JPH01138260A - Polyester resin composition and its production - Google Patents

Abstract

PURPOSE:To obtain the title composition which is excellent in moldability and can give a molding excellent in mechanical properties such as impact resistance, heat resistance and appearance and suitable as, e.g., a material for automobile outside sheets, by mixing a thermoplastic polyester resin with a polar polyolefin, an amine compound and a metal salt of an organic acid. CONSTITUTION:100 pts.wt. crystalline thermoplastic polyester resin (A), for example, polyethylene terephthalate or a copolymer having at least 80mol% ethylene terephthalate repeating units is mixed with 1-100 pts.wt. polyolefin (B) containing 0.01-20wt.% polar groups such as carboxyl, carboxylic acid anhydride or epoxy groups and having an intrinsic viscosity of 0.05-30dl/g (in decalin at 135 deg.C), 0.01-10 pts.wt. amine compound (C) having at least one prim. or sec. amino group in the molecule (e.g., propylamine or aniline), 0.01-20 pts.wt. metal salt (D) of an organic acid such as salt of an ethylene/methacrylic acid copolymer and, optionally, 0.01-20 pts.wt. plasticizer (E) such as diethylene glycol dibenzoate, and the obtained mixture is melt-kneaded.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to thermoplastic polyester resin compositions and thermoplastic polyester resin compositions that provide molded products with good moldability, excellent appearance, and excellent mechanical properties such as dramatic impact resistance. It relates to its manufacturing method.

Technical background of the invention and its problems Polyester resins have excellent mechanical properties, electrical properties, heat resistance, chemical resistance, etc., and are used in many industrial products. However, polyester resins have problems in that they have poor impact resistance, particularly notched impact strength, and poor moldability, and many methods for improving these problems have been proposed. For example, JP-A No. 60-40154 discloses a method of blending an epoxy monomer grafted product of an ethylene/α-olefin copolymer with a polyester resin, and JP-A No. 58-17148 discloses a method of blending both a glycidyl group-containing copolymer consisting of an α-olefin and a glycidyl ester of an α,β-unsaturated acid and an ethylene/α-olefin copolymer with a polyester resin, Zarani Japanese Patent Publication No. 58-38
Publication No. 747 discloses a method of blending an alicyclic carboxylic acid-modified olefin elastomer with a polyester resin, and the polyester resin composition obtained in this way has considerably improved impact resistance. ing.

However, the polyester resin compositions disclosed in the above publications do not have any improvement in moldability. In other words, polyester resins such as polyethylene terephthalate have a slow crystallization rate, so the degree of crystallinity between the surface and interior of the molded product is uneven, resulting in poor appearance, mechanical properties,
Dimensional stability and shape stability deteriorate. Since sufficient crystallization does not occur, a product with good heat resistance cannot be obtained. Therefore, in order to improve the moldability of polyethylene terephthalate, a polyester resin composition in which a nucleating agent and a plasticizer are blended has been proposed. For example, JP-A No. 58-217547 discloses a blend of polyethylene terephthalate, an inorganic filler, a sodium salt or potassium salt of a copolymer of olefin and acrylic acid or methacrylic acid as a nucleating agent, and a plasticizer. A polynisder resin composition that is a blend of an aliphatic carboxylic acid and an alcohol ester has been proposed. This polyester resin composition certainly has excellent moldability, but since it contains an inorganic filler, the surface becomes rough, making it unsuitable for applications that require an excellent appearance. Furthermore, even if the nucleating agent and plasticizer disclosed in JP-A-58-217547 are used in a composition comprising a polyester and a modified olefin elastomer, only a composition with low impact strength can be obtained. I can't.

The present inventors have discovered that it is effective to devise a method for kneading polyester resin and known polyester resin modifying components in order to improve the drawbacks of polyester resin, The technology was disclosed in No.-274154. However, depending on the application, polyester resins with even higher impact strength have been desired.

Purpose of the Invention The present invention aims to solve the problems associated with the prior art as described above, and aims to provide a molded product with good surface properties, mechanical properties such as impact resistance, heat resistance, etc. Excellent in
Moreover, it is an object of the present invention to provide a thermoplastic polyester resin composition with good moldability.

Summary of the Invention The polyester resin composition according to the present invention comprises: (i) 1 part by weight of a thermoplastic polyester resin, (ii > 1 to 100 u parts by weight of a polar group-containing polyolefin (iii > 0.01 to 10 parts by weight of an amine compound) Department,
and (iv) 0.01 to 20 parts of a metal salt of an organic acid.

The method for producing a polyester resin composition according to the present invention includes (i) adding 1 to 100 parts by weight of a polar group-containing polyolefin to the outermost part of 100 thermoplastic polyester resins, melt-kneading the mixture, and then melt-kneading (iii) >0.01 to 10 small parts of an amine compound and (iv) 0.01 to 20 parts by weight of a metal salt of an organic acid are added and melt-kneaded.

In the present invention, an amine compound and a metal salt of an organic acid are added to a polyester resin composition, and a kneading method is specified, so that the surface properties are good and impact resistance, heat resistance, and moldability are improved. A thermoplastic polyolefin resin composition is obtained.

DETAILED DESCRIPTION OF THE INVENTION Each component of the thermoplastic polyester vegetable fat composition according to the present invention and its manufacturing method will be specifically explained below.

Thermoplastic polyester resin The thermoplastic polyester resin used in the present invention (i> is mainly counter-dyed with polyethylene terephthalate,
A part of the terephthalic acid component or diol component may be replaced with another copolymer component. Such copolymer components include isophthalic acid, terephthalic acid component,
Difunctional dicarboxylic acids such as naphthalene dicarboxylic acid, 4,4-diphenoxyethane dicarboxylic acid, adipic acid, sebadic acid, and cyclohexane dicarboxylic acid can be used, and as the diol component, ethylene glycol, trimedecene glycol, tetramethylene glycol, Hexamethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, copolyglycol of polyethylene glycol and polypropylene glycol, etc. can be used. The polyester resin (i>) used in the present invention may be a mixture of two or more of the above polyester resins.

Preferred polyesters are polyethylene terephthalate or crystalline thermoplastic polyesters having 80 mole percent or more of ethylene terephthalate repeating units.

(iv) Polar group-containing polyolefin The polar group-containing polyolefin used in the present invention is a polyolefin having at least one polar group selected from a carboxyl group, a carboxylic acid anhydride group, and an epoxy group. Such polar group-containing polyolefins are composed of a vinyl monomer having a carboxyl group or its anhydride in the molecule, or a vinyl monomer having an epoxy group in the molecule, and an olefin monomer. Epoxy groups are introduced by copolymerization, by graft polymerization of the above-mentioned vinyl monomers onto an olefinic polymer, or by oxidizing the double bonds present in polydienes such as polybutadiene and polyisoprene by a known method. It can be manufactured by methods such as.

Examples of carboxyl group-containing vinyl monomers used to introduce carboxyl groups into polyolefins include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, bicyclo[2,2, 1]] unsaturated carboxylic acids such as heptose-2-ene to 5,6-dicarpone, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo[2,2,1]]heptoe-2-ene- 5,
Examples include anhydrides of unsaturated carboxylic acids such as 6-dicarboxylic anhydride, with maleic anhydride and fumaric acid being particularly preferred.

In addition, in order to introduce a carboxylic acid anhydride group into a polyolefin, the above-mentioned maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo[2,2,1]]hept-2-ene-5, 6-dicarboxylic anhydride and the like are used.

Vinyl monopods having an epoxy group in the molecule that are used when introducing epoxy groups into polyolefins include glycidyl acrylate, glycidyl methacrylate, monoglycidyl itaconate, and 2-methyl butene dicarboxylic acid diglycidyl ester. Allyl glycidyl ether, vinyl glycidyl ether, 3,4-epoxybutene, 3,4-epoxy-3-methyl-1-butene,
Examples include vinylcyclohexene monoxide, p-glycidyl ether, and among these, glycidyl methacrylate is preferred.

Examples of olefin polymers that serve as the base of polar group-containing polyolefins include ethylene, propylene, 1-butene,
1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hegydecene, 1-octadecene, 1
- Non-quality or low crystallinity or crystalline olefin polymers mainly composed of α-olefin components such as eicosene, or in addition to these α-olefin components, small amounts of butadiene, isoprene, 1, 4-hex]nodiene,
5-ethylidene-2-norbornene, 5-vinyl-2-
diene components such as norbornene, vinyl acetate, acrylic acid esters such as acrylic acid (salt), methacrylic acid (salt), glycidyl acrylate, and ethyl acrylate;
Methacrylic esters such as glycidyl methacrylate and ethyl methacrylate, maleic acid, maleic anhydride, maleic esters, 2-norbornene-5,6-
Unsaturated carboxylic acids or their derivatives such as dicarboxylic acid and 2-norbornene-5,6-dicarboxylic anhydride, nitrile components such as acrylonitrile and methacrylate, and halogens such as chlorine, bromine, and iodine can be randomly copolymerized or grafted. Copolymerized or added polymers are used.

Furthermore, as the olefin polymer, a homopolymer or copolymer containing dienes such as butadiene and isoprene as a main component, or a hydrogenated product thereof can also be used.

Among these olefin polymers, examples of non-crystalline or low crystal olefin polymers include ethylene/propylene copolymer, ethylene/1-butene copolymer, and ethylene/1-hexene copolymer. Combined, propylene 1
-butene copolymer, propylene/1-butene/4-methyl-1-pentene copolymer, 1-hexene/4-methyl-1-pentene copolymer, ethylene/propylene/dicyclopentadiene copolymer, ethylene propylene 5
- Ethylidene 2-norbornene combination, ethylene,
propylene/5-vinyl-2-norbornene copolymer,
Ethylene/propylene/1,4-hexadiene copolymer, ethylene/1-butene/dicyclopentadiene copolymer, ethylene/1-butene/5-ethylidene-2-norbornene copolymer, ethylene/1-butene -1,4-hexadiene copolymer, polybutadiene and its hydride, polyisoprene and its hydride, etc. can be exemplified.

In addition, specific examples of crystalline olefin polymers include polyethylene, polypropylene, poly-1-butene,
Poly4-methyl-1-pentene, ethylene/propylene copolymer, ethylene/1-butene copolymer, ethylene/
4-methyl-1-pentene copolymer, ethylene/1-hexene copolymer, ethylene/vinyl acetate copolymer, ethylene/acrylic acid (salt) copolymer, ethylene/methacrylic acid (salt) copolymer, Examples include ethylene/glycidyl acrylate copolymer, ethylene/glycidyl methacrylate copolymer, ethylene/maleic acid copolymer, and ethylene/maleic anhydride copolymer.

Further, as the olefin polymer, acrylic acid, methacrylic acid, methacrylic ester, maleic acid, maleic anhydride, 2
-Olefin polymers obtained by graft copolymerization of unsaturated carboxylic acids such as -norbornene-5,6-dicarboxylic acid and 2-norbornene-5,6-dicarboxylic anhydride or derivative components thereof can be similarly exemplified.

The content of polar groups in such a polar group-containing polyolefin varies greatly depending on the type of vinyl monohung used, but is generally preferably 0.01 to 20% by weight.

If the content of this polar group is less than 0.01% by weight, it is not preferable because the effect of improving impact resistance by blending the polar group-containing polyolefin is not sufficient;
If it exceeds 1% by weight, the impact strength after addition of the nucleating agent tends to decrease, which is not preferable.

The intrinsic viscosity [η] of these olefin polymers measured in decalin at 135°C is 0.05 to 30 dl/g.
, preferably 0.1 to 25 dl/9.

In the present invention, a polar group-containing polyolefin as described above and a polar group-free polyolefin may be mixed and used.

Amine compound (iii) The amine compound used in the present invention is a compound having one or more primary amino groups or secondary @amino groups in the molecule. Specifically, aliphatic primary amines such as propylamine, isopropylamine, butylamine, hexylamine, and cyclohexylamine, aromatic primary amines such as aniline, toluidine, and xylidine, diethylamine, and diethylamine. , dipropylamine, diisopropylamine, dibutylamine, dipentylamine, dicyclohexylamine, piperidine, secondary amines such as n-methylaniline, polyvalent amines such as ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, ethanol Although alkanolamines such as amines and propatool amines can be used, aliphatic primary amines and aliphatic secondary amines are preferred because they do not impair the moldability of the polyester resin composition.

By blending such an amine compound into a polyester resin composition, the impact strength of the resin composition can be further improved.

Metal salts of organic acids The metal salts of organic acids used in the present invention are added to accelerate the crystallization rate of the polyester.

In other words, the organic acid metal salt is considered to contribute to the formation of polynisder crystal nuclei.

Examples of organic acids that form such organic acid metal salts include formic acid, acetic acid, stearic acid, montanic acid, oleic acid, linoleic acid, oxalic acid, phthalic acid, isophthalic acid,
Terephthalic acid, alcoholic acid, sulfuric acid, benzoic acid, carbonic acid, etc. are used, and among these, benzoic acid is preferred. Examples of metals that form salts include sodium, potassium, calcium, magnesium, barium, and zinc. Further, as the organic acid metal salt, sodium, potassium, calcium, zinc salts of copolymers of olefin or styrene and acrylic acid or methacrylic acid are used. Among the two, Shun is preferable. These organic acid metal salts may be used alone or in combination of two or more.

Blending ratio of each component In the polyester resin composition according to the present invention, each of the above components is contained in the following ratio with respect to 100 parts by weight of (i) thermoplastic polyester resin. .

Polar base polyolefin (ii) 1 to 100 parts by weight, preferably 3 to 90 parts by weight The polar group-containing polyolefin is a thermoplastic polyester resin 10 parts by weight.
If the amount is less than 1 part by weight relative to 0 parts by weight, the impact resistance of the resulting polyester resin composition will not be improved so much, which is undesirable. On the other hand, if it exceeds 100 parts by weight, the mechanical properties of the resulting polyester resin composition will deteriorate. This is not preferable because it lowers the temperature.

The amine compound (iii > 0.01 to 10 parts by weight, preferably 0.01 to 7 parts by weight, more preferably 0.05 to 5 parts by weight) is added to 100 parts by weight of the thermoplastic polyester resin. hand,
If it is less than 0.01 part by weight, the impact resistance of the polyester resin composition to be obtained will not necessarily be improved, which is undesirable. On the other hand, if it exceeds 10 parts by weight, the mechanical properties of the polyester resin composition obtained This is not preferable because it reduces the

Metal salt of organic acid (iv) 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight ω of the metal salt of organic acid is thermoplastic polyester resin '1
If it is less than 0.011 parts by weight per 00 parts by weight,
The effect of accelerating the crystallization rate of polyester tends to decrease, which is undesirable. On the other hand, if it exceeds 20 parts by weight, the mechanical properties or heat resistance of the thermoplastic polyester resin obtained tend to decrease, which is undesirable.

Major Ingredients In addition to the above-mentioned components, the polyester composition according to the present invention may also contain plasticizers, antioxidants,
Stabilizers such as ultraviolet absorbers, lubricants, flame retardants, antistatic agents,
Various inorganic or organic compounds such as colorants, mold release agents, glass fibers, fillers such as talc, etc. can be blended.

The plasticizer is preferably an ester of aliphatic alcohol and carboxylic acid, specifically adipic acid.
Di(2-ethylhexyl) ester, adipic acid di-n-butyl ester, poly(butane 1,3-diol adipate), poly(hexane 1,6-diol adipate), poly(butane-1,4-diol adipate) )
, montanic acid ester, alkyl sulfone M-p-phenyl ester, diethylene gelicol di-benzoate, neopentyl glycol di-benzoate, pentaerythritol dibenzoate, thio-di-ethanol di-benzoate, and the like. Such plasticizers may be used alone or in combination. The blending amount of such a plasticizer is usually 100% of the polyester resin.
It is 0.01 to 20 weight ω parts to weight M parts, preferably 0.1 to 10 fffffi parts.

Moreover, polyolefins containing no polar groups can also be blended into the polyester composition according to the present invention.

Manufacturing method The polyester resin composition according to the present invention is prepared by melt-kneading (i) the thermoplastic polyester resin as described above and (ii) the polar group-containing polyolein, and then melt-kneading (iii) the amine compound and (1). It can be produced by adding a metal salt of an organic acid and melt-kneading.The order of addition of the above (ii) amine compound and (iv) metal salt of an organic acid is not particularly limited, but (i) It is preferable to add (iii) an amine compound and then (iv) an ML-containing metal salt to the melt-kneaded mixture of the thermoplastic polyester resin and (ii) the polar group-containing polyolein in this order.

The above four components (i>, (ii>
Even if (iii>) and (iv) are kneaded, the impact resistance of the resulting polyester resin is not improved.

In the present invention, first, (i) thermoplastic polyester resin and (ii > polar group-containing polyolefin are melt-kneaded, and then (iii > amine compound and (iv
) The reason why it is necessary to add a metal salt of an organic acid is considered to be due to the following reasons.

According to the research conducted by the present inventors, the above four components react with each other during the melt-kneading process, and in particular, the reaction between (i) thermoplastic polyester resin and (ii > polar group-containing polyolefin) ii) Improving the impact resistance of the composition by improving the dispersibility of >.

However, (ii > polar group-containing polyolefin and (1■
) The reaction of an organic acid with a metal salt crosslinks (ii) and (
It was found that the dispersibility of (ii> with respect to i> was significantly inhibited. That is, in order to knead the above four components and obtain a composition with excellent impact resistance, it is necessary to mix (i) and (ii>) in advance. It is necessary to prevent the reaction of (ii) and (iV) by melt-kneading and reacting, and then adding (IV).However, even if (i) and (ii) are kneaded in advance, some There may be a reaction residue, and this reaction residue also becomes (ii) by reaction with (iv).
It was found that the dispersibility of > could be an inhibiting factor.

As a result of examining various additives to inactivate this reaction residue, we found that (iii) amine compounds are effective.
This is because it is thought to react with the reactive residue of ii) and inactivate ii>.

Kneading in the method for producing the composition of the present invention can be carried out by a known method. For example, the mixture may be kneaded in an extruder, kneader, or Panbury mixer.

Practically, it is preferable to charge (i) a thermoplastic polyester resin and (ii) a polar group-containing polyolein into an extruder hopper, and feed (iii) (iv) from the middle of the extruder cylinder.

Effects of the Invention The polyester composition obtained by the present invention can be easily molded by conventional methods such as injection molding and extrusion molding, and has a good appearance even when a mold of 130'C or less is used during injection molding. Molded products with excellent mechanical properties can be obtained. The polyester composition according to the present invention can be used in various forms for various purposes, but especially has high impact resistance, high rigidity,
It is suitable for fields that require high heat resistance, such as materials for automobile exterior panels.

EXAMPLES The present invention will be explained below using Examples, but the present invention is not limited to these Examples.

Examples 1 to 6 [I] Production method of composition Polyethylene terephthalate with an intrinsic viscosity of 0.65 dl/y, a homeostatic group-containing polyolefin produced according to the reference example described below, and EBR as necessary in the proportions shown in Table 1. The mixture was mixed at 260° C. and fed to a twin screw extruder set at 260°C for pelletization. After drying the pellets in a vacuum dryer, n-hexylamine was added and kneaded in an extruder to obtain the pellets. Sodium salt of ethylene methacrylic acid copolymer with a degree of neutralization of 60% was added to the pellets as a nucleating agent. (Weight ratio of ethylene/methacrylic acid = 85/15), diethylene glycol dibenzoate was added as a plasticizer and extruded again at 250'C using an extruder. Injection molded under the following conditions. (Sequential Blending Method) Comparative Example 1 in Table 1 shows the results of a polyethylene terephthalate composition obtained by tri-blending and extruding the components in Table 1 at once. (- Blend method> [1] Reference example 1 of manufacturing method of polar group-containing polyolefin Melt index at 190°C is 3.609/1
100 parts by weight of an ethylene-butene copolymer with an ethylene content of 85 mol% and 1 part by weight of maleic anhydride,
After mixing 30,06 parts by weight of 2,5-dimethyl-2,5-di(tajaribdelperoxy)hexyne,
25# Φ, L/D = 28 single screw extruder and 250
' C to obtain a maleic anhydride-modified ethylene-butene copolymer (hereinafter abbreviated as modified EBR). This degeneration E
Dissolve BR in xylene, reprecipitate with acetone and dry.
The amount of maleic anhydride grafted was measured by titration and found to be 0.45% by weight.

Reference Example 2 Glycidyl methacrylate grafted EBR was obtained by following the same procedure as in Reference Example 1 except that maleic anhydride in Reference Example 1 was changed to glycidyl methacrylate. Grafting (2) to glycidyl methacrylate-1 was 0.50% by weight.

Reference Example 3 As the ethylene-glycidyl methacrylate copolymer, BOND FAST-E (trade name) manufactured by Sumitomo Chemical Corporation (2) was used.

[n] Composition evaluation method VFR: Measured according to ASTM D-1238.

Flexural Modulus (FM) and Flexural Strength (FS): 1/8"
The thickness was measured using a test piece according to ASTM D-790-80.

Izod impact strength (IZ>: Measured according to ASTM D-256 using a notched test piece having a thickness of 1/8".

Heat distortion temperature (HDT): AST at a load of 66 PSI
Measured using MD-256.

Crystallization rate (8H,,/Δl1o): Differential thermal analyzer (
Measured using DSC>. The sample was placed in a 1-thick mold and pressed under the conditions of 290° C. and 160 KE/cri, and then cooled with water to obtain a pressed sheet. Weigh out a sample of approximately 10/1lff from the center of this press sheet.
DSC measurements were carried out under the conditions that the temperature was raised at a rate of 290'C/min and held for 1Qmin, and then the temperature was lowered at a rate of 10'C/min. From the obtained calorific curve, the calorific value ΔCho 1 was determined from the peak area at the crystallization temperature when the temperature was raised, and the calorific value ΔHC was determined from the peak area during crystallization when the temperature was lowered. The thus obtained ΔH, /8Ho is an index of the ease of crystallization, and the smaller this value is, the easier it is for the polyester to crystallize.

Claims (1)

[Scope of Claims] 1) (i) 100 parts by weight of thermoplastic polyester resin, (ii) 1 to 100 parts by weight of a polar group-containing polyolefin, (iii) 0.01 to 10 parts by weight of an amine compound, and ( iv) A polyester resin composition comprising 0.01 to 20 parts by weight of a metal salt of an organic acid. 2) To 100 parts by weight of (i) thermoplastic polyester resin, (ii) 1 to 100 parts by weight of a polar group-containing polyolefin is added and melt-kneaded, and then (iii) 0.01 to 10 parts by weight of an amine compound and (iv) A method for producing a polyester resin composition, which comprises adding 0.01 to 20 parts by weight of a metal salt of an organic acid and melt-kneading the mixture.