JPS58185642A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. having greatly improved impact resistance, a high heat distortion temperature and improved boiling water resistance, by blending a rubber-modified imidated polymer and a rubber-modified arom. vinyl copolymer as essential polymers. CONSTITUTION:(A) a thermoplastic resin compsn. contains 10-90pts.wt. rubber- modified imidated polymer obtd. by graft-polymerizing 67-97wt% monomer mixture consisting of 50-60wt% arom. vinyl monomer and 40-50% unsaturated dicarboxylic acid anhydride onto 3-40wt% rubbery polymer and then reacting ammonia and/or a primary amine with the resultant graft copolymer, (B) 90- 10pts.wt. graft copolymer obtd. by copolymerizing 97-20wt% monomer mixture consisting of 40-90wt% arom. vinyl monomer, 0-40wt% vinyl cyanide and 0-50wt% copolymerizable vinyl monomer with 3-80wt% rubbery polymer and (C) 0-80pts.wt. polymer obtd. by polymerizing 40-100wt% arom. vinyl monomer, 0-40wt% vinyl cyanide monomer and 0-40wt% vinyl monomer copolymerizable therewith.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a thermoplastic resin composition with excellent thermal stability, impact resistance, and hot water resistance, more specifically, a rubber-like monomer, an aromatic vinyl monocylindrical body, and an unsaturated dicarbonate anhydride. A mixture of a rubber-modified imidized polymer having an imide group and a rubber-modified aromatic vinyl co-monomer obtained by reacting the co-monomer with ammonia and/or a primary amine is an essential component. The present invention relates to a thermoplastic resin composition.

Conventionally, there have been copolymers in which a rubber-like monomer is grafted with a mixture of an aromatic vinyl monomer, an unsaturated dicarboxylic anhydride, and other monomers, and a rubber-modified copolymer is also used.
It is known that the combination is blended (% Kaisho 48-
No. 42091, JP-A-54-96555). These copolymerized dicarboxylic acid anhydrides still have a heat distortion temperature, but this is due to the presence of acid anhydride groups originating from the unsaturated dicarboxylic anhydride in the copolymer chain. In addition to water at the temperature of a pot, it also undergoes chemical changes when exposed to heat, and is easily decomposed, resulting in significant restrictions when performing injection or extrusion processing, and when the processed product is not brought into contact with water or steam. When it is exposed to high temperatures, it has the disadvantage of causing a decrease in mechanical properties, especially impact strength.

The old ll5P 5,642,949 had the so-called ABS
discloses a composition comprising a comonomer of an aromatic vinyl monomer and an unsaturated dicarboxylic acid anhydride or an imide thereof. However, in such a composition, whether an unsaturated dicarboxylic acid anhydride or an imide made of an unsaturated dicarboxylic acid is used, both I
ki Hayabusa Goura is low and not enough.

The present invention relates to a rubber-modified imidized co-monomer obtained by imidizing the acid anhydride group of the monopolymer obtained by grafting an aromatic vinyl monomer and an unsaturated dicarboxylic acid anhydride to a rubber-like polymer, and a rubber-like polymer. By preparing a polymer essentially consisting of aromatic vinyl and vinyl cyanide monomeric polymer in the form 1 polymer, it has significantly improved impact resistance, high heat distortion temperature, and heat resistance. This is the first success in obtaining a thermoplastic resin composition with improved aqueous properties.

That is, in the present invention, Ag content: 6 to 401% by weight of rubbery polymer and 501% by weight of aromatic vinyl monomer! Ejt% or more 601kii and unsaturated dicarbo7 anhydride 401k1% or more 50
Monomer mixture consisting of 111% or less 60-97111%
Component B: Rubber-like 1 polymer 6 ~80! With respect to li%, aromatic vinyl monomer 40-9[,111%, vinyl cyanide monomer θ-40]! A mixture consisting of 0 to 50 parts of a vinyl monomer that can be combined with 20 to 50 parts of vinyl monomer
Kerafto co-1 polymerized by copolymerizing 973k11% 10~
90 parts, C component: aromatic vinyl monomer 40-10
01 0-40111% of polyvinyl anodized vinyl basemer and 11% of vinyl monomer D-401 which can be combined with these
The object of the present invention is to provide a thermoplastic resin composition containing a combination θ to 80 times IIS.

The present invention is a composition comprising component A, component B, and optionally component C, but it is essential that both component A and component P contain a rubber-like 1-coalescence. Therefore, if any one of these components does not have a rubber-like unity, the ri false impact resistance will be low.

The thermo-EJ plastic resin composition of the present invention may consist only of the A component and the B fraction, but in the past, aromatic vinyl may be used alone or in combination with vinyl cyanide, etc. 8
Even if the thermoplastic resin composition of the present invention is mixed in a range of 0m or less, the excellent tuna customization properties of the thermoplastic resin composition of the present invention will not deteriorate. have

First, the A component polymer and its manufacturing method will be explained.

The A component polymer has a weight of 6 to 40% by weight, preferably 5 to 1%.
Contains 6 oz. of rubbery polymer. Rubber-like polymers include butadiene homomer, copolymers with butadiene and vinyl monomers capable of co-merging, ethylene/propylene copolymers, ethylene-propylene-diene copolymers,
The rubber component in the OA component polymer used is a block co-monomer of butadiene and aromatic vinyl, a co-monomer of acrylic acid ester, and a co-monomer of acrylic ester and a vinyl monomer copolymerizable therewith. This is because if it is less than 311 t%, the impact resistance will be poor, and if it exceeds 40%, the heat resistance and cedar workability will be poor. In addition, the monomers to be crafted into these are aromatic vinyl monomer 50, 11Iiqb or more and less than 60]k storage, and unsaturated cicarbium/anhydride 40
It consists of more than 1i1% and less than 50]k amount,
This is because if the aromatic vinyl content is less than 50% and the aromatic vinyl compound contains styrene, moldability and dimensional stability will be lost, and unsaturated dicarboxylic anhydride If it exceeds 5°lv%, the copolymer becomes brittle and the moldability becomes worse.

The aromatic vinyl monomers constituting component A include methyl/, α-methylstyrene, vinyltoluene, t-butylmethylene/, chlorostyrene, methylene/monomer, and its plow-converted monomer. methyl/and α-
Particularly preferred is methylstyrene.

Maleino rice is an unsaturated dicarboxylic acid anhydride.

There are anhydrides of itaconic acid, citraconic acid, aconite acid, and maleic anhydride is preferred.

The ammonia and primary amino acids used in the imidization reaction of the present invention may be in either an anhydrous state or a water bath solution, and examples of the primary amino acids include methylamine, ethylamine, n-propylamine, Alkylamines such as -o-propylamine, butylamine, bemethylamine, cyclohexylamine, etc., and their chloro- or bromine-substituted alkylamines, aniline, tolylamine, naphthylamine, aromatic amines, and chloro- or bromine-substituted alkylamines. Anili/bonito halogen-substituted aromatic amines are produced.

In the present invention, a catalyst may be present when imidizing the rubber-like monomer-aromatic vinyl-unsaturated dicarboxylic acid anhydride co-monomer with ammonia and/or a primary amine. Commonly used are tertiary amines.

When the imidization reaction is carried out along fb or in a suspended state F
It is preferable to use a reaction vessel such as an autoclave or the like, and in the case of melting the bulk bath, an extruder equipped with a devolatilization device may be used.

The temperature of the imidization reaction is about 80-350°C, preferably 100-300°C. If the temperature is lower than 80°C, the reaction rate is slow and the reaction takes a long time, which is not practical. On the other hand, if the temperature exceeds 650°C, the physical properties will deteriorate due to the heat content S of the 1-combination. Solvent for imidizing the rubber-like 1-combination - aromatic vinyl-unsaturated dicarbonate and anhydride combination in a bath liquid state. Examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, cyclo-, xanone, tetrahydrofuran, toluene, chlorine, chlorobenzene, and chlorobenzene. When imidizing in a suspended state, hebutane, hexano, befuran, octane, 2
- There are aliphatic reconstituted water compounds such as methylpentane, cyclopentane, and cyclohexa7.

Next, we will explain the VCB component and its manufacturing method.

The rubber-like compound used in the F3 configuration is made of a vinyl resin lid that can be combined with butajeno alone or with it.
As the aromatic vinyl monomer of the O B component, the aromatic vinyl monomer of the O B component can be a combination of ethylene-propylene/co-combination or acrylic ester alone or together with a single vinyl monomer. α-methylstyrene, vinyltoluene, t-butylmethylene/,
Stereph ratio ta form such as chlorostyrene and its conversion ratio are integral, and among these, monomers such as stele and α-methelsunarene are preferred.

Examples of vinyl cyanide include acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile, with acrylonitrile being preferred. Also, together with these 1
Examples of vinyl monomers that can be combined include methacrylic acid esters such as methyl acrylic esters, ethyl acrylic esters, butyl acrylic esters, methyl methacrylic esters, ethyl methacrylic esters, acrylic acid, and methacrylic esters. Vinyl carboxylic acid/acid ratio 1 substance, acryl removed amide, methacryl amide, acenaphthylene, N-vinylcarbazole, etc. are available. Among these, methyl methacrylate, acrylic acid, and methacrylic acid are preferred in terms of percentage.

The method for producing the grafted 1-combination of component B is rubber-like 1-combination 3 to 8.
0] kiI% presence) of aromatic vinyl monoxide 40 to 90
] [obtained by graft copolymerizing 20 to 971 L of a monomer mixture consisting of 0 to 40 m-1 of vinyl cyanide and 0 to 5011% of vinyl that can be combined with these. It will be done. Any known polymerization technique can be employed for the polymerization, such as suspension 1 polymerization, aqueous heterogeneous 1 polymerization such as emulsion polymerization, bulk polymerization, bath 1 polymerization, and precipitation of the resulting polymer in a non-solvent. There is a rallying cry.

Next, component C and its manufacturing method will be explained.

As the aromatic vinyl monocap for C17i, styrene, α
- Methyl styrene, vinyltoluene, t-bunalstyrene, chlorostyrene, methylene 7 monomer* and its fi
Among these, methyl/and α-methylstyrene are particularly preferred.

Acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile are available as cyanide-based caps, with acrylonitrile being preferred. Vinyl-based caps that can be combined with these include menal acrylate, ethyl acrylic, etc. Acrylic removal ester jPL integrated with ester, butyl acrylic ester,
Methyl methacrylic acid ester, ethyl methacrylic acid ester, etc., methacrylate-removed ester single noodle, acrylic acid, methacrylic acid, etc., vinyl carboxyl/# monomer, acrylamide, amyl methacrylate r1, acenaphthylene, N-
Vinyl carbazole, N-alkyl substituted maleimide, N
- Aromatically substituted maleimide compounds are discovered.

The composition of the present invention is a mixture of the above-mentioned component A, component B, and optionally component C, but there are no particular restrictions on the mixing method, and known means can be used. Examples of such means include a Banbury mixer, a Henshil mixer, a tumbler mixer, a mixing roll, and a single-screw or twin-screw extruder. As a mixed form) I! There are methods for obtaining a composition by performing bath melt mixing in an i-window, bath melt kneading at each stage using a master pellet, and grafting in the presence of a bath liquid.

The ratio of blending each component of component A, component B, and component C is 10 to 90 parts sodium bicarbonate for component A and 10 to 90 parts for component B.
1' H, C component is 0 to 80 weight ii, preferably 0 to 5%
(lHkii%) The reason for limiting the bleed ratio in this way is to maintain the excellent heat resistance and hot water resistance of component A, prevent deterioration in moldability, greatly improve AS resistance, and In order to maintain the physical properties in a well-balanced manner, V(V′i
It is necessary to blend component B and component C in an appropriate ratio.

It is also possible to further add to the composition of the present invention stabilizers, flame retardants, 5-part W agents, lubricants, glass fibers, light absorbing agents such as rehydrated calcium, colorants, and other filtration absorbers. It is.

The compositions of the present invention have thermal stability and impact resistance of 9e-t'.
It can be used for many purposes, such as automobile parts, electrical and electronic parts, household appliances, office equipment, etc. Furthermore, because it has excellent hydrothermal properties, it can also be used for food and drink products, bathroom parts, and medical/chestnut equipment.

The present invention will be explained below with reference to Examples. In addition, capital and percentage in the examples are all expressed on the same basis.

Examples 1 to 12 Preparation of coalescence In an autoclave equipped with a stirrer, methyl/(hereinafter st
) 57 parts, methyl ethyl ketone (hereinafter referred to as MEK)
) 100 parts of polybutadiene 7 cut into small pieces
After purging the system with nitrogen gas, the rubber was stirred at room temperature all day and night to bathely decompose the rubber. After the temperature was set at 85° C., a solution prepared by dissolving 46 parts of anhydrous Malay/#k (hereinafter referred to as MAR) and 0.2 parts of copper/silver oxide in 150 parts of MEK was continuously added over 6 hours. The temperature was maintained at 85°C for an additional 4 hours after the addition. A portion of the reaction solution was sampled and subjected to gas chromatography to determine the amount of unreacted material, and the 1% ratio and the MAR content in the 1% product excluding the rubber content were calculated. Add MEK i to the remaining reaction solution.
5 Methanol 15 in which Qto was added and stirred vigorously
Pour into 00 parts, precipitate, separate P, and dry to obtain 1 in the form of white powder.
Obtained union. This was designated as experiment rl&11.

In addition, as shown in Table 1, a graft copolymer was obtained in the same manner as in F'i Meiken Nl 1 except that the raw material rights and charge were changed to tλ, and the actual kN was 112 to -8.

Table 1 (Note) The abbreviations in Table 1 indicate the following. (Hereinafter also referred to as N&) BR... Asahi Kasei Corporation butadiene rubber, product name [GEYNR55RJ STR...°Shell C Co., Ltd.] 30% styrene/butadiene block combination rubber, product name [TR 1102] SBR. ...Nippon Zeon Co., Ltd. 23.5% styrene petazier/rubber, product name [Nilaball 502J AR...Nippon Zeon Co., Ltd., acrylic rubber, product name [
Nirabol AR52J aMB 60 parts of the co-1 polymer obtained in experiment %1 of the production experiment example fil of a-methylstyrene was dissolved in MEK 70 m in an autoclave, and 1.02 parts of the maleic anhydride group was added to this. Molar equivalence O aniline 1
1.65 parts were added and reacted at 140°C for 6 hours. The reaction solution was cooled, poured into 300 parts of vigorously stirred methanol to precipitate, separated by r, and dried to obtain an imidized 1 compound (component A). According to C-13 NMR analysis, the conversion rate of acid anhydride groups to imide groups was 100%.

Similar to +=, the co-monomerized compounds obtained in Experiments N2 to 8 of Experimental Example (1) were also subjected to imidization reaction. In all cases, the conversion rate of acid anhydride groups to imide groups was 99 or more. The signs of each of these rubber-modified imidization 1 combinations are shown in the experimental example (
They are represented by ■ to ■ corresponding to Nλ1 to 8 in 1).

S-N9 Polybutadiene/Latex 80 parts (1!il type 50%
, half-Th particle size 0.35 μ, r content 90%), 1 part sodium stearate, 0.1 part sodium formaldehyde sulfoxylate, 0.03 part tetrasodium ethylene thiamine/tetraacetic acid, Acid No. 11
0.003 parts of t-dodecyl mercaptan and 200 parts of water were heated to 65°C, and to this was added 60 parts of a solid mixture consisting of 60% acrylonitrile (hereinafter referred to as AN) and 70% t-dodecyl mercaptan, 0.3 Th of t-dodecyl mercaptan, and 200 parts of t-dodecyl mercaptan. 0.2 m of peroxide was continuously added at 1 hour at 4 hours, and the mixture was heated at 65° C. for 2 hours after finishing painting. The 1 ratio reached 96.5%. After adding antioxidant to the treated latex,
After coagulating with calcium chloride, washing with water, and drying, a graft copolymer was obtained as a white powder, which was designated as Experiment N9.

Experimental experience 0 Polybutadiene latex 1 sos and AN25%, 5
t60% and metal methacrylate ester (hereinafter referred to as IJ
Experiments N and 10 were obtained in the same manner as Experiment No. 9 and IF5, except that 65 parts of a 1-body mixture consisting of 15% (referred to as JA) was used.

Experimental example 11 AN 25 h, st 75 parts, sodium stearate 2
．． 5 fltB, 0.6 s of t-dodecyl mercaptan and 250 parts of water were heated to 70°C, and 0.05 part of potassium persulfate was added thereto to start one cup. 5:00 p.m. from the start of the first match! After that, 0.03 part of potassium persulfate was further added, and the temperature was raised to 75°C and maintained for 6 hours to complete 1 cup.

The success rate reached 97%. The obtained latex is coagulated with calcium chloride! ijL, wash, dry! ! A white powder copolymer of 14 and 111 was obtained in experiments [7]. .

Experimental Problem 12 Except for using 23 parts of AlN and 872 parts of 6M as raw materials, a co-merger was obtained using Vikffi11 and faJ,
It was set as experiment Nn12.

Experimental example (Blend of 5IA & juice, B component and C component A component, 8 losses and C component were blended at the accumulation ratio shown in Table 2, and this blend was put into a screw extrusion machine with a 30 dragon diameter insertion and removal fitting. The mixture was extruded and pelletized. Each blend contained 0.2 parts of octadecyl-(3,5-ditertiarybutyl-4-hydroxyphenyl)-zolobionate (an antioxidant). The physical properties of the resulting composition were controlled and shown in Table 2.
This is an experimental situation showing an example of manufacturing either component C or component C.

Comparative Example 1 Experimental Example (50 parts of the non-imidized rubber-modified maleic anhydride co-monomer (hereinafter referred to as 1"P) obtained in Experiment No. 1 of Experiment 11, &! of the B component of Experimental Example (3)). 65 parts of the rubber modified copolymer obtained in Zukunomi M 9 and Experimental Example (4
15 parts of the co-monomer containing aromatic vinyl as a main component obtained in Experiment 11 of the production of component C of ) was breaded by the method shown in Experiment Example (5+), and the physical properties of the resulting composition were measured, Second
Shown in the table.

Comparative Example 2 An imidized copolymer was obtained from the st-MA)j copolymer obtained in the same manner as in Experimental Example (1) except that polybutadiene/ was not omitted. The conversion rate of acid anhydride groups to imide groups was 100%.

This imidized copolymer (hereinafter referred to as Q) 5C1゜ Soybean Rubber-edible co-polymer 35WIVS obtained in Experiment N9 for the production of component B in Example (3) and the experiment for production of component C in Experimental Example (4) -15 parts of the comonomer mainly composed of aromatic vinyl obtained in step 11 was prepared by the method shown in Experimental Example (5+),
The physical properties of the obtained composition were measured and are shown in Figure 22.

Table 2 shows that the compositions of the present invention exhibit significant improvements in impact strength, thermal stability, and hot water resistance without lowering the conventional processability.

The physical properties were measured as follows.

ill Thermal stability...The temperature f is shown when the decrease in xm of one coalescence is 1% in thermobalance 9+ analysis under the conditions of a nitrogen flow of 50 cc/min and a temperature increase rate of 10°C/f'f.

(2) Vicat softening point...'* * 5 Kp,
According to AsT'MD-1525.

(:3+% impact strength...Izotsu with notch),
According to ASTM D-256.

(4+ Melt flow index...Temperature 25
0°C, 15°C, according to ASTM D-1238.

(5) Hot water resistance: A notched Izot E test piece conforming to xsTMD-256 was placed in hot water at 100°C for 24 hours.
After soaking in the time, I measured it! The retention rate with (3) VC of Il & value is shown.

Patent Applicant: Denki Kagaku Kogyo Co., Ltd., Ministry of Procedural Affairs, May 8, 1980 1+ Commissioner of the Patent Office: Mr. Kazuinu Wakasugi 1, Indication of the Case, 1982 Patent Application No. 68174shij 2 Name of the Invention: Thermoplastic Resin Composition 3 Relationship to the Nagisa case that is supplemented Patent applicant address 1-4-1 Nanraku-cho, Chiyo 1-I, Tokyo Column 5 for detailed explanation of the invention in the specification Contents of the supplement (1) Specification In the 8th row of the second white, pre-stop ``1 graft polymerization'' with ``1 graft polymerization''.

(2) 1 in line 5 of statement 3L4
Revised 1F.

(:(l Less than r on page 6, line 12 of the specification)"
The following is corrected as 1 of the polymer of component A and the composition containing the same.

(4) In the 16th line of the 6th chapter of the specification, ``1 beyond'' is corrected to ``over and over''.

(5) In Specification 1, line 6, line 20, "1-Moldability" is corrected to "Moldability of the polymer of component A and the composition containing it."

(6) "1 metal methacrylate ester" in lines 7 to 8 of No. 18 of the specification is corrected to "1 methyl methacrylate ester."

Claims (1)

[Scope of Claims] A component dirubber-like polymer of 3 to 40 weight tS, an aromatic vinyl fraction of 50 weight fl'- to less than 60 *- and an unsaturated dicarboxylic anhydride exceeding 40111 weight 501 Year body mixture consisting of electric chi and below 60-971+, ii chi.
1ts for rubber-modified imidized 1 polymers 10 to 901 having imide groups obtained by reacting raft-polymerized co-1 polymers with ammonia and/or primary amines, and 8 losses: rubber-like 1 polymers 3 to 801 A ratio lid mixture consisting of aromatic vinyl monomers 40 to 903 mkii%, vinyl cyanide monomers 0 to 40 mkii%, and a vinyl ratio lid body copolymerizable with these O to 501 mkii% to the lid lid. 20-97
) Graft combinations 10 to 901 in which E-chi are combined together
Lid part and C component: aromatic vinyl monomer 40 to 1 ooxt
%, a thermoplastic resin containing 0 to 80 parts by weight of a polymer obtained by polymerizing 0 to 4011% of a vinyl cyanide monomer and 0 to 401% of a vinyl monomer copolymerizable with these. Composition.