JP2000109662A - Polyester resin composition and method for improving flowability of polyester resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyester resin compsn. having an improved flowability by melt mixing and kneading a thermoplastic polyester with an epoxy-group- contg. ethylene copolymer and an aliph. diamine. SOLUTION: This compsn. contains (A) a thermoplastic polyester (e.g. polyethylene terephthalate or polybutylene terephthalate), (B) and epoxy-group-contg. ethylene copolymer, and (C) an aliph. diamine (e.g. 1,6-hexamethylenediamine). The wt. ratio of A/B is (20/80)-(99/1), and the wt. ratio of C/(A+B) is 0.01-20%. Ingredient B comprises 20-99.9 wt.% ethylene units, 0.1-30 wt.% epoxy monomer units, and 0-50 wt.% units derived from an ethylenic unsatd. ester compd. Examples of an epoxy monomer are an unsatd. carboxylic acid glycidyl ester and an unsatd. glycidyl ether.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] The present invention relates to a polyester resin composition. More specifically, the present invention relates to a polyester resin composition obtained by melt-kneading a polyester resin, an epoxy group-containing ethylene copolymer, and an aliphatic diamine.

A polyester resin composition obtained by melt-kneading a polyester resin and an epoxy group-containing ethylene copolymer is already known, and the impact resistance is improved by melt-kneading the epoxy group-containing ethylene copolymer. It is also known (for example, Japanese Patent Publication No. 58-47419). However, when the epoxy group-containing ethylene copolymer is melt-kneaded, the fluidity of the resin composition is significantly deteriorated, resulting in a problem in industrial production that the production capacity at the time of melt-kneading and the like is reduced. On the other hand, in addition to the epoxy group-containing ethylene copolymer, by further using a polyfunctional compound such as adipic acid, isocyanuric acid, ethylene-acrylic acid copolymer, ethylene-maleic anhydride-ethyl acrylate copolymer. It is known that mechanical properties such as heat resistance and rigidity of the polyester resin composition are improved (JP-A-63-245428, JP-A-4-149256), but further combined use of an aliphatic diamine It is not known at all that improving the flowability by doing so.

Under these circumstances, the present inventors have made intensive studies to improve the fluidity of a polyester resin composition obtained by melt-kneading a polyester resin and an epoxy group-containing ethylene copolymer. The inventors have found that diamines can specifically improve the fluidity of the composition, and have made various studies to complete the present invention.

[0004]

That is, the present invention provides a polyester resin composition comprising the following components (A), (B) and (C) melt-kneaded, and the following (A): An object of the present invention is to provide a method for improving the fluidity of a polyester resin composition, which comprises melting and kneading the component, the component (B), and the component (C). (A) component: thermoplastic polyester (B) component: epoxy group-containing ethylene copolymer (C) component: aliphatic diamine

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
As the thermoplastic polyester resin as the component (A) in the present invention, for example, those obtained from a diol and a dicarboxylic acid or a reactive derivative thereof are usually used. Examples of the diol include carbon numbers such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, and neopentyl glycol. About 2 to 20 linear or branched aliphatic diol, 1,4-cyclohexanediol, diol containing an alicyclic group such as 1,4-cyclohexanediethanol, polyethylene glycol having a molecular weight of about 400 to 6000, poly-1, Long-chain glycols such as 3-propylene glycol and polytetramethylene glycol are exemplified. The diol may be a mixture of two or more.

Examples of the dicarboxylic acid include aliphatic dicarboxylic acids having about 2 to 20 carbon atoms, such as azelaic acid, adipic acid, sebacic acid and dodecanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, bis (4- Carboxyphenyl) methane, 1,2-bis (4-carboxyphenyl) ethane, 4,4′-dicarboxybiphenyl ether,
Examples include aromatic dicarboxylic acids such as naphthalenedicarboxylic acid, and dicarboxylic acids containing an alicyclic group such as cyclohexanedicarboxylic acid. The dicarboxylic acid may be a mixture of two or more kinds, but preferably 40% by mole or more is terephthalic acid.

[0007] Representative examples of the thermoplastic polyester resin (A) include, for example, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polycyclohexanediethylene terephthalate, polyneopentyl terephthalate. And mixtures of two or more of these. Among them, polyethylene terephthalate and polybutylene terephthalate are preferably used. Further, the thermoplastic polyester resin (A) is not particularly limited,
Those having an intrinsic viscosity of about 0.5 to 2.0 dl / g measured at 25 ° C. using O-chlorophenol as a solvent and a terminal carboxyl group concentration of about 15 to 200 meq / Kg are usually used.

The epoxy group-containing ethylene copolymer (B) contains an ethylene unit and an epoxy group-containing monomer unit as essential components, and an ethylenically unsaturated ester compound unit as an optional component. Is
For example, a copolymer comprising 20 to 99.9% by weight of an ethylene unit, 0.1 to 30% by weight of an epoxy group-containing monomer unit, and 0 to 50% by weight of an ethylenically unsaturated ester compound unit is exemplified. Examples of the epoxy group-containing monomer include an unsaturated carboxylic acid glycidyl ester unit and an unsaturated glycidyl ether unit.

The unsaturated carboxylic acid glycidyl ester or unsaturated glycidyl ether is represented by the general formula (1) (Wherein, R represents an alkenyl group having 2 to 18 carbon atoms, and X represents a carbonyloxy group, a methyleneoxy group or a phenyleneoxy group). Specific examples of the unsaturated glycidyl carboxylate include glycidyl acrylate, glycidyl methacrylate, and glycidyl itaconate, and examples of the unsaturated glycidyl ether include allyl glycidyl ether, methallyl glycidyl ether, and styrene-p-glycidyl ether. You.

Examples of the ethylenically unsaturated ester compounds other than the above-mentioned glycidyl esters include, for example, vinyl esters of saturated carboxylic acids such as vinyl acetate, vinyl propionate and vinyl butyrate, methyl acrylate, ethyl acrylate, butyl acrylate, methacrylic acid. And alkyl esters of unsaturated carboxylic acids such as methyl acrylate, ethyl methacrylate and butyl methacrylate. Among them, vinyl acetate, methyl acrylate, ethyl acrylate, methyl methacrylate and the like are preferable. The ethylenically unsaturated ester compound unit in the epoxy group-containing ethylene copolymer (B) is usually from 0 to 50% by weight, but when the ester compound unit is present, it is about 3 to 50% by weight. Is preferred.

The epoxy group-containing ethylene copolymer (B) in the present invention may be any of a block copolymer, a graft copolymer, a random copolymer and an alternating copolymer. For example, Japanese Patent No. 6232980 Publication, a copolymer obtained by grafting an epoxy group-containing monomer to a propylene-ethylene block copolymer, and an ethylene-based unsaturated ester compound grafted to an ethylene-epoxy group-containing monomer copolymer described in Patent No. 2600248 May be used.

The epoxy group-containing ethylene copolymer (B) preferably has a melt index of about 0.5 to 100 g / 10 minutes as measured according to JIS K6760,
Those having about 0 g / 10 minutes are more preferable. When the melt index is less than 0.5, the moldability of the obtained polyester composition tends to decrease. If it exceeds 100, the mechanical properties of the obtained polyester composition, for example, the Izod impact strength tend to be insufficient. Further, those having a number average molecular weight of about 10,000 to 100,000 in terms of polystyrene measured by gel-permeation chromatography (GPC) are preferred. If it is less than 10,000, the mechanical properties of the obtained polyester composition, for example, Izod impact strength, tend to be insufficient, and if it exceeds 100,000, the moldability of the obtained polyester composition tends to decrease.

The epoxy group-containing ethylene copolymer of the present invention can be prepared by a known method, for example, by subjecting a monomer to be subjected to copolymerization to:
In the presence of a radical generator, about 500-4000 atm, 100-
A method of copolymerizing at about 300 ° C. in the presence or absence of a suitable solvent or chain transfer agent, mixing an epoxy group-containing monomer with polyethylene, an ethylenically unsaturated ester compound used as necessary, a radical generator, etc. And a method of melt graft copolymerization in an extruder.

The epoxy group-containing ethylene copolymer (B) can be used in the form of a mixture with a rubber component. Examples of such a rubber component include ethylene-propylene rubber, ethylene-butene rubber and ethylene-butadiene rubber. Rubber such as ethylene unit-alpha-olefin unit having 3 or more carbon atoms, ethylene-propylene-non-conjugated diene rubber and the like ethylene unit-ethylene having 3 or more carbon atoms-α-olefin unit-non-conjugated diene unit such as rubber -Based rubber, styrene-butadiene rubber, SBS rubber, styrene-based rubber such as hydrogenated SBS rubber, polyisobutylene rubber, butyl rubber, butadiene rubber, isoprene rubber, Alfie rubber, nitrile rubber, fluorine rubber, vinyl pyridine rubber, silicon rubber, butadiene- Methyl methacrylate rubber, acrylic rubber, Retangomu, epichlorohydrin rubber, chlorobutyl rubber, bromobutyl rubber,
Mixtures of two or more of these rubbers are included. Even if these rubber components are modified with a modifier such as maleic anhydride, halide, vinyl compound, acrylic compound, etc., they are used as long as they do not excessively react with the epoxy group-containing ethylene copolymer and adversely affect them. obtain.

The mixture of the epoxy group-containing ethylene copolymer and the rubber component is, for example, dry-blended with each other,
It can be manufactured by melt-kneading with a single-screw or twin-screw extruder, Banbury mixer, roll, various kneaders, and the like. The ratio of the epoxy group-containing ethylene copolymer to the rubber component is usually about 20 to 70:80 to 30 on a weight basis,
It is preferably about 30 to 60: 70 to 40.

The aliphatic diamines of the component (C) in the present invention include, for example, 1,6-hexamethylenediamine, 1,12-dodecanediamine, trimethylhexamethylenediamine, 1,4 diaminobutane, 1,3 diamino Propane, ethylenediamine, polyetherdiamine and the like, among which 1,6-hexamethylenediamine,
12-Dodecanediamine is preferred.

The weight ratio of the component (A) to the component (B) in the present invention is not particularly limited, but is preferably 20 to 99:80 to 1, and when the component (A) is less than 20 parts by weight, When the rigidity and heat resistance tend to be insufficient, and when the content exceeds 99 parts by weight, the effect of the component (B) tends to decrease.

The amount of the component (C) is usually about 0.01 to 20 parts by weight based on 100 parts by weight of the total of the thermoplastic polyester (A) and the epoxy group-containing ethylene copolymer (B). If the amount of the component (C) is less than 0.01 part by weight, the effect of improving the fluidity tends to be insufficient.
If the amount exceeds the weight part, the effect of increasing the amount tends to be not recognized.

The resin composition of the present invention comprises the above (A)
It can be produced by kneading the components (C) to (C) in a molten state. The temperature is not particularly limited as long as they are molten, but it is usually carried out in a temperature range of about 200 to 320 ° C. Further, the resin composition of the present invention, if necessary, other compounding agents used in the thermoplastic resin, for example, a heat stabilizer,
Antioxidants, weathering agents, light stabilizers, nucleating agents, lubricants, release agents,
It may contain pigments, flame retardants, antistatic agents, fillers, and reinforcing agents such as glass fibers.

[0020]

The resin composition of the present invention further improves the fluidity of the polyester resin composition obtained by melt-kneading the polyester resin and the epoxy group-containing ethylene copolymer by further kneading the aliphatic diamine. And the production capacity in the melt-kneading step and the like can be improved.

[0021]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

<Test Compound> The following polybutylene terephthalate was used as the component (A). A-1: "Duranex" manufactured by Polyplastics Co., Ltd.
600FP ", intrinsic viscosity = 1.0 dl / g, terminal carboxyl group = 72 meq / Kg (B) to (C) The following components were used as components. B-1: "Bond First 7" manufactured by Sumitomo Chemical Co., Ltd.
M ", MI = 9 g / 10 min, glycidyl methacrylate =
6% by weight, methyl acrylate = 30% by weight B-2: Epoxy group-containing ethylene copolymer / EPDM composition
(Sumitomo Chemical Industries, Ltd. “Bond First E (MI = 3g
/ 10 min, glycidyl methacrylate = 12% by weight) and EPDM “Ethylene-propylene-diene monomer copolymer (propylene = 30% by weight, dicyclopentadiene)
1.3% by weight, Mooney viscosity ML _{1 + 4} (121 ° C.) = 68) Kneaded product with 50 parts by weight) C-1: 1,6-hexamethylenediamine C-2: 1,12-dodecanediamine D-1: Adipic acid D-2: Isocyanuric acid D-3: "Bondane AX8390" manufactured by Sumika Atochem (ethylene-ethyl acrylate-maleic anhydride copolymer: ethyl acrylate content = 29% by weight, maleic anhydride content = 3% by weight %, MI = 7 g / 10 min)

Examples 1 to 4 and Comparative Examples 1 to 6 After dry blending the components at the weight ratios shown in Table 1, the mixture was fed to a twin-screw extruder (L / D = 42) of φ30 mm at 230 ° C.
Under the temperature conditions described above, and melt kneading at a screw rotation speed of 200 rpm. The fluidity (MF) of the obtained polyester resin composition
R) was measured and also shown in Table 1 below. MFR (g / 10 minutes)
Was measured according to ASTM D1238 (250 ° C., 2160 g).

[0024]

TABLE 1 implementation example comparisons Example 1 2 3 4 1 2 3 4 5 A-1 90 90 90 90 90 90 90 90 90 B-1 10 - - - 10 - - - - B-2 - 10 10 10 −10 10 10 10 C-1 − − − 0.1 − − − − − C-2 0.2 0.2 0.1 − − − − − − D-1 − − − − − − − 0.2 − − D-2 − − − − − − − − 0.2 − D-3 − − − − − − − − − 5 MFR 24.0 24.3 20.4 20.8 11.8 11.9 13.5 12.8 9.9

Claims (14)

[Claims] 1. A polyester resin composition obtained by melting and kneading the following components (A), (B) and (C). (A) component: thermoplastic polyester (B) component: epoxy group-containing ethylene copolymer (C) component: aliphatic diamine 2. The composition according to claim 1, wherein the component (A) is polyethylene terephthalate and / or polybutylene terephthalate. (3) The component (B) is a copolymer comprising 20 to 99.9% by weight of an ethylene unit, 0.1 to 30% by weight of an epoxy group-containing monomer unit, and 0 to 50% by weight of an ethylenically unsaturated ester unit. Item 3. The composition according to Item 1 or 2. 4. The composition according to claim 3, wherein the epoxy group-containing monomer is an unsaturated carboxylic acid glycidyl ester and / or an unsaturated glycidyl ether. 5. The component (B) having a number average molecular weight of 10,000 to 10
5. The composition according to claim 1, wherein the composition has a melt index of 0.5 to 100 g / 10 min. 6. The composition according to claim 1, wherein the weight ratio of component (A) to component (B) is from 20 to 99:80 to 1. 7. The composition according to claim 1, wherein the amount of the component (C) is 0.01 to 20 parts by weight based on 100 parts by weight of the total of the components (A) and (B). 8. A method for improving the fluidity of a polyester resin composition, comprising melt-kneading the following components (A), (B) and (C). (A) component: thermoplastic polyester (B) component: epoxy group-containing ethylene copolymer (C) component: aliphatic diamine 9. The method according to claim 1, wherein the component (A) is polyethylene terephthalate and / or polybutylene terephthalate. 10. The component (B) is a copolymer comprising 20 to 99.9% by weight of an ethylene unit, 0.1 to 30% by weight of an epoxy group-containing monomer unit, and 0 to 50% by weight of an ethylenically unsaturated ester unit. Item 10. The method according to any one of Items 8 to 9. 11. The method according to claim 10, wherein the epoxy group-containing monomer is an unsaturated carboxylic acid glycidyl ester and / or an unsaturated glycidyl ether. The number average molecular weight of the component (B) is from 10,000 to 10,000.
12. The method according to claims 8 to 11, wherein the melt index is 0.5 to 100 g / 10 min. 13. The method according to claim 8, wherein the weight ratio of the component (A) to the component (B) is 20 to 99:80 to 1 by weight. 14. The method according to claim 8, wherein the amount of the component (C) is 0.01 to 20 parts by weight based on 100 parts by weight of the total of the components (A) and (B).