JP3311176B2 - 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 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 and polybutylene terephthalate are widely used in various fields as engineering plastics having excellent mechanical and physical properties. However, saturated polyesters have the disadvantage of poor impact resistance.

[0003] In order to solve such a drawback of the saturated polyester, there is known a method of melt-kneading a saturated polyester with a polycarbonate or a polycarbonate and a conjugated diene-vinyl monomer copolymer. Bad, sufficient impact resistance was not obtained.
Further, in order to solve this problem, a method of melt-mixing an epoxy group-containing ethylene copolymer and a polyolefin with a saturated polyester or polycarbonate has also been attempted, but sufficient properties have not been obtained with such a composition.

[0004]

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

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies, and as a result, a specific amount of a specific polycarbonate, a specific modified olefin resin, and a specific metal organic carboxylate have been added to a saturated polyester. The inventor has found that the impact resistance is remarkably improved by adding the compound, and the present invention has been completed.

That is, the present invention provides the following components (A) to
It is a polyester resin composition containing (D) in the following compounding ratio. (A) 100 parts by weight of a saturated polyester (B) 5 to 70 parts by weight of a polycarbonate (C) 100 to 100 parts by weight of an olefin-based resin, 0.01 to 20 of an α, β-unsaturated carboxylic acid ester-based monomer having a hydroxyl group A modified olefin resin obtained by subjecting a weight part and an aromatic vinyl compound to 0.01 to 50 parts by weight to a graft polymerization step. 0.1 to 50 parts by weight (D) Organic carboxylate of a metal selected from Group 1 a and Group 2 a of the periodic table 0.05 to 4 parts by weight

[0007] In particular, the above polyester resin composition wherein the modified olefin-based resin has a residual hydroxyl group ratio (described later by a measuring method) of 0.3 to 1.0.

[0008] The polyester resin composition of the present invention incorporates a polycarbonate (B) in order to make use of the mechanical and physical properties of the saturated polyester (A) and to improve impact resistance, and further comprises a modified olefin resin. By blending (C) and a metal organic carboxylate (D), the compatibility between the saturated polyester and the polycarbonate is improved.

When the modified polyester resin (C) and the metal organic carboxylate (D) are melt-mixed with the saturated polyester (A) and the polycarbonate (B), the respective components are transesterified, and the saturated polyester and the polycarbonate are mixed. Good compatibility and improved impact resistance of the molded product. By further adding the metal organic carboxylate (D) to the modified olefin-based resin (C), the saturated polyester and the polycarbonate can be more favorably compatible, and the mechanical strength can be further improved. .

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 uses an aromatic dicarboxylic acid such as terephthalic acid or naphthalenedicarboxylic acid or an ester-forming derivative thereof as an acid component. As the diol component, aliphatic glycols or dihydric phenols such as ethylene glycol, tetramethylene glycol, hexamethylene glycol, cyclohexanediol and bisphenol A, or polycondensates or ester-forming derivatives thereof such as ethylene glycol are used. Representative examples of the saturated polyester (A) include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycyclohexane terephthalate, and mixtures thereof.

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

(2) Polycarbonate (B) Examples of the polycarbonate (B) used in the present invention include aromatic polycarbonates, aliphatic polycarbonates, and aliphatic-aromatic polycarbonates. Among them, 4,4'-dioxydiallylalkane-based polycarbonate represented by 4,4'-dihydroxydiphenyl-2,2'-propane (bisphenol A), 4,4 '
-A known material 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 an α, β-unsaturated carboxylic acid ester monomer having a hydroxyl group and an aromatic vinyl compound. It is obtained by graft polymerization of an olefin resin. In addition, α,
The ratio of the hydroxyl group contained in the modified olefin resin to the total amount of the hydroxyl group of the β-unsaturated carboxylic acid ester monomer, that is, the residual ratio of the hydroxyl group is 0.3 to 1.0.
Are preferred. A specific method for measuring the residual ratio of hydroxyl groups will be described later in the Examples section.

Examples of the α, β-unsaturated carboxylic acid ester monomer having a hydroxyl group for modifying the olefin resin include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, and the like. 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) malate, bis (2,2-hydroxymethyl-3-hydroxypropyl) fumarate, having 4 to 4 carbon atoms
And maleic or fumaric acid esters of ethylene glycol or propylene glycol oligomers.

The maleic acid or fumaric acid ester is not limited to 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 similar monomers.

The above unsaturated carboxylic esters can be used alone or in combination of two or more. Of these, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and methacrylic acid or acrylic acid esters of ethylene glycol or propylene glycol oligomers having 4 to 40 carbon atoms are preferred.

As the aromatic vinyl compound for modifying the olefin resin, styrene, α-methoxystyrene, methylstyrene, dimethylstyrene, 2,4,6-
Examples thereof include aromatic vinyl monomers such as trimethylstyrene, chlorostyrene, dichlorostyrene, bromostyrene, nitrostyrene, chloromethylstyrene, cyanostyrene, t-butylstyrene, and vinylnaphthalene. Among them, styrene, α-methylstyrene and methylstyrene are preferred. These can be used alone or in combination of two or more.

The olefin resin modified with the α, β-unsaturated carboxylic acid ester monomer and the aromatic vinyl compound has at least one α-olefin having 2 to 10 carbon atoms.
It is preferably a polymer of a monomer composed of seeds, which shows a degree of crystallinity at room temperature by X-ray diffraction, and more preferably has a degree of crystallinity of 20% or more and a melting point of 40 ° C. or more. is there. In addition, this olefin-based resin needs to have a sufficient molecular weight as a molding resin at normal 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 the α-olefin which is a monomer of the 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 or octene-1 and the like, and one or more of these α-olefins can be used as a polymerization component.

Among the above preferred α-olefins, ethylene, propylene, butene-1, pentene-
1, hexene-1, 3-methylbutene-1, 4-methylpentene-1, and 3-methylhexene-1. In particular, ethylene, propylene, butene-1,3-
Methylbutene-1,4-methylpentene-1 is more preferred.

Further, as another component, 4-methyl-
Non-conjugated dienes such as 1,4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene and 1,9-decadiene may be used as a part of the polymerization component.

The above-mentioned α, β-unsaturated carboxylic acid ester monomer having a hydroxyl group and an aromatic vinyl compound are used to prepare an olefin resin, and the residual ratio of the hydroxyl group (described later) is 0.3 to 0.3.
The method of modification to the range of 1.0 is not particularly limited, but, for example, an olefin-based resin, an α, β-unsaturated carboxylic acid ester-based monomer having a hydroxyl group, and an aromatic vinyl compound are allowed to coexist and an organic peroxide is used. 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, or a method of contacting with oxygen or ozone.

In modifying the olefin resin, the amount of the α, β-unsaturated carboxylic acid ester monomer having a hydroxyl group to be charged is 0.0 to 100 parts by weight of the olefin resin.
It is 1 to 20 parts by weight, preferably 0.05 to 10 parts by weight. If the amount of the α, β-unsaturated carboxylic acid ester monomer having a hydroxyl group is less than 0.01, the effect of improving the impact strength is small, and if it exceeds 20 parts by weight, there is a problem in the formability due to gelation and the like. Is not preferred.

The amount of the aromatic vinyl compound to be introduced into the olefin resin is 0.01 to 50 parts by weight, preferably 0.05 to 20 parts by weight, per 100 parts by weight of the olefin resin.
Parts by weight. When the charged amount of the aromatic vinyl compound is 0.01
If it is less than 50 parts by weight, the effect of improving the impact strength is small, and if it exceeds 50 parts by weight, the appearance of the molded product may be deteriorated or the mechanical strength may be undesirably reduced. 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. 10
Range. Outside of these ranges, the effect of improving impact resistance is undesirably reduced.

The α, β-unsaturated carboxylic acid ester having a hydroxyl group graft-polymerized to the olefin resin has a hydroxyl group residual ratio (described later in the measuring method) of preferably from 0.3 to 1.0, more preferably from 0 to 1.0. 0.4 to 1.0. If the residual ratio of hydroxyl groups is less than 0.3, the effect of improvement is undesirably small.

The above-mentioned modified olefin resin is JIS
MFR measured according to K 7201 is 0.01 to 2
00g / 10 min, more preferably 0.1 to 1
00 g / 10 minutes.

(4) Organic Carboxylates of Metals (D) The carboxylic acids used in the organic carboxylate of metals selected from Groups 1a and 2a of the Periodic Table used in the present invention include aliphatic carboxylic acids. Copolymers of carboxylic acids or aromatic carboxylic acids or α, β-unsaturated carboxylic acids are mentioned. Examples of the aliphatic and aromatic carboxylic acids include lauric acid, stearic acid, montanic acid, oleic acid, arachinic acid, carnaubaic acid, lignoceric acid, cerotic acid, betroceric acid, erucic acid, linoleic acid, benzoic acid, terephthalic acid and the like. Examples of the copolymer of an α, β-unsaturated carboxylic acid include a copolymer of an α-olefin and an α, β-unsaturated carboxylic acid. Here, the α-olefin includes ethylene and propylene, and the α, β-unsaturated carboxylic acid includes acrylic acid, methacrylic acid, maleic acid, itaconic acid and the like. Examples of the metal species include lithium, sodium, potassium, barium, magnesium, calcium, strontium, and the like.

Preferred examples of the organic carboxylate (D) include sodium stearate, calcium montanate, sodium salt of ethylene-methacrylic acid copolymer and the like.

(5) Additional Component The polyester resin composition of the present invention comprises the above component (A),
In addition to (B), (C) and (D), other components can be contained within a range not to impair the object of the present invention. For example, 0.5 to 3% by weight of an antioxidant, a weather resistance improver, a nucleating agent, a flame retardant, a slip agent, and the like; 3 to 15% by weight of a plasticizer, a fluidity improver, a release agent, and the like; Catalysts such as 2-ethylhexoxy) titanium and dibutyltin oxide can be used as additional components. Furthermore, the addition of 5 to 40% by weight of an organic / inorganic filler and a reinforcing agent, particularly glass fiber, mica, talc, wollastonite, potassium titanate, calcium carbonate, silica, etc. to the resin composition is rigid, heat-resistant. It is effective in improving the properties, dimensional accuracy, dimensional stability, and the like. For practical use, various colorants and their dispersants are also used in amounts of 1 to 10
It can be used in proportions by weight.

Further, other thermoplastic resins and thermosetting resins may be contained.

<Blending Ratio of Constituent Components> The blending ratio of the polycarbonate (B) is 5 to 70 parts by weight, preferably 5 to 50 parts by weight, more preferably 10 to 40 parts by weight with respect to 100 parts by weight of the saturated polyester (A). Parts by weight. If the amount is less than 5 parts by weight, the effect of improving the impact resistance is not sufficient, and if it exceeds 70 parts by weight, the solvent resistance is undesirably reduced.

The mixing ratio of the modified olefin resin (C) is as follows:
0.1 to 100 parts by weight of the saturated polyester (A)
It is 50 parts by weight, preferably 0.5 to 40 parts by weight, more preferably 1 to 30 parts by weight. If the amount is less than 0.1 part by weight, the effect of improving the impact resistance is not sufficient, and if it exceeds 50 parts by weight, the decrease in mechanical strength is extremely undesirable.

The compounding ratio of the organic carboxylate (D) is 0.05 to 4 with respect to 100 parts by weight of the saturated polyester (A).
Parts by weight, preferably 0.1 to 3 parts by weight. 0.05
If the amount is less than 5 parts by weight, the effect of the present invention is not exhibited. If the amount exceeds 4 parts by weight, the mechanical properties of the composition of the present invention are significantly reduced.

<Production and Molding of Composition> The production of the composition of the present invention is carried out by a usual mixer or kneader. That is, each component is charged into a V-type blender, a ribbon mixer, a tumbler or the like, uniformly mixed, melt-kneaded with a usual single-screw or twin-screw extruder, cooled, and then cut into pellets. At this time, some of the glass fibers and other components may be added in the middle of the extruder cylinder. Alternatively, a part of the components may be previously mixed and kneaded, and the remaining components may be added and extruded.

It is preferable that the modified olefin resin (C) and the organic carboxylate (D) are previously melt-kneaded with a part of the component (A) and a part of the component (B) by the above method.

The resin composition thus obtained can be easily molded by any method such as injection molding, extrusion molding, compression molding or rotational molding.

[0039]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples.

REFERENCE EXAMPLE 1 Production of Modified Olefin Resin-1 Propylene homopolymer powder (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-butyl peroxybenzoate (20 g) were mixed by a super mixer, and then a twin screw extruder (manufactured by Nippon Steel Works,
(Trade name: TEX-30), cylinder temperature 1
The mixture was kneaded under reduced pressure at 80 ° C. and a screw rotation speed of 250 rpm to obtain pellets of modified olefin resin-1. 0.3 g of the pellet was completely dissolved in 20 ml of xylene at a temperature of 110 ° C., and then poured into 150 ml of methanol to precipitate the product. Olefin resin-1 was obtained. The content of 2-hydroxyethyl methacrylate in the purified olefin resin-1 determined by the following method was determined by infrared spectroscopy (hereinafter referred to as "IR method") of 1.3.
1% by weight, 0.94% by weight in a proton nuclear magnetic resonance method (hereinafter referred to as “NMR method”), and the residual ratio of hydroxyl groups was 0.7%.
It was 2.

Similarly, the styrene content of this purified product was determined by IR
It was determined using a peak at 700 cm ^-1 derived from monosubstituted benzene according to the method. The result was 0.80% by weight.

Method for measuring residual ratio of hydroxyl groups: (1) IR method: A purified modified olefin resin is formed into a film by using a press, and an infrared spectrum is measured to determine the absorption at 1,724 cm ^-1 derived from carbonyl. Thus, the content of α, β-unsaturated carboxylic acid ester was quantified from a calibration curve prepared in advance.

(2) NMR method: 50 mg of the purified modified olefin resin was added to about 2 ml of o-dichlorobenzene at 130 ° C.
A sample was prepared using heavy benzene as a standard substance, and its NMR spectrum was measured. The methylene bound to the hydroxyl group (chemical shift: 3.7 ppm) and the methylene bound to it (chemical shift: 4.2 ppm) ) Was used to determine the content of α, β-unsaturated carboxylic acid ester.

Using the ratio of the contents obtained by these two kinds of measuring methods, the residual ratio of hydroxyl groups was determined from the following equation. Hydroxyl residue rate = (content% determined from NMR) / (content% determined from IR)

Reference Example 2 Production of Modified Olefin Resin-2 A resin was produced and analyzed under the same conditions as in Reference Example 1, except that 100 g of 2-hydroxyethyl methacrylate and 100 g of styrene were used. The residual ratio of the hydroxyl group was 0.68. The obtained resin is referred to as a modified olefin resin-2.

Examples 1 to 10 and Comparative Examples 1 to 3 The components used are as follows. Component (A) A-1: polyethylene terephthalate (manufactured by Kanebo Co., trade name: Bellpet PBK-1, intrinsic viscosity measured at 23 ° C. in a 1: 1 mixture of phenol and tetrachloroethane: 0.7 dl / g) A-2) Polybutylene terephthalate (manufactured by Mitsubishi Kasei Corporation,
Product name: Novador 5010) Component (B) Polycarbonate (Mitsubishi Engineering Plastics, trade name: Iupilon S2000) Component (C) C-1: Modified olefin resin-1 (Reference Example 1) C-2: Modified olefin resin -2 (Reference Example 2) Component (D) D-1: Sodium stearate D-2: Sodium salt of ethylene-methacrylic acid copolymer (trade name: Himilan 1707, manufactured by DuPont Mitsui)

Each of the components shown in Table 1 was mixed in the mixing ratio shown in the table using a 10 L tumbler, and then mixed using a twin-screw extruder (trade name: TEX-30, manufactured by Nippon Steel Works, Ltd.). Cylinder set temperature 270 ° C, screw rotation speed 2
The mixture was melted and kneaded at 50 rpm at a discharge rate of 20 kg / h. After cooling, pellets were obtained.

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

The weld strength was measured in the same manner as described above, using a mold having gates at both ends of the test piece, producing a test piece having a resin joint at the center, and measuring the tensile strength.

[0050] The Izod specimen was immersed in carbon tetrachloride for one week, and the sample was visually evaluated for the occurrence of cracks, and the solvent resistance was evaluated on the following three levels. 〇: No cracking △: Slight cracking ×: Cracking occurred

Table 2 shows the above results.

[0052]

[Table 1]

[0053]

[Table 2]

[0054]

According to the polyester resin composition of the present invention, the ester exchange between the polyester and the polycarbonate is promoted by using the modified olefin resin (C) and the metal organic carboxylate (D) as assistants, and the compatibility is increased. In addition, the weld strength is improved and the mechanical properties are improved. In particular, by blending the metal organic carboxylate (D), the compatibility is further increased and the mechanical strength is improved.

Claims (2)

(57) [Claims] 1. A polyester resin composition containing the following components (A) to (D) at the following compounding ratio. (A) 100 parts by weight of a saturated polyester (B) 5 to 70 parts by weight of a polycarbonate (C) 100 to 100 parts by weight of an olefin-based resin contains 0.01 to 20 of an α, β-unsaturated carboxylate-based monomer having a hydroxyl group. Parts by weight of a modified olefin-based resin obtained by subjecting an aromatic vinyl compound to 0.01 to 50 parts by weight in a graft polymerization step 0.1 to 50 parts by weight (D) Periodic Table Group 1 a and 2 Organic carboxylate of a metal selected from group a 0.05 to 4 parts by weight 2. The polyester resin composition according to claim 1, wherein the modified olefin resin has a residual hydroxyl group ratio of 0.3 to 1.0.