JPS5966445A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To composition that is produced by adding a polycarbonate resin to an AES resin made through a suspension polymerization process using a specific dispersant, thus showing high mechanical strength, weather resistance and processability and having improved deformation in its plastic deformation range and improved weld strength. CONSTITUTION:The objective composition is obtained by combining (A) 10- 90wt% of an AES resin which is produced by polymerizing a finely crushed ethylene-propylene rubber, aromatic vinyl compounds, vinyl cyanides and/or alkyl esters of unsaturated carboxylic acids in the presence of dispersants selected from cellulosic compounds, acrylic acid compounds, inorganic salts and polyalkylene oxides and (B) 90-10wt% of a polycarbonate resin. The AES resin is a binary copolymer with a molar ratio of 5/1-1/3 ethylene/propylene or a terpolymer containing a non-conjugated diene in an amount of 2-50, when it is calculated with the iodine value.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel thermoplastic resin composition that is excellent in mechanical strength, weather resistance, and workability, and has improved deformation amount in the plastic deformation region and strength of the weld portion.

Polycarbonate resin (PC) is widely known as an engineering plastic having excellent impact resistance and heat resistance, but it has a high melt viscosity and has problems such as moldability and thickness dependence of impact strength. There are already many proposals for improving these shortcomings in PCs.
For example, by reducing the price of PC and improving the thickness dependence of moldability and impact strength, a mixture of PC and ABSl]tf resin (acrylonitrile-diene rubber-styrene polymer) (
Special Publication No. 38-1522m15), fully improved weather resistance and stain resistance iPc, :AES resin (acrylonitrile-
mixture with ethylene/propylene rubber (styrene polymer)
349) etc. are widely known.

However, the PC-ABS resin composition has AB 5l
Due to the diene thread rubber in the resin, it has poor weather resistance and has many problems when used outdoors. Also, PC-ABS
The resin composition is characterized in that the ABS resin used is a solution-polymerized product; 1) the rubber phase in the composition is unstable and flow marks are likely to occur on the surface; The amount of deformation is small and energy absorption is poor (for example, in a normal bending test, if the yield point is exceeded and it enters the plastic deformation region, it is easy to break), and 111) Locations where resin flows intersect within the mold during injection molding. However, it has serious drawbacks such as poor strength of the so-called weld portion.

As a result of intensive research into improving these drawbacks, the present inventors have discovered that A
The advantage of mixing BS resin with PC is that it has excellent mechanical strength, weather resistance, and workability, and also improves the deformation (energy absorption) in the free deformation region and the strength of the weld part. The composition of the present invention has been developed by the VC of the present invention.
Reached.

That is, the present invention combines finely pulverized ethylene-propylene rubber, an aromatic vinyl compound, a vinyl cyanide compound, and an unsaturated carboxylic acid alkyl ester compound into a compound selected from the following chemical group 9. Provides a thermoplastic resin composition consisting of 10 to 90% by weight of 7cABS resin and 90 to 10% by weight of polycarbonate resin, which is obtained by subjecting one unit to suspension polymerization using one or more chemical compounds as a total dispersant. It is.

a) Cellulose compound b) Acrylic acid compound C) Inorganic salt d) Polyalkylene oxide The thermoplastic resin composition of the present invention will be explained in detail below.

Examples of the polycarbonate resin include aromatic polycarbonate, aliphatic polycarbonate, aliphatic-aromatic polycarbonate, and the like. Generally [,2,2
-bis(4-oxyphenyl)alkane, bis(4-
Polymers consisting of bisphenols such as oxyphenyl) ether type, bis(4-oxyphenyl) sulfone, sulfide or sulfoxide type, or co-TL&
It is a polymer using bisphenol gold substituted with halogen depending on the purpose. In particular, aromatic polycarbonate is preferred.

The ethylene-propylene rubber that makes up AES'IXM resin is a binary copolymer of ethylene and propylene (
EPR), terpolymer (EPDM) consisting of ethylene, propylene and non-conjugated diene, etc., and one or more of them may be used.

Examples of the non-conjugated diene in the ternary conjugate Can be mentioned.

Binary copolymers (EPR) and terpolymers (EPDM)
The molar ratio of ethylene to propylene in ) is preferably in the range of 5:1 to 1:3.

Further, in the terpolymer (EPDM), it is preferable that the proportion of non-conjugated diene is in the range of 2 to 50 in terms of iodine value.

The aromatic vinyl compounds to be grafted in the presence of the ethylene-propylene rubber purchasing device include styrene, α
Examples include -methylstyrene, α-chlorostyrene, vinyltoluene, etc., with styrene being particularly preferred. Examples of vinyl cyanide compounds include acrylonitrile and methacrylonitrile. ! VC acrylonitrile is preferred. Further, examples of unsaturated carboxylic acid alkyl ester compounds include acrylic ester compounds such as methyl, ethyl, propyl, butyl, benzyl, hexyl, etc., and methacrylic ester compounds. Methyl is preferred.

The weight ratio of these compounds and rubber can be selected within an appropriate range depending on the purpose. Preferably, the compound is 95-20% by weight, and the rubber is 5-80% by weight, and particularly preferably, the compound is 80-40% by weight, and the rubber is 20-60% by weight.

There is also no particular restriction on the weight ratio of the aromatic vinyl compound to the unsaturated carboxylic acid alkyl ester compound and the vinyl cyanide compound may be selected arbitrarily.

Particularly preferred are 40 to 80% by weight of the aromatic vinyl compound and 60 to 20% by weight of the vinyl cyanide compound/or unsaturated carboxylic acid alkyl ester compound.

A particularly important point in the present invention is that the AES resin is a resin obtained by a suspension polymerization method using a specific compound as a total dispersant. , bulk polymerization method (Special Publication No. 42-662, USP
3435096) and solution polymerization method (USP 353 B
1.90, US 'P 3538191) has been proposed, and industrially, ethylene-propylene rubber is dissolved in whole hexane or toluene to produce polymerizable monomers such as aromatic vinyl compounds and vinyl cyanide compounds. A so-called solution polymerization method in which graft polymerization is carried out in the presence of an all-mer catalyst is common.

However, when mixed with AES resin gold PC produced by solution polymerization, the impact strength according to the Izot impact test method is excellent, but the impact strength according to the falling ball impact test method is not excellent. This is probably related to the small amount of deformation in the plastic deformation region, which tends to break when the yield point is exceeded during the bending test.

Therefore, it has practical disadvantages in absorbing energy when the ball falls. Furthermore, it also has a serious drawback in that the strength of the weld portion, which is the portion where the flow of resin intersects within the mold during injection molding, is low.

Compared to such conventional techniques, suspensions using at least one selected from a group of compounds consisting of a) cellulose compounds, b) acrylic acid compounds, C) inorganic salts, and d) polyalkylene oxides as dispersants. The use of polymerized AES resins overcomes all the conventional drawbacks.

Note that 7'cAE8m fat used for polyvinyl alcohol and polyvinyl acetate, which is well known as a suspending agent in suspension polymerization of vinyl chloride, is not preferred because of poor weld strength.

Examples of cellulose compounds include methylcellulose, ethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxyglobilcellulose,
Examples include carboxymethylcellulose.

Examples of acrylic acid compounds include polyacrylic acid, polyacrylates, and the like.

Inorganic salts include calcium phosphate, calcium carbonate,
Examples of the polyalkylene oxide include barium sulfate, magnesium carbonate, calcium birophosphate, and magnesium oxide. Examples of the polyalkylene oxide include polyethylene oxide and polypropylene oxide.

There is no particular restriction on the amount of the above-mentioned dispersant used.

Total amount of compound and rubber per 100 parts by weight,
Particularly preferred is 1 to 10 parts by weight.

There are no restrictions on the initiator used in suspension polymerization, and any known substance can be used.

The composition of the present invention comprises the above-mentioned AES [fat 10 to 90% by weight]
and PC90 to 103 it%.

If the PC content is less than 10% by weight, the heat resistance will significantly deteriorate, which is undesirable. If the amount of PC is 90% by weight, the workability will decrease and the strength of the weld part of the deformed lid in the plastic deformation region will not be improved. 1. Known mixing methods using gold, such as an extruder, can be mentioned.

In particular, a twin-screw extruder having a mixed wire block is preferred.

It is also possible to add known stabilizers, dyes and pigments, plasticizers, antistatic agents, ultraviolet absorbers, lubricants, fillers, etc. during mixing.

Examples below? Although the present invention will be fully explained in detail using these examples, the present invention is not limited to these in any way.

Examples and comparative examples oW! P-turbidity polymerized AES resin-1 to 450 parts by weight of famous water, various chemical compounds shown below as a suspending and dispersing agent, and EPDM (iodine value 8
．． 5. Mooney viscous i61, propylene content 43% by weight
, diene component: ethylidenenorbornene), 80 parts by weight of styrene, 50 parts by weight of acrylonitrile, and 2.3 parts by weight of t-bunal peroxide as an initiator, and after stirring at 26°C for 1 hour, further
The mixture was heated to ℃ to carry out polymerization. Thereafter, the reaction product was cooled to room temperature, filtered and dried, and the AES1! I fat-1~-zero is a friend.

Weight section! Turbid polymerization A E S fM fat-1: Hydroxyethyl cellulose 0.35! -2 = Sodium polyacrylate l -3: Magnesium hydroxide l -4: Polyethylene oxide l vinyl -5: Boridinyl alcohol/100 solution polymerization AES resin 100% EPDM same as the EPDM used for suspension polymerization 2000 parts hexane 10 parts ethylene dichloride
Further, 50 parts by weight of acrylonitrile, 80 parts by weight of styrene, and 5 parts by weight of benzoyl peroxide as an initiator were added, and the mixture was heated at 67° C. for 10 hours.

The polymerization solution was brought into contact with a large excess of methanol, and the precipitate was completely separated and dried to obtain AES [fat].

An AES resin of aromatic polycarbonate A resin or higher represented by n and a polycarbonate resin were mixed at the ratios shown in Table 1 to obtain various compositions.

Physical properties of various compositions? It is shown in Cloth-2.

-Weld strength- Two gates with gate spacing of 100 mm (each 2.5 x 2, 0
Completely inject the molten resin (van) at 260°C to create a test piece with a thickness of 3 m and a length and width of 150 m each.

Test piece complete jig (height 80m, inner diameter 120m+, outer diameter 12
6 wn).

A 1 kg steel ball is dropped onto the center of the test piece in a cold room adjusted to -30°C, and the maximum energy value (kg·cm2) fr:, which does not cause the test piece to break, is determined.

Procedural amendment (method) July 8, 1980 Kazuo Wakasugi, Commissioner of the Japan Patent Office, 2. Name of the invention: Thermoplastic resin composition 3. Relationship with the person making the amendment. Patent applicant 5. Specification subject to amendment. Pages 5 and 13, page 6, and pages 5 and 13 of the statement of contents of the amendment will be reprinted as separate sheets (no changes to the contents).

Polymers or copolymers consisting of bisphenols such as phenyl)alkanes, bis(4-oxyphenyl)ethers, bis(4-oxyphenyl)sulfones, sulfides, or sulfoxides, depending on the purpose. This is a foot-shaped combination using bisphenols substituted with tenorogen. In particular, aromatic polycarbonate is preferred.

The ethylene-propylene rubber that makes up AES resin is a binary copolymer (EPR) consisting of ethylene and propylene.
), terpolymer (EPDM) consisting of ethylene, propylene and non-conjugated diene, etc., and two or more types of -at and 7t are used.

Non-conjugated dients in the terpolymer (EPDM) include dicyclopentadiene, ethylidene norbornene,
1.4-hexadiene, 1,40 solution polymerization AES resin A 100-layer lid part of the same EPDM used for suspension polymerization was mixed with 2000 parts by weight of hexane and 10 parts by weight of ethylene dichloride.
00 parts by weight, and further added 50 parts by weight of acrylonitrile, 80 parts by weight of Stereph, and 5 parts by weight of benzoyl peroxide as an initiator, and polymerized at 67° C. for 10 hours.

The polymerization solution was brought into contact with a large excess of methanol, and the precipitated precipitate was completely separated and dried to obtain AESIB fat.

Al13 higher than aromatic polycarbonate resin represented by O polycarbonate resin
S resin and polycarbonate M resin are mixed in the ratio shown in Table 1 to obtain a complete composition.

The physical properties of various compositions are shown in Table 2.

Claims (1)

[Claims] ■) Finely ground ethylene-propylene rubber, aromatic vinyl compound, vinyl cyanide compound and/or unsaturated carboxylic acid alkyl ester compound gold, selected from the following compound group: AES resin 10 to 9 obtained by polymerization under suspension polymerization conditions using one or more compounds as a dispersant.
0% to 1% by weight and 90 to 10% by weight of polycarbonate resin? Characteristic thermoplastic resin composition. a) Cellulose compound b) Acrylic acid compound C) Inorganic salt e) Polyalkylene oxide