JPH0912845A - 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 and a phenoxy resin. 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 1-20 pts.wt. at least one modified vinyl polymer having functional groups selected from among carboxyl, epoxy, and their deriv. groups and 1-20 pts.wt. phenoxy resin.

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 blending an acrylic rubber or a diene rubber (Japanese Patent Publication No. 55-9435), a method of blending a polyester elastomer (Japanese Patent Publication No. 61-64752),
Method of blending polyether ester amide
No. 1-81456), a method of blending an ethylene-glycidyl methacrylate copolymer (Japanese Patent Publication No. 58-47).
No. 419) has been proposed. However,
In these methods, the impact resistance has been improved to some extent, but is still insufficient, and the balance between rigidity and impact resistance is not satisfactory.

[0003]

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 20 parts by weight of a modified vinyl polymer containing a functional group such as an epoxy group and an epoxy group and 1 to 20 parts by weight of a phenoxy resin, a molded article having an excellent balance of impact resistance and rigidity is provided. It was found that a polyester resin composition capable of being obtained is obtained, and 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 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 (a) / (b) of (a) to (b) is 0.3 to 5.0, and [(A) +
The weight ratio of (b) + (c)] / [(d) + (e)] is 95.
/ 5 to 10/90, transparent and excellent in flexibility and elastic recovery ability, 40 to 5% by weight of polyether ester amide,
Modified vinyl polymers 1-2 containing (C) a functional group selected from a carboxyl group, an epoxy group or a derivative thereof, relative to 100 parts by weight of a resin mixture consisting of
It is achieved by blending 0 part by weight and (D) 1 to 20 parts by weight of a phenoxy resin.

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,
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) which is the component of the present invention, is an unsaturated fatty acid, for example, 10 carbon atoms. A polymerized fatty acid obtained by polymerizing a monobasic fatty acid having one or more 24 double bonds or triple bonds is used. Specific examples include dimers such as oleic acid, linoleic acid, and erucic acid.

[0008] Commercially available polymerized fatty acids usually contain dimerized fatty acid as a main component and also contain raw material fatty acid and trimerized fatty acid, 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.

The dicarboxylic acid (b) in the polyetheresteramide (B), which is a component of the present invention, is azelaic acid because of its polymerizability, copolymerizability with polymerized fatty acid, and physical properties of the resulting polyetheresteramide. Sebacic acid and mixtures of both are mentioned.

Specific examples of the diamine (c) having 2 to 20 carbon atoms in the polyether ester amide (B) which is a component of the present invention include ethylenediamine, tetramethylenediamine, hexamethylenediamine, nonamethylenediamine, Undecamethylenediamine, dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, bis- (4-aminocyclohexyl) methane, bis- (3-methyl-4-aminocyclohexyl)
Examples include methane and xylylenediamines.

Specific examples of the polyoxyalkylene glycol (d) for deriving the polyether ester amide (B) which is a component of the present invention include polyoxyethylene glycol, polyoxypropylene glycol and polyoxytetramethylene. Examples thereof include glycol, a block or random copolymer of ethylene oxide and propylene oxide, a block or random copolymer of ethylene oxide and tetrahydrofuran, and a mixture 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.

Specific examples of the dicarboxylic acid (e) having 6 to 20 carbon atoms for deriving the polyether ester amide (B) which is a component of the present invention include adipic acid, azelaic acid, sebacic acid and dodecane. Aliphatic dicarboxylic acids such as diacids, terephthalic acid, isophthalic acid, aromatic dicarboxylic acids such as diphenoxyethanedicarboxylic acid,
Examples thereof include alicyclic dicarboxylic acids such as 1,4-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) which is a component of the present invention comprises a polymerized fatty acid (a), azelaic acid and / or sebacic acid (b) and a diamine (c),
Weight ratio of polymerized fatty acid (a) to (b) (a) /
(B) is 0.3 to 5.0 and charged into a reaction vessel in which all three groups are sufficiently replaced with nitrogen so that all amino groups are substantially equivalent to all carboxyl groups, and 170 ° C to 230 ° C. Polycondensation to produce a polyamide oligomer with a number average molecular weight of 500 to 5,000.
~ 3,000 polyoxyalkylene glycols (d)
And a dicarboxylic acid (e) having 6 to 20 carbon atoms, in which all carboxyl groups are substantially equivalent to all hydroxyl groups,
And [(a) + (b) + (c)] / [(d) + (e)]
In a weight ratio of 95/5 to 10/90, heated to 200 to 280 ° C. in the presence of a small amount of catalyst and reacted for 1 to 3 hours, and then reacted under reduced pressure of about 1 mmHg. can get.

In order to obtain the transparent, flexible and excellent elastic recovery ability polyether ester amide (B) which is a component of the present invention, azelaic acid and / or sebacic acid (b) are used.
It is necessary that the weight ratio (a) / (b) of the polymerized fatty acid (a) to (b) is 0.3 to 5.0 and the number average molecular weight of the polyamide oligomer is in the range of 500 to 5,000. When the weight ratio (a) / (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. Conversely, 5,000
As the number average molecular weight of the polyoxyalkylene glycol becomes too large or the polymerized fatty acid content becomes too small, the compatibility between the polyamide oligomer and the polyoxyalkylene glycol decreases in the block copolymerization step. However, 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 polyether ester amide (B) which is a component of the present invention are as follows: the soft component [(d) + (e)] and the hard component [(a) constituting the polyether ester amide (B). + (B) + (c)] copolymerization ratio. Soft component [(d) +
(E)] is preferably 5 to 90% by weight. If the soft component is less than 5% by weight, the flexibility and low-temperature properties of the obtained polyetheresteramide will be insufficient, and conversely, if it exceeds 90% by weight, the mechanical strength and melting point will decrease, which is not preferable.

The modified vinyl polymer (C) having a functional group selected from a carboxyl group, an epoxy group or a derivative thereof in the present invention is one or two or more vinyl monomers polymerized or co-polymerized. A polymer obtained by polymerization and having 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 preferably in the range of 1 to 30% by weight based on 100 parts by weight of the modified vinyl copolymer.

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 vinyl monomers used for the polymerization of the modified vinyl polymer (C) include aromatic vinyl 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.

The phenoxy resin used as the component (D) of the present invention is epichlorohydrin and bisphenol A.
Or, it is a polycondensate with its nuclear substituent, and comprises a structural unit represented by the following general formula (I).

Embedded image (X _{1 to} X ₄ in the formula may be the same or different and each represents a hydrogen atom; a lower alkyl group such as a methyl group and an ethyl group; or a halogen atom such as chlorine and bromine.) The phenoxy resin preferably used in (1) is derived from epichlorohydrin and bisphenol A and has a number average molecular weight of 10,000 to 75,000.

The polyetheresteramide (B) in the present invention is excellent in flexibility and elastic recovery ability and excellent in compatibility with the saturated polyester resin (A). When melted and kneaded with the saturated polyester resin (A), the polyetheresteramide (B) is easily dispersed as fine particles of 1 μm or less in the matrix phase of the saturated polyester resin (A), and the impact resistance of the saturated polyester resin is improved. Is improved. Saturated polyester resin (A) and polyether ester amide (B) further containing a modified vinyl polymer (C) and a phenoxy resin (D) containing a functional group such as a carboxyl group and an epoxy group.
By blending, the dispersed particles of the polyetheresteramide in the matrix phase of the saturated polyester resin become finer, and the impact resistance of the saturated polyester resin is further improved.

The blending ratio of the saturated polyester resin (A) and the polyetheresteramide (B) in the composition of the present invention is 60 to 95 of the saturated polyester resin (A).
4% by weight of polyetheresteramide (B)
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.

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

In the composition of the present invention, 100 parts by weight of a resin mixture of the saturated polyester resin (A) and the polyetheresteramide (B) is added to a modified vinyl system containing a carboxyl group, an epoxy group and the like. 1 to 20 parts by weight of polymer (C) and 1 to 2 of phenoxy resin (D)
It is necessary to mix it in a proportion of 0 parts by weight. If the amount of each of the modified vinyl polymer and the phenoxy resin is less than 1 part by weight, the impact resistance is insufficiently improved, and the amount of each of the modified vinyl polymer and the phenoxy resin is 20 parts by weight. If it exceeds, heat resistance and rigidity are deteriorated, which is not preferable.

The resin composition of the present invention may contain various additives such as antioxidants, heat stabilizers, plasticizers, ultraviolet absorbers, lubricants, and the like, if desired, within a range that does not impair the object of the present invention.
Additives such as flame retardants, 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.

As the method for adjusting the resin composition of the present invention, a method of melt kneading is preferable, and a known method can be used as the method of melt kneading. 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, such as injection molding, extrusion molding, blow molding, vacuum molding and the like. Can be molded by the method of.

[0029]

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.

[0030]

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), a temperature rising rate of 10 ° C. /
The melting point was measured in minutes, the temperature was lowered at 10 ° C./minute, 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 < Polyether ester amide
Synthesis > (TPAE-1) 1000 ml of 4 equipped with a stirrer, nitrogen inlet and distillation tube
In the neck flask, the composition of the resulting polyamide copolymer is
Hexamethylenediamine-polymerized fatty acid polycondensate / hexamethylenediamine-azelaic acid polycondensate = 5 by weight ratio
0/50 hydrogenated polymerized fatty acid (carbon number
36, product name Pripol 1009, manufactured by Unichema) 10
9.4 g, azelaic acid 81.4 g, and hexamethylene diamine 72.5 g were charged together with a 5% phosphorous acid aqueous solution 0.8 g, and the temperature was raised while flowing a constant amount of nitrogen, to obtain 158 ° C.
The water produced by the polycondensation reaction came out from the. The content at this time was a uniform transparent liquid. When the temperature was raised to 190 ° C., the contents were sampled, and the acid value and the amine value were adjusted so as to have an equivalent relationship. Finally, a transparent polyamide oligomer having a terminal group concentration of 41.2 mgKOH / g and a number average molecular weight of 1362 was obtained. Azelaic acid 5 at this temperature
When 6.9 g was added and the content 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) were sequentially added, and when uniform, 0.1 g of antimony trioxide and monobutylhydroxy were added. Tin oxide 0.1g
Was 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 ° C, hard segment (polyamide copolymer) / soft segment (azelaic acid to polyoxytetramethylene glycol) =
A 50/50 (weight ratio) transparent polyetheresteramide (TPAE-1) was obtained.

In Examples and Comparative Examples, the following were used as the saturated polyester resin as the component (A), the modified vinyl polymer as the component (C) and the phenoxy resin (D).

(A) Saturated polyester resin Polybutylene terephthalate (PBT) manufactured by Toray, 140
1 x 06

(C) Modified Vinyl Polymer (C-1) Ethylene-Glycidyl Methacrylate-Vinyl Acetate Copolymer Sumitomo Chemical Co., Bondfast 7M, Glycidyl Methacrylate-6 wt% (C-2) Ethylene-Glycidyl Methacrylate Graft copolymer obtained by graft-polymerizing a styrene-acrylonitrile copolymer to a copolymer of NOF CORPORATION, MODIPER A4
400

(D) Phenoxy resin Union Carbide, PKHH

Examples 1 to 4 and Comparative Examples 1 to 5 Polybutylene terephthalate, Polyester ester amide (TPAE-1) obtained in Production Example, Modified vinyl polymer (C-1 to 2) and Phenoxy resin. Were blended in the proportions shown in Table 1 and melt-kneaded at 255 ° C. using a 35 mmφ kneader kneader (manufactured by Kasamatsu Kako Kenkyusho) to form pellets.

After drying the obtained pellets, a predetermined test piece was 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 parts by weight of the modified vinyl polymer and the phenoxy resin are parts by weight with respect to 100 parts by weight of the resin mixture of PBT resin and polyetheresteramide.

[0045]

[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] 0040

[Correction method] Change

[Correction contents]

(C) Modified vinyl polymer (C-1) ethylene-glycidyl methacrylate-methyl acrylate copolymer manufactured by Sumitomo Chemical Co., Ltd., Bondfast 7M, chrysidyl methacrylate-6 wt% (C-2) ethylene-chrysidyl methacrylate Graft copolymer obtained by graft-polymerizing a styrene-acrylonitrile copolymer on the copolymer, manufactured by NOF CORPORATION, MODIPER A4400

[Procedure amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0045

[Correction method] Change

[Correction contents]

[0045]

 ─────────────────────────────────────────────────── ─── 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) 60 to 95% by weight of a saturated polyester resin, and (B) (a) 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
Modified vinyl system containing (C) a functional group selected from a carboxyl group, an epoxy group or a derivative thereof, based on 100 parts by weight of a resin mixture consisting of 40 to 5% by weight of a polyether ester amide of 0/90. A polyester resin composition comprising 1 to 20 parts by weight of a polymer and 1 to 20 parts by weight of (D) a phenoxy resin.