JPS58183729A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To prepare a thermoplastic resin composition having improved thermal stability and impact resistance, by compounding a thermoplastic resin containing a polymer having imide group in the side chain with a specific amount of a specific phosphorus compound. CONSTITUTION:The objective thermoplastic resin composition is prepared by compounding (A) 70-99.9pts.wt. of a thermoplastic resin (e.g. methyl methacrylate-butadiene-styrene copolymer) containing a polymer having imide group in the side chain (e.g. a polymer obtained by imidating a copolymer of an aromatic vinyl monomer and an unsaturated dicarboxylic acid anhydride) with (B) 0.1-30pts.wt. of one or more phosphorus compounds selected from phosphoric acid ester, phosphorous acid ester, phosphonic acid ester, acidic phosphoric acid ester, acidic phosphorous acid ester, metal salt of acidic phosphoric acid ester and metal salt of acidic phosphorous acid ester, and if necessary, adding an antioxidant, a flame-retardant, a plasticizer, etc. to the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a thermoplastic resin composition with improved thermal stability and impact resistance, and more particularly, a polymer having an imide group in the side chain and a compound having an imide group in the side chain. The present invention relates to a thermoplastic resin composition.

A method for producing a monomer having an imide group on its base has been known for a long time. (υspy, 840,499° and 1s) 6,
998,907) Also known are compositions in which impact resistance is improved by adding rubber grafts or polycarbonate to polymers carrying imide groups. (USP 3
, 652.7261' TJspro, 642.949.
(Japanese Patent Publication No. 49-12576) Polymers having imide groups on these sides have a high heat distortion temperature, but have the drawbacks of poor impact resistance and poor color tone due to heat retention.

In addition, compositions prepared by blending rubber grafts or polycarbonate have a certain degree of improvement in impact resistance, but are not sufficient, and these also have the disadvantage of deteriorating color tone due to heat retention.

The present inventor conducted intensive research in order to improve the drawbacks of polymers having one imide group in their side chains and compositions containing the polymers, and found that by adding a specific glue/compound, impact resistance could be improved. We have succeeded in producing a thermoplastic resin composition in which the resin composition is clearly modified in terms of its composition, and at the same time shows no deterioration in color tone due to heat retention. That is, the present invention can detect V
70 to 99.9 parts by weight of a thermoplastic resin containing a t-imide group 111-1 and a phosphoric acid ester, a functional phosphoric acid ester, a phosphonic acid ester, an acidic acid ester,
Acid phosphite, acid phosphite/acid ester gold) II
The thermoplastic resin composition is characterized in that it contains one or more phosphorus compounds (1 to 301M) selected from the gold lI4 salt of acidic phosphite and a part of 1 to 301M.

As the polymer having an imide group to be detected in the VC of the present invention, 1) a co-1 polymer in which an aromatic vinyl mass and an unsaturated dicarboxylic acid anhydride are polymerized in 1 in the presence or absence of a rubbery polymer; 11) An aromatic vinyl polymer, an unsaturated dicarboxylic acid anhydride, and a vinyl content lid body that can be combined with these are combined in the presence or absence of the rubbery 1 polymer. 111, an imidized electrolyte,
) a co-1 polymer imidized 1-combined olefin/and unsaturated carvone #k in the presence or absence of a rubber-like 1-combinator, 1v) in the presence or absence of a rubber-like 1-combinator An imidized monopolymer obtained by copolymerizing a monopolymer copolymerizable with acrylic acid and/or methacrylic acid, an aromatic vinyl monomer, and a maleimide in the presence or absence of a rubbery polymer. A polymer obtained by polymerizing P and/or mono-substituted maleimide, v+') Aromatic vinyl compound, maleimide and/or N-[substituted maleimide and these together in the presence or absence of a rubbery polymer. There are monomers made by increasing the length of vinyl polymers capable of co-merging.

In addition, as the thermoplastic resin containing the main polymer having an imide group for detection in the present invention, the polymer having an imide group on the 9111 chain as exemplified in the preceding configurations) to vi) is
) acrylonitrile-butadiene/-styrene and/or α-methylstyrene copolymer, vm) methyl methacrylate-butadiene/-styrene copolymer, 1x) acrylonitrile-ethylene/furobile/-styrene copolymer, X) Acrylonitrile-ru-styrene/and/or α-methylstyrene combination, ×1) Rubber modified Sunare/3m combination, ×11) Polycarbonate, X111) Styrene-
1 polymer that has been retired from butadiene block copolymer etc. is 1
An example is thermoplastic resin blended with glaze or more. Of course, the thermoplastic resin includes one polymer having an imide group in the measurement, and also includes one polymer having an imide group on the side as a thermoplastic resin.

In the present invention, the specific phosphorus compounds added to the thermoplastic resin containing one compound having an imide group at 01lI@ are phosphoric esters, phosphoric esters, phosphonic esters, acidic phosphoric esters, acidic phosphoric esters, It is one or more phosphorus compounds selected from phosphite esters, gold maple salts of acidic phosphoric acid esters, and gold maple salts of acidic phosphite esters.

Phosphate esters include trimethyl phosphate, triethyl phosphate, triethyl phosphate, trioctyl phosphate, triftquine ethyl phosphate, triphenyl phosphate, tricresyl phosphate, tokki/renyl phosphate, trinonylphenyl phosphate, cresyl diphenyl. phosphate, quinolenyl diphenyl phosphate, octylsophenyl phosphate, trilauryl phosphate, tricetyl phosphate, tristearyl phosphate, trioleyl phosphate, and their halodef-substituted phosphates.

Phosphite esters include trimethyl phosphite, triethyl phosphite, tributyl phosphite, trioctyl phosphite, triphenyl phosphite, tricresyl phosphite, tricylenyl phosphite, trinonylphenyl phosphite, cresyl sifuenino. L-phosphite, trilauryl phosphite, tricetyl phosphite, tristearyl phosphite, trioleyl phosphite, triphenyl trithiophosphite, trilauryl trithiophosphite, tristearyl trithioposphite and these halogen-substituted phosphites There is something like that.

Phosphonate esters include diethyl ethyl, phosphosulfate, dibutylbutyl phosphonate, diphenylphenyl phosphonate, dicresyl resinyl phosphonate, di(2-ethylhexyl) 2-ethylhexylphosphonate, and these halokes/esters. Conversion phosphor compound etc. are shown.

Examples of acidic phosphoric acid esters include monomethyl acetate phosphate, dimethyl acid phosphate, monoinzolobyl acid 1j.Sufney 1 diisozolobyl acid phos7ate, monopteranthodophosphate, dibutyl acid phosphate, monooctyl acid phosphate, and dimethyl acid. Phosphate, monomethyl andophosphate, zolauryl anthodophosphate, monostearyl andophosphate, cystearyl andophosphate, monophenyl acid phosphate, diphenyl acid phosphate, monocresyl acid phosphate, dimethyl acid phosphate, tunonyl chloride phenyl acid phosphate, dinylphenyl acid phosphate and their halo r
/ Iikyaya 7 Sodophosphate etc.

Examples of acidic phosphites include monomethyl anthodophosphite, dimethyl acid phosphite, monoisopropyl acid phosphite, diisoprogyl acid phosphite, monobutyl acid phosphite, dibutyl acid phosphite, monooctyl acid phosphite, and dioctyl acid phosphite. Phosphite, monolauryl acid phosphite, dilauryl acid phosphite, monostearyl acid phosphite, distearyl acid phosphite, monophenyl acid phosphite, diphenyl acid phosphite, monobutyl acid phosphite, dibutyl acid phosphite, seven Tunonylphenyl acid phosphite, dinonylphenyl acid phosphite and these
There are acid phosphites that replace rodene, etc.

Examples of the metal salts of acidic phosphoric acid esters and hostile phosphite esters include the above-mentioned acidic +JZeR esters and acidic phosphorus/acid esters), 1gj4, Zn, aluminum salts, and the like.

1 liter of a specific phosphorus compound that can be used in the present invention
TiJw contains a single complex with an imide group in the detection.
70-99. It is 0.1 to 30 parts per lJ. More preferably, it is 0.5 to 10 parts by weight. If the amount of the phosphorus compound is less than 0.1 m3, the impact resistance of the composition and the color stability in the heat-extinguishing box are insufficiently improved.

On the other hand, if the amount exceeds 1 or 30 parts/compound, the composition will have a markedly reduced deformability and mechanical strength.

The composition of the present invention is a mixture of a thermoplastic resin containing an imide group and a phosphorus compound.
The mixing method #'i% is not limited, and known means can be used. Examples of such means include a bar/i-mixer, a tumbler mixer, a mixing roll, a single-screw extruder, or a 2III extruder. Examples of mixing methods include water flow bath v i* mixing, multi-stage bath melt mixing using a master veil, etc., and bath liquid blur/P.

Further, in the composition v/J of the present invention, an antioxidant, a flame retardant,
ultraviolet#! It is also possible to add absorbents, plasticizers, lubricants, glass cords, carbon fibers, fillers such as calcium carbonate, colorants, gold powder, etc. The composition of the present invention has good thermal stability and impact resistance. You can use gender correctly.

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

Incidentally, all parts and parts in the examples are expressed on a weight basis.

760 parts of l-chire, which is an imidized mixture of all 1-combined compounds;
100 parts of methyl ethyl keto/(MEK) and 10 parts of polybutadiene cut into small pieces were charged, and after purging the inside of the thread with gold nitrogen gas, the mixture was stirred at room temperature all day and night to dissolve the rubber. After setting the turbidity to 85°C, add 40 parts of maleinoic anhydride/Silver Oxai V
A bath solution containing 12 parts of O and 50 parts of MEK was continuously added over 6 hours.

After the addition, the temperature was maintained at 85° C. for another 4 hours and the single chamber was closed with a fixed lid, and as a result, the 1 ratio was 97%. Here, 0.5 part of triethylamine was added to the anhydrous Malay/&, 38.0 parts of triethylamine, and 14
The reaction was carried out at 0°C for 6 hours.

Methyl ether ketone 1 sos was added to the anti-KIS bath solution, cooled to room temperature, poured into 1000 parts of methanol with stirring, precipitated, separated by volume, and dried to obtain imidized 1 compound. This is called lk stand body A. c'-13 NMR5+ analysis showed that the conversion of 4U to imide groups from the acid anhydride difference was approximately 100%.

60 parts of methylene chloride and 10 parts of acrylonitrile were used instead of 60 parts of styrene in Experimental Example (]), 40 parts of maleinoic anhydride was changed to 30 parts, and 38.0 parts of aniline was changed to 28 parts of aniline. An imidized monomer was obtained by carrying out exactly the same operation as in Experimental Example (1) except that .5 sounds were used. This is called 1 combination B. The 1st rate at this time is 95%
.

The conversion rate to imide groups was 99%.

-Methylstyrene 60Th, N-phenylmaleimide 1
5 parts, 10 parts of acrylonitrile, 10.4 tons of dodecylpe/sene sulfone drinking ivy
4+1 and 210 parts of water were charged, and the inside of the system was replaced with nitrogen gas. Potassium perrate 1 at a temperature raised to 70°C
Polymerization was started by adding 10% water bath solution. From the beginning, 15 parts of acrylonitrile was added to each yarn over 6 hours. 2I after addition! 1 potassium sulfate 1 t aqueous solution,
10'' was added, and further 1 cup was added for 4F #f, then -h of 0 polymerization was added, and the unreacted body was stored by gas chromatography, and the result was 1 cup. The rate was 97%. The thus obtained 1-comb emulsion was soaked in calcium chloride, dehydrated, and dried to obtain a white powdery polymer.

This is called 1 combination C.

80 parts of phoribtadiene latex (1 cedar content: 50%, average particle size: 0.65μ, 90% discrepancy), stearic acid powder 1b1 sodium formaldehyde sulfoxy
) 0.1 part, 0.06 part of tetrasodium ethylenediamine tetraacetic acid, 0.0 part of ferrous iron
0.03 parts and 200S of water were heated to 65°C, and to this was added 60sS of a lid mixture consisting of 30% acrylonitrile and 70% styrene - 0.311S of dodecyl mercaptan.
, 0.2 s of cumene hydronoxide were continuously added over 4 hours, and after the addition was completed, 1M and 1M were combined for 2 hours at 65°C. The polymerization rate was 96%. After adding an anti-saponification agent to the obtained latex, it was hardened by IR with calcium chloride,
A light blue, dry*-white powdery compound was obtained. AB this
Display as S.

Example 1 Infusion example (1 coalescence obtained from 1+*70 ftls, ABS 30 h obtained in Experimental Example (4) and tristearylphon sulfate 1iTh were mixed in a hexyl mixer, extruded in a vented extruder, and pelletized. 0.0% in the blend.
Two parts of the antioxidant Irganox 1076 (manufactured by Ciba Geigy) was included.

Irganox 10 was used in all Examples and Comparative Examples hereinafter.
76 was contained in an amount of 0.2 part. The physical properties of the composition thus obtained are shown in Table 1.

Imidized polymers A, B, and C (1) and ABS obtained in Experimental Example (4) and acrylonitrile-styrene (1)
Combined (Sunrex 5AN-B: manufactured by Mitsubishi Motors Corporation, hereinafter referred to as As), rubber-modified styrene polymer (Dencastyrol HIU-2: 11L manufactured by Kaikaji Co., Ltd., hereinafter referred to as HIPS), polycarbonate (Panlight-1300: Manufactured by Konjin Kasei Co., hereinafter referred to as pc) 1
Compositions were prepared by mixing each axial compound with a hot plastic machine fat blended with each of the above compounds, and the physical properties of each were measured and are shown in Table 1.

Table 1 shows that the compositions of the present invention are significantly improved in impact resistance and retention heat stability compared to compositions that do not contain a specific phosphorus compound.

The following methods were used to measure the physical properties of the specimen.

ill Resistance @Izot strength with notch, D
According to D-256.

(2! Vicat softening point... 5'i-p AS
According to TMD-1525.

(31) The change in color tone of the molded product injection molded at 280°C was visually determined.

0: Almost no change in color tone.

X: Obvious yellowing.

Patent applicant Denki Kagaku Kogyo Co., Ltd.

Claims (1)

[Claims] Thermoplastic resin 70 to 99.9114 containing a polymer having an imide group on the side Q; A thermoplastic resin characterized by containing a gold maple salt of a phosphoric acid ester and a part of 0.1 to 3 Dfi of one or more phosphorus compounds separated from the gold maple salt of a phosphite ester. Composition.