JPS62172051A - Polyester resin composition - Google Patents

Abstract

PURPOSE:A good composition having improved mechanical strength and impact resistance and low warpage, obtained by blending a mixture containing an aromatic polyester, a glycidyl group-containing copolymer and an ethylene copolymer with mica powder and a fiber-reinforcing material. CONSTITUTION:100pts.wt. polyester resin mixture containing (A) 98-40wt% aromatic polyester, (B) 1-40wt% glycidyl group-containing copolymer consisting of an alpha-olefin and a glycidyl ester of an alpha,beta-unsaturated acid and (C) 1-40wt% ethylene copolymer obtained by copolymerizing ethylene with >=3C alpha-olefin is blended with (D) 3-100pts.wt. mica powder having <=100mu diameter and (C) 0-60pts.wt. fiber reinforcing material. Mica powder pretreated with an epoxy resin of silane coupling agent is preferably used as the component D.

Description

[Detailed description of the invention] <Industrial application field> The present invention relates to polyester resin compositions.

In more detail, it has excellent mechanical strength J3 and σ impact resistance.
The present invention also relates to a polyester resin composition with good low warping properties.

<Prior Art> Aromatic polyesters represented by polyethylene terephthalate and polyethylene terephthalate are used in a wide range of fields such as electrical and electronic equipment parts and automobile parts due to their excellent properties. However, since aromatic polyester has low mechanical strength, a method of adding reinforcing materials such as glass fiber has been proposed and commercialized, but in this case, although it provides occupational strength, it causes warping. This problem happened very often. In order to solve the problem of warpage, a method has been proposed in which a plate-like or granular filling such as mica is added. In this case, although the problem of warping can be solved, the disadvantage is that the impact resistance is significantly reduced.
For example, there are two methods such as the method of preparing a polyether ester block copolymer by 71%, which is described in Japanese Patent Publication No. 58-53663.

However, with these methods, the effect of improving street narrowing is very small, and sufficient impact strength can be obtained. And aromatic polyesters with excellent impact resistance and no warping problems are available.

<Problems to be Solved by the Invention> Therefore, the present inventors conducted intensive studies to find an aromatic polyester that has excellent mechanical strength and impact resistance and does not have the problem of warping, and found that aromatic polyester and mica It has been found that the above object can be achieved by roughly including a specific glycidyl group-containing copolymer and a specific ethylene-based copolymer into a powder or a composition of aromatic polyester, mica J3, and fibrous reinforcing material. We have arrived at the present invention.

Means for Solving the Problems〉 That is, the present invention provides aromatic polyester (A) 98-4
0 weight percent, glycidyl group-containing copolymer (B) consisting of α-olefin and glycidyl ester of α/β-unsaturated acid
1 to 40% by weight and an ethylene copolymer obtained by copolymerizing ethylene with an α-olefin having at least 3 carbon atoms (
C) 3 to 100 parts by weight of mica powder (D) with a diameter of 100 μ or less and fibrous reinforcing material (E) per 100 parts by weight of a polyester resin mixture containing 1 to 40% by weight.
A polyester resin composition containing 0 to 60 parts by weight is provided.

The aromatic polyester (A) used in the present invention is a polyester having an aromatic ring in the chain unit of the polymer, and is composed of an aromatic dicarboxylic acid (or an ester-forming derivative thereof) and a diol (or an ester-forming derivative thereof). It is a polymer or copolymer obtained by a condensation reaction containing as a main component.

The aromatic dicarboxylic acids mentioned here include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis(p-
carboxyphenyl)methane, an-1-racendicarboxylic acid, 4.4"-diphenyldicarboxylic acid, 4.4'-
Examples include diphenyl ether dicarboxylic acid, 1,2-bis(phenoxy)ethane-4,4'-dicarboxylic acid, and ester-forming derivatives thereof.

In addition, if the acid component is 40 mol% or less, fatty Δ group dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, etc. Dicarboxylic acids other than aromatic dicarboxylic acids such as alicyclic dicarboxylic acids and ester-forming derivatives thereof may be substituted.

In addition, the diol component includes aliphatic diols having 2 to 10 carbon atoms, such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-bentanediol, 1,6-hexanediol, and decamethylene. diglycol, cyclohexanediol, cyclohequinane dimethanol, etc., and mixtures thereof, some of which have a molecular weight of 400 to 6°OO.
O long chain glycols, i.e. polyethylene glycol, poly-1,3-propylene glycol, polyte 1-
It may also be substituted with ramethylene glycol and mixtures thereof.

Examples of preferred aromatic polyesters used in the present invention include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexylene dimethylene terephthalate, polyethylene-2,6-naphthalate, polyethylene-1,2- Examples include his(phenoxy)ethane-4,4'-dicarboxylate, among which polybutylene terephthalate, which has appropriate mechanical strength, is most preferred.

The aromatic polyester used in the present invention is 0.5%
The relative viscosity of the 0-chlorophenol solution measured at 25°C is preferably 1.15 to 2.0, particularly preferably 1.3 to 1.85.

The α-olefin in the glycidyl group-containing copolymer (B) consisting of an α-olefin and a glycidyl ester of an α,β-unsaturated acid used in the present invention is ethylene, propylene, butene-1, etc., and ethylene is preferable. Can be used.

In addition, the glycidyl ester of an α,β-unsaturated acid has the general formula (wherein R is a hydrogen atom, a lower alkyl 1.16, or a lower alkyl group substituted with a glycidyl ester group).
Examples of the compounds include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and glycidyl itaconate, among which glycidyl methacrylate is preferably used. The copolymerized amount of glycidyl ester of α,β-unsaturated acid in the glycidyl group-containing copolymer is suitably in the range of 1 to 50% by weight, particularly 2 to 30% by weight.

In addition, unsaturated polymers, i.e., vinyl ethers, which can be copolymerized with the above copolymers if the content is approximately 40% by weight or less,
One or more types of vinyl esters such as vinyl acetate and vinyl propionate, acrylic mt3 and methacrylic acid esters such as methyl, ethyl, propyl, and butyl, acrylonitrile, styrene, and carbon oxide may be combined together.

Preferred examples of the glycidyl group-containing copolymer according to the present invention include ethylene/glycidyl methacrylate copolymer, ethylene/monyl acetate/glycidyl methacrylate copolymer, and ethylene/-QQ carbon/glycidyl methacrylate copolymer.
Nor copolymers, ethylene/lycidyl acrylate copolymers, ethylene/lycidyl acrylate/vinyl acetate copolymers, among others, ethylene/lycidyl methacrylate copolymers and ethylene/lycidyl methacrylate copolymers. Particularly preferred are vinyl acetate copolymers.

Next, in the ethylene copolymer (C) in which ethylene is copolymerized with at least an α-olefin having at least 3 carbon atoms, the α-olefins having at least 3 carbon atoms are propylene, butene-1, pentene-1 , 3-methylpentene-1, octacene-1, etc., propylene,
Butene-1 is preferably used. The ethylene copolymer may further be copolymerized with a non-conjugated diene.

These non-covalent 1Ω dienes include 5-methylidene-2-norbornene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-brobenyl-2-norbornene, 5-isopropenyl-2-norbornene, 5-
Crotyl-2-norbornene, 5-(2-methyl-2-
butenyl)-2-norbornene, 5-(2-ethyl-2
Norbornene compounds such as -butenyl)-2-norbornene, 5-methacrylnorbornene, 5-methyl-5-gonylnorbornene, dicyclopentadiene, methyltetrahydroindene, 4.7.8.9-tetrahydroindene, 1,5 -cyclooctadiene, 1,4-hequinadiene, isoprene, 6-methyl-1,5-hebutadiene, 11-ethyl-111-tridecadiene, etc., preferably 5-methylidene-2-norbornene, 5-
Ethylidene-2-norbornene, dicyclopentadiene, 1,4-hexadiene, etc. can be used.

Ethylene and α-olefin having 3 or more carbon atoms in an ethylene copolymer consisting of ethylene and α-olefin having 3 or more carbon atoms
When the olefin copolymerization ratio t does not contain a non-conjugated diene, it is preferably 40/60 to 99/1 (molar ratio), more preferably 70/30 to 9515 (molar ratio).

When containing a non-conjugated diene, the copolymerization amount of the α-olefin having 13 or more carbon atoms is preferably 5 to 80 mol%, more preferably 20 to 60 mol%, and the copolymerization amount of the non-conjugated diene is preferably is 0.1 to 20 mol%, preferably 0.5 to 10 mol%.

Aromatic polyester (A), glycidyl group-containing copolymer (B) and ethylene copolymer (C) in the present invention
The usage ratio is (A) / (B) / (C) = 98~4
0 width%/1 to 40 weight%/1 to 40% m%, preferably 95 to 60% by weight/2.5 to 25 weight%/2.
It is 5-25% square.

The amount of the glycidyl group-containing copolymer (3) and the ethylene copolymer (C) according to the present invention is 1% by weight, respectively.
If the amount is less than 40, the mechanical strength of the aromatic polyester decreases, which is not preferable.

Roughly, the mica powder (b) used in the present invention is obtained by refining and crushing natural mica as a raw material into powder form, that is, muscovite (muscovite), phlogopite (phlogopite 1), and black mica. You can choose from a wide range of synthetic products such as mica and scad mica.

The size of the mica powder used in the present invention is approximately 1 mm in diameter.
It needs to be 00μ or less.

If the diameter of the mica powder exceeds 100 μm, the impact resistance will decrease, making it difficult to achieve the object of the present invention, and furthermore, the surface of the molded product will become very poor.

Furthermore, it is also a preferable method to previously treat mica powder with a silane-based or titanium-based coupling agent such as an epoxy resin in order to increase the internal strength of the composition of the present invention.

The amount of mica powder added in the present invention is 3 to 3 parts by weight based on 100 parts by weight of the aromatic polyester (A), the glycidyl group-containing copolymer (B), and the ethylene copolymer (C).
100 parts by weight, preferably 5 to 70 parts by weight, 10
-50 parts by weight is more preferred. If the amount of mica powder added is less than 3 parts by weight, the mechanical strength will not be improved sufficiently, and the
If it exceeds 0 parts by weight, the impact resistance will decrease, making it difficult to achieve the object of the present invention.

Additionally, a coarse fibrous reinforcement (E) is added to the composition of the present invention.
) is effective in further improving the regularity. Specific examples of fibrous reinforcement include:
These include glass fiber, carbon fiber, asbestos, titanate potassium whisker, ceramic fiber, and metal fiber such as brass and stainless steel, among which glass fiber is preferably used. The fibrous reinforcing material is particularly preferably treated with a silane type such as epoxy silane, a titanium type or the like, a conventional coupling agent, Yaeboxy resin, vinyl acetate resin, or the like.

As the glass fiber, a normal chopped strand or roving type can be used, but a chopped strand with a length of 3 to 6 pieces is preferred from the viewpoint of ease of handling and surface gloss of the molded product.

The amount of glass fiber added in the present invention is preferably 60 parts by weight or less based on 100 parts by weight of the total amount of the aromatic polyester (A), the glycidyl group-containing copolymer (B), and the ethylene copolymer (C). must be 40 times or less, more preferably 25 times or less. If the amount added exceeds 60 parts by weight, warpage becomes large, making it difficult to achieve the object of the present invention.

Incidentally, when a compound that promotes the reaction between an epoxy compound and a carboxylic acid is added to the composition of the present invention, the impact resistance can be improved by a large amount.

These compounds include triphenylamine, 2.4
．． 6-1 ~ Tertiary amines such as lith(dimethylaminemethyl)phenol, phosphite esters such as triphenylphosphite and triisodecylphosphite, phosphonium compounds such as triphenylallylphosphonium bromide, triphenylphosphine, etc. Carphonic acid metal salts such as Bosphin, stearic lithium, calcium stearate, sulfonic acid metal salts such as sodium dodecylbenzenesulfonate, sodium 3,5-cylcarbomethoxybenzenesulfone, and !a-acid ester salts such as lauryl (sodium 11). It is preferable to add 0.001 to 5 parts by weight per 100 parts by weight of polyester.

The composition of the present invention (in addition, conventional additives such as mold release agents, ultraviolet absorbers, pigments, dyes, nucleating agents, antioxidants, flame retardants, flame retardant aids, etc.) may also be blended. .

The method for producing the composition of the present invention is not particularly limited, but preferably aromatic polyester, glycidyl group-containing copolymer, ethylene copolymer, mica powder, and other necessary additives are extruded. Examples include a method of melt-mixing using a vented twin-screw extruder).

The composition of the present invention can be made into molded products by extrusion molding, injection molding, compression molding, etc., and these molded products have excellent mechanical strength, impact resistance, mechanical properties, etc.
It is particularly useful as an exterior part for automobiles.

The present invention will be explained in detail below with reference to Examples.

Relative viscosity means 0 when O-chlorophenol is used as a solvent.
．． A 5% polymer solution was measured at 25°C.

<Examples> Examples 1 to 6, Comparative Examples 1 to 4 To polybutylene lentiphthalate-1 having a relative viscosity of 1.55, the glycidyl group-containing copolymer, the ethyl-1 non-based copolymer, and the After tri-blending mica in the proportions shown in Table 1, it was melt-mixed and pelletized at 250° C. using a 40 mφ twin-screw extruder with a vent. Next, the obtained beret is 2
An ASTM No. 1 dumbbell, an Izotz impact test piece, and a 100 mmφX2H1 disc were molded using a 3'A screw in-line injection molding machine set at 50°C. ASTM D638 for these specimens
A tensile test was carried out according to ASTM D256, an Izod impact test was carried out according to ASTM D256, and a flexural modulus was measured roughly according to ASTM D790.

The warp of the disk was measured using the method shown in Figure 1. That is, three holes 2 with a diameter of 2 mm are made at the positions shown in FIG. Measure the clearances d73 and d' and determine the warpage of the molded product.

<Effects> The polyester resin composition of the present invention is produced by mixing an aromatic polyester with a specific amount of an α-olefin and a glycidyl group-containing copolymer consisting of a glycidyl ester of an α/β-unsaturated acid, and an ethylene copolymer. Since it is a mixture of specific mica powder, it has excellent tensile strength, flexural modulus, and impact resistance, and in particular, the molded product has little warpage and has a good surface condition.

[Brief explanation of drawings]

FIG. 1 is a diagram of a test piece for measuring the warpage of the resin composition of the present invention, where A is a side view and B is a plan view. 1191 disc, 2. ,,hole, 3. ,,jig.

Claims (1)

[Claims] 98 to 40% by weight of aromatic polyester (A), 1 to 40% by weight of glycidyl group-containing copolymer (B) consisting of glycidyl ester of α-olefin and α/β-unsaturated acid, and at least 3 or more carbon atoms in ethylene. 1 to 40% by weight of ethylene copolymer (C) copolymerized with α-olefin of
Mica powder (D) with a diameter of 100μ or less per 100 parts by weight of a polyester resin mixture containing 3 to 10
A polyester resin composition containing 0 parts by weight and 0 to 60 parts by weight of a fibrous reinforcing material (E).