JP2001123042A - Ester type thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide ester type thermoplastic resin compositions having excellent impact resistance with reduced deterioration of the properties due to residence at high temperatures. SOLUTION: The ester type thermoplastic resin compositions having excellent impact resistance and a reduction in temperature of deflection under load of <=5 deg.C when retained at >=200 deg.C for 10 minutes are obtained by incorporating (C) 0.5-15 pts.wt. elastic polymer having an epoxy group in the molecule and (D) 0-15 pts.wt. elastic polymer free of epoxy group in the molecule into 100 pts.wt. resin composition comprising (A) 95-5 wt.% aromatic polycarbonate resin and (B) 5-95 wt.% aromatic polyester resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ester-based thermoplastic resin composition having excellent impact resistance with little deterioration in physical properties due to residence at a high temperature.

[0002]

2. Description of the Related Art A resin composition obtained by blending an ester resin, for example, a blend composition of an aromatic polycarbonate resin and an aromatic polyester resin, has a high heat resistance, a high dimensional stability and a high aromatic polyester content. It has the characteristics of resin's chemical resistance and excellent moldability by blending, and is widely used for electric and electronic parts, automobile parts and the like.

When a plurality of ester resins are melt-kneaded in producing this ester-based resin blend composition, a polymerization catalyst remaining in the resin accelerates the transesterification reaction, and causes coloring of the resin, lowering of heat deformation temperature, Problems such as a remarkable increase in fluidity occur.

To solve these problems, Japanese Patent Laid-Open Publication No.
JP-A-111956 proposes to deactivate a polymerization catalyst remaining in a polyester resin by blending a phosphoric ester-based or phosphite-based phosphorous stabilizer.

However, since the thermal stability of the phosphorus-based stabilizer itself is not sufficient, the decomposition product of the phosphorus-based stabilizer promotes the hydrolysis of the carbonate bond of the aromatic polycarbonate resin or the ester bond of the polyester resin,
There is a possibility that problems such as molding difficulty due to an increase in fluidity and a decrease in load deflection temperature may occur.

[0006]

An object of the present invention is to provide an ester-based thermoplastic resin composition having a low impact deflection temperature and excellent impact resistance even after stagnation at a high temperature such as during injection molding. With the goal.

The inventors of the present invention have conducted intensive studies to achieve the above object. As a result, an aromatic polycarbonate resin, an aromatic polyester resin, an elastic polymer containing an epoxy group in the molecule, and an epoxy resin in the molecule were used. By blending an elastic polymer that is not included in the above, it is possible to obtain an ester-based thermoplastic resin composition having excellent impact resistance with a small decrease in the deflection temperature under load due to stagnation during heat processing such as injection molding. And completed the present invention.

[0008]

[Means for Solving the Problems] That is, the present invention provides (A)
95 to 5% by weight of an aromatic polycarbonate resin, and
(C) 0.5 to 15 parts by weight of an elastic polymer containing an epoxy group in a molecule, based on 100 parts by weight of a resin composition comprising 5 to 95% by weight of an aromatic polyester resin, and
(D) Elastic polymers 0 to 1 containing no epoxy group in the molecule
A composition comprising 5 parts by weight, wherein a decrease in the deflection temperature under load when heated and held at a temperature of 200 ° C. or more for 10 minutes during heating such as injection molding is within 5 ° C. The present invention provides an ester-based thermoplastic resin composition having excellent impact resistance.

[0009]

DETAILED DESCRIPTION OF THE INVENTION The component (A) aromatic polycarbonate resin used in the present invention will be described. The aromatic polycarbonate resin in the present invention has the following formula

[0010]

Embedded image

(Each R represents phenylene, halogen-substituted phenylene or alkyl-substituted phenylene having 1 to 20 carbon atoms, A and B each represent a hydrogen atom, a hydrocarbon having 1 to 12 carbon atoms not containing aliphatic unsaturation, or And a group forming a cycloalkane group with adjacent carbon atoms).

In the present invention, an aromatic polycarbonate resin obtained by a usual production method can be used. As a method for producing a normal aromatic polycarbonate resin, there are a method of producing a polycarbonate by reacting diphenol and phosgene (phosgene method) and a method of transesterifying diester carbonate and diphenols (ester exchange method). Can be used in the present invention.

Here, diphenols usable as raw materials for the aromatic polycarbonate resin include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, and 2,2-bis (4-hydroxyphenyl) butane. Screw (4
-Hydroxyphenyl) -4-methylpentane, 4,4
'-Dihydroxy-2,2,2, -triphenylethane, 2,2-bis (4-hydroxyphenyl) octane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2 -Bis (4-hydroxy-
3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-isopropylphenyl) propane, 2,
2-bis (4-hydroxy-3-secondarybutylphenyl) propane, 2,2-bis (4-hydroxy-3
-Tert-butylphenyl) propane and the like. Among them, 2,2-bis (4-hydroxyphenyl) propane is preferable. Further, two or more of the above-mentioned diphenols may be used.

Examples of the carbonic acid diester used in the transesterification method include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (biphenyl) carbonate, diethyl carbonate, dimethyl carbonate, dibutyl carbonate. Carbonate and dicyclohexyl carbonate. Of these, diphenyl cartonate is particularly preferred.

The aromatic polycarbonate resin used in the present invention may be any of those produced by the phosgene method or the transesterification method. However, the transesterification between the aromatic polycarbonate resin and the aromatic polyester resin may occur. From the viewpoint of ease, the terminal hydroxyl group concentration of the aromatic polycarbonate resin is preferably 10 mol% or less.

The terminal hydroxyl group concentration is determined by 13C-NMR using a measurement mode gated coupling.
It can be measured from the ratio between 14.80 ppm and 129.50 ppm.

Next, the component (B) used in the present invention
The aromatic polyester resin will be described. The aromatic polyester resin is a polyester having an aromatic ring in a chain unit of a polymer, and is a polycondensate or a copolymer mainly composed of an aromatic dicarboxylic acid and a diol (or an ester-forming derivative thereof).

The aromatic dicarboxylic acids which can be used as a raw material for the aromatic polyester resin include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, naphthalene-2,5-dicarboxylic acid,
Naphthalene-2,6-dicarboxylic acid, biphenyl 3,3
'-Dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, diphenylether-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, diphenylisopropylidene-4,4'dicarboxylic acid, 1,2
-Bis (phenoxy) ethane-4,4'-dicarboxylic acid, anthracene-2,5-dicarboxylic acid, p-terphenylene-4,4'-dicarboxylic acid, pyridine-2,5
-Dicarboxylic acid and the like, among which terephthalic acid is preferable. These aromatic dicarboxylic acids may be used as a mixture of two or more kinds.

The diol component includes ethylene glycol, propylene glycol, butylene glycol,
Hexylene glycol, neopentyl glycol, 2-
Examples thereof include aliphatic diols such as methylpropane-1,3-diol, diethylene glycol, and triethylene glycol; and alicyclic diols such as cyclohexane-1,4-dimethanol. Among them, butylene glycol and ethylene glycol are preferable. These diols can be used alone or in combination of two or more.

Specific examples of the aromatic polyester resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene aphthalate, and polybutylene naphthalate. Of these, polyethylene terephthalate and polybutylene terephthalate are preferred.

Next, the component (C) used in the present invention
Is described. The elastic polymer having an epoxy group in the molecule of the component (C) refers to a polymer having an epoxy group in its structure, or a polymer having an epoxy group in its structure and a polyolefin resin or a vinyl aromatic polymer. Means a copolymer of

Examples of the polymer having an epoxy group include glycidyl ethers and glycidyl esters, and polymers obtained by epoxidizing a hydrocarbon polymer having an unsaturated bond in its structure.

Here, glycidyl ethers and glycidyl esters include, for example, glycidyl acrylate, glycidyl methacrylate and allyl glycidyl ether. Examples of the hydrocarbon polymer having an unsaturated bond in its structure include: , Polybutadiene and polyisoprene.

As the polyolefin resin, for example,
Α-olefin homopolymers such as polyethylene, polypropylene, polybutene-1, and poly-4-methylpentene-1; ethylene-vinyl acetate copolymer; and ethylene-propylene copolymer.

Examples of the vinyl-based aromatic polymer include polymers such as styrene, methylstyrene, vinyltoluene, ethylvinyltoluene, and chlorostyrene.

Among these elastic polymers containing an epoxy group in the molecule, preferred are epoxidized diene-based block copolymers, especially vinyl-based aromatic polymers and diene-based polymers, or hydrogen-containing polymers. An epoxidized block copolymer comprising the added diene polymer is preferred.

The term "diene-based block copolymer" as used herein means a block copolymer composed of a polymer block mainly composed of a vinyl aromatic compound and a polymer block mainly composed of a conjugated diene compound. The weight ratio between the group III compound and the conjugated diene compound (the weight ratio of the block copolymer) is 5/95 to 70/30, particularly 10/90 to 70/30.
A weight ratio of 60/40 is preferred. The number average molecular weight of the block copolymer used in the present invention is from 5,000 to 1,0.
00,000, preferably 10,000-800,00
0 and the molecular weight distribution [weight average molecular weight (Mw)]
(Mw / Mn)] and the number average molecular weight (Mn) is 10
It is as follows. The molecular structure of the block copolymer may be linear, branched, radial, or any combination thereof.

For example, XYX, YXYX,
It is a vinyl aromatic compound (X) block-conjugated diene compound (Y) block copolymer having a structure such as (XY-) 4Si or XYXYX. And at least one vinyl aromatic compound-conjugated diene compound block copolymer selected from the group consisting of: Further, the unsaturated bond of the conjugated diene compound of the diene-based block copolymer may be partially hydrogenated.

Examples of the vinyl aromatic compound constituting the diene block copolymer include styrene, α-methylstyrene, vinyltoluene, p-tertiary butylstyrene, divinylbenzene, p-methylstyrene, 1,1-
One or more of diphenylstyrene and the like can be selected, and among them, styrene is preferable. As the conjugated diene compound, for example, butadiene, isoprene,
1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, phenyl-1,3-butadiene, etc.
A species or two or more species are selected, and among them, butadiene, isoprene and a combination thereof are preferred.

As a method for producing the block copolymer used in the present invention, any production method having the above-mentioned structure can be adopted. For example,
23798, JP-B-47-3252, JP-B-48-
No. 2423, JP-A-51-33184, JP-B-46-
No. 32415, JP-A-59-166518, Japanese Patent Publication No. Sho 4
Nos. 9-36957, JP-B-43-17979, JP-B-46-32415, JP-B-56-28925, and the like. A compound-conjugated diene compound block copolymer can be synthesized. Further, hydrogenation in an inert solvent in the presence of a hydrogenation catalyst by a method described in JP-B-42-8704, JP-B-43-6636, or JP-A-59-133203, The partially hydrogenated block copolymer used in the present invention can be synthesized.

The elastic polymer having an epoxy group in the molecule in the present invention can be obtained by reacting the above-mentioned block copolymer with an epoxidizing agent such as hydroperoxides and peracids in an inert solvent. it can. As the peracids, formic acid, peracetic acid, perbenzoic acid, trifluoroperacetic acid and the like can be used. Of these, peracetic acid is a preferred epoxidizing agent because it is industrially produced in large quantities, is available at low cost, and has high stability. Hydroperoxides include hydrogen peroxide, tertiary butyl hydroperoxide, cumene peroxide and the like.

At the time of epoxidation, a catalyst can be used if necessary. For example, in the case of peracid, an alkali such as sodium carbonate or an acid such as sulfuric acid can be used as a catalyst. Also,
In the case of hydroperoxides, a catalytic effect can be obtained by using a mixture of tungstic acid and caustic soda with hydrogen peroxide, an organic acid with hydrogen peroxide, or molybdenum hexacarbonyl with tertiary butyl peroxide.

There is no strict limit on the amount of epoxidizing agent,
The optimal amount in each case will depend on variables such as the particular epoxidizing agent used, the degree of epoxidation desired, the particular block copolymer used, and the like.

As the inert solvent, the viscosity of the raw material is reduced,
It can be used for the purpose of stabilization by dilution of an epoxidizing agent, and in the case of peracetic acid, aromatic compounds, ethers, esters and the like can be used. Particularly preferred solvents are hexane, cyclohexane, toluene, benzene, ethyl acetate, carbon tetrachloride and chloroform.

The epoxidation reaction conditions are not strictly limited. The reaction temperature range that can be used is determined by the reactivity of the epoxidizing agent used. For example, for peracetic acid,
70 ° C. is preferable. When the temperature is lower than 0 ° C., the reaction is slow.
If it exceeds, decomposition of peracetic acid occurs. No special operation of the reaction mixture is required. For example, the mixture may be stirred for 2 to 10 hours. Isolation of the selected epoxidized diene-based block copolymer can be carried out by a suitable method, for example, a method of precipitating with a poor solvent, a method of pouring the reaction mixture into hot water with stirring and distilling off the solvent, and a direct removal method. It can be performed by a solvent method or the like.

The epoxy equivalent of the obtained epoxidized (hydrogenated) diene block copolymer is preferably from 320 to 8
000.

Next, the component (D) of the elastic polymer containing no epoxy group in the molecule will be described.

The elastic polymer having no epoxy group in the molecule used in the present invention is mainly used for imparting impact resistance to the composition, and various types can be used. A copolymer obtained by polymerizing one or more vinyl monomers in the presence of a rubbery polymer is preferred. Here, as the rubbery polymer, an acrylic polymer or methacrylic polymer mainly containing alkyl acrylate or alkyl methacrylate, a diene polymer mainly containing conjugated diene such as butadiene or isoprene, or a polyorganosiloxane is mainly used. Or two or more polymers such as silicone polymers. Examples of the vinyl monomer include styrene, aromatic vinyl compounds such as α-methylstyrene, acrylates such as methyl acrylate and ethyl acrylate, methacrylates such as methyl methacrylate and ethyl methacrylate, and acrylonitrile. And vinyl cyanide compounds. Known rubbery polymers such as MAS resin and MBS resin can be used as the rubbery polymer.

These copolymers are commercially available, for example, under the names of Paraloid (Kureha Chemical) and Metablen (Mitsubishi Rayon), and can be easily obtained.

Other elastic polymers having no epoxy group in the molecule include butadiene rubber (B
R), styrene-butadiene rubber (SBR), isobutylene-isoprene rubber (IIR), ethylene-propylene rubber (EPR), ethylene-propylene-diene rubber (EPDM), acrylonitrile-butadiene rubber (N
BR), styrene-butadiene-styrene rubber (SB
S), hydrogenated styrene-butadiene rubber (SEB)
S), styrene-isoprenego (SIS), styrene-
And hydrogenated isoprene rubber (SEPS). This component (D) can be added, if necessary, in an amount of 0 to 15 parts by weight based on 100 parts in total of (A) and (B).

The ester-based thermoplastic resin composition of the present invention may contain additives, pigments, dyes, reinforcing agents, flame retardants, fillers, antioxidants when mixing or molding the resin, as long as the physical properties are not impaired. , A stabilizer, a lubricant, a release agent, a crystal nucleating agent, a plasticizer, a flow improver, an antistatic agent and the like.

In producing the ester-based thermoplastic resin composition of the present invention, each component can be mixed by a conventionally known method. For example, a method in which the components are dispersed and mixed by a high-speed mixer represented by a turnbull mixer, a Henschel mixer, a ribbon blender, and a super mixer, and then melt-kneaded by an extruder, a Banbury mixer, a roll, or the like is appropriately selected.

[0043]

EXAMPLES Examples of the present invention will be described below.
The present invention is not limited by these examples.

The epoxidized diene block copolymer used in the examples and comparative examples was prepared by the following method. [Example of adjustment] A block copolymer of polystyrene-polybutadiene (trade name: TR2, manufactured by JSR Corporation) was placed in a jacketed reactor equipped with a stirrer, a reflux condenser, and a thermometer.
000) and 1500 g of ethyl acetate were charged and dissolved. Then, 169 of a 30% by weight solution of peracetic acid in ethyl acetate.
g was continuously dropped, and an epoxidation reaction was performed at 40 ° C. for 3 hours with stirring. The reaction solution was returned to room temperature, taken out of the reactor, and a large amount of methanol was added to precipitate a polymer. The polymer was separated by filtration, washed with water, and dried to obtain an epoxidized block copolymer. The epoxidized diene-based block copolymer thus obtained was designated as copolymer A (the epoxy equivalent of copolymer A was 540).

Other compounds used in Examples and Comparative Examples are as follows.

Aromatic polycarbonate is synthesized by the phosgene method and has a terminal hydroxyl group concentration of 7.4 mol%.
2200 (Idemitsu Petrochemical Co., Ltd.) and Lexan 141 (Nippon GE Plastics Co., Ltd.) synthesized by a transesterification method and having a terminal hydroxyl group concentration of 24 mol% were used.

As the aromatic polyester resin, polybutylene terephthalate, DURANEX 400F
P (Polyplastics Co., Ltd.) was used.

The elastic polymer containing no epoxy group in the molecule includes paraloid EX which is an MBS elastic polymer.
L3600 (Rohm & Haas) and SEPTON 4033 (Kureha Chemical Co., Ltd.) which is a SEPS elastic polymer
Was used.

As the antioxidant, PE manufactured by Asahi Denka Kogyo KK
P36 and AO60 were used. [Examples 1 to 5] Test pieces having the composition shown in Table 1 were prepared using an injection molding machine PS60E manufactured by Nissei Plastics Co., Ltd., and the deflection temperature under load, the deflection temperature under load after staying at a high temperature, and
Each physical property value of Izod impact strength was measured. Table 1 shows the measurement results.

The physical properties were measured by the following methods. (1) Deflection temperature under load: According to ASTM D648,
The deflection temperature under load was measured with a 6.4 mm thick test piece.
(Mold temperature: 50 ° C., cylinder temperature: 240 ° C.) (2) Load deflection temperature after staying at a high temperature: After the injection cycle of the previous shot is completed, the resin composition is measured in a state where the measurement of the resin is completed (240 ° C.). After holding for 10 minutes, AST
According to MD648, the deflection temperature under load was measured using a 6.4 mm thick test piece. (Mold temperature: 50 ° C., cylinder temperature: 240 ° C.) (3) Izod impact strength: Notched Izod impact strength of a 6.4 mm thick test piece was measured according to ASTM D256. (Mold temperature: 50 ° C., cylinder temperature: 240 ° C.) [Comparative Examples 1 to 7] Test pieces having the compositions shown in Table 2 were prepared using an injection molding machine PS60E manufactured by Nissei Plastics Co., Ltd. The deflection temperature under load after stagnation, and
Each physical property value of Izod impact strength was measured. Table 2 shows the measurement results. In addition, the measuring method of each physical property value is the same as that of an Example.

[0051]

[Table 1]

[0052]

[Table 2]

[0053]

As shown in Tables 1 and 2, the ester-based thermoplastic resin composition of the present invention has excellent initial heat resistance and heat resistance after staying at a high temperature, and also has an impact strength. Because of its high cost, it is useful in the fields of electric and electronics, automobiles, etc.

Claims (5)

[Claims] (A) Aromatic polycarbonate resin 95
-5% by weight and (B) aromatic polyester resin 5-9
With respect to 100 parts by weight of the resin composition comprising 5% by weight,
(C) an elastic polymer containing an epoxy group in the molecule 0.5 to 1
A composition comprising 5 parts by weight and (D) 0 to 15 parts by weight of an elastic polymer not containing an epoxy group in a molecule, and a load when retained at 200 ° C. or more for 10 minutes. An ester-based thermoplastic resin composition having excellent impact resistance, wherein a decrease in deflection temperature is within 5 ° C. 2. The ester-based thermoplastic resin composition according to claim 1, wherein the aromatic polyester resin (B) is at least one selected from polyethylene terephthalate and polybutylene terephthalate. 3. The ester-based thermoplastic resin composition according to claim 1, wherein the terminal hydroxyl group concentration of the aromatic polycarbonate resin (A) is 10 mol% or less. 4. The ester-based thermoplastic resin composition according to claim 1, wherein (C) the elastic polymer containing an epoxy group in a molecule is an epoxidized diene-based block copolymer. . 5. The epoxidized diene-based block copolymer is obtained by epoxidizing a block copolymer composed of a block composed of a vinyl aromatic compound and a block composed of a conjugated diene compound or a partially hydrogenated product thereof. The ester-type thermoplastic resin composition according to claim 4, characterized in that: