JPH01289856A - Weathering-resistant resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition of a good balance among properties such as heat resistance, chemical resistance, impact resistance and molding shrinkage by adding an acrylate rubber-grafted polymer to a composition comprising a polycarbonate and a saturated polyester. CONSTITUTION:The title weathering-resistant resin composition is prepared by adding 1-300pts.wt. graft polymer (the degree of grafting is desirably 90-40wt.%) formed by grafting at least one monomer selected from among an aromatic vinyl compound such as styrene, a vinyl cyanide monomer such as acrylonitrile and an unsaturated carboxylic acid ester such as methyl methacrylate onto a 1-16C, desirably, 2-12C alkyl acrylate rubber (of a particle diameter of, desirably, 0.1-0.4mum) to 100pts.wt. resin composition comprising 90-10wt.% polycarbonate and 10-90wt.% saturated polyester.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention provides a weather-resistant resin composition that is excellent in heat resistance, chemical resistance, impact resistance, balance of molding shrinkage rate, falling ball impact strength, weld strength, and appearance. It is related to.

<Prior art> Polycarbonate has excellent heat resistance and impact resistance, and is widely used in the vehicle field and other areas.
It has the disadvantages of poor chemical resistance and high dependence of impact strength on thickness.

For this reason, it has been proposed to improve the chemical resistance by mixing it with a saturated polyester such as polybutylene terephthalate, but this would compromise the impact resistance, which is a feature of polycarbonate, and also reduce the molding shrinkage rate. Inferior. Furthermore, the current situation is that the thickness dependence of impact strength has not been improved.

In recent years, various three-component resin compositions made by blending rubber or copolymers with compositions made of polycarbonate and saturated polyester have been proposed, but they have poor heat resistance, chemical resistance, impact resistance, and mold shrinkage. In addition, due to the composite composition, falling ball impact strength and weld strength are poor.

<Means for solving the problems> As a result of intensive research into the above-mentioned problems, the present inventors have found that
A composition made by blending a specific amount of a specific graft polymer into a composition consisting of polycarbonate and saturated polyester has excellent heat resistance, chemical resistance, impact resistance, balance of mold shrinkage, falling ball impact strength, weld strength, and It was discovered that this material has an excellent appearance, and the present invention was developed based on this discovery.

That is, the present invention provides an alkyl acrylate rubber having 1 to 16 carbon atoms containing at least one type selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers, and unsaturated carboxylic acid alkyl ester monomers. Graft polymer
Heat resistance, chemical resistance, impact resistance and The present invention provides a weather-resistant resin composition with excellent balance in molding shrinkage, ball impact strength, weld strength, and appearance.

The resin composition of the present invention will be explained in detail below.

The alkyl acrylate rubber constituting the graft polymer (c) in the present invention refers to one or more alkyl acrylates in which the alkyl group has 1 to 16 carbon atoms, in the presence or absence of a crosslinking agent, and It is an elastic body obtained by polymerizing or copolymerizing one or more types of other copolymerizable monomers as required, and one or more types are used.

Examples of the alkyl acrylate having 1 to 16 carbon atoms in the elastic body include methyl acrylate, ethyl acrylate,
Examples include butyl acrylate, 2-ethylhexyl acrylate, etc., and the carbon number is preferably in the range of 2 to 12 in order to obtain sufficient rubber elasticity.

Other monomers that can be copolymerized with alkyl acrylate include aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyltoluene; vinyl cyanide compounds such as acrylonitrile and methacrylate; methacrylic acid esters such as methyl methacrylate; Examples include conjugated diene compounds such as butadiene, 2-chloroethyl vinyl ether, monochlorovinyl acetate, and methoxyethyl acrylate. The amount of these monomers used in the elastic body is 90% by weight or less, preferably 60% by weight or less from the viewpoint of impact resistance of the final composition.

As a crosslinking agent, divinylbenzene, ethylene glycol dimethacrylate, diallyl maleate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, trimethylolpropane triacrylate,
Examples include allyl methacrylate, and the total amount of alkyl acrylate and monomers copolymerizable with it is 100
It is preferable to use within a range of 15 parts by weight or less.

Known polymerization methods such as emulsion polymerization, bulk polymerization, suspension polymerization, solution polymerization, or a combination thereof are used to produce alkyl acrylate rubber, but it is important to control the morphology and particle size of the rubber particles. Emulsion polymerization is preferred because it is easy to remove. For example, it is also possible to adjust the particle size of the rubber particles by adding an acidic substance to the latex of the rubber particles to coagulate and enlarge the latex particles.

Examples of acidic substances include sulfuric acid, phosphoric acid, acetic acid, and acetic anhydride.

The average particle size (weight average) of the alkyl acrylate rubber particles is not particularly limited, but is preferably 0.02 to 0.5.
If it is less than 0.02 μm, the impact resistance of the final composition will not be sufficiently exhibited, and if it exceeds 0.5 μm, it will adversely affect the appearance of the final composition. A particularly preferable range is 0.1
~0.4 μm. In addition, it is also possible to mix two or more types of rubber particles with different average particle diameters and adjust the average particle diameter to the above-mentioned preferred range, and the mixing method is as follows:
Mixing in the rubber latex state before graft polymerization, mixing in the graft latex state after graft polymerization, mixing in the graft powder state after salting out the graft latex, or mixing in the pellet state after melting and pelletizing the graft latex. Any method such as mixing can be used.

Examples of aromatic vinyl monomers include styrene, α-methylstyrene, P-methylstyrene, vinyltoluene, methyl-α-methylstyrene, butylstyrene, chlorostyrene, etc., and one or more of them are used. be able to.

Styrene is particularly preferred.

Examples of vinyl cyanide monomers include acrylonitrile and methacrylate trile, and one type or two or more types can be used. Acrylonitrile is particularly preferred.

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 and glycidyl methacrylate, which can be used alone or in combination of two or more. In particular, methyl methacrylate, glycidyl acrylate, and glycylate are graft-polymerized in the presence of an alkyl acrylate rubber to form a graft polymer (3).

In particular, the monomers used in the graft polymerization (c) include styrene, acrylonitrile, and the composition ratio of the alkyl acrylate rubber to the monomer in the methyl metagraft polymer (c). In terms of physical properties, it is preferable that the alkyl acrylate rubber contains 5 to 95% by weight and the monomer content is 95 to 5% by weight, and particularly the alkyl acrylate rubber contains 10 to 60% by weight and the monomer content is 90 to 4%.
Preferably it is 0% by weight.

The polycarbonates used in the present invention include aromatic polycarbonates, aliphatic polycarbonates, aliphatic-aromatic polycarbonates, and the like.

Among them, aromatic polycarbonates made of bisphenols such as 2,2-bis(4-oxyphenyl)alkanes, bis(4-oxyphenyl)ethers, bis(4-oxyphenyl)sulfones, sulfides, or sulfoxides are used. preferable.

Further, polycarbonate made of bisphenols substituted with halogen can also be used if necessary.

Regarding the manufacturing method and types of polycarbonate, please refer to 5 Polycarbonate Resin' (1968) published by Nikkan Kogyo Shimbun.
(Published September 30, 2016).

Saturated polyester 0 refers to an acid component mainly consisting of an aromatic dicarboxylic acid or its ester-forming derivative and a carbon number of 2 to 2.
It is an aromatic polyester obtained from 10 low molecular weight glycols or their ester-forming derivatives, and a small amount of aliphatic dicarboxylic acid having 2 to 32 carbon atoms, alicyclic dicarboxylic acid, or their ester-forming derivatives are used together as an acid component. You can also do that.

To illustrate these components, aromatic dicarboxylic acids or their ester-forming derivatives include terephthalic acid,
Isophthalic acid, naphthalene dicarboxylic acid, dibenzoic acid,
Examples include alkali metal salts of dicarboxybenzenesulfonic acid, lower alkyl esters, cycloalkyl esters, aryl esters, hydroxyalkyl esters, and acid halides thereof, and one type or two or more types thereof may be used.

Examples of low molecular weight glycols having 2 to 10 carbon atoms or ester-forming derivatives thereof include ethylene glycol, propylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, decamethylene glycol, cyclohexane dimetatool, neopentyl glycol, diethylene glycol, Examples include 2.2-bis(4-hydroxyphenyl)propane and p-xylylene glycol, and one or more of them may be used.

Examples of aliphatic dicarboxylic acids having 2 to 32 carbon atoms, alicyclic dicarboxylic acids, or ester-forming derivatives thereof include adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, cyclohexanedicarboxylic acid, dimer acid, etc.; Examples include alkyl esters, cycloalkyl esters, aryl esters, hydroxyalkyl esters, acid halides, etc., and one type or two or more types may be used.

Particularly preferred saturated polyesters (q include polyethylene terephthalate, polytetramethylene terephthalate, polybutylene terephthalate, etc.), and one or more of them can be used.

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

The HIIllll resin composition of the present invention is composed of the above-mentioned graft polymer (A), polycarbonate (1), and saturated polyester (q), and the composition ratio thereof is 100% by weight in total of (g) and (q). Per part (A) 1-3
00 parts by weight, and ◎ and (q is (g) and 0
(G) 90 to 10% by weight, (C) to ~
It is 90% by weight.

If it exceeds the weight part, heat resistance, impact resistance, falling ball impact strength, and weld strength will deteriorate, which is undesirable. In particular, from the viewpoint of physical property balance, 5 to 200 parts by weight is preferable.

Also, the amount of (g) in the total of (g) and 0 is 90% by weight
If it exceeds 10% by weight, the chemical resistance will be poor, and if it is less than 10% by weight, the heat resistance will be poor and the molding shrinkage will be large, which is not preferable. In particular, from the viewpoint of chemical resistance, heat resistance, and molding shrinkage rate, (g) 80 to 20% by weight and (C) 20 to 80% by weight are preferable in the sum of (1) and (Q).

Examples of mixing methods for graft polymer (3), polycarbonate ◎, and saturated polyester (q) include known mixing methods using a Banbury mixer, a single-screw extruder, a twin-screw extruder, or a combination thereof. , these respective components may be mixed at the same time,
Further, after mixing any two components, this mixture may be mixed with another component.

The weather-resistant resin composition of the present invention may optionally contain known additives such as dyes and pigments, antioxidants, plasticizers, antistatic agents, ultraviolet absorbers, lubricants, fillers, flame retardants, etc.
S resin, MBS resin, ABSM resin, AES resin, AC
3 resins, polyvinyl chloride, ethylene-vinyl chloride copolymer, chlorinated polyethylene, ethylene-vinyl acetate copolymer, styrene-maleic anhydride copolymer, styrene-acrylonitrile-maleic anhydride copolymer, styrene-
Maleimide copolymer, styrene-acrylonitrile
Other thermoplastic resins such as maleimide copolymers, polyester elastomers, polyamides, polyacetals, and polysulfones can also be blended.

Although the present invention will be described with reference to examples, the present invention is not limited to the examples in any way.

95 parts by weight of butyl acrylate, 5 parts by weight of acrylonitrile and 1 part by weight of ethylene glycol dimethacrylate are polymerized based on a known emulsion polymerization method to produce an alkyl acrylate rubber latex with an average particle size (weight average) of rubber particles of 0.23 μm. I got it.

Next, 50 parts by weight of a monomer mixture solution consisting of 70% by weight of styrene, 20% by weight of acrylonitrile and 10% by weight of methyl methacrylate was added to 50 parts by weight of solid content in this latex, and graft polymerization was carried out by a known emulsion polymerization method. A graft polymer A-1 was obtained.

Graft Polymer (A-2)> A monomer mixture solution consisting of 70% by weight of styrene, 20% by weight of acrylonitrile and 10% by weight of methyl methacrylate was added to a solution of a monomer mixture consisting of 70% by weight of styrene and 30% by weight of acrylonitrile. , change to A-1
Polymerization was carried out in the same manner to obtain graft polymer A-2.

Graft polymer (a)> Iodine number 15.3, Mooney viscosity 67, propylene content 50% by weight, 100 parts by weight of EPDM containing ethylidene norbornene as the diene component was mixed with 1250 parts by weight of n-hexane.
parts by weight and 850 parts by weight of ethylene dichloride, 35 parts by weight of acrylonitrile, 100 parts by weight of styrene and 3 parts by weight of benzoyl peroxide were added, and polymerization was carried out at 67° C. for 10 hours in a nitrogen atmosphere.

The polymerization solution was brought into contact with a large excess of methanol, and the deposited precipitate was separated and dried to obtain a graft polymer (a).

Polycarbonate (c)> Below - polycarbonate with a molecular weight of about 25,000 indicated by the hole.

○ Saturated polyester (Q> O Polybutylene terephthalate (C-1) ○ Polyethylene terephthalate (C-2) Based on the blending ratios shown in Tables 1 and 2, the above-mentioned graft polymer, polycarbonate, and saturated polyester were subjected to twin-screw extrusion. The mixture was mixed all at once using a machine to obtain various compositions.

Thereafter, test pieces were prepared using an injection molding machine, and their physical properties were measured. The results obtained are shown in Tables 1 and 2.

Table-1 Table-2 Heat resistance: ASTM D-648 1/4 inch, 264 psi non-annealed impact resistance:
ASTM D256 (notched isot) 4 inches, 23°C Mold shrinkage rate: Calculated from the difference in dimensions between the mold dimensions of ASTM No. 1 dumbbell and the actual molded product Weld strength: Two gates with a gate spacing of 401 LI (each 4. OX 2. molten resin (270℃
) to create a test piece with a thickness of 3 & 11 and 60-a in length and width.

Test 1 Jig with steep piece (Height 80u1 Inner diameter 45mm, Outer diameter 50u
) on top of the center. Furthermore, a center of impact of 1/4 inch radius is placed on the center of the test piece.

In a cold room adjusted to -30°C, a steel ball weighing 1 kg is dropped onto the center of the test piece from just above the center of impact (at 10 cm intervals in the height range of 10 to 120 cm) to ensure that the test piece does not break (respectively). The number of test pieces used in the test conducted from a height of 10 cm intervals is 5, and the maximum energy value (Kq-cm) is determined (without breaking any test piece).

Falling ball impact strength: (Non-weld part) ・ Using a mold for weld strength measurement, Create a test piece using the one-point gate method, Same as weld strength measurement Find the energy value. In addition, IK9 The steel balls were replaced with 9 steel balls instead of 5. Ta.

Chemical resistance: A bending strain of 1% was applied to an h-inch test piece according to ASTM D-648, and a wax cleaner (MC-21 manufactured by BEL-RAY) was applied to the test piece, and the test piece was judged by the presence or absence of breakage after being left for 48 hours.

○; No breakage ×;〃〃〃〃〃 Effects of the invention〉 The composition of the present invention has an excellent balance of heat resistance, chemical resistance, impact resistance, and molding shrinkage rate compared to conventional polycarbonate/saturated polyester compositions, Furthermore, it has excellent ball impact strength and weld strength, and can be used as vehicle parts, light electrical parts, and industrial parts.

Claims (1)

[Claims] Graft polymerization of one or more monomers selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers, and unsaturated carboxylic acid alkyl ester monomers to alkyl acrylate rubber having 1 to 16 carbon atoms. The graft polymer (A) was mixed with 90 to 10% by weight of polycarbonate (B).
and saturated polyester (C) in an amount of 1 to 300 parts by weight per 100 parts by weight of a composition comprising 10 to 90% by weight of a saturated polyester (C).