JPH0730163B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention relates to a thermoplastic resin composition excellent in heat resistance, chemical resistance, impact resistance and molding shrinkage balance, falling ball impact strength, weld strength and appearance. It is about.

<Prior Art> Polycarbonate has excellent heat resistance and impact resistance, and is widely used in the vehicle field and the like.
It has drawbacks such as poor chemical resistance and large thickness dependence of impact strength.

Therefore, it has been proposed to improve chemical resistance by mixing it with a saturated polyester typified by polybutylene terephthalate, but impact resistance, which is a characteristic of polycarbonate, is sacrificed, and molding shrinkage is also poor. At present, the thickness dependence of impact strength has not been improved.

In recent years, various three-component resin compositions prepared by blending a rubber or a copolymer with a composition of polycarbonate and saturated polyester have been proposed, but heat resistance, chemical resistance, impact resistance, and molding shrinkage ratio. However, there is a problem in that the falling ball impact strength and the weld strength are poor due to the composite composition.

<Means for Solving Problems> As a result of earnest research on the above problems, the present inventors have found that
A composition obtained by blending a specific amount of a specific copolymer in a composition composed of a polycarbonate and a saturated polyester has a balance of heat resistance, chemical resistance, impact resistance and molding shrinkage,
The inventors of the present invention have found that they have excellent falling ball impact strength, weld strength and appearance, and have reached the present invention.

That is, the present invention is an ethylene-α olefin rubber 10
In the presence of 0 part by weight, 0.2 to 300 parts by weight of an unsaturated epoxy monomer and one or more compounds selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds and unsaturated carboxylic acid alkyl ester compounds 10 The copolymer (A) obtained by polymerizing ~ 500 parts by weight of the polycarbonate (B) is mixed with 90 to 10% by weight of the saturated polyester (C) 10.
~ 100 parts by weight of composition per 100 parts by weight of the composition, 1 to 300 parts by weight, characterized by a balance of heat resistance, chemical resistance, impact resistance and molding shrinkage, falling ball impact strength, weld strength And a thermoplastic resin composition excellent in appearance.

Hereinafter, the resin composition of the present invention will be described in detail.

Ethylene-α constituting the copolymer (A) in the present invention
The olefin rubber is a binary copolymer (EPR) composed of ethylene and propylene or butene, a terpolymer (EPDM) composed of ethylene, propylene or butene and a non-conjugated diene, and one or more kinds thereof. Used.

As the non-conjugated diene in the terpolymer (EPDM),
Dicyclopentadiene, ethylidene norbornene, 1,4
-Hexadiene, 1,4-cycloheptadiene, 1,5-cyclooctadiene and the like.

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

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

The unsaturated epoxy monomer constituting the copolymer (A) is
It is a monomer having at least one polymerizable unsaturated bond and at least one epoxy group in each molecule. Examples of such unsaturated epoxy monomers include those represented by the general formula (Wherein R represents a hydrocarbon group having a polymerizable ethylenically unsaturated bond) and an unsaturated glycidyl ester represented by the general formula (Here, R is the same as that of the formula [I], X is —CH ₂ —O
-Or An unsaturated glycidyl ether represented by the formula: and a general formula (Here, R is the same as that of the formula [I], R'is hydrogen or a methyl group), and the like epoxy alkene.

Specifically, glycidyl acrylate, glycidyl methacrylate, mono- and diglycidyl esters of itaconic acid, mono-, di- and triglycidyl esters of butenetricarboxylic acid, mono- and diglycidyl esters of citraconic acid, endo-cis-bicyclo (2,2 , 1] Hept-5-ene-2,3-dicarboxylic acid (trade name: nadic acid)
Mono- and diglycidyl esters of endo-cis-bicyclo [2,2,1] hept-5-ene-2-methyl-2,3-
Mono- and diglycidyl esters of dicarboxylic acid (trade name: methyl nadic acid), mono- and diglycidyl esters of allyl succinic acid, glycidyl esters of p-styrenecarboxylic acid, allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-p-glycidyl Ether or p-glycidyl styrene, 3,4-epoxy-1-butene, 3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-1-pentene, 3,4-epoxy-
Mention may be made of 3-methyl-1-pentene, 5,6-epoxy-1-hexene and vinylcyclohexene monoxide.

The compound constituting the copolymer (A) is styrene or α-
Methylstyrene, α-chlorostyrene, pt-butylstyrene, p-methylstyrene, O-chlorostyrene,
Aromatic vinyl compounds such as p-chlorostyrene, 2,5-dichlorostyrene, 3,4-dichlorostyrene, p-bromostyrene, O-bromostyrene, 2,5-dibromostyrene, 3,4-dibromostyrene (i. ), Acrylonitrile,
Vinyl cyanide compounds (ii) such as methacrylonitrile, maleonitrile and fumaronitrile, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, etc. Is one or more compounds selected from the unsaturated carboxylic acid alkyl ester compounds (iii). In addition, unsaturated carboxylic acid compounds (iv) such as methacrylic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, aconitic anhydride, and unsaturated dicarboxylic acid anhydrides (v) such as hymic acid anhydride, maleimide, Maleimide compounds (vi) such as N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-laurylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-o-chlorophenylmaleimide.
You may use such compounds as a copolymerization component.

The copolymer (A) is an unsaturated epoxy monomer 0.2 to 300 in the presence of 100 parts by weight of the above-mentioned ethylene-α-olefin rubber.
It is a copolymer obtained by polymerizing 10 parts by weight to 10 to 500 parts by weight of another copolymerizable monomer.

When the unsaturated epoxy monomer is outside the range of 0.2 to 300 parts by weight,
The impact resistance and weld strength of the final composition are not improved.

Even if the amount of other copolymerizable monomer is out of the range of 10 to 500 parts by weight, the impact resistance and weld strength of the final composition are not improved.

Examples of the polycarbonate (B) used in the present invention include aromatic polycarbonate, aliphatic polycarbonate, and aliphatic-aromatic polycarbonate. Among them, 2,2-bis (4-oxyphenyl)
Alkane type, bis (4-oxyphenyl) ether type,
Aromatic polycarbonates composed of bisphenols such as bis (4-oxyphenyl) sulfone, sulfides or sulfoxides are preferred. Further, a polycarbonate composed of bisphenols optionally substituted with halogen can also be used.

The production method and type of polycarbonate are described in detail in "Polycarbonate Resin" published by Nikkan Kogyo Shimbun (published on September 30, 1969).

The saturated polyester (C) is an aromatic polyester obtained from an acid component mainly composed of an aromatic dicarboxylic acid or an ester-forming derivative thereof and a low molecular weight glycol having 2 to 10 carbon atoms or an ester-forming derivative thereof. As a small amount, an aliphatic dicarboxylic acid having 2 to 32 carbon atoms, an alicyclic dicarboxylic acid, or an ester-forming derivative thereof can be used in combination.

Examples of these components include terephthalic acid as an aromatic dicarboxylic acid or its ester-forming derivative,
Isophthalic acid, naphthalenedicarboxylic acid, dibenzoic acid,
Examples thereof include dicarboxybenzene sulfonic acid alkali metal salts and the like, or lower alkyl esters, cycloalkyl esters, aryl esters, hydroxyalkyl esters, acid halides and the like, and one kind or two or more kinds are used.

As the low molecular weight glycol having 2 to 10 carbon atoms or its ester-forming derivative, ethylene glycol, propylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, decamethylene glycol, cyclohexanedimethanol, neopentyl glycol, diethylene glycol, 2 2,2-bis (4-hydroxyphenyl) propane, p-xylylene glycol and the like can be mentioned, and one kind or two or more kinds are used.

Examples of the aliphatic dicarboxylic acid having 2 to 32 carbon atoms, the alicyclic dicarboxylic acid or their ester-forming derivatives include adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, cyclohexanedicarboxylic acid, dimer acid and the like, or lower ones thereof. Examples thereof include alkyl esters, cycloalkyl esters, aryl esters, hydroxyalkyl esters, acid halides and the like, and one kind or two or more kinds are used.

As particularly preferable saturated polyester (C), polyethylene terephthalate, polytetramethylene terephthalate, polybutylene terephthalate, etc. may be mentioned, and one kind or two or more kinds may be used.

These saturated polyesters (C) can be produced by a known polycondensation method.

The thermoplastic resin composition of the present invention is composed of the above-mentioned copolymer (A), polycarbonate (B) and saturated polyester (C), and the composition ratio thereof is
1 to 300 parts by weight per 100 parts by weight of (B) and (C) in total, and (B) and (C) are (B) 90 with respect to the total of (B) and (C). ~ 10 wt%, (C) 10 ~
90% by weight.

If the amount of the copolymer (A) is less than 1 part by weight, the impact resistance is poor, which is not preferable. If it exceeds 300 parts by weight, the heat resistance and the impact resistance are
Poor ball impact strength and weld strength, which is not preferable. Particularly, from the viewpoint of physical property balance, 5 to 200 parts by weight is preferable.

Further, if the amount of (B) in the total of (B) and (C) exceeds 90% by weight, the chemical resistance is poor, and if it is less than 10% by weight, the heat resistance is poor and the molding shrinkage ratio is large, which is not preferable. Especially in terms of chemical resistance, heat resistance and molding shrinkage, (B) 80 to 20% by weight, (C) 20 to 80% by weight in the total of (B) and (C)
Is preferred.

Examples of the method for mixing the copolymer (A), the polycarbonate (B) and the saturated polyester (C) include known mixing methods using a Banbury mixer, a single screw extruder, a twin screw extruder or a combination thereof. In addition, as for the mixing of each of these constituent components, the three components may be mixed at the same time,
Further, after mixing arbitrary two components, this mixture may be mixed with another component.

The thermoplastic resin composition of the present invention, if necessary, dyes and pigments, antioxidants, plasticizers, antistatic agents, ultraviolet absorbers, lubricants,
Not only known additives such as fillers and flame retardants, but also AB
S resin, MBS resin, ABSM resin, AAS resin, ACS resin, polyvinyl chloride, ethylene-vinyl chloride copolymer, chlorinated polyethylene, ethylene-vinyl acetate copolymer, styrene-
Other thermoplastic resins such as maleic anhydride copolymer, styrene-acrylonitrile-maleic anhydride copolymer, styrene-maleimide copolymer, styrene-acrylonitrile-maleimide copolymer, polyester elastomer, polyamide, polyacetal, polysulfone and the like. Can also be blended.

The present invention will be described with reference to examples, but the present invention is not limited to the examples.

Example (1) Copolymer (A-1) Iodine value 8.5, Mooney viscosity 61, propylene content 43% by weight, containing ethylidene norbornene as a diene component
Dissolve 100 parts by weight of EPDM in 1200 parts by weight of n-hexane and 800 parts by weight of ethylene dichloride, and add 20 parts by weight of glycidyl methacrylate and 0.4 parts by weight of benzoyl peroxide.
Polymerization was carried out at ℃ for 10 hours in a nitrogen atmosphere. The polymerization liquid was brought into contact with a large excess of methanol, and the precipitated precipitate was separated and dried to obtain a copolymer.

(2) Copolymer (A-2) Iodine number 15.3, Mooney viscosity 67, propylene content 50% by weight, containing ethylidene norbornene as a diene component
EPDM 100 parts by weight is dissolved in n-hexane 1250 parts by weight and ethylene dichloride 850 parts by weight, and glycidyl methacrylate 15 parts by weight, acrylonitrile 35 parts by weight, styrene 100
Parts by weight and 3 parts by weight of benzoyl peroxide are added, (1)
A copolymer was obtained by the same procedure as described above.

(3) Copolymer (A-3) The amounts of glycidyl methacrylate, acrylonitrile, styrene and benzoyl peroxide used were changed to 8 parts by weight, 100 parts by weight, 250 parts by weight and 8 parts by weight, respectively, and (2) A copolymer was obtained by the same operation.

(4) Copolymer (a-1) EPDM used for the production of copolymer (A-1).

(5) Copolymer (a-2) A copolymer was obtained by the same operation as in (2) without using glycidyl methacrylate.

(6) Polycarbonate (B) Polycarbonate represented by the following general formula and having a molecular weight of about 25,000.

(7) Saturated polyester (c-1) Polybutylene terephthalate (8) Saturated polyester (c-2) Polyethylene terephthalate The above copolymer, polycarbonate and saturated polyester are biaxial based on the compounding ratios shown in Tables -1 to 3. Various compositions were obtained by batch mixing using an extruder.

Then, a test piece was prepared using an injection molding machine and the physical properties were measured. The obtained results are shown in Tables 1-3.

Heat resistance: ASTM D-648 1/4 inch, 264 psi, no annealing Impact resistance: ASTM D-256 (notched Izod) 1/4 inch, 23 ° C Molding shrinkage: ASTM No. 1 dumbbell mold dimensions and actual Weld strength: A molten resin (270 ° C) is injected from two gates (4.0 x 2.0 mm each) with a 40 mm gate spacing, and test pieces with a thickness of 3 mm and a length and width of 60 mm are made. Place the test piece on the center of the jig (height 80 mm, inner diameter 45 mm, outer diameter 50 mm). Furthermore, on the center of the test piece
Put a 1/4 inch R on the shot.

In a low temperature room adjusted to -30 ° C, drop a 1kg steel ball directly above the impact (10cm intervals in the height range of 10 to 120cm) to the center of the test piece so that the test piece does not break (each 10cm interval). The number of test pieces used in the test performed from the height of 5 is 5, and the maximum energy value (kg · cm) which does not break any test piece is obtained.

Falling ball impact strength: (Non-weld part) Using a mold for weld strength measurement, a test piece is prepared by a one-point gate method, and the maximum energy value is obtained in the same manner as the weld strength measurement. The 1 kg steel ball was replaced with a 5 kg steel ball.

Chemical resistance: Apply 1% bending strain to a 1/8 inch test piece of ASTM D-648, apply wax cleaner (MC-21 made by BEL-RAY), and judge by the presence or absence of breakage after standing for 48 hours. did.

◯: No breakage; 〃 Ali <Effect of the invention> The composition of the present invention has an excellent balance of heat resistance, chemical resistance, impact resistance and molding shrinkage ratio as compared with the conventional polycarbonate / saturated polyester-based composition, Furthermore, it has excellent falling ball impact strength and weld strength, and can be used as vehicle parts, light electric parts, and industrial parts.

Claims (1)

[Claims] 1. A composition comprising 0.2 to 300 parts by weight of an unsaturated epoxy monomer, an aromatic vinyl compound, a vinyl cyanide compound and an unsaturated carboxylic acid alkyl ester compound in the presence of 100 parts by weight of an ethylene-α-olefin rubber. Copolymer (A) obtained by polymerizing 10 to 500 parts by weight of one or more compounds selected from the group, polycarbonate (B) 90 to 10% by weight and saturated polyester (C) 10 to 90% by weight A thermoplastic resin composition comprising 1 to 300 parts by weight per 100 parts by weight of the composition.