolymer Kind A-1 A-1 A-1 A-1 A-2 A-3 A-4 A-5 A-6 (A) Amount 3 5 7 10 5 5 5 5 5 Additive [%] A-3750 0.24 0.24 0.24 0.24 0.24 0.24 0.24 0.24 0.24 Charpy impact 23 C. [kJ/m.sup.2] 63 64 53 47 61 64 64 64 55 strength 30 C. [kJ/m.sup.2] 30 50 42 38 47 43 42 48 44 Flame Combustion time 51 57 49 56 79 59 97 55 71 retardance [second] Presence or absence Absent Absent Absent Absent Absent Absent Absent Absent Absent of drip External Flow mark A A A A A A A A A appearance determination Comparative Example 2-1 2-2 2-3 2-4 2-5 2-6 2-7 2-8 Thermoplastic PC 100 95 95 95 95 95 95 95 resin [%] Graft copolymer Kind A-7 A-8 A-9 A-10 A-11 A-12 A-13 (A) Amount 5 5 5 5 5 5 5 Additive [%] A-3750 0.24 0.24 0.24 0.24 0.24 0.24 0.24 0.24 Charpy impact 23 C. [kJ/m.sup.2] 78 66 71 70 69 68 62 60 strength 30 C. [kJ/m.sup.2] 11 54 55 53 54 57 55 51 Flame Combustion time 264 285 29 254 292 226 121 189 retardance [second] Presence or absence Present Absent Present Absent Absent Absent Absent Absent of drip External Flow mark A A A A A B B A appearance determination

[0293] Since the resin composition according to Comparative Example 2-1 did not contain a graft copolymer, the low-temperature impact strength and the flame retardance were low.

[0294] The molded products according to Examples 2-1 to 2-9 containing a polymer containing alkali metal atoms of a specific amount and a specific particle diameter had more favorable flame retardance as compared with the molded products according to Comparative Examples 2-1 to 2-8.

[0295] As compared with the graft copolymers according to Examples 2-1 to 2-9, the graft copolymers according to Comparative Examples 2-6 and 2-7 were inferior in external appearance properties due to having a small particle diameter.