JPH0912844A - Polyester resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyester resin compsn. which can give a molding excellent in the balance between impact strength and stiffness by compounding a resin mixture comprising a satd. polyester resin and a specific polyetheresteramide with a modified vinyl polymer. SOLUTION: This compsn. is prepd. by melt mixing 100 pts.wt. resin mixture comprising 60-95wt.% satd. polyester resin and 40-5wt.% polyetheresteramide formed from a 20-48C polymeric fatty acid (a), azelaic acid and/or sebacic acid (b), a 2-20C diamine (c), a polyoxyalkylene glycol having a number-average mol.wt. of 200-3,000 (d), and a 6-20C dicarboxylic acid (e) in a wt. ratio of a/b of 0.3-5.0 and in a wt. ratio of (a+b+c)/(d+e) of (95:5)-(10:90) with 1-30 pts.wt. at least one modified vinyl polymer having functional groups selected from among carboxyl, epoxy, and their deriv. groups.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel polyester resin composition having improved impact resistance. More specifically, the present invention relates to a polyester resin composition having excellent mechanical properties suitable as a material in the fields of automobiles, electric / electronics, etc., particularly excellent balance of impact resistance and rigidity.

[0002]

2. Description of the Related Art Saturated polyester resins have excellent weather resistance, electrical characteristics, chemical resistance, and abrasion resistance.
It is widely used as an engineering resin in various fields. However, the impact resistance of the molded product is not satisfactory, and its application is limited.

Various methods have been proposed for the purpose of improving the impact resistance, which is a drawback of the saturated polyester resin. For example, a method of compounding an acrylic or diene rubber (Japanese Patent Publication No. 55-9435) or a method of compounding a polyester elastomer (Japanese Patent Publication No. 61-6475).
No. 2), a method of blending a polyether ester amide (JP-A-61-81456), a method of blending an ethylene-glycidyl methacrylate copolymer (JP-B-58-47419), and the like. There is. However, in these methods, although the impact resistance is improved to some extent, it is still insufficient, and the balance between the rigidity and the impact resistance is not satisfied.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, saturated polyester resins 60 to 95 are obtained.
100 parts by weight of a resin mixture consisting of 40% by weight of polyether ester amide derived from polymerized fatty acid, azelaic acid and / or sebacic acid, diamine, polyoxyalkylene glycol and dicarboxylic acid. By blending 1 to 30 parts by weight of a modified vinyl-based polymer containing a functional group such as an epoxy group and an epoxy group, a polyester resin composition capable of giving a molded article having an excellent balance of impact resistance and rigidity is obtained. Therefore, the present invention has been completed based on this finding. That is, an object of the present invention is to obtain a polyester resin composition capable of giving a molded article having an excellent balance of impact resistance and rigidity, and the objective thereof is (A) saturated polyester resin 60 to 95. % By weight and (B) (a) polymerized fatty acid having 20 to 48 carbon atoms, (b)
Azelaic acid and / or sebacic acid, (c) diamine having 2 to 20 carbon atoms, (d) number average molecular weight of 200 to
3,000 polyoxyalkylene glycols, (e)
A copolymer derived from a dicarboxylic acid having 6 to 20 carbon atoms, wherein the weight ratio of (a) to (b) is (a).
/ (B) is 0.3 to 5.0, and [(a) + (b) +
The weight ratio of (c)] / [(d) + (e)] is 95/5 to 1
100 parts by weight of a resin mixture consisting of 40 to 5% by weight of polyether ester amide which is 0/90 and is transparent and excellent in flexibility and elastic recovery ability, and is selected from (C) a carboxyl group, an epoxy group or a derivative thereof. 1 to 3 of at least one modified vinyl polymer containing a functional group
This is achieved by blending 0 parts by weight.

The details of the present invention will be described below. The saturated polyester resin used as the component (A) of the present invention is a polyalkylene terephthalate obtained by a polycondensation reaction of terephthalic acid or its dialkyl ester with an aliphatic glycol, or a copolymer containing the polyalkylene terephthalate as a main component. Specific examples thereof include polyethylene terephthalate and folybutylene terephthalate.

Examples of the above-mentioned aliphatic glycols include ethylene glycol, propylene glycol, tetramethylene glycol, hexamethylene glycol, and the like. In addition to these aliphatic glycols, other diols or polyhydric alcohols, for example, aliphatic glycols. 30% by weight or less of cyclohexanediol, cyclohexanedimethanol, xylylene glycol,
2,2-bis (4-hydroxyphenyl) propane, glycerin, pentaerythritol and the like may be mixed and used.

In addition to terephthalic acid or a dialkyl ester thereof, other dibasic acid, polybasic acid or an alkyl ester thereof, for example, 50% by weight or less of terephthalic acid or a dialkyl ester thereof, phthalic acid,
Aromatic carboxylic acids such as isophthalic acid and naphthalene dicarboxylic acid, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid or aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as adipic acid and dodecanedicarboxylic acid, and alkyl esters thereof You may mix and use.

The polymerized fatty acid having 20 to 48 carbon atoms, which is used as the component (a) for deriving the polyether ester amide (B) of the present invention, is an unsaturated fatty acid such as dicarboxylic acid having 10 to 24 carbon atoms. A polymerized fatty acid obtained by polymerizing a monobasic fatty acid having one or more heavy or triple bonds is used. Specific examples include dimers such as oleic acid, linoleic acid, and erucic acid.

[0009] Commercially available polymerized fatty acids usually contain dimerized fatty acid as a main component and other raw material fatty acids and trimerized fatty acids, but the dimerized fatty acid content is 70% or more,
It is preferably 95% by weight or more, and hydrogenated to reduce the degree of unsaturation. Especially, the pre-pole 10
09, PRIPOL 1004, PRIPOL 1010 (above made by Unichema) and EMPOL 1010 (made by Henkel)
Commercially available products such as Of course, mixtures of these are also used.

Examples of the dicarboxylic acid (b) in the polyether ether amide (B) of the present invention include azelaic acid, sebacic acid and a dicarboxylic acid due to their polymerizability, copolymerizability with polymerized fatty acid, and physical properties of the resulting polyether ester amide. A mixture of these two can be mentioned.

Specific examples of the diamine (c) having 2 to 20 carbon atoms in the polyether ester amide (B) of the present invention include ethylenediamine, tetramethylenediamine, hexamethylenediamine, nonamethylenediamine and undecamethylene. Diamine, dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, bis- (4-aminocyclohexyl) methane, bis- (3
-Methyl-4-aminocyclohexyl) methane, xylylenediamines and the like.

Specific examples of the polyoxyalkylene glycol (d) for deriving the polyether ester amide (B) of the present invention include polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol and ethylene. Examples thereof include block or random copolymers of oxide and propylene oxide, block or random copolymers of ethylene oxide and tetrahydrofuran, and mixtures thereof. Polyoxytetramethylene glycol is preferably used because of the heat resistance, water resistance, mechanical strength, elastic recovery ability and the like of the obtained polyetheresteramide. The number average molecular weight of the polyoxyalkylene glycol used in the present invention needs to be in the range of 200 to 3000. When the number average molecular weight is less than 200, polyether ester amide having excellent physical properties cannot be obtained. On the other hand, when it exceeds 3,000, the compatibility between the polyoxyalkylene glycol and the polyamide oligomer is reduced in the block copolymerization step, coarse phase separation occurs, and uniform polycondensation cannot be performed. As a result, the molecular weight does not increase, and the transparency and mechanical strength of the obtained polyetheresteramide decrease, which is not preferable.

As the dicarboxylic acid (e) having 6 to 20 carbon atoms for deriving the polyether ester amide (B) of the present invention, specifically, adipic acid, azelaic acid, sebacic acid and dodecanedioic acid can be used. Aromatic dicarboxylic acids such as aliphatic dicarboxylic acids, terephthalic acid, isophthalic acid, diphenoxyethanedicarboxylic acid, 1,4-
Examples thereof include alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. In particular, dicarboxylic acids such as azelaic acid, sebacic acid, terephthalic acid, isophthalic acid and 1,4-cyclohexanedicarboxylic acid are preferable from the viewpoint of polymerizability and physical properties of polyetheresteramide.

The polyether ester amide (B) of the present invention comprises the polymerized fatty acid (a), azelaic acid and / or sebacic acid (b) and the diamine (c), and the weight of the polymerized fatty acid (a) relative to (b). Ratio (a) / (b) is 0.3-
The number average molecular weight was 5.0 and charged into a reaction vessel in which all three groups were sufficiently substituted with nitrogen so that all amino groups were substantially equivalent to all carboxyl groups and polycondensed at 170 ° C to 230 ° C. A polyamide oligomer of 500 to 5,000 is prepared, and a polyoxyalkylene glycol (d) having a number average molecular weight of 200 to 3,000 and a carbon number of 6 to
20 dicarboxylic acids (e), with all carboxyl groups being substantially equivalent to all hydroxyl groups, and [(a) +
The weight ratio of (b) + (c)] / [(d) + (e)] is 95.
/ 5 to 10/90, heated to 200 to 280 ° C. in the presence of a small amount of catalyst, reacted for 1 to 3 hours, and then reacted under reduced pressure of about 1 mmHg.

In order to obtain the transparent, flexible and elastic recoverable polyetheresteramide of the present invention, the weight ratio of polymerized fatty acid (a) to azelaic acid and / or sebacic acid (b) (a) / (b) is obtained. ) Is 0.3 to 5.0, and the number average molecular weight of the polyamide oligomer is 500 to 5,000.
Must be within the range. Weight ratio (a) /
When (b) is less than 0.3, the obtained polyetheresteramide has insufficient flexibility and elastic recovery ability. Further, in the block copolymerization step of polyamide oligomer and polyoxyalkylene glycol, the compatibility between the two decreases, coarse phase separation occurs and homogeneous polycondensation cannot be performed, the molecular weight does not increase, and the resulting polyether ester is obtained. The transparency and mechanical strength of the amide are reduced.
When (a) / (b) exceeds 5.0, the cohesive force of the hard segment decreases, and the mechanical strength and melting point of the polyether ester amide decrease. When the number average molecular weight of the polyamide oligomer is less than 500, the cohesive force of the hard segment decreases, and the mechanical strength and melting point of the polyetheresteramide decrease. On the other hand, when it is more than 5,000, in the block copolymerization step of the polyamide oligomer and the polyoxyalkylene glycol, both the number average molecular weight of the polyoxyalkylene glycol is too large and the content of the polymerized fatty acid is too small. The compatibility between them decreases, coarse phase separation occurs, homogeneous polycondensation cannot be performed, the molecular weight does not increase, and the transparency and mechanical strength of the obtained polyetheresteramide decrease.

The physical properties of the (B) polyetheresteramide of the present invention are as follows: the soft component [(d) + (e)] and the hard component [(a) + (b) constituting the (B) polyetheresteramide. ) + (C)]. The soft component [(d) + (e)] is 5 to 9
It is preferably 0% by weight. 5% by weight of soft ingredient
If it is less than 90% by weight, the flexibility and low-temperature properties of the obtained polyetheresteramide become insufficient, and conversely, if it exceeds 90% by weight, mechanical strength and melting point decrease, which is not preferable. The modified vinyl polymer (C) containing a functional group selected from a carboxyl group, an epoxy group or a derivative thereof in the present invention is obtained by polymerizing or copolymerizing one or more vinyl monomers. The obtained polymer is a polymer containing at least one functional group selected from a carboxyl group, an epoxy group or a derivative thereof in the molecule. The mode of the copolymerization may be any of random copolymerization, block copolymerization, and graft copolymerization. The content of the compound containing these functional groups is such that the modified vinyl-based copolymer 10
The range is preferably from 1 to 30% by weight per 0 parts by weight.

The carboxyl group-containing monomer is preferably an unsaturated carboxylic acid or an anhydride thereof, and examples thereof include monocarboxylic acids such as acrylic acid and methacrylic acid, dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid. Maleic anhydride, itaconic anhydride, endo-bicyclo-
Examples include [2,2,1] -5-heptene-2,3-dicarboxylic acid anhydride, and dicarboxylic acid and its anhydride are particularly preferable.

Examples of the epoxy group-containing monomer include glycidyl acrylate, glycidyl methacrylate,
Glycidyl ethacrylic acid, glycidyl itaconate, allyl glycidyl ether, styrene-p-glycidyl ether
Tellurium, p-glycidyl styrene and the like.

Examples of the vinyl-based monomer (C) used in the polymerization of the modified vinyl-based polymer include aromatic vinyl-based monomers such as styrene and α-methylstyrene, and cyanation such as acrylonitrile and methacrylonitrile. Vinyl monomers, (meth) acrylic acid ester type monomers such as methyl methacrylate, ethyl methacrylate, methyl acrylate and butyl acrylate, olefin type monomers such as ethylene, propylene and butene, and vinyl acetate and butadiene. And so on.

The method for producing these functional group-containing modified vinyl polymers is not particularly limited, and known so-called radical (co) polymerization methods are used.

Since the (B) polyetheresteramide of the present invention is excellent in flexibility and elastic recovery ability, and (A) is highly compatible with the saturated polyester resin, the (B) polyetheresteramide is preferable. When (A) the saturated polyester resin and (A) are melt-kneaded, the (B) polyethylene ester amide is easily dispersed as fine particles of 1 μm or less in the matrix phase of the (A) saturated polyester resin to obtain the impact resistance of the saturated polyester resin. Is improved. By adding (C) a modified vinyl polymer having a functional group such as a carboxyl group or an epoxy group to the saturated polyester resin (A) and the polyether ester amide (B), the polyester in the matrix phase of the saturated polyester resin is added. The dispersed particles of the terester amide become finer, and the impact resistance of the saturated polyester resin is further improved.

The blending ratio of the (A) saturated polyester resin and the (B) polyetheresteramide in the composition of the present invention is (A) saturated polyester resin 60 to 95.
4% (B) polyetheresteramide based on weight%
It is necessary to set the ratio to 0 to 5% by weight. If the blending ratio of the polyetheresteramide is less than 5% by weight, the impact resistance of the saturated polyester resin is insufficiently improved.

Further, if the blending ratio of the polyetheresteramide exceeds 40% by weight, the heat resistance and the rigidity are lowered and the characteristics of the saturated polyester resin are impaired.

Further, the composition of the present invention contains (C) a carboxyl group, an epoxy group, etc. per 100 parts by weight of a resin mixture of (A) saturated polyester resin and (B) polyetheresteramide. It is necessary to mix the modified vinyl polymer in a ratio of 1 to 30 parts by weight. When the blending amount of this modified vinyl polymer is less than 1 part by weight,
The impact resistance is not sufficiently improved, and when the amount of the modified vinyl polymer added exceeds 30 parts by weight, heat resistance and rigidity are deteriorated, which is not preferable.

In the composition of the present invention, various additive components such as antioxidants, heat stabilizers, plasticizers, ultraviolet absorbers, lubricants, flame retardants, and the like may be added, if desired, within a range that does not impair the object of the present invention. Additives such as fillers and pigments, and reinforcing agents such as silica, carbon black, clay, glass beads, glass fibers, carbon fibers, organic fibers and calcium carbonate can be contained.

The method of preparing the resin composition of the present invention is preferably a melt kneading method, and a known method can be used as the melt kneading method. For example,
A resin composition can be obtained by melt-kneading using a Banbury mixer, a rubber roll machine, a single-screw or twin-screw extruder, and the like.

The saturated polyester resin composition of the present invention thus obtained is a known method generally used for molding thermoplastic resins, for example, injection molding, extrusion molding, blow molding, vacuum molding, etc. Can be molded by the method of.

[0028]

Since the polyester resin composition of the present invention can provide a molded article having an excellent balance of impact resistance and rigidity, it is suitable for various applications in the fields of automobiles, electric / electronics, etc. Used for.

[0029]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples. Each property in the production examples and examples was measured by the following methods.

(1) Melt viscosity Using a flow tester CFT-500 manufactured by Shimadzu Corporation,
Measurement temperature 250 ℃, die 1mm (diameter) × 10mm (length), load 10k
It was measured under the condition of g.

(2) Acid value and amine value The acid value was obtained by dissolving 1 g of the sample in 50 g of benzyl alcohol and using a phenolphthalein indicator in a methanol solution of 1/10 N NaOH. It was dissolved in 50 g of a 1/1 mixed solution and titrated with a 1/10 N hydrochloric acid methanol solution using a bromphenol blue indicator.

(3) Melting point and crystallization temperature Using a differential scanning calorimeter (DSC), the heating rate is 10 ° C. /
The melting point was measured in minutes, the temperature was lowered at 10 ° C./min, and the crystallization temperature was measured.

(4) Bending strength and elastic modulus A bending test was conducted according to JIS K7203 using a test piece having a shape of length (L) 80 mm × height (h) 4 mm × width (W) 10 mm. .

(5) Izod impact strength The shape has a length (L) of 64 mm x thickness (t) of 2.5 mm x width (b) of 12.7 mm, a tip radius of 0.25 mm and a depth of 2.5.
Using a test piece having a notch of mm, JIS K711
The Izod impact test was performed in accordance with 0.

(6) Vicat softening temperature Shape is length (L) 13 x thickness (t) 3.1 x width (W) 1
Using a 3 mm test piece, JIS K7206-1991
The Vicat softening point was measured according to A120. Production Example <Synthesis of Polyether Esteramide> (TPAE-
1)

In a 1000 ml four-necked flask equipped with a stirrer, a nitrogen inlet and a distillation tube, the composition of the obtained polyamide copolymer was such that the weight ratio of hexamethylenediamine to polymerized fatty acid polycondensate / hexamethylenediamine to azelaine was adjusted. Hydrogenated type polymerized fatty acid (C36, trade name Pripol 1009, manufactured by Unichema) 109.4 g, azelaic acid 81.4 g, and hexamethylenediamine 72.5 g so that the acid polycondensate = 50/50. 5% phosphorous acid aqueous solution 0.8
When charged with g and heated at a constant flow rate of nitrogen, water generated by the polycondensation reaction was distilled out from 158 ° C. The content at this time was a uniform transparent liquid. 190 ° C
When the temperature was raised to 1, the contents were sampled and the acid value and amine value were adjusted so as to be in an equivalent relationship. Eventually,
A transparent polyamide oligomer having a terminal group concentration of 41.2 mgKOH / g and a number average molecular weight of 1362 was obtained. At this temperature, 56.9 g of azelaic acid was added, and when the contents became transparent, 206.4 g of polyoxytetramethylene glycol having a number average molecular weight of 341 and N, N'-hexamethylene-
Bis (3,5-di-t-butyl-4-hydroxycinnamic acid amide) (trade name Irganox 1098, antioxidant) 1.0 g was sequentially added, and when uniform,
0.1 g of antimony trioxide and 0.1 g of monobutylhydroxytin oxide were added. Then, the temperature was raised to 270 ° C. while allowing the water produced by the reaction to flow away, and this temperature was maintained for 30 minutes. Next, at this temperature, the pressure was reduced to 25 mmHg and the reaction was continued for 30 minutes, then the pressure was reduced to 1 mmHg and the reaction was further advanced. After 2 hours and 30 minutes, the melt viscosity was 102.2 Pa.
s / 250 ° C, melting point 157.8 ° C, crystallization temperature 137.3
A transparent polyether ester amide (TPAE-1) having a hard segment (polyamide copolymer) / soft segment (azelaic acid to polyoxytetramethylene glycol) = 50/50 (weight ratio) was obtained at ℃.

In the examples and comparative examples, the following were used as the component (A) saturated polyester resin and the component (C) modified vinyl polymer. (A) Saturated polyester resin Polybutylene terephthalate (PBT) Toray, 140
1 × 06 (C) Modified vinyl polymer (C-1) Ethylene-glycidyl methacrylate-vinyl acetate copolymer Sumitomo Chemical Co., Ltd., Bondfast 7M Glycidyl methacrylate 6 wt% (C-2) Ethylene-glycidyl methacrylate copolymer Graft copolymer obtained by graft-polymerizing styrene-acrylonitrile copolymer, manufactured by NOF CORPORATION, MODIPER A4
400 (C-3) Styrene-maleic anhydride copolymer Arco
Chemical, Dailark D232 maleic anhydride 8 wt%

Examples 1 to 7 and Comparative Examples 1 and 2 Polybutylene terephthalate, the polyetheresteramide (TPAE-1) obtained in the production example, and the modified vinyl polymers (C-1 to 3) are shown in Table 1. Mix in the proportions shown in 3
It was melt-kneaded at 255 ° C. using a 5 mmφ kneader kneader (manufactured by Kasamatsu Kako Kenkyusho) and pelletized.

After drying the obtained pellets, predetermined test pieces were prepared by injection molding at a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C. Using this test piece, flexural strength, flexural modulus, Izod impact strength and Vicat softening point were measured, and the results are summarized in Table 1.

The weight part of the modified vinyl polymer is P
Resin mixture of BT resin and polyether ester amide 1
This is parts by weight relative to 00 parts by weight.

[0041]

[Table 1]

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[Procedure amendment]

[Submission date] September 29, 1995

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0037

[Correction method] Change

[Correction contents]

In the examples and comparative examples, the following were used as the component (A) saturated polyester resin and the component (C) modified vinyl polymer. (A) Saturated polyester resin Polybutylene terephthalate (PBT) Toray, 140
1 × 06 (C) Modified vinyl polymer (C-1) Ethylene-glycidyl methacrylate-methyl acrylate copolymer Sumitomo Chemical Co., Ltd., Bondfast 7M chrysidyl methacrylate 6 wt% (C-2) ethylene-glycidyl methacrylate copolymer Kraft copolymer made by graft-polymerizing styrene-acrylonitrile copolymer with NOF, MODIPER A4
400 (C-3) Styrene-maleic anhydride copolymer Arco
Chemical, Dailark D232 maleic anhydride 8 wt%

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0041

[Correction method] Change

[Correction contents]

[0041]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Motohiro Fujimoto, Miyoshi-cho, Iruma-gun, Saitama 2 253 Takemasawa, Fujimasei Kogyo Co., Ltd. Research Institute (72) Inventor Kijuro Tashiro, Miyoshi-cho, Iruma-gun, Saitama Takemazawa No. 253 2 Fuji Kasei Kogyo Co., Ltd. Technical Research Center

Claims (1)

[Claims] 1. A saturated polyester resin (A) 60 to 95
% By weight, and (B) (a) a polymerized fatty acid having 20 to 48 carbon atoms, (b) azelaic acid and / or sebacic acid,
(C) a diamine having 2 to 20 carbon atoms, (d) a polyoxyalkylene glycol having a number average molecular weight of 200 to 3,000, and (e) a copolymer derived from a dicarboxylic acid having 6 to 20 carbon atoms. Therefore, the weight ratio (a) / (b) of (a) to (b) above is 0.3 to 5.0, and [(a)
+ (B) + (c)] / [(d) + (e)] is 9 by weight.
100 parts by weight of a resin mixture consisting of 40 to 5% by weight of polyether ester amide of 5/5 to 10/90 contains (C) a functional group selected from a carboxyl group, an epoxy group or a derivative thereof. A polyester resin composition comprising 1 to 30 parts by weight of at least one modified vinyl polymer.