JPH01152148A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the present composition excellent in weather resistance, heat resistance and cold processability and excellent in the mar resistance of the surface of an article obtained from it, by mixing a composition comprising a specified resin and a polyester block copolymer with an aromatic polycarbonate resin and a linear saturated polyester resin. CONSTITUTION:The present composition is obtained by mixing 50-98pts.wt. total (A) of 30-70wt.% resin (a) obtained by graft-copolymerizing a monomer mixture based on an aromatic vinyl monomer and a vinyl cyanide monomer with an ethylene/propylene rubbery polymer and 70-30wt.% polyester block copolymer (b) with 1-35pts.wt. aromatic polycarbonate resin (B) and 1-35pts. wt. linear saturated polyester resin, provided that the total sum of the components is 100pts.wt. This composition is excellent in weather resistance, heat resistance and cold processability, and can give a product excellent in mar resistance of surface, so that it can be used without coating when extruded or injection-molded.

Description

DETAILED DESCRIPTION OF THE INVENTION a. Field of Industrial Application The present invention relates to a thermoplastic resin composition that has excellent weather resistance and cold workability, as well as excellent scratch resistance and heat resistance on the surface of the resulting product.

b. Conventional technology Conventionally, materials such as soft vinyl chloride resin or thermoplastic polyurethane have been used as materials for automobile parts and various industrial products, but since these materials have poor weather resistance, they cannot be coated or metallized. In most cases, it is necessary to perform surface treatments such as the following, which results in relatively high processing costs.Therefore, there has been a desire for a material that does not require surface treatment.

On the other hand, recently, for automotive exterior parts such as radiator grilles and rearview mirror housings, monomer mixtures containing ethylene-propylene rubbery polymers, aromatic vinyl monomers, and vinyl cyan monomers as main components are being used. A resin obtained by graft copolymerizing (hereinafter referred to as AES resin) has come to be used without coating because of its excellent weather resistance.

It would be convenient if such AES resin could be used as a material for industrial parts, etc. However, since AES resin is a hard material, cracks easily occur during the cold working process in applications where AES resin is cold worked, so it is difficult to use it alone. It is difficult to do so.

In order to solve these problems with AES resin,
A composition that is given flexibility by blending an ES resin with a thermoplastic elastomer (Japanese Patent Publication No. 60-28313)
, JP 60-17281, JP 6l-126160
) are provided. - Problems to be solved by the C0 invention However, although the composition made of AES resin and thermoplastic elastomer is a resin material with excellent weather resistance, cold workability, and dimensional stability, the resulting product surface is soft. Due to its poor scratch resistance, when used as an exterior material for automobiles,
There is a problem that it is easily damaged by brushes etc. when washing the car.

In addition, due to poor heat creep resistance, if used for a long period of time,
The actual situation is that the range of application is limited, as there are problems such as loosening of the bolted part to the vehicle body, causing the product to wobble.

In addition to the resins mentioned above, various other resin materials have been proposed as automotive materials and various industrial materials, but automatic car wash equipment has become particularly popular recently, and it is important to avoid scratches on resin materials caused by rotating brushes. It is a major issue to prevent this and improve the heat resistance quality of resin parts for export specification vehicles, and existing resin materials are not necessarily sufficient to meet market demands.

Means for Solving the d0 Problem Therefore, as a result of intensive studies to provide a high-performance material, the present inventors added aromatic polycarbonate resin ( By blending a linear saturated polyester resin (hereinafter also referred to as PC resin in some cases), it has excellent weather resistance, heat resistance, and cold workability, and the resulting molded product has excellent scratch resistance on the product surface. The present invention has been completed based on the discovery that a composition can be obtained.

That is, the present invention provides (I) (A) AES resin 30
~70% by weight and (B) polyester block copolymer 7
(II
) A thermoplastic resin composition comprising 1 to 35 parts by weight of an aromatic polycarbonate resin and (III) 1 to 35 parts by weight of a linear saturated polyester resin, the total of which is 100 parts by weight. It is a thing.

(A) AES resin of the present invention is obtained by graft copolymerizing a monomer mixture containing an aromatic vinyl monomer and a vinyl cyan monomer as main components to an ethylene-propylene rubbery polymer. It is a resin, and can be obtained by a graft polymerization method in which the entire amount of the above monomers is graft-polymerized in the presence of an ethylene-propylene rubbery polymer, or a polymer of at least one monomer selected from the above monomers or It can also be produced by a so-called graft blend method in which copolymers are produced separately and then blended.

The graft polymerization method is not particularly limited, and may include solution polymerization, bulk polymerization, suspension polymerization, bulk-suspension polymerization, and emulsification using latex re-emulsified from an ethylene-propylene rubbery polymer. A graft polymerization method or the like for polymerization can be arbitrarily employed as needed.

As the ethylene-propylene rubbery polymer, for example, ethylene-propylene binary copolymer, ethylene-propylene-diene terpolymer, etc. are used. A suitable weight ratio of ethylene and propylene is 90:10 to 20:80. In addition, the type of diene monomer used is
These include norbornenes such as alkenylnorbornene, cyclic dienes such as dicyclopentadiene, and aliphatic dienes such as hexadiene, preferably 5-ethylidene-
2-norbornene and dicyclopentadiene.

Examples of the aromatic vinyl monomer used in graft polymerization include styrene, nuclear-substituted alkylstyrene, nuclear-substituted halogenated styrene, and styrene derivatives such as α-methylstyrene.

Further, as the vinyl cyanide monomer, for example, acrylonitrile derivatives such as acrylonitrile and methacrylonitrile can be used.

Furthermore, if necessary, it is also possible to use acrylic acid alkyl ester derivatives such as methyl acrylate and ethyl acrylate, and methacrylic acid alkyl ester derivatives such as methyl methacrylate.

In addition, maleimide, N
- By using a maleimide compound such as methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-chlorophenylmaleimide, N-cyclohexylmaleimide, etc., the heat resistance of the resulting composition can be improved. can.

Furthermore, (A) AES resin, carboxyl group-containing monomers such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, acid anhydrides such as maleic anhydride and itaconic anhydride, 2-hydroxyethyl acrylate, Methacrylic acid-2-
At least one selected from hydroxyl group-containing monomers such as hydroxyethyl, amino group-containing monomers such as allylamine, aminoethyl methacrylate, and aminostyrene, and epoxy group-containing monomers such as glycidyl acrylate and glycidyl methacrylate. By doing so, the compatibility between the resin components constituting the composition of the present invention can be improved.

The combination of monomers in the AES resin (A) is preferably a combination of styrene and acrylonitrile, and its composition has a styrene:acrylonitrile weight ratio of 80:2.
A range of 0 to 60:40 is preferred. (A)AE
The proportion of the ethylene-propylene rubbery polymer in the S resin is suitably in the range of 10 to 50% by weight, and more preferably in the range of 10 to 50% by weight.
0 to 30% by weight is preferred.

Preferred AES resin (A) has a graft ratio of 20 to 80.
Weight %, intrinsic viscosity of matrix component (30°C, MEK
) is 0.3 to 0.6 dl/g, and the content of the rubber component is 8 to 40% by weight.

The polyester block copolymer (B) of the present invention is a copolymer consisting of a high melting point polyester segment and a low melting point polymer segment with a molecular weight of 400 to 6000, and forms a high polymer only with the high melting point polyester segment constituent components. It is a polyester block copolymer consisting of constituent components having a melting point of 150° C. or higher when the temperature is measured, and a melting point or softening point of 80° C. or lower when measured only with the low melting point polymer segment constituent components.

Examples of the high melting point polyester segment components include terephthalic acid, isophthalic acid, 1.5-naphthalenedicarboxylic acid, 2.6-naphthalenedicarboxylic acid, 4.
Aromatic dicarboxylic acids such as 4'-diphenyldicarboxylic acid, bis(4-carboxyphenyl)methane, bis(4-carboxyphenyl)sulfonic acid, or esters thereof, and ethylene glycol, propylene glycol, tetramethylene glycol, pentamethylene Glycol, 2,2-dimethyltrimethylene diglycol, hexamethylene glycol, decamethylene glycol, p-
Polyesters produced from diols such as xylylene glycol and cyclohexane dimetatool, or polyesters using two or more of these dicarboxylic acids or two or more diols, or p-(β-hydroxyethoxy)benzoic acid, Polyesters derived from oxyacids such as p-oxybenzoic acid and their esters, polylactones such as boribivalolactone or
,2-bis(4,4'-dicarboxyphenoxy)
There are polyether esters produced from aromatic ether dicarboxylic acids such as ethane and the aforementioned diols, and copolyesters made by combining the above dicarboxylic acids, oxyacids, and diols.

Examples of the low-melting segment component include polyalkylene ether glycols such as poly(ethylene oxide) glycol, poly(propylene oxide) glycol, and poly(tetramethylene oxide) glycol, and mixtures thereof, as well as combinations of these polyether components. Polymerized copolymerized polyether glycols, or aliphatic compounds having 2 to 12 carbon atoms such as polyethylene adipate, polytetramethylene adipate, polyethylene sebacate, polyneopentyl sebacate, polyhexamethylene azelate, and poly-δ-caprolactone. Examples include polyesters produced from dicarboxylic acids and aliphatic glycols having 2 to 10 carbon atoms, and polyesterulium polyether copolymers obtained by combining these polyethers and polyesters. The proportion of this low melting point segment component in the polyester block copolymer is preferably 5 to 80 parts by weight. These polyester block copolymers can be produced by conventional polycondensation methods.

In the thermoplastic resin composition of the present invention, (I) (A)
A component consisting of 30 to 70% by weight of AES resin and 70 to 30% by weight of (B) polyester block copolymer (hereinafter referred to as
In some cases, it is also simply referred to as component (1). ) is (A)
AES resin and CB) polyester block copolymer should be blended in a ratio of 30-70% by weight to 70-30% by weight. (A) 30% by weight of AES resin
If it is less than 7, the weather resistance, heat resistance and surface hardness will be poor.
When it exceeds 0% by weight, flexibility is poor, elongation is simply poor, and cold workability is reduced. A particularly preferable blending ratio is (
A) All! The S resin is 40 to 60 parts by weight, and the (B) polyester block copolymer is 60 to 40 weight %.

The aromatic polycarbonate resin (If) used in the present invention is a linear or branched thermoplastic polycarbonate polymer made by reacting an aromatic dihydroxy compound or a small amount of a polyhydroxy compound with a diester of phosgene or carbonic acid. It is. Examples of aromatic dihydroxy compounds include 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), tetramethylbisphenol A1, tetrabromobisphenol A1, bis(4-hydroxydiphenyl)-p-diisopropylbenzene, and hydroquinone. , resorcinol, 4°4-dihydroxydiphenyl, etc., with bisphenol A being particularly preferred. In addition, to obtain a branched aromatic polycarbonate resin, phloroglucin,
4.6-dimethyl-2.4.6-tri(4-hydroxyphenyl)hebutene-2,4,6-dimethyl-2.
4. 6-1-li(4-hydroxyphenyl)hebutane, 2,6-dimethyl-2.4.6-)su(4-hydroxyphenyl)hebutane-3,4,6-dimethyl-2.
4.6-)li(4-hydroxyphenyl)hebutane,
1.3.5-) polyhydroxy compounds exemplified by (4-hydroxyphenyl)benzene, 1,1.1-tri (hydroxyphenyl)ethane, and 3.3
-bis(4-hydroxyaryl)oxindole (
= isatin bisphenol), 5-chloroisatin, 5
．． 7-dichloroisatin, 5-bromiisatin, etc. may be substituted as part of the dihydroxy compound.

Furthermore, monovalent aromatic hydroxy compounds suitable for controlling the molecular weight include 0- and p-methylphenol;
Preferred are 0- and p-propylphenol, p-butylphenol, p-tert-butylphenol and p-long chain alkyl-substituted phenol. Typical aromatic polycarbonate resins include polycarbonates whose main raw material is bis(4-hydroxyphenyl)alkane dihydroxy compounds, especially bisphenol A. Aromatic polycarbonate resins may also be used as a mixture of two or more types.

In addition, as the linear saturated polyester resin (II) in the present invention, a polyalkylene terephthalate homopolymer containing terephthalic acid as the main acid component and an aliphatic diol having 2 to 10 carbon atoms as the main diol component, 15
It refers to a copolymer mainly composed of polyalkylene terephthalate copolymerized with other dicarboxylic acid components and diol components in a mole % or less range, and mixtures of these polymers. As the copolymerization acid component, dicarboxylic acids such as isophthalic acid, adipic acid, sebacic acid, p-β-oxyethoxybenzoic acid, diphenyl ether-4,4'-dicarboxylic acid, and diphenoxyethane-4,4'-dicarboxylic acid are used. In addition to the above-mentioned diol components, cyclohexane dimetatool, cyclopentanedimetatool, etc. are used as the copolymerized diol component. Such (I[I
) Specific preferred examples of the linear saturated polyester resin include polyethylene terephthalate (PUT resin), polytetramethylene terephthalate (PBT resin), polytetramethylene terephthalate-isophthalate copolymer, polytetramethylene terephthalate and polyethylene terephthalate, and polytetramethylene terephthalate-isophthalate copolymer. Examples include mixtures of the following.

(I[) It is preferable to use a PBT resin as the linear saturated polyester resin because it provides significantly superior flexibility and thermoplasticity.

In the thermoplastic resin composition of the present invention, the blending ratio of component (1), (II) aromatic polycarbonate, and (III) linear saturated polyester resin is 50 to 98 parts by weight: 1 to 35 parts by weight. :1 to 35 parts by weight, total 100
Must be parts by weight.

(1) If the blending ratio of the components is less than 50 parts by weight, flexibility and elongation will be poor and cracks will easily occur during cold working.
Not preferred because of poor weather resistance. If it exceeds 98 parts by weight, it is not preferable because the surface scratch resistance and heat resistance are poor. Particularly preferably 60 to 80 parts by weight.

In addition, (If) aromatic polycarbonate and (III
) The blending ratio of linear saturated polyester resin is 1 to 3, respectively.
5 parts by weight, particularly preferably 2 to 25 parts by weight.

(II) If the amount of aromatic polycarbonate is less than 1 part by weight, sufficient surface scratch resistance, heat resistance and elongation cannot be obtained, and if it exceeds 35 parts by weight, flexibility will decrease, which is preferable. do not have.

(I[I) If the amount of the linear saturated polyester resin is less than 1 part by weight, the elongation will be poor, which is not preferable. If it exceeds 35 parts by weight, the flexibility will be poor, which is not preferable.

The above components (II) and (I[I) cannot withstand cold working because if they are blended alone with component (1), the compatibility will be significantly deteriorated and the tensile elongation will be lowered. Therefore, it is impossible to obtain a product that meets the purpose of the present invention.

The thermoplastic resin composition of the present invention may optionally contain a stabilizer,
Various additives such as pigments, dyes, flame retardants, UV agents, and lubricants can be blended, and further, other resin components can be mixed as long as they do not impair the properties of the composition of the present invention. good.

Further, in preparing the thermoplastic resin composition of the present invention, conventionally known methods may be used, and methods of kneading with an extruder, Banbury mixer, rolls, etc. are appropriately selected.

e. Function Automotive materials and various industrial materials are desired to be cold-workable and to have excellent heat resistance. More specifically, the flexural modulus (ASTM 0790) is 1800
kg/d or less, a tensile elongation of 200% or more, and a heat distortion temperature (ASTM D64B) of 70° C. or more.

The thermoplastic resin composition of the present invention comprises (I) component, (II)
This is a composition in which aromatic polycarbonate and (III) linear saturated polyester resin are blended in a specific ratio, and this composition provides a resin composition having desirable performance as the various materials mentioned above.

f, Examples 1-7. Comparative Examples 1 to 6 The present invention will be specifically explained below using Examples, but the present invention is not limited thereto.

Samples having the compounding ratios shown in Table 1 were melted into pellets using a 50"φ extruder at a cylinder temperature of 240°C.

In addition, each test piece for physical property evaluation was 1s-8O manufactured by Toshiba Machine Co., Ltd.
It was produced by molding using an injection molding machine A at a cylinder temperature of 240°C.

The testing method for physical properties is as shown below.

Flexural modulus -4sTM 0790 (unit: kg/
ci) Tensile elongation - 4sTM 0638 (Unit: %) Heat distortion temperature -ASTM D648 (Unit: °C) 1/2', 264psi, surface hardness without annealing...---JISK5401 (-)Pencil hardness Load 1kg Weather resistance - Using a sunshine weather meter (black panel temperature 63°C, rainfall 18/120 minutes), the glossiness of the molded product before and after the accelerated weathering test was measured, and the retention rate was calculated using the following formula.

Exam time: 1000 hours From the results shown in Table 1, the following can be seen.

The resin compositions of Examples 1 to 6 are compositions of the present invention consisting of AES resin, polyester block copolymer, PC resin, and PBT resin, and the flexible thermoplastic resin compositions targeted by the present invention can be obtained. It is being

The resin composition of Example 7 is the same resin composition as the resin composition of Example 1, except that PET resin was used in place of the PBT resin of Example 1. With this resin composition,
A flexible thermoplastic resin composition, which is the object of the present invention, has been obtained.

The resin composition of Comparative Example 1 has a composition ratio of AES resin and polyester block copolymer of 20/80 (wt%), and the resin composition of Comparative Example 2 has a composition ratio of 80/80 (wt%).
0/20 (wt%), both of whose composition ratios are outside the scope of the present invention. ) and weather resistant. - On the other hand, the composition of Comparative Example 2 has a high flexural modulus and poor flexibility, and also has low elongation, resulting in poor cold workability.

The composition of Comparative Example 3 has a PC resin blending ratio below the range of the present invention, and has poor elongation, heat resistance, and surface hardness. The resin composition of Comparative Example 4 has a PBT resin blending ratio below the range of the present invention, has low elongation, and has poor cold workability.

The resin composition of Comparative Example 5 is a composition in which the total amount of AES resin and polyester block copolymer is less than the range of the present invention, and has a high flexural modulus and poor flexibility, and also has poor elongation and weather resistance.

The resin composition of Comparative Example 6 is a composition in which the total amount of AES resin and polyester block copolymer exceeds the range of the present invention, and has poor heat resistance and surface hardness.

g0 Effects of the Invention The thermoplastic resin composition of the present invention is a resin composition that has excellent weather resistance and heat resistance, has excellent scratch resistance on the surface of the resulting product, and has excellent cold workability.

Therefore, the thermoplastic resin composition of the present invention can be used without coating by extrusion molding or injection molding, and is extremely useful industrially.

Claims (2)

[Claims] (1) (I) (A) A resin obtained by graft copolymerizing a monomer mixture containing an aromatic vinyl monomer and a vinyl cyan monomer as main components to an ethylene-propylene rubbery polymer. A total of 50 to 98 parts by weight of 30 to 70% by weight and (B) 70 to 30% by weight of polyester block copolymer, (II) 1 to 35 parts by weight of aromatic polycarbonate resin, and (III) linear saturation. 1. A thermoplastic resin composition comprising 1 to 35 parts by weight of a polyester resin, the total of which is 100 parts by weight. (2) The thermoplastic resin composition according to claim (1), wherein the linear saturated polyester resin (III) is a polytetramethylene terephthalate resin.