JP2000191893A - Polyester resin composition and method for improving flowability of polyester resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition remarkably improved in flowability by melting and kneading a thermoplastic polyester, epoxidized ethylene copolymer and vulcanization accelerator. SOLUTION: The thermoplastic polyester (A) preferably comprises polyethylene terephthalate or polybutylene terephthalate in particular. The epoxidized ethylene copolymer (B) comprises essentially ethylene units and epoxidized monomer units and optionally contains ethylenically unsaturated ester compound units. The component B preferably comprises one having a number-average molecular weight of about 10,000 to 100,000 and a melt index of about 0.5-100. Examples of the vulcanization accelerator (C) include thiazole and its derivatives, guanidine and its derivatives, dithioic acid salts, and thiuram and its derivatives. The weight ratio of component A to component B is usually about (20 to 99):(1 to 80). The amount of component C used is usually about 0.01-20 pts.wt. based on 100 pts.wt. total of component A and component B.

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 having excellent fluidity, which is obtained by melt-kneading a polyester resin, an epoxy group-containing ethylene copolymer, and a vulcanization accelerator.

[0002]

2. Description of the Related Art A polyester resin composition obtained by melt-kneading a polyester resin and an epoxy group-containing ethylene copolymer is already known. Impact resistance is obtained by melt-kneading an epoxy group-containing ethylene copolymer. It is known to improve. (For example, Japanese Patent Publication No. 58-47419)

[0003]

However, by melt-kneading the epoxy group-containing ethylene copolymer,
As a result, 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 or the like is reduced.

[0004]

Under these circumstances, the present inventors have been keen to improve the fluidity of a polyester resin composition obtained by melt-kneading a thermoplastic polyester resin and an epoxy group-containing ethylene copolymer. As a result of repeated studies, by melt-kneading the composition and the vulcanization accelerator,
The inventors have found that the flowability of the polyester resin composition is significantly improved, and have completed the present invention. That is, the present invention provides a polyester resin composition obtained by melt-kneading the following components (A), (B) and (C), and a method for improving the fluidity of the polyester resin composition. (A): thermoplastic polyester (B): epoxy group-containing ethylene copolymer (C): vulcanization accelerator

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The component (A) in the present invention is not particularly limited as long as it is a thermoplastic polyester resin. For example, those obtained from a diol and a dicarboxylic acid or a reactive derivative thereof are usually used. Examples of the diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,
Linear, cyclic or branched aliphatic diols having about 2 to 20 carbon atoms, such as 10-decanediol, neopentyl glycol, 1,4-cyclohexanediol, and 1,4-cyclohexanediethanol, polyethylene having a molecular weight of about 400 to 6000 Long-chain glycols such as glycol, poly-1,3-propylene glycol, polytetramethylene glycol, and mixtures of two or more thereof are exemplified.

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, but preferably at least about 40 mol% is terephthalic acid.

Representative examples of component (A) include, for example, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polycyclohexanediethylene terephthalate, polyneopentyl terephthalate, and the like. Mixtures of two or more are mentioned. Among them, polyethylene terephthalate and polybutylene terephthalate are preferable, and polybutylene terephthalate is more preferably used. Further, those having an intrinsic viscosity of about 0.5 to 2.0 dl / g and a terminal carboxyl group concentration of about 15 to 200 meq / Kg are usually used when measured at 25 ° C. using O-chlorophenol as a solvent.

The component (B) contains an ethylene unit and an epoxy group-containing monomer as essential components and an ethylenically unsaturated ester compound unit as an optional component. About 99.9% by weight, epoxy group-containing monomer about 0.1 to 30% by weight,
And a copolymer composed of about 0 to 50% by weight of an ethylenically unsaturated ester compound unit.

The epoxy group-containing monomer of the component (B) includes, for example, the following general formula (1) (Wherein, R represents an alkenyl group having 2 to 18 carbon atoms, and X represents a carbonyloxy group, a phenyloxy group, or a methyleneoxy group).
Specific examples include allyl glycidyl ether, 2-methylallyl glycidyl ether, and unsaturated glycidyl ether units such as styrene-p-glycidyl ether and unsaturated glycidyl ester units such as glycidyl acrylate, glycidyl methacrylate and glycidyl itaconate. And the like.

As the ethylenically unsaturated ester compound, usually, other than the above unsaturated glycidyl ester, for example, vinyl esters of saturated carboxylic acids such as vinyl acetate, vinyl propionate and vinyl butyrate, methyl acrylate,
Examples include alkyl esters of unsaturated carboxylic acids such as ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, and butyl methacrylate.
Among them, vinyl acetate, methyl acrylate, ethyl acrylate, methyl methacrylate and the like are preferable. The unit of the ethylenically unsaturated ester compound in the component (B) is usually from 0 to 50.
It is about 3% by weight, but when the ester compound unit is present, it is preferably about 3 to 50% by weight.

The component (B) in the present invention may be any of a block copolymer, a graft copolymer, a random copolymer and an alternating copolymer. For example, a propylene-ethylene block described in Japanese Patent No. 6232980 may be used. Copolymer obtained by grafting an epoxy group-containing monomer onto a copolymer, patent
Copolymers obtained by grafting an ethylenically unsaturated ester compound to an ethylene-epoxy group-containing monomer copolymer described in JP-A-2600248 are exemplified. Component (B) is
Melt index measured according to JIS K6760,
Usually, it is preferably about 0.5 to 100 g / 10 minutes, and 2 to 50 g / 1.
About 0 minutes is more preferable. Melt index
If it is less than 0.5 g / 10 minutes, the moldability tends to decrease. If it exceeds 100 g / 10 minutes, the resulting polyester composition tends to have insufficient mechanical properties, for example, Izod impact strength. In addition, the kale mission chromatography
Those having a number average molecular weight of about 10,000 to 100,000 in terms of polystyrene measured by (GPC) are preferred. When the number average molecular weight is less than 10,000, the mechanical properties of the obtained polyester composition, for example, the Izod impact strength tends to be insufficient, and when it exceeds 100,000, the moldability tends to decrease.

The component (B) in the present invention may be prepared by subjecting a monomer to be subjected to a known method, for example, copolymerization, to a solvent of about 500 to 4000 atm, about 100 to 300 ° C. A method in which copolymerization is carried out in the presence or absence of a chain transfer agent, a method in which an epoxy group-containing monomer, an ethylenically unsaturated ester compound used as necessary, a radical generator, and the like are mixed with polyethylene, and a melt graft copolymer is mixed in an extruder. It can be produced by a polymerization method or the like.

The component (B) can be used after being diluted with a rubber component. Examples of the rubber component used include ethylene units such as ethylene-propylene rubber, ethylene-butene rubber, and ethylene-butadiene rubber.
Rubbers comprising α-olefin units having 3 or more carbon atoms, ethylene-based rubbers such as rubbers comprising ethylene units such as ethylene-propylene-non-conjugated diene rubber, α-olefin units having 3 or more carbon atoms-non-conjugated diene units, styrene butadiene Rubber, SBS rubber, styrene rubber such as hydrogenated SBS rubber, polyisobutylene bomb, butyl rubber, butadiene rubber, isoprene rubber, Alfie rubber, nitrile rubber, fluorine rubber, vinyl pyridine rubber, silicon rubber,
Butadiene-methyl methacrylate rubber, acrylic rubber, urethane rubber, epichlorohydrin rubber, chlorobutyl rubber, bromobutyl rubber, and mixtures of two or more of these rubbers. When these rubber components are modified with a modifying agent such as maleic anhydride, halide, vinyl compound, acrylic compound, etc., the epoxy group-containing ethylene copolymer excessively reacts with the modifying agent to cause the copolymer and the rubber component to react. A modifier may be used as long as it does not hinder the melt-kneading or molding.

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.

As the vulcanization accelerator of the component (C) in the present invention, for example, 2-mercaptobenzothiazole, 2,2 ′
Thiazoles such as -dithiobisbenzothiazole, N-cyclohexylbenzothiazolesulfenamide, N-oxydiethylenebenzothiazolesulfenamide, zinc salt of 2-mercaptobenzothiazole, 1,3-diphenylguanidine, 1,3 Guanidines such as -di-O-tolylguanidine, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc di-n-butyldithiocarbamate, zinc N-ethyl-N-phenyldithiocarbamate,
Dithioacid salts such as diethyldithiocarbamate tellurium,
Thiurams such as tetraethylthiuram disulfide, tetrabutylthiuram disulfide, tetramethylthiuram monosulfide, dipentamethylenethiuram tetrasulfide and the like, and a mixture of two or more thereof are exemplified. Among them, thiazoles include N-cyclohexylbenzothiazolesulfenamide, 2,2′-dithiobisbenzothiazole, zinc salt of 2-mercaptobenzothiazole, and guanidines include 1,3-di-O-tolyl Guanidin and the like are particularly preferable as dithioacid salts such as zinc dimethyldithiocarbamate and thiurams as tetraethylthiuram disulfide.

The weight ratio of the components (A) and (B) of the present invention is
Usually, it is preferably about 20 to 99: 1 to 80. If the component (A) is less than 20 parts by weight, rigidity and heat resistance tend to decrease, and if it exceeds 99 parts by weight, the effect of improving impact resistance tends to decrease. The weight ratio of component (B) used is
When the epoxy group-containing ethylene copolymer is used alone, the value is calculated using a value obtained by subtracting the value of the rubber component from the value obtained by diluting the value with the rubber component.

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 components (A) and (B). If the amount of component (C) added is less than 0.01 part by weight, the improvement in fluidity tends to remain low, and if it exceeds 20 parts by weight, the degree of improvement in fluidity tends to be lower than the amount used. .

The above components (A), (B) and (C)
Usually, it can be manufactured by a method of kneading in a molten state. The kneading temperature is not particularly limited, but is usually 200 to 3
The test is performed in a temperature range of about 20 ° C. At this time, if necessary, other compounding agents used in the thermoplastic resin, for example, heat stabilizers, antioxidants, weathering agents, light stabilizers, nucleating agents, lubricants, release agents, pigments , A flame retardant, an antistatic agent, a filler, and a reinforcing agent such as glass fiber.

[0019]

According to the present invention, the flowability of a polyester resin composition obtained by melt-kneading a polyester resin and an epoxy group-containing ethylene copolymer by adding a vulcanization accelerator is remarkably improved. The method of the present invention is industrially advantageous since the production capacity of the present invention can be improved.

[0020]

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. The evaluation was performed by the following method. MFR (Melt Flow Rate): ASTM D1238
(250 ° C., 2160 g). Unit g / 10 minutes

<Each component> The following polybutylene terephthalate was used as component (A). A-1: "Duranex 600FP" manufactured by Polyplastics Co., Ltd., intrinsic viscosity = 1.0 dl / g, terminal carboxyl group = 72 meq / Kg

A mixture of the ethylene copolymer containing the following epoxy group-containing monomer and the rubber component obtained in Reference Example 1 was used as the component (B). B-1: Sumitomo Chemical Co., Ltd. “Bond First 7”
M ", MI = 9 g / 10 min, glycidyl methacrylate =
6% by weight, methyl acrylate = 30% by weight B-2: Epoxy group-containing ethylene copolymer / ethylene-propylene-diene monomer copolymer composition obtained in Reference Example 1

Reference Example 1 "Bond First E (MI =
3g / 10min, glycidyl methacrylate = 12% by weight) "
50 parts by weight of an ethylene-propylene-diene monomer copolymer (propylene = 30% by weight, dicyclopentadiene 1.3% by weight, Mooney viscosity ML _{1 + 4} (121 ° C.) = 68,
Hereinafter, it is referred to as EPDM. ) 50 parts by weight with a Banbury mixer
The mixture was kneaded for 10 minutes to obtain an epoxy group-containing ethylene copolymer / EPDM composition.

The following were used as the component (C). C-1: N-cyclohexylbenzothiazolesulfenamide C-2: 2,2'-dithiobisbenzothiazole C-3: Zinc salt of 2-mercaptobenzothiazole C-4: 1,3-di-O -Tolylguanidine C-5: zinc dimethyldithiocarbamate C-6: tetraethylthiuram disulfide

Examples 1 to 8 and Comparative Examples 1 and 2 After the components (A), (B) and (C) shown in parts by weight in Table 1 were dry blended, a twin-screw extruder (φ30 mm) was used. L / D = 42) and melt-kneaded at a temperature of 230 ° C. at a screw rotation speed of 200 rpm. For confirming the fluidity of the obtained polyester resin composition, MFR was measured and shown together.

[0026]

[Table 1] 1) The component (B) is equivalent to 5 parts with respect to 90 parts of the component (A).

Continued on the front page F-term (reference) 4J002 AC03Y AC06Y AC07Y AC08Y AC11Y AC12Y BB05Y BB10X BB15Y BB18Y BB20Y BB24Y BD12Y BJ00Y BN03X BN21X BP01Y BP03X CD19X CF03W CF04W CF05W CF06W CF07W EV06 156

Claims (20)

[Claims] A polyester resin composition obtained by melt-kneading the following components (A), (B) and (C). (A): thermoplastic polyester (B): epoxy group-containing ethylene copolymer (C): vulcanization accelerator 2. The weight ratio of components (A) and (B) is from 20 to
The resin composition according to claim 1, wherein the ratio is 99:80 to 1. 3. The resin 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). Composition. 4. The resin composition according to claim 1, wherein the component (A) is polyethylene terephthalate and / or polybutylene terephthalate. 5. 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, and 0 to 50% by weight of an ethylenically unsaturated ester unit. The resin composition according to any one of claims 1 to 4. 6. An epoxy group-containing monomer as component (B),
The following equation (1) The resin composition according to claim 5, wherein R represents an alkenyl group having 2 to 18 carbon atoms, and X represents a carbonyloxy group, a phenyloxy group, or a methyleneoxy group. 7. The component (B) having a number average molecular weight of 10,000 to 10
7. The resin composition according to claim 1, wherein the resin composition has a melt index of 0.5 to 100 g / 10 minutes. 8. The resin composition according to claim 1, wherein the component (B) is diluted with a rubber component. 9. The resin composition according to claim 1, wherein the component (C) is at least one vulcanization accelerator selected from thiazoles, guanidines, dithioates and thiurams. object. 10. Component (C) is a zinc salt of N-cyclohexylbenzothiazolesulfenamide, 2,2′-dithiobisbenzothiazole, 2-mercaptobenzothiazole,
The resin composition according to any one of claims 1 to 9, wherein the resin composition is at least one vulcanization accelerator selected from 3-di-O-tolylguanidine, zinc dimethyldithiocarbamate, and tetraethylthiuram disulfide. 11. A method for improving fluidity of a polyester resin composition, comprising melt-kneading the following components (A), (B) and (C). (A): thermoplastic polyester (B): epoxy group-containing ethylene copolymer (C): vulcanization accelerator 12. The weight ratio of components (A) and (B) is 20
The method for improving fluidity according to claim 11, wherein the ratio is from 99 to 80: 1. 13. The fluid according to claim 11, 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). Sex improvement method. 14. The method according to claim 11, wherein the component (A) is polyethylene terephthalate and / or polybutylene terephthalate. 15. 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, and 0 to 50% by weight of an ethylenically unsaturated ester unit. 15. The method for improving fluidity according to 11 to 14. 16. The epoxy group-containing monomer of the component (B) has the following formula (1) The method of claim 15, wherein R represents an alkenyl group having 2 to 18 carbon atoms, and X represents a carbonyloxy group, a phenyloxy group or a methyleneoxy group. 17. The component (B) having a number average molecular weight of 10,000 to
17. The method for improving fluidity according to claim 11, wherein the melt index is 100,000 and the melt index is 0.5 to 100 g / 10 minutes. 18. The method for improving fluidity according to claim 11, wherein the component (B) is diluted with a rubber component. 19. The fluidity according to claim 11, wherein component (C) is at least one vulcanization accelerator selected from thiazoles, guanidines, dithioates and thiurams. How to improve. (20) Component (C) is a zinc salt of N-cyclohexylbenzothiazolesulfenamide, 2,2′-dithiobisbenzothiazole, 2-mercaptobenzothiazole,
20. The method for improving fluidity according to claim 11, wherein the vulcanization accelerator is at least one type selected from the group consisting of 3-di-O-tolylguanidine, zinc dimethyldithiocarbamate, and tetraethylthiuram disulfide.