JPH07331040A - Polyester resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition remarkably increased in compatibility with a saturated polyester and a polycarbonate and remarkably improved in solvent resistance, weld strength and mechanical characteristics, especially impact resistance. CONSTITUTION:This polyester resin composition contains (A) 100 pts.wt. of a saturated polyester, (B) 5-70 pts.wt. of a polycarbonate, (C) 0.1-50 pts.wt. of a modified olefinic resin, especially having 0.3-1.0 residual ratio of the hydroxyl group and obtained by subjecting 100 pts.wt. of an olefinic resin to graft polymerization with 0.01-20 pts.wt. of an alpha,beta-unsaturated carboxylic acid ester having hydroxyl group and 0.01-50 pts.wt. of an aromatic vinyl compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester resin composition having excellent moldability, solvent resistance and mechanical properties, especially impact resistance.

[0002]

2. Description of the Related Art Saturated polyesters such as polyethylene terephthalate or polybutylene terephthalate are widely used in various fields as engineering plastics having excellent mechanical and physical properties. However, saturated polyesters have the drawback of poor impact resistance. In order to solve such a drawback of the saturated polyester, a method of melt-kneading a saturated polyester with a polycarbonate or a polycarbonate and a conjugated diene-vinyl monomer copolymer is known,
The compatibility of each of these components is poor, and sufficient impact resistance has not been obtained. Further, in order to solve this problem, a method of melt-mixing a saturated polyester or a polycarbonate with an epoxy group-containing ethylene copolymer and a polyolefin has been attempted, but even such a composition has not obtained sufficient properties.

[0003]

SUMMARY OF THE INVENTION In order to solve the above problems, the present invention improves the compatibility of saturated polyester, polycarbonate and olefin resin to improve moldability,
It is an object of the present invention to provide a polyester resin composition having excellent solvent resistance and mechanical properties, especially impact resistance.

[0004]

The inventors of the present invention have diligently studied for this reason. As a result, by blending a specific amount of a specific polycarbonate and a specific modified olefin resin with a saturated polyester, the impact resistance is remarkably increased. The present invention has been completed by finding that it is improved.

That is, the present invention provides the following components (A) to
A polyester resin composition containing (C) in the following compounding ratio. (A) 100 parts by weight of saturated polyester (B) 5 to 70 parts by weight of polycarbonate (C) 0.01 to 20 parts by weight of an α, β-unsaturated carboxylic acid ester monomer having a hydroxyl group and an aromatic vinyl compound of 0. 01 to 50 parts by weight is a modified olefin resin graft-polymerized on 100 parts by weight of an olefin resin 0.1 to 50 parts by weight. Particularly, the residual hydroxyl group ratio of the modified olefin resin is 0.3 to
The above polyester resin composition is 1.0.

The polyester resin composition of the present invention contains polycarbonate (B) in order to make use of the mechanical and physical properties of saturated polyester (A) and to improve impact resistance, and further a modified olefin resin. By blending (C), the compatibility between the saturated polyester and the polycarbonate is improved. When the modified polyolefin resin (C) is melt-mixed with the saturated polyester (A) and the polycarbonate (B), the respective components undergo transesterification, the saturated polyester and the polycarbonate are well compatibilized, and the impact resistance of the molded product is improved. Can be made.

Hereinafter, the composition of the present invention will be described in more detail. <Constituent Components> (1) Saturated Polyester (A) The saturated polyester (A) used in the present invention comprises an aromatic dicarboxylic acid such as terephthalic acid or naphthalenedicarboxylic acid or an ester-forming derivative thereof as an acid component, and a diol component. An aliphatic glycol such as ethylene glycol, tetramethylene glycol, hexamethylene glycol, cyclohexanediol, or bisphenol A or a divalent phenol, or a polycondensate or ester-forming derivative of ethylene glycol thereof is used. Typical examples of the saturated polyester (A) include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycyclohexane terephthalate, or a mixture thereof.

The saturated polyester used in the present invention has an intrinsic viscosity of 0.4 to 1.2 when measured at 23 ° C. using a mixed solvent of phenol and tetrachloroethane in a weight ratio of 1: 1.
It is preferably in the range of dl / g, particularly 0.5 to 1.0 dl / g. When it is less than 0.4 dl / g, the mechanical properties of the resin composition are not good, and when it exceeds 1.2 dl / g, the fluidity of the composition is extremely poor and the moldability is deteriorated.

(2) Polycarbonate (B) Examples of the polycarbonate (B) used in the present invention include aromatic polycarbonate, aliphatic polycarbonate, and aliphatic-aromatic polycarbonate. Among them, 4,4'-dioxydiallyl alkane-based polycarbonate represented by 4,4'-dihydroxydiphenyl-2,2'-propane (bisphenol A), 4,4 '
-A known one such as a dioxyhalogenated alkane-based polycarbonate can be used.

(3) Modified olefin resin (C) The modified olefin resin (C) used in the present invention comprises a hydroxyl group-containing α, β-unsaturated carboxylic acid ester monomer and an aromatic vinyl compound. It is obtained by graft polymerization with an olefin resin. Also, graft-polymerized α,
The ratio of the hydroxyl groups contained in the modified olefin resin to the total amount of the hydroxyl groups of the β-unsaturated carboxylic acid ester-based monomer, that is, the hydroxyl group residual rate is 0.3 to 1.0.
The range of is preferable. A specific method for measuring the residual ratio of hydroxyl groups will be described in the section of Examples below.

Examples of the α, β-unsaturated carboxylic acid ester monomer having a hydroxyl group for modifying the olefin resin include, for example, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, 2,3-dihydroxypropyl acrylate, 2
-Hydroxymethyl-3-hydroxypropyl methacrylate, 2-hydroxymethyl-3-hydroxypropyl acrylate, 2,2-dihydroxymethyl-3-hydroxypropyl methacrylate, 2,2-dihydroxymethyl-3-hydroxypropyl acrylate,

Methacrylic acid or acrylic acid ester of oligomer of ethylene glycol or propylene glycol having 4 to 40 carbon atoms, bis (2-hydroxyethyl) malate, bis (2-hydroxyethyl) fumarate, bis (2-hydroxypropyl) malate , Bis (2-hydroxypropyl) fumarate, bis (2,3
-Hydroxypropyl) malate, bis (2,3-hydroxypropyl) fumarate, bis (2-hydroxymethyl-3-hydroxypropyl) malate, bis (2-
Hydroxymethyl-3-hydroxypropyl) fumarate, bis (2,2-hydroxymethyl-3-hydroxypropyl) fumarate, bis (2,2-hydroxymethyl-3-hydroxypropyl) fumarate, C4-4
And maleic acid or fumaric acid ester of an oligomer of ethylene glycol or propylene glycol of 0.

The maleic acid or fumaric acid ester is not limited to the one in which two carboxyl groups are both esterified with a hydroxyalkyl group as described above.
Those in which only one is esterified can be exemplified as the similar monomer. The above unsaturated carboxylic acid esters can be used alone or in combination of two or more. Among these, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, methacrylic acid or acrylic acid ester of an oligomer of ethylene glycol or propylene glycol having 4 to 40 carbon atoms is preferable.

As the aromatic vinyl compound for modifying the olefin resin, styrene, α-methoxystyrene, methylstyrene, dimethylstyrene, 2,4,6-
Aromatic vinyl monomers such as trimethylstyrene, chlorostyrene, dichlorostyrene, bromostyrene, nitrostyrene, chloromethylstyrene, cyanostyrene, t-butylstyrene, vinylnaphthalene and the like can be mentioned. Of these, styrene, α-methylstyrene and methylstyrene are preferable. These may be used alone or in combination of two or more.

The olefin resin modified with an α, β-unsaturated carboxylic acid ester monomer and an aromatic vinyl compound is at least one α-olefin having 2 to 10 carbon atoms.
A polymer of a monomer composed of seeds, which preferably exhibits crystallinity at room temperature by X-ray diffraction, more preferably has a crystallinity of 20% or more and a melting point of 40 ° C. or more. . Further, this olefin resin needs to have a sufficient molecular weight as a molding resin at room temperature. For example, when propylene is the main component, JIS K675
Melt flow rate (hereinafter referred to as "MF
R ") is preferably 0.01 to 500 g / 10 min, more preferably 0.05 to 100 g / 10 min.

Examples of α-olefin which is a monomer of olefin resin include ethylene, propylene and butene-
1, pentene-1, hexene-1, 3-methylbutene-
1,4-methylpentene-1,3,3-dimethylpentene-1,3-methylhexene-1,4-methylhexene-1,4,4-dimethylhexene-1,5-methylhexene-1, allylcyclo Pentane, allylcyclohexane, allylbenzene, 3-cyclohexylbutene-1,
Vinylcyclohexane, 2-vinylbicyclo [2.2.
1] Heptane, heptene-1, octene-1, and the like, and one or more of these α-olefins can be used as a polymerization component.

Of the above, preferred α-olefins are ethylene, propylene, butene-1, pentene-
1, hexene-1,3-methylbutene-1,4-methylpentene-1,3-methylhexene-1 can be mentioned. Especially ethylene, propylene, butene-1,3-
Methylbutene-1 and 4-methylpentene-1 are more preferred. In addition, as other components, 4-methyl-1,4
-Hexadiene, 5-methyl-1,4-hexadiene,
Non-conjugated dienes such as 7-methyl-1,6-octadiene and 1,9-decadiene may be used as part of the polymerization component.

An olefin resin containing the above-mentioned α, β-unsaturated carboxylic acid ester monomer having a hydroxyl group and an aromatic vinyl compound and having a hydroxyl group residual ratio (measurement method described later) of 0.3 to.
The method of modifying to a range of 1.0 is not particularly limited, but, for example, an olefin resin, an α, β-unsaturated carboxylic acid ester monomer having a hydroxyl group, and an aromatic vinyl compound are allowed to coexist to produce an organic peroxide. There is a method of reacting in the presence or absence of a radical generator such as a substance, a method of irradiating ultraviolet rays or radiation, a method of contacting with oxygen or ozone, and the like.

The content of the α, β-unsaturated carboxylic acid ester monomer having a hydroxyl group introduced into the olefin resin is 0.01 to 100 parts by weight based on 100 parts by weight of the olefin resin.
20 parts by weight, preferably 0.05 to 10 parts by weight. If the content of the α, β-unsaturated carboxylic acid ester-based monomer having a hydroxyl group is less than 0.01 parts by weight, the impact resistance improving effect is small, and if it exceeds 20 parts by weight, the moldability is caused by gelation or the like. This is not preferable because it causes difficulties.

The content of the aromatic vinyl compound introduced into the olefin resin is 0.01 to 50 parts by weight, preferably 0.05 to 20 parts by weight, based on 100 parts by weight of the olefin resin. When the content of the aromatic vinyl compound is less than 0.01 parts by weight, the impact resistance improving effect is small, and when it exceeds 50 parts by weight, the appearance of the molded product may be deteriorated or the mechanical strength may be deteriorated, which is not preferable. . Moreover, the ratio of the α, β-unsaturated carboxylic acid ester monomer having a hydroxyl group to the aromatic vinyl compound is preferably in the range of 1:99 to 99: 1 by weight, more preferably 10:90 to 90. 1 to
The range is 0. If it is out of these ranges, the effect of improving impact resistance becomes small, which is not preferable.

The residual hydroxyl group ratio of the α, β-unsaturated carboxylic acid ester having a hydroxyl group graft-polymerized with the olefin resin (described later in the measuring method) is preferably in the range of 0.3 to 1.0, more preferably 0. It is in the range of 0.4 to 1.0. When the residual ratio of hydroxyl groups is less than 0.3, the improvement effect becomes small, which is not preferable. The above modified olefin resin is JI
MFR measured according to SK 7201 is 0.01
~ 200 g / 10 min is preferred, more preferably 0.1-1
It is 00g / 10 minutes.

<Blending Ratio of Constituent Components> The blending amount of the polycarbonate (B) is 5 to 70 parts by weight, preferably 5 to 50 parts by weight, more preferably 5 to 40 parts by weight based on 100 parts by weight of the saturated polyester (A). Parts by weight. If it is less than 5 parts by weight, the impact resistance improving effect is not sufficient, and if it exceeds 70 parts by weight, the solvent resistance is lowered, which is not preferable. The blending amount of the modified olefin resin (C) is 10% of the saturated polyester (A).
It is 0.1 to 50 parts by weight, preferably 0.5 to 40 parts by weight, and more preferably 1 to 30 parts by weight with respect to 0 parts by weight.
Parts by weight. If it is less than 0.1 part by weight, the impact resistance improving effect is not sufficient, and if it exceeds 50 parts by weight, the mechanical strength is remarkably lowered, which is not preferable.

<Production and Molding of Composition> The composition of the present invention is produced by an ordinary mixer, kneader or the like. That is, each component is put into a V-type blender, a ribbon mixer, a tumbler, or the like, uniformly mixed, and then melt-kneaded with an ordinary extruder such as a uniaxial or biaxial extruder, cooled, and then cut into pellets. At this time, some of the glass fibers and other components may be added from the middle of the extruder cylinder. Alternatively, a part of the components may be mixed and kneaded in advance, and the remaining components may be added and extruded. The modified olefin resin as the component (C) is preferably melt-kneaded in advance with a part of the component (A) and a part of the component (B) by the above method.

The polyester resin composition of the present invention may contain other components in addition to the above components (A), (B) and (C) within a range not impairing the object of the present invention. For example, an antioxidant, a weather resistance improver, a nucleating agent, a flame retardant, a slip agent, a plasticizer, a fluidity improver release agent, etc. can be used. Furthermore, adding organic / inorganic fillers, reinforcing agents, particularly glass fibers, mica, talc, wollastonite, potassium titanate, calcium carbonate, silica and the like to the resin composition,
Effective in improving rigidity, heat resistance, dimensional accuracy, dimensional stability, etc. For practical use, various colorants and their dispersants can also be used.

Further, addition of a rubber component, particularly styrene-butadiene copolymer rubber, styrene-isoprene copolymer rubber or hydrogenated products thereof; ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber. , Or their α, β-unsaturated carboxylic acid anhydride modified product, unsaturated glycidyl ester or unsaturated glycidyl ether modified product; or a copolymer of an unsaturated epoxy compound and ethylene, an unsaturated epoxy compound or ethylene and ethylene A copolymer or the like composed of a system unsaturated compound is effective for further improving the impact resistance of the composition. Further, other thermoplastic resin or thermosetting resin may be contained. The composition thus obtained can be easily molded by any method such as injection molding, extrusion molding, compression molding or rotational molding.

[0026]

EXAMPLES The present invention will be described in more detail below with reference to examples.

Reference Example 1: Production of Modified Olefin Resin-1 Homopolymer powder of propylene (MFR at 230 ° C. is 1
g / 10 minutes, melting point about 164 ° C.) 2,000 g, 2-hydroxyethyl methacrylate 60 g, styrene 40 g and t
After mixing 20 g of butyl peroxybenzoate with a super mixer, a cylinder temperature of 180 was obtained using a twin-screw extruder (manufactured by Japan Steel Works, trade name: TEX-30 type).
The mixture was kneaded under reduced pressure at a temperature of 250 ° C. and a screw rotation speed of 250 rpm to obtain modified olefin resin-1 pellets. 0.3 g of these pellets were completely dissolved in 20 ml of xylene at a temperature of 110 ° C., then poured into 150 ml of methanol to precipitate the product, and filtration and washing were repeated twice, followed by vacuum drying for purification. Olefin-based resin-1 ("C-
1 "). The content of 2-hydroxyethyl methacrylate of the purified olefin resin-1 obtained by the following method was measured by infrared spectroscopy (hereinafter, "IR
Method)) and the proton nuclear magnetic resonance method (hereinafter referred to as "NMR method") were 0.94%, and the residual hydroxyl group ratio was 0.72. Similarly, the styrene content of this purified product is 700 derived from monosubstituted benzene by IR method.
It was determined using the peak at cm ^-1 . The result was 0.80%.

Hydroxyl group residual ratio measuring method: (1) IR method: Purified modified olefin resin was molded into a film using a press, and an infrared spectroscopic spectrum was measured. From the absorption at 1724 cm ⁻¹ derived from carbonyl, The content of α, β-unsaturated carboxylic acid ester was quantified from a calibration curve prepared in advance. (2) NMR method: 50 mg of purified modified olefin resin
Was dissolved in about 2 ml of o-dichlorobenzene under heating at 130 ° C., a sample was prepared by using deuterated benzene as a standard substance, and an NMR spectrum was measured. The content of α, β-unsaturated carboxylic acid ester was quantified using the absorption of methylene (chemical shift: 4.2 ppm) bound thereto.
Using the ratio of the contents obtained by these two kinds of measuring methods, the residual ratio of hydroxyl groups was calculated from the following formula. Hydroxyl group residual rate = (content% determined by NMR method) / (IR
Content% obtained by the method)

Reference Example 2: Production of Modified Olefin Resin-2 The procedure of Reference Example 1 was repeated except that 100 g of 2-hydroxyethylmethacrylate and 100 g of styrene were used and analyzed. The hydroxyl group residual ratio of this product was 0.68. The obtained resin is modified olefin resin-2 ("C
-2 "is displayed).

Reference Example 3: Production of Modified Olefin Resin-3 2,000 g of the same propylene homopolymer powder as used in Reference Example 1, 100 g of 2-hydroxyethyl methacrylate and 10 g of t-butyl peroxybenzoate.
Was mixed with a super mixer, and then manufactured under the same conditions as in Reference Example 1 and analyzed. The residual ratio of hydroxyl groups was 0.2.
The obtained resin is modified olefin resin-3 ("C-3").
Is displayed).

Examples 1 to 9 and Comparative Examples 1 to 7 The components used are as follows. Component (A) A-1: polyethylene terephthalate (intrinsic viscosity 0.7
dl / g, manufactured by Kanebo, product name: Bellpet PBK-1) A-2: polybutylene terephthalate (manufactured by Mitsubishi Kasei Co.,
Trade name: Novador 5010) Component (B) Polycarbonate (manufactured by Mitsubishi Gas Chemical Co., Inc., trade name: Iupilon S2000) Component (C) C-1: manufactured in Reference Example 1 C-2: manufactured in Reference Example 2 C-3: manufactured in Reference Example 3 C-4: ethylene-vinyl acetate-glycidyl methacrylate copolymer (Sumitomo Chemical Co., Ltd., trade name: Bond First 2B) glass fiber (Nippon Electric Glass Co., Ltd., trade name: T123H)

The respective components shown in Table 1 were mixed in a mixing ratio shown in the same table using a 10 L tumbler, and then mixed using a twin-screw extruder (manufactured by Japan Steel Works, trade name: TEX-30 type). Cylinder set temperature 270 ℃, screw speed 2
Melt kneading was performed at 50 rpm and a discharge rate of 20 kg / h, and pellets were obtained after cooling.

[0033]

[Table 1]

The pellets were dried at 130 ° C. for 5 hours,
6 oz (170 g) injection molding machine (Nippon Steel Works, N
-100BII) is used, and the cylinder set temperature is 275.
A molding test piece was obtained at a mold temperature of 90 ° C. Measurement of tensile strength and Izod (non-notch) impact strength is JIS K
7113 and 7110.

The weld tensile strength was measured by using a mold having gates at both ends of the test piece, forming a test piece molded so as to form a resin joint at the center, and measuring the tensile strength in the same manner as above. The solvent resistance was evaluated by visually observing the state of crack generation in a sample in which a test piece for measuring Izod impact strength was immersed in carbon tetrachloride for 1 week, and evaluated in the following three stages. ◯: No cracks occurred Δ: Slight cracks occurred ×: Cracks occurred The above results are shown in Table 2.

[0036]

[Table 2]

[0037]

The polyester resin composition of the present invention promotes transesterification of polyester and polycarbonate by using the modified olefin resin as an auxiliary agent, increases compatibility, improves solvent resistance and weld strength, and improves mechanical properties. , Especially the impact resistance is dramatically improved.

Claims (2)

[Claims] 1. A polyester resin composition containing the following components (A) to (C) in the following compounding ratio. (A) 100 parts by weight of saturated polyester (B) 5 to 70 parts by weight of polycarbonate (C) 0.01 to 20 parts by weight of an α, β-unsaturated carboxylic acid ester monomer having a hydroxyl group and an aromatic vinyl compound of 0. 01-50 parts by weight is a modified olefin resin obtained by graft polymerization of 100 parts by weight of olefin resin 0.1-50 parts by weight 2. The polyester resin composition according to claim 1, wherein the modified olefin resin has a hydroxyl group residual ratio of 0.3 to 1.0.