JPS60208352A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide the titled composition of outstanding heat and impact resistance and fluidity, containing heat-resistant copolymer with high content of alpha-methylstyrene. CONSTITUTION:The objective composition comprising (A) 5-40wt% of a copolymer from (A) 50-83wt% of alpha-methylstyrene, (A2) 10-35wt% of acrylonitrile, (A3) 3-20wt% of methyl methacrylate and (A4) 0-25wt% of styrene, (B) 30- 90wt% of a graft copolymer prepared by grafting, in the presence of (B1) 10- 50wt% of diene rubbery polymer, 50-90wt% of a mixture consisting of (B2) 50-95wt% of alpha-methylstyrene or its combination with styrene, (B3) 5-30wt% of acrylonitrile and (B4) 0-20wt% of copolymerizable vinyl monomer, and (C) 5-30wt% of a second graft copolymer prepared by grafting to (C1) 30-60wt% of a blend of polybutadiene rubber and styrene-butadiene copolymer rubber, (C2) 40-70wt% of a mixture of styrene and acrylonitrile. Said composition is to contain 5-40wt% of the diene rubbery polymer, the melt indices of the components (A), (B) and (C) being 0.1-3.0, respectively.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides α methyl 7 tyrene 1421 containing h1 III
#! Heat-resistant 1'l containing VF copolymer and lateral shock, 1 tohir'flow;

A HS i degreasing is [1 ship ψtya'' + W air 1 → 2
Although ABS resin is used in large quantities in ABS resins, there is a trend towards thinner products due to the recent trend toward lighter products, and as a result, there is a strong demand for improved heat resistance of ABS resins. ing.

As a method to increase the heat resistance of AB and S resins, Tokuko Sho 3!
As described in No. 1-18194, there is a heat-resistant ABS resin that is a mixture of α-methylstyrene-acrylonitrile copolymer and ABS resin. Since the temperature is only slightly over 100° C., there have been no restrictions in applications requiring even greater heat resistance.

In order to improve this, attempts have been made to carry out emulsion polymerization using methyl methacrylate as a third vinyl monomer in a copolymer consisting of α-methylstyrene and acrylonitrile.

For example, in Japanese Patent Publication No. 45-18016, a copolymer of α-methylstyrene, acrylonitrile, and methyl methacrylate in a certain composition range, a diene rubber-like polymer, acrylonitrile in a certain composition range, α - By mixing a graft copolymer of methylstyrene,
P+/1 In particular, it is stated that a ballistic resistant resin with a low high temperature shrinkage rate of molded products was obtained.

However, the mixture of the copolymer described in -]2 and the copolymer of Graph 1 has a slightly higher ## resistance than the graft copolymer obtained by graft copolymerizing a diene rubber-like polymer, acrylonitrile, and α-methylstyrene. Although it has properties, it is problematic in that it lacks impact resistance and fluidity, and particularly lacks a balance between heat resistance and fluidity.

The index of heat resistance is often indicated by the heat distortion temperature of ASTM D-648 or the cut softening temperature of ASTM D-1525, but many products have complex shapes,
In addition, since the wall thickness is not uniform, the residual strain of the product after injection molding is not constant, so the surface of the product J#'! Since it is insufficient to judge the quality of the product based on the above measurements alone, we recommend Currently, heat resistance tests are conducted on the product itself to evaluate its properties.

3- In that case, if the fluidity of the heat-resistant ABS resin is poor, the molding distortion remaining in the product will be large, so in the heat resistance test of the molded product without load, the temperature at which deformation begins is determined by the temperature at which the heat-resistant ABS resin begins to deform. ASTM D-648 heat distortion temperature or ASTM
Since the softening temperature of D-1525 is about 5 to 10° C. lower, if the fluidity is insufficient as described in Section 2, there is a drawback that the practical heat-resistant temperature becomes low.

As a result, (N) a copolymer of α-nonalsutene, acrylonitrile, and methyl methacrylate, and an IBI diene-based rubbery polymer, and a monomer mixture of α-methylstyrene, acrylonitrile, and/or methyl methacrylate were polymerized. A mixture of a graph I copolymer formed by C) and a graft copolymer obtained by polymerizing a monomer mixture of styrene and acrylonitrile in the presence of a rubbery polymer; Component melting index [Nor 1 flow rate, 230°C, load 5L9
] was found to be in the range of 0.1 to 30, and the present invention was completed based on the discovery that a balance of impact strength, fluidity, etc. can be maintained without impairing heat resistance. That is, A. Invention (~50-85% by weight of α-methylstyrene, 10-35% by weight of acrylonitrile, 3-2% by weight of methyl methacrylate)
A copolymer consisting of 0 weight 1% and J: and styrene 0 to 25 weight, which is obtained by completing the polymerization by additionally adding acrylonitrile or styrene to produce the copolymer. Copolymer 5~
40% by weight and (B) diene rubbery polymer 10-50%
Presence of 1.alpha.-methylstyrene or 50-90% by weight of an intermediate mixture thereof of 0-20% by weight of vinyl monomer copolymerizable with 50-95% by weight of styrene and 5-30 parts by weight of acrylonitrile. % to react? () Graph 1 - Copolymer 30-90% fiΦ and C] Mixture of polybutadiene rubber and O.styrene-getadiene copolymer rubber 30-600-60% by weight and mixture of acrylonitrile monomer 40- It consists of a mixture of 5-30% graft copolymer obtained by reacting with 70% FI, and the chef's thread rubber-like polymer in the mixture is 5-40% by weight, making it a special enemy for mold engraving. It is a thermal RIJ plastic resin composition.

In the copolymer used in the present invention, it is particularly important to avoid lengthening of the α-methylstyrene-methyl methacrylate chain during polymerization, and to prevent it from affecting thermal stability. The goal is to incorporate as many of them as possible. To achieve this, it becomes difficult to control particularly when the polymerization conversion rate becomes high, so in the first aspect of the present invention (inside the polymer, acrylonitrile or a monomer consisting of it and styrene is additionally added in the latter half of the polymerization to complete the polymerization reaction). thermal stability is improved.

Furthermore, when a mixture of methyl methacrylate, styrene, and acryl(y-)lyl is polymerized in a region where the amount of α-methylstyrene is 50% by weight or more, as the polymerization progresses, the amount of α-mesal in the unreacted monomer is ! The amount of polymer increases, making it easier to produce polymer 111 with poor thermal stability. In the copolymer of the present invention) (・C is α-methylnutylene 50 to 85
i%, methyl methacrylate 3-20% by weight, Aku IJ
1+::1 lil 10-35 %, and 0 sutisine
Polymerization is started using 65 to 85 parts by weight of a monomer consisting of a mixture of 25 to 25% by weight, and during the polymerization, preferably at a point where the polymerization conversion rate is 10 to 50%, acrylonitrile is added.
+/or monomers 15 to 35 consisting of it and styrene
Thermal stability is improved by adding 1° of weight part continuously or intermittently.

In the copolymer of the present invention, when the amount of α-mebulussten is less than 50% by weight, the heat resistance 1'F strength becomes low, and the
If it exceeds 5% by weight, a product with good thermal stability of 1-[ cannot be obtained.

If the amount of acrylonitrile is less than 10% by weight, the impact resistance will decrease, and if it exceeds 35% by weight, the polymerization stability V1 will deteriorate and the energizing property will decrease.

If the amount of methyl methacrylate is less than 3% by weight, #!悄fl(10-L, resistance of the resin composition finally obtained,
In particular, the heat shrinkage rate of the molded article will be poor, and if it exceeds 20% by weight, the thermal stability will be poor.

The copolymer (B) used in the present invention is a monomer mixture consisting of α-methylstyrene or styrene, acrylonitrile and/or methacrylic acid, and methyl lItate in the presence of a diene-based rubbery latex. It is obtained by emulsion polymerization using a natural initiator.

The diene-based rubbery polymer latenoxt of the present invention contains 50% by weight or more of butadiene polymer or getadiene.
Examples include copolymer latexes of butadiene containing 1-butadiene and other copolymerizable monomers.

Preferably, butanoene polymer or styrene-containing 1it
It is a styrene-butadiene copolymer containing 40% by weight or less.

As a radical initiator, use persulfuric acid! l, if5 sulfur sulfate, ammonium persulfate, cumene hydroperoxide, neu horn.

As the emulsifier used in the redox catalytic emulsification polymerization of lobil hydroper oxide, any emulsifier for '/ may be used, but ayuin-based emulsifiers are preferred (particularly preferred is sodium lauryl sulfate.

In addition, in order to obtain good impact resistance, it is desirable that the diameter of the grains of butanol-based rubber be relatively large.
In order to achieve the purpose of the present invention, the butadiene-based rubbery polymer latex used must have a polymerization fraction of 10 to 50% by weight of diene rubber having a 400 to 900 If the amount is less than 10% by weight, the addition efficiency of the rubbery polymer is insufficient, and the resulting resin composition has poor MC properties.

On the other hand, if it exceeds 50% by weight, the stability of the graph 1 polymerization reaction will be compromised, making it impossible to obtain the desired Gubufto polymer.

The composition of the graft copolymer of the present invention (Part B) used is α-methylstyrene or it and styrene, 50%
95% by weight, 5 to 30% by weight of acrylonitrile, and 0 to 20% by weight of a copolymerizable vinyl element.

Examples of copolymerizable vinyl monomers include lower alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate.

The Graph 1 copolymer C) used in the present invention is obtained by graft copolymerizing a monomer mixture of styrene and acrylonitrile in the presence of TT' of polybutadiene rubber and sterene butadiene rubber.

Examples of the rubber used in the graft copolymer C) include butadiene polymers and copolymer latexes of butadiene and styrene containing 50% by weight IR1-flf or 60% by weight or more of butadiene.

Bucnoene polymerization t+ and styrene 7-phtadiene (the ratio of polymers used is in the range of 70/30 to 9515,
Preferably it is 70/30 to 90/10. When this range is exceeded, Shogeki F1, which is a characteristic of the resin composition of the present invention,
− is difficult to maintain.

Particles of these guk diene rubber and styrene-buk diene rubber latex (previously latte with an average particle size of 100 to 4 ooi, which are used in ordinary ABS laJ resins).

particles can be used, but preferably particles t'l 400i,
1. Contains 10 to 35% by weight of polymer particles of J.
It is preferable to use a sotenx.

This diene-based rubbery polymer latenokume may be prepared in the same polymerization system containing 10 to 35% by weight of particles with a particle size of 400'At:J, J-17, or two or more types of particles as appropriate. It may also be obtained by mixing a diene rubber polymer latex with a diameter of .

In 4F, which uses a mixed system of sitadiene polymer and styrene-butadiene copolymer as rubber latex, and in skewers that balance the rubber particles, the resin composition of the present invention impairs heat resistance 1'1. The balance of various properties 141 such as impact resistance and fluidity can be maintained without any problems.

JJI of monomers used in graft copolymer C) of the present invention
The compositions are 30 to 60% by weight of a mixture of polysitate rubber and styrene-butanoene copolymer rubber, and 40 to 70% by weight of a mixture of styrene and acrylonitrile monomers.

In the present invention, the content of the rubber component in the mixture of components (3), (3) and (C) is 5 to 40% by weight, and if it is less than 5% by weight, the intership impact resistance is low, and if it exceeds 40% by weight, it is heat resistant. This is not preferable because it reduces performance.

Melt index of each of (B) and C) in the copolymer used in the present invention [melt flow rate, 230 IC1 grape weight 5 to 9
] is in the range of 01-30. If it is less than 0.01, the fluidity decreases significantly, and it is used as a structural material in the automobile field, N gas equipment field, etc. [This is a major drawback in moldability.

On the other hand, when the temperature is 30 or more, although the fluidity is improved, the orientation of the flow direction during injection molding is t! E becomes large and sufficient impact resistance cannot be obtained.

Although the reason is not clear, copolymers containing α-methylstyrene, acrylonitrile, and notyl methacrylate have an effect on heat resistance. However, compared to copolymers of acrylonitrile and styrene, compatibility with ABS resin is 11
．． Since this is not good, a mixture system with a copolymer obtained by polymerizing a monomer mixture of α-methylstyrene, acrylonilyl and/or methyl tutaacrylate to the tsene thread rubber-like polymer of component 1B) is used. In this case, it is thought that the rubber content is insufficiently dispersed during the heating and kneading process carried out by a conventional extruder, making it difficult for the resin to exhibit its original impact properties11.

However, a graft obtained by polymerizing a mixture of styrene and acrylonitrile in the presence of a rubber-like polymer containing a butadiene polymer and a styrene-butadiene copolymer as component C) is added to the mixture of the above-mentioned recovered parts and recovered parts. By mixing the copolymer, the ingredients that should make you sleepy and f
The component C) is dispersed at the interface between both phases of the component B and the heat resistance is lost.
)flow! '1st class special features t' 7th degree within 1st class will be different.

/ i'fi Mml & Melt-off [I-rate, 23 (It, 〆lI', 9 i', 9 i', ri-flow V1 ん・
Even if improved, extrusion molding, - (extrusion cost (!2 incense J) IJl
, 71 < ξ I culm 1 here, Tani no 1, polymerization Ihon or lamellar l Cori 1111 L LJ, < 1 (impact of the polymer mixture t'l or 1 Mr. 1).

Component σ to 1) hit Zorento. So, type 2-11
It can be carried out by any known method such as a mill or an extruder.

Also, @Itka's f? Colorants, lubricants, plasticizers, ballasts, strength fibers, and other additives are added to the mix.

If the J method of the present invention is applied to 1゛J'') in the Example
To clarify, it was invented by these guys...fil p
, there are no restrictions.

13. The addition of natural additives shown in Example 1 represents 1% of the total weight and 1% of the total weight of 1 swamp without any special ingredients or J-mi.
Also, the value of the manufactured convex product can be determined by the following methods 1 to 6.

3. Isohashi finger νshi: ASTMD, -12381-1? Kaede 1
7, mel 1) 11-re], 230 te 7, oil 1 city 51
If'1 of u - CY 1 ax in C1, no/s)
v 6 川*-(4111''-'t.

・Scary of Izots operation; ASTM I) 25
6 i・7. Measured at 20°C and 65% R11.

0 strength softening temperature: ASTM I]-152
51,7 compliant 17, 7011.

III Heat M1 in the product] Molded product (1 method 50”L
'9 (9g thickness 3gm, 211.1 Tan M tl+,)
Step Z11 cuff (7°) was set in a hot air drying oven for 3 hours. Before and after / 1 law change [
l: is set to 2 as the heat shrinkage rate with a 71 ratio with the J method before the test.

Reference 4 Examples A-]~A2 Table 11 Small! II blj compared to 10 - (g yo, j?
1 Leseur/! To chestnut 1] Lil't61Jl and O.
Methacrylic acid, etc. J) Medium ta ++ iii,
11 parts of alpha and turn yaritodenlumerkanotan () 4 parts
It was mixed and emulsified.

Stir with 2 streams of nitrogen (F) for 70 minutes at a temperature of 40 degrees, then add ion-exchanged water to dissolve 1 liter of sodium, altehyde sulfoxylate, sodium ethylenediaminetetoxyacetate, and ferrous sulfate. and cumenehyde 1'' peroxide to start the polymerization reaction. End of delivery-T <ring, iI! I'm going to do this
) If the product is heated to 60℃ 1
After the polymerization was carried out for 1 hour, acrylic [J21-Ryl was added for 2 hours] was continuously added (7. After the addition was completed, water and styrene were emulsified. Add the above emulsifier and initiator.

The polymerization reaction was carried out for 2 hours to complete the polymerization. The obtained j (
Add calcium chloride to the polymer latex and solidify it,
After holding at a temperature of 0°C or higher for 10 to 20 minutes with stirring 17, decompose, wash with water, and dry the composition ratio shown in Table II.
Add nitrogen to the reactor with a stirrer.
], latex and potassium persulfate were heated in one tank to 701°C, without stirring r-), and a single-produce mixture containing tanyaridodenolmercaptan (7l)f. An aqueous solution of methyl styrene, styrene, and acrylic acid (methyl styrene and methyl methacrylate) and notrium lauryl sulfate is continuously added for 1 to 5 hours. After the addition was completed, vA formation was carried out at 70°C for 3 hours.

After coagulating the latex with an aqueous solution of aluminum sulfate, the latex was filtered, washed with water (1), dried (1) and dried (1).
B-2 and B-3.

Reference Examples C-1 to C-2 At the composition ratios shown in Table 1t, ion-exchanged water, styrene,
Acrylonyl, potassium stearate, tanyari
A solution of 3 iU of Ial, 2 A mixed with water, 75% vanothylene-butane-1 copolymer containing polybutane lateenox and tutadiene was added and emulsified. The latex mixture was placed in a reactor that was purged with nitrogen and had a stirrer turned off, and was emulsified.

After raising the temperature to 40℃ without stirring under a nitrogen stream, add sodium pyrophosphate, glucose, and sulfuric acid to ion-exchanged water.
A solution in which iron was dissolved and cumenehyde'robar oxide were added, and the temperature was maintained at 70C for 1 hour to react.

Next, the remaining portions of the emulsified solution fi11 of monomers, etc., and cumene hydroperoxide were each continuously added to the polymerization system over a period of 3 hours.

Calcium chloride is added to the copolymer latex obtained in this way to coagulate it, and it is made into 10
After being kept under stirring for ~20 minutes, it was decomposed, washed with water, and dried to obtain a resin powder.

These are referred to as CI, c-2.

Examples 1 to 3, Comparative Examples 1 to 4 IAI high α-methylstyrene content copolymers (A in Table 1)
-1), +Bl-high α-notimethys goulen-containing nail graft copolymer (B-1 in Table 1), C) graft copolymer containing a mixture of polybutadiene rubber and styrene-tutatsuene copolymer rubber (C-1 in Table 1) was mixed with the ingredients shown in Table 2 to make a blend, pelletized using an extruder at a Schilling temperature of 250°C, and thermoplastic 11. A resin composition was obtained.

Further, a test piece was prepared by using an injection molding machine with a cylinder temperature of 250C. Table 2 shows their blending ratios and properties.

In the thermoplastic resin composition i of the present invention, by mixing component C-1 with the mixed system of components AI and B-1, it exhibits excellent properties such as excellent hit resistance and fluidity without impairing heat resistance. Indicates that the balance of characteristics is maintained. These properties cannot be obtained from each resin component alone.

19, Examples and Comparative Examples are compared using the same amount of rubber.

As in Comparative Example 1, without mixing the graft copolymer (C-1 in Table 1) comprising a mixture of polybutadiene rubber and nutylene-butadiene copolymer rubber, the impact properties It can be seen that the balance of properties such as fluidity and fluidity is poor, making it impractical.

As in Comparative Example 2, if the high α-methylstyrene content copolymer in Example 1 (B-1 in Table 1) is not combined with 11, the impact strength and fluidity can be maintained, but the heat resistance will be significantly reduced. I understand.

As in Comparative Example 3, instead of the copolymer with high α-methylstyrene content (B-1 in Table 1) in Example 1, a copolymer with 140% by weight of α-methylstyrene (B-3 in Table 1) was used.
), impact resistance can be maintained, but heat resistance is significantly reduced, making it impractical.

As in Comparative Example 4, instead of C) a graft copolymer (C-1 in Table 1) comprising a mixture of polybutanoene rubber and styrene-getadiene copolymer rubber in Example 3,
Rohm & Haas+j: tt) MBS resin (KM
It can be seen that when using -653), the heat resistance and the impact resistance are reduced, making it impractical.

Example 4, Comparative Examples 5 to 7 When the graft copolymer with high α-methyl content in Example 1e contains methyl methacrylate, that is, B- in Table I
The results obtained when B-2 was used instead of B-1 are shown in Example 4 in Table 2.

Clearly, 4f is a composition that retains excellent heat resistance without compromising impact properties and fluidity.

As in Comparative Example 5, if C) in Example 4 is not mixed with a graft copolymer containing a mixture of polybutadiene rubber and styrene-butadiene copolymer rubber (C-1 in Table 1),
Compared to Example 41, the heat resistance is not much different, but the impact t
It can be seen that the balance of properties such as IJ: and fluidity is poor, making it impractical.

As in Comparative Example 6, a copolymer containing 30% by weight of methyl methacrylate (Table 1) was used in place of A-1 in Table 1, which was a copolymer with a high α-methylstyrene content (Table 1).
When A-2) is used, the flowability is slightly better than that of Example 4, but the anti-impact properties are lowered and the molded product becomes blue, indicating that it is not practical.

In place of the graft copolymer (C-1 in Table 1) containing a mixture of all of Comparative Example 7 (C in Example 4) polyzotadiene 1 and styrene-butadiene covalent polymer, /# Melt index (Meltoff+1-rate, 230
When using a polycitadiene-based kraft copolymer (C-2 in Table 1) with a t: , load 5 ky) of 21 and no fly-zotadiene copolymer rubber (C-2 in Table 1), fluidity is significantly improved, but heat resistance and It can be seen that the impact resistance is reduced and it is not practical.

Claims (1)

[Scope of Claims] 1) FAI copolymer consisting of α-methylstyrene 50 to 857 rf%, acrylic 11 nitrile 10 to 351i%, methyl methacrylate 3 to 20% by weight, and O.styrene 0 to 25% by weight 5 to 40
% by weight and (uniformly) Presence of diene-based rubbery polymer 10-50% by weight 10 α-methylstyrene or styrene 50-95% by weight ■ Acrylic IJ nitrile 5-30% by weight vinyl monomer copolymerizable Polymer of O~20 monomers 50~
Gra-7i combination obtained by reacting 90 city star shapes 30~904+ City 2 compound 3 () ~ 00 city 1% of tongo com and aku IJI
)−,−] Re! Add 40 to 70% of Ili polymers to 1%. [1.3 Obtained by l,rug shift J
l) from a polymer with 5 to 30% of l), non] in the mixture; v) -r
'L-shaped city combination or 5-40 city hanging% III special (
pHJ plastic #1 resin composition. 2) A -i combination K t, 'V, +Ill, 0) each 4 no R: m finger pt ['l / root) low -
-shi -1 (230y, (a ding III 5 kv
) ) or 01 to 30 + claim number 1r
Oral thermoplastic resin composition.