JPH02294348A - Thermoplastic resin composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a thermoplastic resin composition having excellent impact resistance, weather resistance and moldability.

(Prior art) ABS resin has traditionally been used as a thermoplastic resin with a good balance of impact resistance, thermal/mechanical properties, and moldability for light electrical parts,
It is used in various fields such as automobile parts and miscellaneous goods. However, this ABS resin has many chemically unstable double bonds in its main chain, which is a butadiene-based polymer that is the rubber component for imparting impact resistance.
It is well known that it is easily degraded by UV rays and has poor weather resistance.

As a method to improve the weather resistance of this ABS resin, a method has been proposed to use a saturated rubbery polymer that has almost no double bonds in the main chain, and a typical example is ethylene-propylene. - Products using non-conjugated diene copolymer rubber are known.

Methods for producing these impact-resistant resins include bulk polymerization (U.S. Pat. No. 3,435,096) and solution polymerization (
US Pat. No. 3,538,190 and US Pat. No. 3,5381
No. 91 Specification) etc. have been proposed.

(Problem to be Solved by the Invention) However, the graft copolymer obtained by the production method described in the above specification etc. uses ethylene-brobylene-nonconjugated diene copolymer rubber as the rubber component. Although it has better weather resistance than ABS resin,
The surface appearance and gloss of the molded product were poor, and a thermoplastic resin with excellent weather resistance and excellent molded appearance was not obtained.

The present inventors graft-polymerized an aromatic vinyl compound and/or an ethylenically unsaturated compound onto a specific ethylene-propylene-nonconjugated diene copolymer rubber latex by an emulsion polymerization method, and optionally created a hard thermoplastic resin. In JP-A-6:1-95211, it was proposed that a thermoplastic resin composition having excellent resistance to 5, good surface gloss of molded products, and excellent impact resistance could be obtained by blending the following.

After that, as a result of intensive studies, we found that when an organosilicon compound with a specific structure is added to the thermoplastic resin composition obtained by the above method, it becomes impact resistant! I. The present invention was achieved by discovering that the performance of the patient can be significantly improved.

(Means for Solving the Problems) That is, the thermoplastic resin composition of the present invention is prepared in the presence of 5 to 90% by weight (as solid content) of the latex of ethylene-propylene-nonconjugated diene copolymer rubber (a). , an aromatic vinyl compound and the general formula CH2=l;RX (wherein R is I or CH, and X is CN or GOOR
' indicates. However, R1 is an alkyl group having 1 to 8 carbon atoms. At least one monomer (b) selected from the group consisting of ethylenically unsaturated compounds represented by 95 to 1
0% by weight《Total of (a) and (b) 11 100ffi
Graft polymer resin (1) obtained by polymerizing %)
20-100 parts by weight, hard thermoplastic resin (2) 0-8
0 parts by weight (<1) and (2) total amount 100 weight ~ R5 each independently represents an alkyl group or allyl group having 1 to B carbon atoms, and m represents an integer of 1 or more. ), a silane compound (d) represented by the general formula R"R3R'R'Si, and a silane compound (d) represented by the general formula R'
From the group consisting of organo-octarosilane compounds Te represented by lsIYn (where n is an integer of 1 to 3, Y represents a halogen atom, and R6 is an alkyl group or allyl group having 1 to 8 carbon atoms) A thermoplastic resin composition comprising 0.01 to 15 parts by weight of one or more selected organosilicon compounds (:1).

[Effect]

The ethylene-propylene-nonconjugated diene co-mercury rubber (a) used in the present invention includes ethylene, brobylene, and as a third component, for example, dicyclopentadiene, ethylidene norbornene, 1.4-hexadiene, 1.5-hexadiene, 2-methyl-1,5-hexadiene, 1,4-
It is an ethylene-propylene-nonconjugated dienter polymer (hereinafter abbreviated as EPDM) consisting of one or more nonconjugated dienes such as cyclohebutadiene and 1,5-cyclooctadiene.

It is preferable to use one or more of dicyclopentadiene and ethylidene norhornene as the non-conjugated gene component in EPDM.

The molar ratio of ethylene and brobylene in EPDM is 5:
Preferably, the ratio is in the range of 1 to 1:3, and EP
The proportion of unsaturated groups in DM is 4 to 50 in terms of iodine value.
It is preferable that it be within the range of .

Although there are no particular limitations on the method for producing EPDM latex, it is common to apply mechanical shearing force to EPDM in the presence of an emulsifier to stabilize fine dispersion in water to form a latex.

The particle size of the EPDM latex is preferably in the range of 0.05 to 2 μm. If less than 0.05μs is used, sufficient impact strength will not be developed, and if it is more than 2μs, polymerization will become unstable and the resulting graft polymer resin will not exhibit gloss. Tend.

The EPDM used in the present invention must be crosslinked.

When a non-crosslinked material is used, the development of Iiff strength is poor, and when molded at a high temperature, significant defects occur in the appearance of the molded product. When the degree of crosslinking is expressed in terms of gel content, it is preferably in the range of 30 to 95%. 3
If less than 0% is used, molding anisotropy will be significant,
Moreover, the gloss of the molded article will be poor, and if it exceeds 95%, the impact strength development will be poor.

The EPDM latex may contain a small amount (30% by weight or less) of one or more other rubbers depending on the purpose. Examples of such rubbers include polybutadiene, polyisoprene, styrene-butadiene rubber. Although other rubbers may be blended in this way, when the objective is weather resistance, it is preferable that the proportion of εPDM in the rubber latex is as high as possible.

The graft polymer resin (1) in the present invention is produced by an emulsion polymerization method.

In producing the thermoplastic resin composition of the present invention, the graft polymer resin (1) is a latex of EPDM (a) 5-90%! % (as solid content), an aromatic vinyl compound and the general formula (:H,=CRX (where R is H or GtCH*, X is ON or GOOR).
' indicates. However, Rl is an alkyl group having 1 to 8 carbon atoms. ) at least one monomer selected from the group consisting of ethylenically unsaturated compounds (b) 95
~10% by weight《《《》》and (b) total ilI00% by weight
>> in the presence of a radical polymerization initiator, the entire amount of monomer (b) is added all at once, in portions, or continuously into a latex for polymerization. As a polymerization initiator, a thermal decomposition type initiator such as potassium persulfate or ammonium persulfate, or a redox type initiator such as a sugar-containing birophosphate formulation which is a combination of cumene hydroperoxide-iron compound-sodium pyrophosphate dextrose is used. Can be used. Instead of cumene hydroperoxide, tert-butyl hydroperoxide, diisobutylbenzene hydroperoxide, etc. can also be used. It is also possible to use sodium salt of ethylenediaminetetraacetic acid (EDTA-2Na) instead of sodium birophosphate. It is also possible to use sodium formaldehyde sulfoxylate instead of dextrose.

During graft polymerization, it is preferable to add an additional emulsifier to stabilize the polymerization. As the emulsifier, any anionic emulsifier that can be used in normal emulsion polymerization can be used without any particular restriction, but fatty acid soaps, rosin acid soaps, etc. are common.

Typical examples of the aromatic vinyl compound include styrene, α-methylstyrene, vinyltoluene, terL-butylstyrene, and the like. Also general 2C}
Representative examples of the ethylenically unsaturated compound represented by l, = CRX include acrylonitrile, methacrylonitrile, and methyl, ethyl, proyl, and butyl esters of acrylic acid or methacrylic acid.

It is also possible to use a small amount of a crosslinking agent or a grafting agent in combination when graft polymerizing the above monomers or a mixture thereof. Examples of the crosslinking agent or grafting agent include divinylbenzene, ethylene glycol dimethacrylate, triallyl cyanurate, triallyl isocyanurate, allyl methacrylate, and the like.

The graft ratio of the obtained graft polymer resin (1) is preferably 5 to 150%. In addition, the reduced viscosity of the free lIl (co)polymer extracted from the graft polymer resin (1) with acetone (ηsp/c: 0.2% by weight in dimethylformamide, 25°C) is in the range of 0.3 to 1. It is preferable that the graft ratio is less than 5%, the development of impact strength is poor and the gloss of the molded product is reduced.
If the grafting ratio exceeds 150%, processability (fluidity) and impact strength will decrease. Free rs<ηsp of co)polymer/
When c is less than 0.3, impact strength decreases, and when it exceeds l, processability (fluidity) decreases.

The graft copolymer resin <<1>> thus obtained can be used as it is as the thermoplastic resin composition of the present invention, but the separately produced hard thermoplastic resin (2) (
They can also be used by mixing them in such a proportion that the proportion of graft polymer resin (1) in the total of 1) and (2) is 20 to 100% by weight.

As the hard thermoplastic resin (2), any resin that is hard at room temperature can be used without any particular restrictions, but acrylonitrile-butadiene-styrene tamamoto copolymer (
ABS resin), acrylonitrile-acrylic rubber-styrene copolymer (AAS resin), aromatic vinyl compound-acrylonitrile copolymer, aromatic vinyl compound-acrylonitrile-methyl methacrylate terpolymer, methyl methacrylate polymer , styrene-acrylonitrile N
- Phenylmaleimide terpolymer, α-methylstyrene-styrene-acrylic nitrile-N-phenylmaleimide quaternary copolymer, α-methylstyrene-acrylic nitrile-N-phenylmaleimide terpolymer, aromatic vinyl Preferred examples include compounds such as acrylonitrile-lower alkyl acrylate terpolymers, acrylonitrile-lower alkyl acrylate copolymers, and polycarbonates. It is also possible to use a hard trade resin in combination.

The organosilicon compound (3) used in the present invention generally independently represents an alkyl group or an allyl group having 1 to 8 carbon atoms, and m represents an integer of 1 or more. ) Organosiloxane (
Cl. Silane compound (d) represented by the general formula R2R3R'R5S i and the general formula R' ta-nl S
From the group consisting of organo-octarosilane compounds te) represented by IYn (wherein n is an integer of 1 to 3, Y represents a halogen atom, and R6 is an alkyl group or allyl group having 1 to 8 carbon atoms) At least one type selected.

Specific examples of organosiloxane (C) include polydimethylsiloxane, polymethylethylsiloxane, polydiethylsiloxane, and polymethylphenylsiloxane.

Specific examples of the silane compound (d) include tetraethylsilane, trimethylhexylsilane, and the like.

Further, specific examples of the organo-octarosilane compound (e) include triethylchlorosilane, phenyltricylsilane, diphenyldicilsilane, and the like.

When selecting and using these organosilicon compounds, it is necessary that the compound has a boiling point of 120° C. or higher and is thermally and chemically stable within the molding temperature range of the resin composition. Examples of polysiloxanes that satisfy this condition include polysiloxanes having a viscosity of 0.5 to 500,000 centistokes (at 25°C), preferably 50,000 to 50,000 centistokes.

As the organosilicon compound (3), one of the above compounds may be used alone, or a number a may be used in combination. The amount used is the graft polymer resin (1) and the hard thermoplastic resin (1).
2) Total! 00! '0.01 to 1 for Ij quantity part
5 parts by weight, more preferably O. Ol~IOjli parts. 0.0! If it is less than 1 part by weight, the impact resistance will be insufficient, and if it exceeds 15 parts by weight, the heat resistance will be greatly reduced.

Addition of the organosilicon compound (3) by cross-linking to the resin latex is not very effective, so it is preferable to add it to the resin powder.

The thermoplastic resin composition of the present invention may optionally contain various coloring agents such as dyes and pigments, lubricants such as metal soap, and hindered amine compounds, penzotriazole compounds, and penzophenone compounds as stabilizers against light. alone or in combination with a hindered phenol compound, thioether compound, phosphite compound as a stabilizer against heat, an inorganic or organic granular, powder or fibrous filler, A blowing agent etc. can be added.

In addition, this composition can be molded by various processing methods such as injection molding and extrusion molding, and can be used as various molded products with excellent impact resistance, weather resistance, and sliding properties, and as a component of laminate structures, such as sunlight. It can also be used as the outermost layer exposed to

(Example) Hereinafter, the present invention will be explained in more detail with reference to Examples.

In the examples, % and parts represent weight % and parts by weight, respectively.

The evaluation method was as follows.

Evaluation method (1) Izod impact strength (Iz) ^STMD-258 (unit: kg - cm/ca
).

(2) Melt flow index (M1) manufactured by Toyo Baldwin, ASTMD-1 by melt indexer
238 (200°C, load 5kg).

(3) Rockwell hardness (R) Measured according to STM 0785 (R scale).

(4) Vicat Softening Temperature (VST) Measured according to ISO R-306 (unit: °C). (
Load: 5 κg) (5) Glossiness Measured using a digital angle gloss meter (incident angle = 60°) manufactured by Suga Test Instruments.

(6) Gel content: After 6 hours of reflux in boiling toluene, the insoluble content was reduced to 10
The mixture was filtered through a 0-mesh wire mesh, dried, and weighed, and the insoluble content was determined as the gel content.

Example I EPDM latex (average particle size 0.5-, gel content 60%, use of ethylidene norhorne, iodine value 15)
(as solid content) 50 parts disproportionated potassium dinate
1 part Sodium birophosphate
0.5 part ferrous sulfate 0.005
0.6 parts dextrose 200 parts ion-exchanged water The above composition was heated to 70°C in a reaction vessel. Separately prepared acrylonitrile (AN) 15 parts, styrene (ST) 35 parts, cumene hydroperoxide ((:HP) 0.25
and tert-dodecylmercabutane (t-DI)
0.2 part of the solution was added dropwise over 2 hours with stirring.

After the dropwise addition was completed, stirring was continued for an additional hour to obtain a graft polymer resin.

The latex of the obtained graft polymer resin was coagulated with dilute sulfuric acid, dehydrated and dried to recover white powder.

[Measurement of graft ratio and ηsp/c of graft polymer resin: These measurement methods are common to the following examples and reference examples. ] From the latex of the graft polymer resin mentioned above, 1 g of powder coagulated with isobrobyl alcohol and dried was mixed with 2 g of acetone.
00- and reflux at 70°C for 4 hours.
The acetone dispersion was separated into soluble and insoluble components using a centrifuge, the insoluble components were dried, and the glut ratio was calculated.2
It was 5%. In addition, acetone is evaporated from the acetone-soluble portion to free acrylonitrile-styrene copolymer (AS
resin” was collected. 0.1 g of this As@4 was dissolved in 50% dimethylformamide, and the reduced viscosity at 25°C (
ηsp/c) was measured and found to be 0.55.

[Preparation of resin composition] 48 parts of the graft polymer resin powder obtained above and separately manufactured AS resin I (AN/ST=30/70
(weight ratio), ηsp/c=0.65) 0.5 parts of calcium stearate, 0.2 m of triphenyl phosphite and 0.2 m of polydimethylsiloxane (viscosity at 25° C. 100 centistokes). 0
2 parts were added and mixed in a Henschel mixer. Next, 200℃, 150r in a 40a + φ single screw extruder
It was pelletized using p- and its basic physical properties were evaluated. Table 1 shows the results.
It was shown to.

Example 2 EPDM latex《Average particle size 0.53 m, gel content 50%, use of ethylidene norbornene, iodine value 20
》《As solid content》60 parts potassium oleate
1 part Sodium pyrophosphate
0.5 parts ferrous sulfate 0.005 parts dextrose 0.6 parts ion-exchanged water 200 parts The above composition was charged into a reaction vessel and the temperature was raised to 70°C.

4.5 parts of AN, 10.5 parts of ST, 0.075 parts of triallyl cyanurate and CHP O. One part of the mixed solution was added dropwise over 60 minutes. Continued ^ N4.5 part, ST
0.5 parts I, 0.06 parts t-DM and 0 CIIP
．． 075 parts of the mixed solution was added dropwise over 60 minutes, and stirring was continued for 60 minutes to maintain the temperature at 70°C to complete polymerization. The grafting rate was 28% and ηsp/c=0.41. Hereinafter, coagulated powder of graft polymer resin was collected in the same manner as in Example 1, and 33.3 parts of this graft polymer was added to
68.7 parts of the above AS resin I, 0.5 parts of calcium stearate, 0.0 parts of trisnonylphenyl phosphite.
2 parts and polydimethylsiloxane (viscosity at 25°C 1
0.00 centistokes) was added and mixed using a Henschel mixer, and then mixed using a 40@■φ extruder.
The pellets were pelletized at 0° C. and 150 rpm, and the basic physical properties and molded appearance were evaluated. The results are shown in Table 1.

Examples 3 to 6 and Comparative Examples 1 to 2 Bulleting was obtained in the same manner as in Example 1, except that the type and amount of the organosilicon compound added were changed as shown in Table 1. , basic physical properties and molded appearance were evaluated. The results are shown in Table 1.

Comparative Example 3 In Example 1, the amount of t-DM used was changed from 0.2 parts to 1 part.
．． Graft polymerization was carried out in the same manner as in Example 1 except that the amount was increased to 0 parts. The grafting rate of the obtained graft polymer tree was 8%, and ηsp/c=0.25. The same procedure as in Example 1 was carried out except that polydimethylsiloxane was not added, and AS resins were blended in the same proportions to form pellets, and the basic physical properties and molded appearance were evaluated. The results are shown in Table 1.

Comparative Example 4 In Example 1, the amount of t-DM used was 0.2 parts or 60 parts.
Graft polymerization was carried out in the same manner as in Example 1, except that The graft ratio of the obtained graft polymer resin was 45
%, and ηsp/c=1.32.

The AS resin I was blended in the same proportion as in Example 1, except that polydimethylsiloxane was not added, and pelletized, and the basic physical properties and molded appearance were evaluated. The results are shown in Table 1.

Comparative Example 5 Graft polymerization was carried out in the same manner as in Example 1 except that the average particle diameter of the EPDM latex was changed from 0.5 μm to 2.5 μm. During the process, the polymerization system became unstable and coagulated, making it impossible to continue the polymerization to the end. Comparative Example 6 EPDM with a gel content of 20% in Example 1
A graft polymer resin was obtained in exactly the same manner as in Example 1, except that . The graft polymer resin was blended with AS resin in the same proportion as in Example 1, except that polydimethylsiloxane was not added, and evaluated. The results are shown in Table 1.

Examples 7 to 12 35 parts of the graft polymer resin obtained in Example 2 and 65 parts of various isthmic resins were each blended, and further 0.5 parts of calcium stearate, 0.2 parts of triphenyl phosphite, and polydimethyl were added. Siloxane (viscosity 100 at 25°C
centistokes) was added and mixed in a Henschel mixer, pelletized in a 40 mmφ extruder, and the basic physical properties and molded appearance were evaluated. The results are shown in Table 2.

The following hard resins were used.

Copolymer technology: ^N-α methylstyrene (αMS) copolymer (8N/αMS = 20/80 (weight ratio), ηsp
/c=0.5) Copolymer ■: ^N-αMS-N-phenylmaleimide (
NPM) copolymer (^N/αMS/NPM = 20/6
5/15 (il amount ratio), ηsp/c=0.6) Polycarbonate resin (PC): 7022PJ (manufactured by Sanro Kasei Kogyo ■) ABS resin: Diabet ■^BS #1001 (manufactured by Santsuri Rayon $I) AAS resin: Dialac ■＾AS S31G (manufactured by Mitsubishi Rayon ■) PMMA resin: Acryvet ■VH (manufactured by Mitsubishi Rayon ■) Comparative Examples 7 to 10 The following city version AES resins were evaluated in the same manner as in Example 1. ．The results are shown in Table 2.

A E st! IJl1 (I): AES #1
10 (Made by El synthesis = 1'mu I1) [High impact brand] AES resin (II): ES [47 (Made by Japan Synthetic Rubber)] {Heat-resistant brand] AES resin (m): U-B-7 13B-500
(Manufactured by Sumitomo Naugatac ■) <<High impact brand>> AES resin (IV): Unibright DB-800 (Manufactured by Sumitomo Naugatack ■) (Heat-resistant brand) (Effects of the invention) The thermoplastic resin composition of the present invention has a heat-resistant 2. Compared to AES resins obtained by methods other than conventional emulsion polymerization methods, it is particularly superior in terms of gloss, and is Compared to the composition containing no compound, the HIl resistance is significantly improved.

Patent applicant: Mitsubishi Rayon Co., Ltd.

Claims (1)

[Claims] (1) Ethylene-propylene-nonconjugated diene copolymer rubber (a) latex 5 to 90% by weight (as solid content)
in the presence of an aromatic vinyl compound and the general formula CH_2
=CRX (in the formula, R represents H or CH_3, X represents CN or COOR^1, provided that R^1 has a carbon number of 1 to
8 alkyl group. ) at least one monomer selected from the group consisting of ethylenically unsaturated compounds (b) 95 to 10% by weight (total amount of (a) and (b) 1
00% by weight) obtained by polymerizing the graft polymer resin (
1) 20 to 100 parts by weight, hard thermoplastic resin (2) 0
~80 parts by weight (total amount of (1) and (2) 100 parts by weight)
, and the general formula R^2▲ mathematical formulas, chemical formulas, tables, etc. ), a silane compound (d) represented by the general formula R^2R^3R^4R^5Si, and a general formula R^6_(_4_-_n_)Si.
An organohalosilane compound represented by Y_n (where n is an integer of 1 to 3, Y represents a halogen atom, and R^6 is an alkyl group or allyl group having 1 to 8 carbon atoms) (
A thermoplastic resin composition comprising 0.01 to 15 parts by weight of one or more organosilicon compounds (3) selected from the group consisting of e).