JPS62141049A - Weather-resistant resin composition having excellent rib strength - Google Patents

Abstract

PURPOSE:To provide a weather-resistant resin compsn. having excellent resistance to impact and heat and rib strength, etc., containing a graft polymn. reaction product composed of an ethylene/alpha-olefin rubber as a base and a polycarbonate resin as essential components. CONSTITUTION:A monomer selected from among arom. vinyl monomers, vinyl cyanide monomers and alkyl esters of unsaturated carboxylic acids is graft- polymerized onto an ethylene/alpha-olefin rubber. In this way, a graft polymn. reaction product having a soluble matter (in a solvent mixture of tetrahydrofuran with n-hexane in a ratio of 1:4 by volume) content of 40wt% or below and a tetrahydrofuran-insoluble matter content of 60wt% or below can be obtd. 5-80wt% said reaction product is mixed with 95-20wt% polycarbonate and 0-75wt% polymer composed of an arom. vinyl monomer, a vinyl cyanide monomer and an alkyl ester of an unsaturated carboxylic acid.

Description

Detailed Description of the Invention <Industrial Field of Application> The present invention is a polymeric polymer comprising a graft polymerization reaction product based on n-r-tyrene-α-olefin rubber and a polycarbonate resin or a (co)polymer thereof. This invention relates to a weather-resistant resin composition that has excellent impact resistance, weld strength, heat resistance, moldability, appearance, and lip strength.

<Conventional technology> Conventionally, high impact polystyrene (HIPS), AB
As can be seen in S resins, mechanical customization of resins, especially technology that completely incorporates rubber into the resin is used to improve impact resistance.In recent years, non-conjugated diene rubbers such as polybutadiene Weather resistant resins that use non-conjugated diene rubber as a rubber component, such as AES resin, AC8 resin, A
AS resin is attracting attention.

Furthermore, as a resin composition that completely improves the heat resistance of these weather-resistant resins, we have developed a resin composition that is a mixture of a resin based on a non-conjugated diene rubber such as ethylene-αonfin rubber (AES resin) and a polycarbonate resin. have been proposed in Japanese Patent Publication No. 51-24540, Japanese Patent Publication No. 41145/1982, Japanese Patent Application Laid-Open No. 53-65349, etc.

However, although these resin compositions have excellent weather resistance and heat resistance, ABS using conjugated diene rubber
A resin composition that is a mixture of resin and polycarbonate resin (
Compared to ABS/PC alloy), etc., it is inferior in lip strength, impact resistance, moldability, appearance, etc., and the strength of the weld part of injection molded products is not sufficient, so it is not practical in terms of strength. At present, it is insufficient and cannot be said to be a practically excellent material.

Means for Solving the Problems> The present inventors have conducted extensive research in view of the problems in the weather-resistant resin compositions described above, and as a result, have determined that the conventional non-conjugated diene rubber reinforced resin-polycarbonate The present invention was achieved by discovering that a composition having excellent lip strength that could not be obtained with a resin mixture can be obtained.

Furthermore, the composition of the present invention has impact resistance, weld strength,
Excellent heat resistance, moldability, and appearance.

That is, the present invention provides an ethylene-α olefin rubber containing one or more monomers selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers, and unsaturated carboxylic acid alkyl ester monomers. is graft polymerized,
The soluble content of the graft polymer in a tetrahydrofuran-n-hexane mixed solvent (volume ratio 1:4) is 40% by weight or less, and the insoluble content in tetrahydrofuran is 60M.
Graft polymerization reaction product (I) having a weight ratio of 5 to 80
Weight factor, polycarbonate resin (II) 20-95 weight factor or less, one or more monomers selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers, and unsaturated carboxylic acid alkyl ester monomers A (co)polymer (I) consisting of a (co)polymer (I) having a weight coefficient of 0 to 75% or less, and having excellent impact resistance, weld strength, heat resistance, moldability, and appearance, as well as excellent lip strength. It is something that provides something.

The present invention will be explained in more detail below.

0 Ethylene-α-olefin rubber The ethylene-α-olefin rubber in the present invention is a binary copolymer consisting of ethylene and propylene or butene (
EPR), terpolymer (EPDM) consisting of ethylene, propylene or butene, and non-conjugated diene, etc., and one or more types thereof are used.

Examples of the non-conjugated diene in the terpolymer (FJPDM) include dicyclopentadiene, ethylidenenorpoline, 1,4-hexadiene, 1,4-cycloheptadiene, 1.5-cyclooff-tadiene, etc. It will be done.

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

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

Monomer kraft polymerization reaction product (I) and (co)polymer (monomers constituting the button include the following compounds).

Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, methyl-α-methylstyrene, -methylstyrene, chlorstyrene, etc., and one or more of them may be used. be able to.

Examples of the cyan f-hibinyl monomer include acrylonitrile and methacrylate trile, and one or more types thereof can be used.

Examples of unsaturated carboxylic acid alkyl ester monomers include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and those containing an epoxy group in the molecule. Examples include glycidyl acrylate, glycidyl methacrylate, etc., and one or more of them may be used.

One or more monomers selected from the above-mentioned compounds are subjected to craft polymerization or (co)polymerization in the presence or absence of the ethylene-α olefin rubber. Especially styrene, acrylonitrile, and methyl methacrylate! It is preferable to have two or more types of friends.

Graft polymerization reaction product (I) ethylene in vc
There is no particular restriction on the composition ratio of α-olefin rubber and monomer, but in terms of physical properties of the final resin composition, the ratio of ethylene-α-olefin rubber to 5 to 95% by weight and monomer to 95 to 5% by weight should be as follows. Preferably L<, '1m-r-tyrene-thione-
α-olefin 0-60% by weight, monomer 90-40% by weight
It is preferable that

The soluble content of 1-hexane mixed solvent (volume ratio 1:4) is 4
0% by weight or less, and the content insoluble by tetrahydrofuran is 60% by weight or less.0 If the soluble content by mixed solvent exceeds 40% by weight, moldability improves, but lip strength and impact resistance decrease. This is not preferable, as there is a tendency for the weld strength to decrease significantly.

From the balance of impact resistance and moldability, the soluble content is 10
It is preferably from 20 to 40% by weight, particularly preferably from 20 to 40% by weight.

Moreover, if the insoluble content due to tetrahydrofuran exceeds 60% by weight, the appearance (gloss and flow marks) will be poor, which is not preferable. In terms of appearance, the content is preferably 50% by weight or less.

In graft polymerization, it is difficult to bind (graft) the entire amount of the monomers subjected to the graft polymerization reaction onto the rubber, and during the kraft polymerization, it is difficult to bind (graft) the entire amount of the monomers subjected to the graft polymerization reaction onto the rubber.
There are cases where polymers are produced as by-products.

In the present invention, the by-produced (co)polymer is also regarded as the same as the true kraft body obtained by graft polymerization, and is referred to as the graft polymerization reaction product (I).

However, in the present invention, the kraft polymerization reaction product (
Although the soluble and insoluble components of the graft in I) are fully defined, this graft does not include the (co)polymer by-produced during kraft polymerization. In the present invention, the graft polymerization reaction product (I) methyl ethyl ketone obtained by graft polymerization is used to obtain a dicraft body, which is then subjected to measurement of soluble and insoluble components.

The soluble content and insoluble content of the graft body in the graft polymerization reaction product (I) mean values measured under the following conditions.

The graft polymerization reaction product (I) was immersed in about 100 times the amount of methyl ethyl ketone for 24 hours (at room temperature), and then centrifuged (I).
2, OOORPM for 20 minutes) to separate the methyl ethyl ketone soluble and insoluble components to obtain a non-bath grafted product.

The obtained graft body is heat-pressed (200° C., 5 minutes) to form a sheet of about 1 mm.

Graft body composition) 19'tTetrahydrofuran-n-hexane mixed solvent (volume ratio 1:4) 200ml V
After soaking at room temperature for 48 hours, the sample was passed through the mouth at 300 ml to calculate the soluble content.

Similarly, the sheet 1y of the grafted body was
After soaking in 00 resistance for 48 hours (at room temperature), it was passed through a 300 mesh to calculate the insoluble content.

As a method for obtaining a graft body in which the content soluble in tetrahydrofuran-n-hexane mixed solvent is 40% by weight or less and the content insoluble in tetrahydrofuran is 60% by weight or less, ff1a of ethylene-α olefin rubber is used.
(iodine value, Mooney viscosity), the type and amount of the initiator or molecular weight regulator, and the polymerization temperature.

The intrinsic viscosity (30° C.) of the (co)polymer (I) in dimethylformamide is preferably 0.50 to 1.10 from the viewpoint of lip strength, moldability, etc. of the final composition. 05
If it is less than 0, the lip strength tends to decrease;
If it exceeds 0, moldability tends to be poor and lip strength also tends to decrease.

A (co)polymer (I) having an intrinsic viscosity of 0.50 to 1.10
f) can be obtained by varying the composition and polymerization conditions.

Graft polymerization reaction product (I) and (co)polymer (I
Examples of the production method include known polymerization methods such as emulsion polymerization, suspension polymerization, bulk polymerization, solution polymerization, emulsion-suspension polymerization, and bulk-suspension polymerization. Particularly, as a method for producing the graft polymerization reaction product (I), the suspension polymerization method or the solution polymerization method is preferred because the above-mentioned polymerization conditions can be easily adjusted.

〇Polycarbonate resin Next, as the polycarbonate resin (...) constituting the weather-resistant resin composition of the present invention, aromatic polycarbonate,
Examples include aliphatic polycarbonates, aliphatic-aromatic polycarbonates, and the like. Generally, 2,2-bis(4-oxyphenyl)alkanes, bis(4-oxyphenyl)ethers, bis(4-oxyphenyl)
These are polymers made of bisphenoyls such as sulfone, sulfide, or sulfoxide, or co-M polymers, and depending on the purpose, polymers or copolymers using bisphenols substituted with halogen can also be used.

In particular, the polycarbonate resin (...) used in the present invention preferably has a reduced viscosity of 0.40 to 0.55 in chloroform (25°C).
If it is less than 0, the impact strength and weld strength of the final resin composition will be low, and if it exceeds 0.55', the moldability will be poor and the weld strength will be low. Polycarbonate resin (II), which is No. 55, can be obtained by varying the composition and polymerization conditions.

Note that the reduced viscosity in chloroform is determined using an Ostwald viscometer as follows.

Reduced viscosity - '7sp C specific viscosity) / C (@ degrees) specific viscosity:
W5p=T/To I To=flow time of chloroform alone Concentration C: 0.4y-polycarbonate/100yin-chloroform Graft polymerization reaction product (]) in the weather-resistant resin composition of the present invention, polycarbonate The composition ratio of resin (II) and (co)polymer (I) is the same as that of the graft polymerization reaction product (
I) 5-80% by weight, polycarbonate resin (II)
20 to 95% by weight, (co)polymer (I) 0 to 75% by weight. If the polycarbonate resin (II) is less than 20% by weight, the heat resistance and weld strength will be significantly reduced, and the kraft polymerization reaction product (I) If the weight value is less than 5, the effect of improving lip strength is small, and the problems of insufficient weather resistance and impact resistance are not solved at all.

The blending amount of the (co)polymer (El) is determined by the method for producing the graft polymerization reaction product (I), #! Although it varies depending on the kraft polymerization ratio of the fvc ethylene-α-olefin rubber and the monomer, in terms of impact resistance, a (co)polymer (■) weight ratio of 0 to 75 is preferable.

The method for mixing the kraft polymerization reaction product (I), the polycarbonate resin (Ill) and the (co)polymer (II) is a Banbury mixer-1-screw extruder, a twin-screw extruder having a kneading block, or a combination thereof. Known mixing methods using combinations and the like can be mentioned.

The weather-resistant resin composition of the present invention may contain dyes and pigments, acid f.
antistatic agent, plasticizer, antistatic agent, ultraviolet absorber, lubricant,
In addition to known additives such as fillers and flame retardants,
BS resin, MBS resin, ABSM@fat, AAS resin, AC31 resin, polyvinyl chloride, ethylene-vinyl chloride copolymer, chlorinated polyethylene, styrene-maleic anhydride copolymer, styrene-acrylonitrile-maleic anhydride do-acid copolymer, styrene-maleimide copolymer,
Styrene-acrylonitrile-maleimide copolymer,
thermoplastic polyester, polyamide, polyacetal,
Other thermoplastic resins such as polysulfone can also be blended.

The present invention will be explained by giving Examples, but the present invention is not limited to the Examples in any way.

Example <Production of graft polymerization reaction product (I)> - Suspension polymerization method - 50 tti of ethylene-α olefin rubber, 3 tti of styrene
Grafting was carried out using 5 parts by weight and 15 parts by weight of acrylonitrile based on a known suspension polymerization method.

In addition, in the polymerization, graft polymerization reaction products with different soluble and insoluble contents can be obtained by using rubbers with different iodine values and Mooney viscosity, changing the amount and type of initiator, using molecular weight regulators, and changing the polymerization temperature. I got (I).

- Solution polymerization method - Graft polymerization was carried out using 20 M parts of ethylene-α olefin rubber, 55 parts by weight of styrene, and 25 parts by weight of acrylonitrile based on a known solution polymerization method.

In addition, in the polymerization, graft polymerization reaction products (I) having different soluble and insoluble components were obtained by changing the type of initiator.

The graft polymerization recipe and polymerization results are shown in Table 1.

<Production of polycarbonate resin (II)> Based on the known phosgene method, polycarbonate resin (II)-1 with a reduced viscosity of 0.50 and polycarbonate with a reduced viscosity of 0.30 in chloroform (25°C) were prepared by varying the reaction temperature and time. Resin (I
)-24- Obtained 0 <Production of copolymer (I)> Based on the known bulk-suspension polymerization method, the intrinsic viscosity in dimethylformamide (30°C) of 35 parts by weight of styrene, 30% by weight of acrylonitrile, 0.60 copolymer (II
A copolymer (l-2) of l)-1 and 1.05 was obtained.

Accounting amount of the obtained graft polymerization reaction product (I), polycarbonate resin (lI) and copolymer (I): 100
451.5 parts by weight of carbon and 40 parts by weight were mixed.
The mixture was kneaded and granulated using a φ extruder at 230°C to obtain the composition shown in Table 2.

The resulting composition was injection molded and evaluated for lip strength, weld strength, impact strength, heat resistance, moldability, and gloss.

The evaluation results are shown in Table-2.

1. Molding conditions 1. Toshiba Machine injection molding machine 15-90B (5 oz) Molding temperature: 260°C Mold temperature: 70°C Injection pressure: 1ookg/crA<hydraulic) Injection speed: 7
0% - Evaluation method - 1) Rib strength: Has a film gate with a thickness of 0.5 rrrm on one side,
A rib with a thickness of 1.5 m + n and a height of 10 m over the entire length from the gate side to the anti-gate side trench in the center of the molded product 1
A test piece of 20 x 120 x 3 mIn was molded according to the above-mentioned molding conditions, and three test pieces for lip strength measurement with a width of 10 mm were cut from the gate side parallel to the side with the gate metal.
One end of the specimen was fixed with an autograph chuck.

The other chuck of the autograph is fully equipped with a jig that hooks the rib base of the test piece, and the jig is attached at a speed of 10 mm/min.
The breaking strength of the ribs at 3°C was measured and expressed as the average value of three test pieces.

2) Weld strength: 2 gates with gate spacing of 100 mm (each 2, 5
A test piece of 150 x 150 x 3 mm having a diameter of 2 mm) was molded under the above-mentioned molding conditions.

The test piece was placed in a cylindrical jig (height 80m+n, inner diameter 120+
rr1n, outer diameter 126wn) and -30°C.
In a cold room adjusted to
cm) was calculated.

3) Impact strength Izot impact test pieces having a thickness of V4# were molded under the above-mentioned molding conditions, and the notched isot impact strength at 23° C. was completely measured.

(Based on ASTM D 256vc) 4) Heat distortion temperature test piece with heat resistance thickness W was molded under the above-mentioned molding conditions, and the heat distortion temperature without annealing at 18.6 A7/crA was measured.

(Based on ASTM D 648) 5) Molding property The composition was kneaded and granulated using a 40φ extruder, and the composition was kneaded and granulated using a Koka type flow tester at 230°C and 6oC.
All fluidity measurements were made in tcg/crit.

6) Gloss The glossiness (human, reflection angle 60°) of a 120×120×3 test piece having the above-mentioned lip was measured.

<Effects of the Invention> The soluble content of the graft polymer of the graft polymerization reaction product obtained by base-tossing an ethylene-α olefin rubber containing tetrahydrofuran-n-hexane mixed solvent is 40% by weight or less, and The insoluble content is 60
A weather-resistant resin composition comprising a graft polymerization reaction product (I) and a polycarbonate resin (II, L) or a (co)polymer (co-)polymer (I) and a polycarbonate resin (II) in an amount of % or less by weight has excellent lip strength, impact resistance, Weld strength, heat resistance and appearance (gloss)
has.

Claims (1)

[Claims] 1.) One or more monomers selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers, and unsaturated carboxylic acid alkyl ester monomers are added to the ethylene-α-olefin rubber. The polymer is obtained by graft polymerization of the grafted material in a mixed solvent of tetrahydrofuran and n-hexane (volume ratio 1:4).
) 5 to 80 wt % of a graft polymerization reaction product (I) with a soluble content of 40 wt % or less and an insoluble content of tetrahydrofuran of 60 wt % or less, a polycarbonate resin (II) 20 to 95 wt %, and (Co)polymer (III) consisting of one or more monomers selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers, and unsaturated carboxylic acid alkyl ester monomers (III) 0 to 75% by weight %.A weather-resistant resin composition with excellent rib strength. 2.) The graft polymerization reaction product (I) is ethylene-
α-olefin rubber 10-60% by weight, 90-4 monomers
0% by weight, and the soluble content in a tetrahydrofuran-n-hexane mixed solvent is 20 to 40%.
% by weight, insoluble matter due to tetrahydrofuran is 50% by weight
The weather-resistant resin composition according to claim 1, which is as follows. 3.) Reduced viscosity of polycarbonate resin (II) (25℃
, chloroform) is 0.40 to 0.55.