JP3355667B2 - Impact resistant polyester resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an impact-resistant polyester resin composition having a good balance of stable impact resistance from room temperature to low temperature and excellent moldability.

[0002]

BACKGROUND OF THE INVENTION Generally, saturated polyester resins are widely used as engineering plastics because of their excellent weather resistance, electrical properties, chemical resistance, abrasion resistance and heat aging resistance. I have. However, the impact resistance of the molded product is not satisfactory, and this is an obstacle in developing practical applications.

[0003] Many compositions have been proposed for the purpose of improving the impact resistance, which is a drawback of such saturated polyester resins. For example, a composition with an ethylene-glycidyl methacrylate copolymer (Japanese Patent Publication No. 58-47419) and a composition with a terpolymer such as ethylene-glycidyl methacrylate-methyl acrylate (Japanese Patent Publication No.
No. 28223) has been proposed. Further, the composition comprises a composition of an ethylene-glycidyl methacrylate copolymer and a maleic anhydride-grafted ethylene-propylene random copolymer (JP-A-61-212260), an ethylene-glycidyl methacrylate copolymer and an ethylene-α-olefin. Compositions with a terpolymer comprising a binary copolymer or an ethylene-α-olefin-specific non-conjugated diene (JP-B-63-4566, JP-B-1-26380) have been proposed. I have.

However, according to the study of the present inventors,
In the above prior art, a molded article having relatively improved impact resistance can be obtained, but it is still insufficient, and from the viewpoint of the balance of physical properties such as rigidity and impact resistance and impact resistance and moldability. Has also proved unsatisfactory overall.

[0005]

In view of the above circumstances, the present inventors have made a stable polyester resin having a saturated polyester resin as a main component and excellent impact resistance over a wide range from room temperature to low temperature.
At the same time, as a result of diligent studies on a saturated polyester resin composition having excellent mechanical properties such as moldability, heat resistance and rigidity, an epoxy group-containing ethylene copolymer having a specific structure, a specific ethylene-based copolymer and a specific By melt-kneading the polyfunctional compound of the above, the molded article has excellent stability in impact resistance over a wide range from room temperature to low temperature, a good balance of rigidity and heat resistance, and excellent moldability and appearance. Can be obtained, which has reached the present invention.

That is, the present invention relates to (A) 100 parts by weight of a saturated polyester resin, (B) 50-99% by weight of (a) an ethylene unit, and (b) glycidyl ester unit of an unsaturated carboxylic acid or unsaturated unit. 0.1 to 5 carboxylic acid glycidyl ether units
0% by weight, (c) 1 to 50 parts by weight of an epoxy group-containing ethylene copolymer containing 0 to 28 % by weight of ester units selected from ethylenically unsaturated compound units, (C) (a) 30 to 30% by weight of ethylene units (B) 1 to 50 parts by weight of an ethylene copolymer comprising 10 to 70 mol% of α-olefin units having 3 or more carbon atoms and 0 to 20 mol% of non-conjugated diene units; Compound containing at least two identical or different functional groups selected from the group consisting of a group, an amino group, a carboxylic anhydride group and a unit of the following formula (1) 0.0
It is intended to provide an impact-resistant polyester resin composition containing 1 to 20 parts by weight. (Wherein X and Y are both an oxygen atom or a sulfur atom,
Alternatively, one represents an oxygen atom and the other represents a sulfur atom. )

Hereinafter, the present invention will be described in detail. The (A) saturated polyester resin in the present invention comprises a dicarboxylic acid component in which at least 40 mol% of the dicarboxylic acid component is terephthalic acid and a diol component. As the dicarboxylic acid component other than terephthalic acid, adipic acid,
2-2 carbon atoms such as sebacic acid and dodecanedicarboxylic acid
0, an aromatic dicarboxylic acid such as an aliphatic dicarboxylic acid, isophthalic acid, or naphthalenedicarboxylic acid; or an alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid, alone or in a mixture. Examples of the diol component include aliphatic diols such as ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, and 1,4-cyclohexanediol; The cyclic diols may be used alone or as a mixture.

[0008] Among these (A) saturated polyester resins, polybutylene terephthalate or polyethylene terephthalate is preferred. The (A) saturated polyester resin preferably has an intrinsic viscosity in the range of 0.5 to 3.0 dl / g measured at 25 ° C. using o-chlorophenol as a solvent.

The (B) epoxy group-containing ethylene copolymer of the present invention is defined as (a) 50 to 99% by weight of ethylene units,
(B) 0.1 to 50% by weight of an unsaturated carboxylic acid glycidyl ester unit or unsaturated glycidyl ether unit,
An epoxy group-containing ethylene copolymer having 0.5 to 20% by weight and (c) an ethylenically unsaturated compound unit of 0 to 28 % by weight is preferred. (B) In the epoxy group-containing ethylene copolymer, (b) the unsaturated carboxylic acid glycidyl ester unit and the unsaturated glycidyl ether unit are represented by the following general formulas (2) and (3). (In the formula, R represents an alkenyl group having 2 to 18 carbon atoms.) (Wherein, R represents an alkenyl group having 2 to 18 carbon atoms;
Represents -CH ₂ -O- or the following general formula (4). )

Specific examples include glycidyl acrylate, glycidyl methacrylate, glycidyl itaconate, allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-p-glycidyl ether and the like. In addition, the epoxy group-containing ethylene copolymer of the present invention includes (a) ethylene (b) an unsaturated carboxylic acid glycidyl ester or unsaturated glycidyl ether and (c) an ethylenically unsaturated compound in a tertiary or higher copolymer. Coalescence can also be used. Examples of the (c) ethylenically unsaturated compound include α, β-unsaturated carboxylic acid alkyl esters, carboxylic acid vinyl esters, vinyl ethers, and styrenes.

(B) Examples of the epoxy group-containing ethylene copolymer include ethylene-glycidyl methacrylate-copolymer, ethylene-glycidyl methacrylate-methyl acrylate terpolymer, and ethylene-glycidyl methacrylate-ethyl acrylate terpolymer. And a terpolymer of ethylene-glycidyl methacrylate-vinyl acetate. The melt index (JIS K6760) of the epoxy group-containing ethylene copolymer is not particularly limited, but is 0.5 to 100 g / 1.
0 minutes is preferred.

The method for producing the epoxy group-containing ethylene copolymer is not particularly limited, and a random copolymerization method in which the unsaturated epoxy compound is introduced into the main chain of the copolymer and a copolymerization method in which the unsaturated epoxy compound is used. Any of the graft copolymerization methods introduced as a side chain of the polymer is possible. As a production method, for example, an unsaturated epoxy compound and ethylene are added at a pressure of 500 to 4000 atm in the presence of a radical generator,
A method of copolymerizing at 100 to 300 ° C. in the presence or absence of a suitable solvent or chain transfer agent, a method of mixing an unsaturated epoxy compound and a radical generator with polyethylene, and performing melt graft copolymerization in an extruder. And the like.

The amount of the epoxy group-containing ethylene copolymer (B) is 1 to 50 parts by weight, preferably 2 to 35 parts by weight, per 100 parts by weight of the saturated polyester resin. (B) If the addition amount of the epoxy group-containing ethylene copolymer is less than 1 part by weight, a satisfactory effect of improving impact resistance cannot be obtained, and if it exceeds 50 parts by weight, molding processability deteriorates and mechanical properties deteriorate. No favorable results such as a decrease in

In the ethylene copolymer (C) used in the present invention, the α-olefin unit having 3 or more carbon atoms is
For example, propylene, 1-butene, 1-pentene, 2-methyl-1 pentene, 1-hexene, 1-octene and the like can be mentioned, and propylene and 1-butene are preferable.
Non-conjugated diene units include, for example, 5-ethylidene-2-norbornene, 5-methylidene-2-norbornene,
Examples include propenyl-2-norbornene, 5-vinyl-norbornene, 5-methacryl-2-norbornene, dicyclopentadiene, 1,4-hexadiene, 1,5-cyclooctadiene, isoprene, and the like. In particular, 5-ethylidene-2 -Norbornene, dicyclopentadiene,
1,4-Hexadiene is preferably used.

(C) In the ethylene copolymer, the content of the ethylene unit is 30 to 90 mol%, preferably 40 to 80 mol%, and the content of the α-olefin unit having 3 or more carbon atoms is 10 to 70 mol%. Preferably it is 20 to 60 mol%. Further, the content of the non-conjugated diene unit is 0 to 20 mol%,
Preferably it is 0.1 to 10 mol%. The content of α-olefin units having 3 or more carbon atoms is less than 10 mol% or 70
If it exceeds mol%, a sufficient impact resistance improving effect cannot be obtained.

The amount of the ethylene copolymer (C) used in the present invention is 1 to 50 parts by weight, preferably 2 to 40 parts by weight, based on 100 parts by weight of the saturated polyester resin.
If the amount is less than 1 part by weight, a satisfactory effect of improving impact resistance cannot be obtained, and if it exceeds 50 parts by weight, the mechanical properties of the molded article are deteriorated.

The (D) polyfunctional compound used in the present invention includes a carboxyl group, an amino group, a carboxylic anhydride group and two functional groups selected from the units of the above formula (1) per molecule. The molecular weight of the polyfunctional compound is not particularly limited, and a high molecular compound is also included.

Examples of the polyfunctional compound (D) containing two or more carboxyl groups in one molecule include oxalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, carballylic acid, and cyclohexanedicarboxylic acid. , Aliphatic polycarboxylic acids such as cyclopentanedicarboxylic acid, ethylene-acrylic acid copolymer, ethylene-
Methacrylic acid copolymer, ethylene-acrylic acid-acrylic acid methyl ester copolymer, ethylene-acrylic acid-
Acrylic acid ethyl ester copolymer, ethylene-acrylic acid-butyl acrylate copolymer, ethylene-
Acrylic acid-vinyl acetate copolymer, ethylene-
Methacrylic acid-methyl methacrylate copolymer,
Polymeric polycarboxylic acids such as ethylene-methacrylic acid-ethyl methacrylate copolymer, ethylene-methacrylic acid-butyl methacrylate copolymer, ethylene-methacrylic acid-vinyl acetate copolymer,
Aromatic polycarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, trimesic acid, trimellitic acid, and the like, among which adipic acid, dodecanedicarboxylic acid, ethylene-acrylic acid copolymer And an aliphatic polycarboxylic acid such as ethylene-methacrylic acid copolymer and a polymer type polycarboxylic acid.

Examples of the (D) polyfunctional compound having two or more amino groups in one molecule include 1,6-hexamethylenediamine, trimethylhexamethylenediamine, 1,4-diaminobutane, 1,3-diamino Propane, ethylenediamine, aliphatic diamines such as polyetherdiamine, hexamethylenediaminecarbamate, carbamates such as ethylenediaminecarbamate, diethylenetriamine, triethylenetetramine,
Aliphatic polyamines such as tetraethylenepentamine, ethylaminoethylamine, methylaminopropylamine, aminoethylethanolamine and bis (hexamethylene) triamine; alicyclic polyamines such as N-aminopiperazine and mensendiamine; m- Alicyclic polyamines having an aromatic ring such as xylylenediamine, aromatic polyamines such as m-phenylenediamine, o-phenylenediamine, diaminophenyl ether, benzine, 2,4-toluenediamine, ethylene and N, N-dimethyl An ethylene copolymer comprising an ethylene unit and an α, β-unsaturated carboxylic acid N, N-dialkylaminoalkyl ester, such as a copolymer of aminoethyl methacrylate,
And hydrazide compounds such as succinic dihydrazide and adipic dihydrazide. 2,4,6
-Tris (dimethylaminomethyl) phenol, imidazoles and the like can also be used.

Examples of the polyfunctional compound (D) containing two or more carboxylic acid anhydride groups in one molecule include an ethylene copolymer comprising ethylene units and maleic anhydride units, and a copolymer of isobutene and maleic anhydride. Examples thereof include polymers, copolymers of styrene and maleic anhydride, and the like. These copolymers may further contain α, β-unsaturated carboxylic acid alkyl ester or carboxylic acid vinyl ester as a copolymer component. For example, alkyl acrylates and alkyl methacrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, ethyl methacrylate, and butyl methacrylate, vinyl acetate,
Vinyl esters such as vinyl propionate may be mentioned as copolymer components.

Examples of the polyfunctional compound (D) containing two or more units of the formula (1) in one molecule include a heterocyclic compound, an alicyclic compound and an aromatic compound. Specific examples of the heterocyclic compound include parabanic acid, isocyanuric acid, alloxan, alloxanthine, alloxan-5-oxime, barbituric acid, 5,5-diethylbarbituric acid, 5-ethyl-5-phenylbarbituric acid , 5- (1-methyl-butyl) -5-allylbarbituric acid, 5,5-diallylbarbituric acid and the like, and compounds in which the oxygen atom of —CＯO in these compounds is substituted by a sulfur atom, for example, 2 , 4-dithiobarbituric acid, 2-thiobarbituric acid, and the like. As the aromatic compound,
Examples thereof include thioimides corresponding to these, such as pyromellitic diimide and 1,4,5,8-naphthalic diimide. As the aliphatic compound, for example, triuret,
Examples thereof include thiouret corresponding to 1-methyltriuret, 1,1-diethyltriuret, tetrauret and the like.

It is also possible to use 12-aminododecanoic acid, hydantoic acid or the like having different functional groups in the same molecule among the functional groups shown above. All of the above-mentioned polyfunctional compounds may be used in combination.

The amount of the polyfunctional compound (D) used in the present invention is based on 100 parts by weight of the saturated polyester resin.
It is 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight. If the amount is less than 0.01 part by weight, the reaction is insufficient, so that satisfactory properties in terms of physical properties such as impact resistance and moldability cannot be obtained. If the amount exceeds 20 parts by weight, the moldability is extremely difficult due to excessive reaction. , And physical properties are significantly reduced.

The method for producing the composition of the present invention is not particularly limited. For example, the components can be melt-kneaded together using an extruder.
The component (D) can also be added to a composition in which (B) and (C) are melt-kneaded in advance.

As accelerators for the reaction between (D) the polyfunctional compound and (B) an ethylene copolymer containing an epoxy group or (C) an ethylene copolymer, quaternary ammonium salts, quaternary phosphonium salts, A compound selected from phosphines can be used. In particular, when a compound having the above-mentioned formula (1) unit is used as the polyfunctional compound, it is preferable to use the compound together. Examples of the quaternary ammonium salts include tetrabutylammonium bromide, n-dodecyltrimethylammonium bromide, octadecyl-trimethylammonium bromide and the like. Examples of the quaternary phosphonium salts include triphenylbenzylphosphonium chloride, triphenyl, benzylphosphonium iodide, and tetrabutylphosphonium bromide. Examples of the phosphines include triphenylphosphine and tri-2,6-dimethoxyphenylphosphine.

The amount of the reaction accelerator used in the present invention is 5 parts by weight or less based on 100 parts by weight of the saturated polyester resin. Even when used in an amount exceeding 5 parts by weight, no effect of increasing the amount is observed.

In the present invention, in order to further improve the impact resistance, it is effective to add a block copolyetherester elastomer in combination. Examples of block copolyetherester elastomers include hard segments consisting of terephthalic acid units and ethylene glycol, propylene glycol, 1,4-butanediol and the like, and polyalkylene oxides such as polyethylene oxide glycol, polypropylene oxide glycol and polytetramethylene oxide glycol. Examples include a copolymer of a soft segment made of glycol.

The impact-resistant polyester resin composition of the present invention contains other components such as pigments, dyes, reinforcing agents, heat stabilizers, as long as the physical properties and moldability are not impaired.
Additives such as antioxidants, weathering agents, nucleating agents, antistatic agents, flame retardants, plasticizers, and the like, or other polymers can be added and blended. Particularly useful by adding reinforcing agents and fillers such as glass fiber, carbon fiber, talc, calcium carbonate, magnesium hydroxide, etc., which have been subjected to various surface treatments, and have excellent balance of physical properties of impact resistance and rigidity Material can be obtained. The resin composition obtained by the present invention is molded by injection molding, extrusion molding, or other various molding methods.

[0029]

As described in detail above, according to the present invention,
It is possible to provide an impact-resistant polyester resin composition having excellently excellent impact resistance over a wide range from room temperature to low temperature, and having an extremely good balance between mechanical properties, thermal properties, etc., and moldability. Further, the impact-resistant polyester resin composition obtained according to the present invention can be easily formed into a molded product, a film, a sheet, or the like by a molding method used for an ordinary polyester-based resin composition, for example, a molding method such as injection molding or extrusion molding. It is possible to obtain a product which is excellent in the balance of physical properties such as impact resistance, rigidity, heat resistance and the like, and which has extremely excellent appearance uniformity and smoothness.

[0030]

The present invention will be described below with reference to examples, but the present invention is not limited to these examples. The measurement of physical properties in Examples and Comparative Examples was performed by the following methods.

(1) Melt flow rate (MI) This is a measurement result according to JIS K 6760 (230 ° C., 2160 g). (2) Izod impact strength This was carried out in accordance with JIS K7110 (sample thickness 3.2 mm, measurement temperatures 23 ° C. and −10 ° C., with V-notch). (3) Flexural modulus It was carried out in accordance with JIS K7203 (sample thickness 3.2 mm). (4) Thermal deformation temperature The thermal deformation temperature was measured in accordance with JIS K7207 (sample thickness 3.2 mm, bending stress 4.6 kg / cm ² ).

In Examples and Comparative Examples, component (A)
The following were used as the saturated polyester resin, the component (B) the epoxy group-containing ethylene copolymer, the component (C) the ethylene copolymer and the component (D). (A) Saturated polyester resin Polybutylene terephthalate (abbreviated as PBT) Toughpet N1000 (manufactured by Mitsubishi Rayon) (B) Epoxy group-containing ethylene copolymer Copolymer (1) E / GMA = 88/12% by weight, MI = 3 g / 10 min Copolymer (2) E / VA / GMA = 83/5/12% by weight, MI = 8 g
/ 10 min Copolymer (3) E / MA / GMA = 66/28/6% by weight, MI = 10
g / 10 minutes (C) Ethylene-based copolymer Copolymer (4) E / propylene / 5-ethylidene-2-norbornene =
60.2 / 39.6 / 0.2 mol%, Mooney viscosity = 6
8 copolymer (5) E / propylene / 5-ethylidene-2-norbornene =
60.0 / 38.6 / 1.4 mol%, Mooney viscosity = 6
0 copolymer (6) E / propylene / dicyclopentadiene = 66.6 / 3
3.1 / 0.3 mol%, Mooney viscosity = 44 Copolymer (7) E / propylene / dicyclopentadiene = 62.3 / 3
5.6 / 2.1 mol%, Mooney viscosity = 35 Copolymer (8) E / propylene = 64/36 mol%, Mooney viscosity = 4
5 (D) Polyfunctional Compound Adipic acid, isocyanuric acid, hexamethylenediamine carbamate, maleic anhydride and the following copolymer were used as the polyfunctional compound. Copolymer (9) E / AA = 80/20% by weight, MI = 250 g / 10 min Copolymer (10) E / MAH / EA = 69/3/28% by weight, MI = 35
g / 10 minutes, where E: ethylene, VA: vinyl acetate, GMA: glycidyl methacrylate, MA: methyl acrylate,
MAH: maleic anhydride, EA: ethyl acrylate,
AA: acrylic acid, MI: melt flow rate measured at 190 ° C. under a load of 2.16 kg.

Examples 1 to 11 and Comparative Examples 1 to 4 Using an Banbury mixer, (B) an ethylene copolymer containing an epoxy group and (C) an ethylene copolymer were melt-kneaded at 160 ° C. and extruded at 65 mmφ. Pellets having rubber elasticity were obtained by a machine. Further, using a twin screw extruder equipped with a 30 mmφ vent, the pellets obtained above, (A) the saturated polyester resin and (D) the polyfunctional compound were melt-kneaded at 260 ° C. to obtain polyester resin compositions, respectively. In addition, the component amount of each composition is as showing in Table 1. For each composition, at 140 ° C., 2
After drying for an hour, a test piece for measuring physical properties was prepared at a molding temperature of 260 ° C. and a mold temperature of 70 ° C. using a 5-ounce injection molding machine. Table 2 shows the results of MI, Izod impact strength, flexural modulus, and heat distortion temperature of the obtained test pieces.

[0034]

[Table 1]

[0035]

[Table 2]

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁷ Identification code FI C08L 23:08) (72) Inventor Kenzo Konari 5-1, Anesaki Kaigan, Ichihara-shi, Chiba Prefecture Sumitomo Chemical Co., Ltd. (56) Reference Document JP-A-3-122158 (JP, A) JP-A-62-153338 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 67/00-67/02

Claims (6)

(57) [Claims] (B) (A) 50 to 99% by weight of an ethylene unit, (b) Unsaturated carboxylic acid glycidyl ester unit or unsaturated carboxylic acid glycidyl ether, based on 100 parts by weight of a saturated polyester resin (A) Unit is 0.1 to 5
0% by weight, (c) 1 to 50 parts by weight of an epoxy group-containing ethylene copolymer containing 0 to 28 % by weight of ester units selected from ethylenically unsaturated compound units, (C) (a) 30 to 30% by weight of ethylene units (B) 1 to 50 parts by weight of an ethylene copolymer comprising 10 to 70 mol% of α-olefin units having 3 or more carbon atoms and 0 to 20 mol% of non-conjugated diene units; Compound containing at least two identical or different functional groups selected from the group consisting of a group, an amino group, a carboxylic anhydride group and a unit of the following formula (1) 0.0
An impact-resistant polyester resin composition comprising 1 to 20 parts by weight. (Wherein X and Y are both an oxygen atom or a sulfur atom,
Alternatively, one represents an oxygen atom and the other represents a sulfur atom. ) 2. The impact-resistant polyester resin composition according to claim 1, wherein the α-olefin of the ethylene copolymer (C) is propylene or 1-butene. 3. The impact-resistant polyester resin composition according to claim 1, wherein (D) the polyfunctional compound is a heterocyclic compound having a unit represented by the above formula (1). 4. The polyester resin composition according to claim 1, wherein (D) the polyfunctional compound is a dicarboxylic acid compound. 5. An impact-resistant polyester resin composition comprising the composition according to claim 1 and a filler. 6. A molded article obtained by molding the composition according to claim 1.