JPH09221588A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin compsn. which is excellent in resistances to heat and solvents and has moldability suitable for blow molding. SOLUTION: This compsn. comprises a polycarbonate resin and an arom. copolyester resin which has a content of a branch-forming unit having at three ester-forming groups of 0.01-20mol% based on the total number of moles of arom. polycarboxylic acid units and exhibits an intrinsic viscosity of 0.35-2.50dl/g at 25 deg.C in a 1wt./1wt. phenol/tetrachloroethane mixture.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition, and more specifically, a thermoplastic resin composition having excellent heat resistance and solvent resistance and moldability suitable for blow molding, and The present invention relates to a thermoplastic resin composition having excellent impact resistance by adding a rubber-like elastic body.

[0002]

2. Description of the Related Art Polycarbonate resins are known as resins having the highest impact resistance among engineering plastics and good thermal deformation resistance, and are utilized in various fields by taking advantage of these characteristics. However, it is inferior in chemical resistance and moldability, and has a thickness dependency of impact strength,
It has the disadvantages such as. On the other hand, aromatic polyester resins represented by polyethylene terephthalate, polybutylene terephthalate, polycyclohexane dimethylene terephthalate, polybutylene naphthalate, etc. have excellent solvent resistance and molding processability, but impact resistance and dimensional stability. It has disadvantages such as inferiority. For the purpose of complementing defects while making the best use of their respective characteristics, for example, Japanese Patent Publication No. 36-14035, Japanese Patent Publication No. 39-20434,
Japanese Patent Application Laid-Open No. 59-176345 discloses a technique for improving molding fluidity and chemical resistance by adding a polyester resin to a polycarbonate resin.

[0003]

As the viscosity behavior of polycarbonate resin, the viscosity of the resin does not easily depend on the shear rate, that is, it has characteristics similar to what is called Newtonian fluid, and the melt tension is low. However, in the process of forming the parison during molding, the resin tends to sag due to its own weight, resulting in uneven thickness distribution of the molded body during molding. Therefore, the resin was not suitable for the blow molding field. In order to solve these problems, JP-A-4-239551 and JP-A-5-255
578, etc. disclose that a resin suitable for blow molding can be obtained from a polycarbonate-based resin and a polyester-based resin having a branched structure. However, even if the resins produced by these methods are used, the melt tension does not improve epoch-making, and it cannot be said that the resin is still suitable for blow molding.

Further, since the aromatic polyester resin also has a low viscosity when melted, when it is applied to a field such as blow molding, in the process of forming the parison at the time of molding, the resin is liable to sag due to its own weight. As a result, the thickness distribution of the molded body tends to be biased during the molding process. For this reason, when blow molding an aromatic polyester resin in the molding of PET bottles, etc., an injection blow molding method is mainly used, in which the resin is injected into a mold to form a preform, and then air is blown into the preform. It is used. However, the injection blow molding method has a drawback that the process is more complicated than the direct blow molding method which is a general blow molding method.

[0005]

DISCLOSURE OF THE INVENTION As a result of intensive investigations by the present inventors to solve the above problems,
By blending a polycarbonate resin and an aromatic copolyester resin obtained by copolycondensing a polyvalent ester moldable group, melt viscosity and melt tension are remarkably improved,
It has been found that a thermoplastic resin composition having improved blow moldability can be obtained. At the same time, they have found that a resin composition having excellent impact strength can be obtained by adding a rubber-like component to the resin composition, which led to the present invention.

That is, the first aspect of the present invention includes a thermoplastic resin composition comprising the following components (A) and (B). (A) Polycarbonate-based resin, (B) Containing at least 3 ester-forming group-containing branching units in the range of 0.01 to 20 mol% with respect to the total number of moles of the aromatic polycarboxylic acid unit. , Phenol / tetochloroethane =
An aromatic copolyester resin having an intrinsic viscosity (IV) of 0.35 to 2.50 dl / g when measured at 25 ° C. in a 1/1 (weight ratio) mixed solution.

The second aspect of the present invention is to provide the following component (A),
The content is a thermoplastic resin composition comprising (B) and (C). (A) Polycarbonate-based resin, (B) Containing at least 3 ester-forming group-containing branching units in the range of 0.01 to 20 mol% with respect to the total number of moles of the aromatic polycarboxylic acid unit. An aromatic copolyester resin having an intrinsic viscosity (IV) of 0.35 to 2.50 dl / g when measured at 25 ° C. in a phenol / tetrachloroethane = 1/1 (weight ratio) mixed solution, (C ) Phenol / tetrachloroethane = 1/1 (weight ratio) in a mixed solution, 25
Intrinsic viscosity (IV) measured at 0 ° C is 0.40-2.
A linear aromatic polyester resin having a density of 00 dl / g.

In a third aspect of the present invention, 0.01 to 25 parts by weight of (E) a rubber-like elastic material is added to 100 parts by weight of the (D) thermoplastic resin composition of the first or second invention. The content of the thermoplastic resin composition is as follows.

The polycarbonate resin (A) used in the present invention is specifically obtained by reacting a bisphenol compound with phosgene or a carbonic acid ester such as diphenyl carbonate. Specific examples of the bisphenol compound include hydroquinone, 4,4'-dihydroxyphenyl, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane and 2,2-bis (. 4-hydroxyphenyl) butane, bis (4-hydroxyphenyl) sulfone, 4,4′-dihydroxydiphenyl ether and the like can be mentioned, and these can be used alone or in combination of two or more kinds. A particularly preferred bisphenol compound for the present invention is the widely commercially available 2,2-bis (4-hydroxyphenyl) propane.

These polycarbonate resins have 3
It is also possible to further enhance the blow moldability of the obtained thermoplastic resin by copolymerizing a polyphenol compound having a functionality or higher. As a polyhydric phenol compound,
1,1,1, -Tris (4-hydroxyphenyl) ethane and the like are preferably used. As the terminal terminator during polymerization of the polycarbonate resin, various known ones can be used. For example, p-tert-butylphenol, phenol, p-cumylphenol, p
-Tert-octylphenol and the like can be mentioned, and these can be used alone or in combination of two or more kinds.

The viscosity average molecular weight of the polycarbonate resin is not particularly limited, but from the viewpoint of the strength of the obtained resin, it is preferably 10,000 or more. It is more preferably 13,000 or more, still more preferably 18,000 or more. Further, from the viewpoint of mixing with the aromatic copolyester-based resin, it is preferably 90000 or less,
More preferably 70,000 or less, still more preferably 50.
000 or less. These polycarbonate resins are used alone or in combination of two or more having different molecular weights and polymerization components.

The (B) aromatic copolyester resin (hereinafter referred to simply as "aromatic copolyester") containing a branching unit having at least three ester-forming groups is used in the present invention. It is used for the purpose of increasing the melt viscosity of the plastic resin composition in the low shear rate region and improving the melt tension. The aromatic copolyester resin is an aromatic copolyester obtained by polycondensing an aromatic dicarboxylic acid component, a diol component, and a polyfunctional component having at least three ester-forming groups. Such an aromatic copolyester can be produced by a method similar to the ordinary polyester production method. For example, a desired aromatic dicarboxylic acid component, a diol component, and a polyfunctional component having at least three ester-forming groups are mixed in a molten state, and a mixture of about 0.2 to 1.0 mmHg is applied for about 3 to 12 hours. The high vacuum increases the molecular weight as the volatile components are removed and produces an aromatic copolyester.

As the aromatic dicarboxylic acid component, a divalent aromatic carboxylic acid having 8 to 22 carbon atoms and an ester-forming derivative thereof are used. Specific examples of these include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, bis (p-carbophenyl) methaneanthracene dicarboxylic acid, 4-4′-diphenyldicarboxylic acid,
Examples thereof include carboxylic acids such as 1,2-bis (phenoxy) ethane-4′4-dicarboxylic acid and diphenylsulfonedicarboxylic acid, and derivatives having an ester forming ability thereof, and these are used alone or in combination of two or more kinds. Among them, terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid are preferably used from the viewpoints of easy handling, easy reaction, and physical properties of the obtained resin.

The diol component is an aliphatic compound having 3 to 15 carbon atoms, an alicyclic compound having 6 to 20 carbon atoms, or an aromatic compound having 6 to 40 carbon atoms and having two hydroxyl groups in the molecule. Examples thereof include compounds and their ester-forming derivatives. Specifically, ethylene glycol, propylene glycol, butanediol, hexanediol, decanediol, neopentyl glycol, cyclohexanedimethanol, cyclohexanediol, 2,
2'-bis (4-hydroxyphenyl) propane, 2,
Examples thereof include compounds such as 2′-bis (4-hydroxycyclohexyl) propane and hydroquinone, and derivatives having the ability to form an ester thereof, which may be used alone or in combination of two or more. Among them, ethylene glycol, butanediol, and cyclohexadimethanol are preferably used from the viewpoints of easy handling, easy reaction, and physical properties of the obtained resin. More preferred are ethylene glycol and 1,4-butanediol.

Examples of the polyfunctional component having a branching unit having at least three ester-forming groups include trimellitic acid, trimesic acid, pyromellitic acid, benzophenonetetracarboxylic acid and other trifunctional or higher polyfunctional carboxylic acid components. And trihydric or higher polyfunctional alcohol components such as acid anhydrides, glycerin, trimethylolpropane, trimethylolethane, and pentaethasitol, dihydroxycarboxylic acids, hydroxydicarboxylic acids, dihydroxydicarboxylic acids, and esters thereof. A moldable derivative is used. These may be used alone or in combination of two or more. Among these, glycerin is preferably used because it is easy to control the degree of polymerization.

The polyfunctional component having at least three ester-forming groups used in the present invention is contained in a proportion of 0.01 to 20 mol% based on the total number of moles of the aromatic dicarboxylic acid unit, The content is preferably 0.05 to 10 mol%, more preferably 0.1 to 5 mol%. When the amount of the polyfunctional component is less than the above range, the effect of modifying the melt viscosity and melt tension of the polyester by the polyfunctional component is not exhibited, and when the amount exceeds the above range, it becomes difficult to control the degree of polymerization.

In addition to the above-mentioned components, the aromatic copolyester resin contains a divalent or higher aliphatic carboxylic acid having 4 to 12 carbon atoms, a divalent or higher alicyclic carboxylic acid having 8 to 15 carbon atoms, and the like. The carboxylic acids and the ester moldable derivatives thereof may be partially copolymerized. Specific examples of these include dicarboxylic acids such as adipic acid, sebacic acid, dodecanedioic acid, maleic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid when azelaine or a derivative having an ester forming ability thereof. And these are used alone or in combination of two or more. Further, oxy acids such as p-oxybenzoic acid and p-hydroxybenzoic acid, ester-forming derivatives thereof, cyclic esters such as ε-caprolactone, etc. can be used alone or in combination of two or more kinds. Further, polyethylene glycol, polypropylene glycol, poly (ethylene oxide / propylene oxide) block and / or random copolymer, bisphenol A copolymer polyethylene oxide addition polymer, propylene oxide addition polymer, tetrahydrofuran addition polymer, polytetra It is also possible to use one obtained by partially copolymerizing one or more polyalkylene glycol units such as methylene glycol in the polymer chain. The copolymerization amount of the above components is generally 20% by weight or less, preferably 15% by weight or less, and more preferably 10% by weight or less. The (B) aromatic copolyester resin preferably has an alkylene terephthalate unit of 6 units.
A resin composition having an excellent balance of physical properties can be obtained by using a resin having 0 wt% or more, more preferably 70 wt% or more, and further preferably 75 wt% or more.

The intrinsic viscosity (IV) of the aromatic copolyester resin (B) measured at 25 ° C. in a phenol / tetrachloroethane = 1/1 (weight ratio) mixed solvent is:
0.35 to 2.50 dl / g, but preferably 0.
40-2.00 dl / g, more preferably 0.45-
It is 1.50 dl / g. When the intrinsic viscosity is less than the above range, the effect of modifying the polyester such as melt viscosity and melt tension is difficult to be exhibited, and when it exceeds the above range, melt molding becomes difficult. The aromatic copolyester resin may be used alone or as a mixture of two or more kinds having different copolymerization components and / or intrinsic viscosities.

In the present invention, the (C) linear aromatic polyester resin may be used in combination with the (B) aromatic copolyester resin. By using these two kinds of aromatic polyester resins in combination, a resin having a desired melt viscosity and melt tension can be manufactured inexpensively and easily. The linear aromatic polyester-based resin is an aromatic polyester obtained by polycondensing an aromatic dicarboxylic acid component and a diol component. Such an aromatic polyester can be produced by an ordinary polyester production method.

As the aromatic dicarboxylic acid component, a divalent aromatic carboxylic acid having 8 to 22 carbon atoms and ester-forming derivatives thereof are used. Specific examples of these include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, bis (p-carbophenyl) methaneanthracene dicarboxylic acid, 4-4′-diphenyldicarboxylic acid,
Examples thereof include carboxylic acids such as 1,2-bis (phenoxy) ethane-4′4-dicarboxylic acid and diphenylsulfonedicarboxylic acid, and derivatives having an ester forming ability thereof, and these are used alone or in combination of two or more kinds. Among them, terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid are preferably used from the viewpoints of easy handling, easy reaction, and physical properties of the obtained resin.

The diol component is an aliphatic compound having 3 to 15 carbon atoms, an alicyclic compound having 6 to 20 carbon atoms, or an aromatic compound having 6 to 40 carbon atoms and having two hydroxyl groups in the molecule. Examples thereof include compounds and their ester-forming derivatives. Specifically, ethylene glycol, propylene glycol, butanediol, hexanediol, decanediol, neopentyl glycol,
Cyclohexanedimethanol, cyclohexanediol, 2,2'-bis (4-hydroxyphenyl) propane, 2,2'-bis (4-hydroxycyclohexyl)
Examples thereof include compounds such as propane and hydroquinone, and derivatives thereof having an astaxanthin-forming ability, and these are used alone or in combination of two or more. Among them, ethylene glycol and butanediol are easy to handle,
It is preferably used in terms of easiness of reaction and physical properties of the obtained resin.

In addition to the above-mentioned components, the linear aromatic polyester resin contains a divalent or higher aliphatic carboxylic acid having 4 to 12 carbon atoms and an alicyclic carboxylic acid having 8 to 15 carbon atoms. Carboxylic acids such as and ester-forming derivatives thereof may be partially copolymerized. Specific examples thereof include dicarboxylic acids such as adipic acid, sebacic acid, dodecanedioic acid, maleic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid at the time of azelaine, or an ester forming ability thereof. Derivatives may be mentioned, and these may be used alone or in combination of two or more. Further, oxy acids such as p-oxybenzoic acid and p-hydroxybenzoic acid, ester-forming derivatives thereof, cyclic esters such as ε-caprolactone, etc. can be used alone or in combination of two or more kinds. Further, polyethylene glycol, polypropylene glycol, poly (ethylene oxide / propylene oxide) block and / or random copolymer, bisphenol A copolymer polyethylene oxide addition polymer, propylene oxide addition polymer, tetrahydrofuran addition polymer, polytetra It is also possible to use one obtained by partially copolymerizing one or more polyalkylene glycol units such as methylene glycol in the polymer chain. The copolymerization amount of the above components is generally 20% by weight or less, preferably 15% by weight or less, and more preferably 10% by weight or less. Further, as the linear aromatic polyester resin (C), an alkylene terephthalate unit is preferably 8
By using polyalkylene terephthalate having 0% by weight or more, more preferably 85% by weight or more, and further preferably 90% by weight or more, a composition having an excellent balance of physical properties can be obtained.

(C) a linear aromatic polyester resin,
Intrinsic viscosity (IV) when measured at 25 ° C. in a mixed solvent of phenol / tetrachloroethane = 1/1 (polymerization ratio)
Is 0.40 to 2.00 dl / g, preferably 0.45 to 1.80 dl / g, and more preferably 0.5.
0 to 1.60 dl / g. If the intrinsic viscosity is less than the above range, the mechanical strength of the molded product will decrease, and if it exceeds the above range, it will be difficult to mix with the (A) polycarbonate resin. The linear aromatic polyester resin may be used alone or in combination of two or more kinds having different copolymerization components and / or intrinsic viscosities.

When (B) an aromatic copolyester having at least three ester-forming groups and (C) a linear aromatic polyester are used in combination, the amounts of (C) used are (B) and (C). When the total of 100) is 100% by weight, 99.
5% by weight or less. The lower limit of (C) is not particularly limited because it exerts the above-mentioned effect even in an extremely small amount. (B) is 0.
If it is less than 5% by weight, properties such as melt viscosity and melt tension are deteriorated, which is not preferable.

(A) a polycarbonate resin and (B)
The weight ratio (A) / (B) or (A) / [(B) + (C)] of the polyester resin is 95/5 to 30/70, more preferably 90/10 to 50/50, More preferably, it is 85/15 to 55/45. If the weight ratio of (A) is less than 30, the impact strength and heat resistance of the obtained molded article will decrease, and if it exceeds 95, the solvent resistance will decrease, which is not preferable.

In the present invention, in order to increase the impact strength of the obtained molded product, the rubber-like elastic material (E) can be added to the resin composition (D) obtained as described above. The rubber-like elastic material preferably has a glass transition temperature of 0.
By using a material having a temperature of not higher than 0 ° C, more preferably not higher than -20 ° C, a composition having improved impact strength can be obtained. Specific examples of the rubber-like elastic body include, for example, polybutadiene, styrene-butadiene rubber, acrylonitrile-butadiene rubber, (meth) acrylic acid alkyl ester-
Diene rubber such as butadiene rubber, acrylic rubber, ethylene-propylene rubber, siloxane rubber and the like,
These may be used alone or in combination of two or more.

Further, in order to further increase the impact strength of the obtained molded product, (a) an aromatic vinyl compound, 90 to 10 parts by weight of a monomer mixture containing at least one monomer selected from the group consisting of a cyanvalent vinyl compound and (meth) acrylic acid alkyl ester and (b) another vinyl compound copolymerizable therewith. It is preferable to use a rubbery copolymer obtained by polymerization. Examples of the aromatic vinyl compound copolymerized with the rubber-like elastic material include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene,
Chlorostyrene, bromostyrene, vinyltoluene, etc. are mentioned, and these are used individually or in combination of 2 or more types. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile, which may be used alone or in combination of two or more. Examples of the (meth) acrylic acid alkyl ester include butyl acrylate, butyl methacrylate, ethyl acrylate, ethyl methacrylate, methyl acrylate, and methyl methacrylate, and these may be used alone or in combination of two or more. Examples of the other copolymerizable vinyl compound include unsaturated acids such as acrylic acid and methacrylic acid, (meth) acrylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate, vinyl acetate, maleic anhydride, and N-phenyl. Maleimide etc. are mentioned, These are used individually or in combination of 2 or more types. The proportion of the other copolymerizable vinyl compound (b) is 0 to 100 parts by weight of the monomer (a).
10 parts by weight. If it exceeds 10 parts by weight, the impact strength tends to decrease.

When the rubber-like elastic material and the monomer mixture are copolymerized, the copolymerization ratio is preferably 10/90 by weight.
To 90/10, more preferably 30/70 to 80/20
It is. When the weight ratio of the rubber-like elastic body is less than 10, the impact resistance improving effect is small, and when it exceeds 90 (A),
The compatibility with the resin (B) tends to decrease.

(E) The compounding amount of the rubber-like elastic material is 0.01
-25 parts by weight, preferably 0.1-20 parts by weight, more preferably 0.5-15 parts by weight. If it is less than 0.01 parts by weight, the effect of improving impact resistance cannot be obtained, and if it exceeds 25 parts by weight, rigidity, heat resistance and the like are deteriorated.

The composition of the present invention further comprises any other thermoplastic or thermosetting resin within the range not impairing the present invention, such as liquid crystal polyester resin, polyester ester elastomer resin, polyester ether elastomer resin, Polyolefin resin, polyamide resin, rubbery polymer reinforced styrene resin, polyphenylene sulfide resin, polyphenylene ether resin, polyacetal resin, polysulfone resin, polyarylate resin, etc. are added alone or in combination of two or more. May be.

In order to improve the performance of the resin composition of the present invention, antioxidants such as phenolic antioxidants and thioether antioxidants, heat stabilizers such as phosphorus stabilizers, etc. Are preferably used alone or in combination of two or more. Further, if necessary, usually well-known inorganic or organic crystallization nucleating agent, stabilizer, lubricant, release agent, plasticizer, flame retardant, flame retardant auxiliary agent, ultraviolet absorber, light stabilizer, pigment. , Dyes, antistatic agents, conductivity-imparting agents, dispersants, compatibilizers, antibacterial agents, etc. can be used alone or in combination of two or more kinds.

The method for producing the composition of the present invention is not particularly limited. For example, it can be produced by a method in which the above-mentioned components, other additives, resins and the like are dried and then melt-kneaded in a melt-kneader such as a single-screw or twin-screw extruder. When the compounding agent is a liquid, it can be produced by adding it to a twin-screw extruder halfway using a liquid supply pump or the like. The molding method of the thermoplastic resin composition produced in the present invention is not particularly limited, a forming method generally used for thermoplastic resins, for example, blow molding,
Extrusion molding, vacuum molding, injection molding, press molding, calender molding and the like can be applied. However, it is preferably used for blow molding, extrusion molding, vacuum molding and the like in view of the characteristics of the obtained resin.

[0033]

The present invention will be described below with reference to examples, but the present invention is not limited thereto. In the following description, “part” means part by weight unless otherwise specified. The method for evaluating the thermoplastic resin composition is shown below.

Solvent resistance: After drying the obtained pellets at 120 ° C. for 5 hours, a 75-ton injection molding machine was used to prepare ASTM No. 1 dumbbell test pieces at a cylinder temperature of 300 ° C. and a mold temperature of 70 ° C. 0.5% for the test pieces
After applying the strain of honey, the fragrance of Honey Kisslime (registered trademark manufactured by SOFT99 Corporation), which is an air freshener for automobiles, was sufficiently applied to the entire test piece, and left for 1 hour at room temperature. Was visually evaluated. ◯: No change in appearance Δ: Cracking occurred ×: Test piece rupture

Heat resistance: After drying the obtained pellets at 120 ° C. for 5 hours, using a 75t injection molding machine, at a cylinder temperature of 300 ° C. and a mold temperature of 70 ° C., a 1/4 inch thick bar (width 12 mm, length) The test piece thus obtained was measured for HDT (heat distortion temperature, load 0.45 MPa) according to ASTM D-648 (unit:
° C).

Impact strength: After drying the obtained pellets at 120 ° C. for 5 hours, they were molded at a cylinder temperature of 300 ° C. and a mold temperature of 70 ° C. using a 75t injection molding machine, and a 1/8 inch thick bar (width 12.7 mm, length 127 mm) test piece was prepared, and the obtained test piece was prepared according to ASTM D-25.
According to 6, the Izod impact strength with notch was evaluated at 23 ° C. (unit: J / m).

Melt tension (an index of blow molding): The pellets obtained were dried at 120 ° C. for 5 hours, and then extruded with a capillary rheometer (Capillograph manufactured by Toyo Seiki Co., Ltd.) at an extrusion piston speed of 10 mm / min. The melt tension of the strand was measured at 280 ° C. using a die having a take-up speed of 3 m / min, a length of 10 mm and a diameter of 1 mm (unit: 10 ⁻³ N).

Melt viscosity ratio (an index of blow molding):
After drying the obtained pellets at 120 ° C. for 5 hours, using a capillary rheometer (Capillograph manufactured by Toyo Seiki Co., Ltd.), a die having a length of 10 mm and a diameter of 1 mm was used.
The shear rate dependence of melt viscosity was measured at 0 ° C. The melt viscosity ratio was calculated by the formula (viscosity at a shear rate of 6.08 sec ^-1 ) / (viscosity at a shear rate of 182 sec ^-1 ).

Reference Example 1: Production of aromatic copolyester resin (GPET1) Polycondensation of dimethyl terephthalate (15.0 mol), ethylene glycol (30.0 mol) and glycerin (0.15 mol) according to a conventional method using germanium dioxide as a catalyst. 29
After the temperature was raised to 0 ° C., the pressure was reduced to 133 Pa (1 Torr) to remove methanol and excess ethylene glycol, so that the glycerin unit was contained at a ratio of 1 mol% with respect to the total number of moles of terephthalic acid units. Intrinsic viscosity is 0.
60 dl / g aromatic copolyester resin (GPET
1) was obtained.

Reference Example 2: Production of aromatic copolyester resin (GPET2) 15.0 mol of dimethyl terephthalate, 30.0 mol of ethylene glycol and 0.45 mol of glycerin were polycondensed by a conventional method using germanium dioxide as a catalyst. By removing methanol and excess ethylene glycol under reduced pressure, the fragrance containing the glycerin unit at a ratio of 3 mol% with respect to the total number of moles of terephthalic acid units and having an intrinsic viscosity of 0.75 dl / g. Group copolyester resin (G
PET2) was obtained.

Reference Example 3: Production of aromatic copolyester resin (GPBT1) 15.0 mol of dimethyl terephthalate, butanediol 3
0.0 mol and 0.45 mol of glycerin were subjected to polycondensation according to a conventional method using titanium tetrabutoxide as a catalyst, and methanol and excess butanediol were removed under reduced pressure to convert the glycerin unit to the total mol of terephthalic acid unit. Aromatic copolyester resin (GP with an intrinsic viscosity of 0.65 dl / g, contained at a ratio of 3 mol% with respect to the number)
BT1) was obtained.

Reference Example 4: Production of aromatic copolyester resin (GPET3) Velpet EFG-70 (registered trademark manufactured by Kanebo Kogyo Co., Ltd. hereinafter EFG, which is a linear polyethylene terephthalate resin having an intrinsic viscosity of 0.75 dl / g. Abbreviated as -70.) 1
After drying 00 parts at 140 ° C. for 4 hours, it was mixed with 0.5 parts of pyromellitic dianhydride (reagent manufactured by Wako Pure Chemical Industries, Ltd.) and using a TEX44XCT-38 same-direction twin-screw extruder manufactured by Japan Steel Works,
By melt-kneading at a set temperature of 280 ° C., an aromatic copolyester resin (GPET3) having an intrinsic viscosity of 0.65 dl / g was obtained.

Example 1 (A) Tufflon A25 as a polycarbonate resin
No. 00 (viscosity average molecular weight: about 23500, a registered trademark of Idemitsu Petrochemical Co., Ltd., hereinafter abbreviated as A2500) dried at 120 ° C. for 4 hours 78 parts, (B) as an aromatic copolyester resin, Reference Example 1 Synthesized by GPET1
22 parts dried at 140 ° C. for 4 hours were thoroughly mixed, and then pelletized by melt-kneading at a set temperature of 280 ° C. using a TEX44XCT-38 same-direction twin-screw extruder manufactured by Japan Steel Works. Then, a resin composition was obtained.

Example 2 In Example 1, the mixing ratio of (A) and (B) was 65 /.
35, and as a stabilizer, ADEKA STAB AO-
60 (registered trademark manufactured by Asahi Denka Kogyo Co., Ltd., hereinafter AO-60
0.2 parts, ADEKA STAB PEP-36 (registered trademark manufactured by Asahi Denka Kogyo Co., Ltd., hereinafter abbreviated as PEP36) 0.
3 parts was added and a resin composition was obtained in the same manner as in Example 1.

Example 3 100 parts by weight of the resin composition (D) used in Example 1 and comprising the mixture of (A) and (B) was added to (E) a rubber-like elastic material, Paraloid EXL-2602 (butadiene). And methyl methacrylate, Kureha Chemical Co., Ltd. registered trademark, abbreviated as EXL2602 hereinafter), 5 parts, AO-6
0.2 part of 0 and 0.3 part of PEP-36 were added, and Example 1 was added.
In the same manner as in the above, a resin composition was obtained.

Example 4 (A) Tufflon A22 as a polycarbonate resin
65 parts of 00 (viscosity average molecular weight: about 21600, a registered trademark of Idemitsu Petrochemical Co., Ltd., abbreviated as A2200 hereinafter) for 4 hours at 120 ° C., (B) 35 parts of GPET1 as an aromatic copolyester resin. , E as E
5 parts XL2602, 0.2 parts AO-60, PEP-
0.3 part of 36 was obtained in the same manner as in Example 1 to obtain a resin composition.

Example 5 (A) 45 A2500 as a polycarbonate resin
Part, (B) GPET as an aromatic copolyester resin
55 parts of 1 and 5 parts of EXL2602 as (E), AO
A resin composition was obtained in the same manner as in Example 1 except that 0.2 parts of -60 and 0.3 parts of PEP-36 were used.

Example 6 A2500 was used as the polycarbonate resin (A).
0 part, 15 parts obtained by drying GPET2 synthesized in Reference Example 2 as a (B) aromatic copolyester resin at 140 ° C. for 4 hours, and (C) a linear aromatic polyester resin, EFG-70 Was dried at 140 ° C for 4 hours to obtain 15 parts, and (E) as a rubber-like elastic material, Kane Ace M-
511 (copolymer of butadiene, styrene, and methyl methacrylate, registered trademark of Kanegafuchi Chemical Industry Co., Ltd., hereinafter M
Abbreviated as -511. ) 2 parts, AO-60 0.2 parts, P
A resin composition was obtained in the same manner as in Example 1 except that 0.3 part of EP-36 was used.

Example 7 (A) 75 A2500 as a polycarbonate resin
Part, (B) GPET as an aromatic copolyester resin
3 parts by weight, (C) 24 parts by weight of EFG-70 as a linear aromatic polyester resin, and (E) EEA A- which is an ethylene / ethyl acrylate copolymer as a rubber-like elastic material.
713 (trade name of Mitsui DuPont Chemical Co., Ltd. abbreviated as EEA hereinafter), 6 parts, AO-60, 0.2 parts, PE
A resin composition was obtained in the same manner as in Example 1 except that 0.3 part of P-36 was used.

Example 8 (A) A2500 was used as a polycarbonate resin.
0 part, (B) 30 parts of GPBT1 synthesized in Reference Example 3 as an aromatic copolyester resin, dried at 120 ° C. for 4 hours, and (E) a rubber-like elastic body, Paraloid EXL-2311 (acrylic rubber). Copolymer of Kureha Chemical Industry Co., Ltd., abbreviated as EXL2311, hereinafter) 3 parts, AO-60 0.2 parts, ADEKA STAB 2
112 (registered trademark of Asahi Denka Kogyo Co., Ltd., 2112 below
Abbreviated. ) 0.3 part was obtained in the same manner as in Example 1 to obtain a resin composition.

Example 9 (A) Tufflon A27 as a polycarbonate resin
00 (viscosity average molecular weight: about 26300, a registered trademark of Idemitsu Petrochemical Co., Ltd., abbreviated as A2700 hereafter) for 4 hours at 120 ° C., 70 parts, (B) 15 parts of GPBT1 as an aromatic copolyester resin. , (C) PB having an intrinsic viscosity of 0.85 dl / g as a linear polyester resin
T-120 (polybutylene terephthalate resin registered trademark manufactured by Kanebo Co., Ltd., abbreviated as PBT120 hereinafter) 140
15 parts dried at ℃ for 4 hours, EXL as (E)
A resin composition was obtained in the same manner as in Example 1 except that 1 part of 2602, 0.2 part of AO-60 and 0.3 part of 2112 were used.

Example 10 (A) As a polycarbonate resin, Tufflon IB, which is a polycarbonate resin having a branched structure in the main chain
2,500 (viscosity average molecular weight: about 25,000, registered trademark of Idemitsu Petrochemical Co., Ltd., abbreviated as IB2500 hereinafter) 12
70 parts dried at 0 ° C. for 4 hours, 2 parts of (B) aromatic copolyester resin as GPET2, (C) linear aromatic polyester resin as EFG-70 of 28 parts
Part, (E) 2 parts of M-511, AO-60 of 0.
A resin composition was obtained in the same manner as in Example 1 except that 2 parts and 0.3 part of PEP-36 were added.

[0053]

[Table 1]

As is clear from Table 1, the obtained resin composition has excellent solvent resistance, heat resistance and blow moldability,
Furthermore, by adding a rubber-like substance, a composition having excellent impact resistance can be obtained.

Comparative Examples 1 to 6 Resin compositions were obtained and evaluated in the same manner as in Example 1 with the formulations shown in Table 2. However, in Comparative Examples 1 and 2,
Commercially available pellets were directly used for evaluation.

[0056]

[Table 2]

As is clear from Table 2, in Comparative Examples 1 and 2, since the (B) aromatic copolyester resin was not contained, the solvent resistance was insufficient. In Comparative Examples 3 and 4,
Since the (B) aromatic copolyester resin is not contained in the polyester resin, the melt tension and the melt viscosity ratio are lowered, which is not suitable for blow molding. In Comparative Example 5, (A) a polycarbonate-based resin having a branch suitable for blow molding is used, so that although it is superior to Comparative Examples 3 and 4 and the like, it still has a melt viscosity and a melt as compared with the Examples. The characteristics such as tension are inferior. In Comparative Example 6,
(A) Since it does not contain a polycarbonate resin,
Insufficient heat resistance and impact resistance.

[0058]

The thermoplastic resin composition of the present invention has excellent heat resistance and solvent resistance, and has a melt viscosity and melt tension suitable for blow molding. Moreover, by adding a rubber-like elastic body as the third component, a resin composition having excellent impact resistance can be obtained. These resin compositions have excellent properties that cannot be obtained by conventional polycarbonate resin / polyester resin alloys and are industrially very useful.

Claims (9)

[Claims] 1. A thermoplastic resin composition comprising the following component (A) and component (B). (A) Polycarbonate-based resin, (B) Containing at least 3 ester-forming group-containing branching units in the range of 0.01 to 20 mol% with respect to the total number of moles of the aromatic polycarboxylic acid unit. , Phenol / tetochloroethane =
An aromatic copolyester resin having an intrinsic viscosity (IV) of 0.35 to 2.50 dl / g when measured at 25 ° C. in a 1/1 (weight ratio) mixed solution. 2. A weight ratio of (A) / (B) is 95/5 to 3
The thermoplastic resin composition according to claim 1, which is 0/70. 3. A thermoplastic resin composition comprising the following components (A), (B) and (C). (A) Polycarbonate-based resin, (B) Containing at least 3 ester-forming group-containing branching units in the range of 0.01 to 20 mol% with respect to the total number of moles of the aromatic polycarboxylic acid unit. An aromatic copolyester resin having an intrinsic viscosity (IV) of 0.35 to 2.50 dl / g when measured at 25 ° C. in a phenol / tetrachloroethane = 1/1 (weight ratio) mixed solution, (C ) Phenol / tetrachloroethane = 1/1 (weight ratio) in a mixed solution, 25
Intrinsic viscosity (IV) measured at 0 ° C is 0.40-2.
A linear aromatic polyester resin having a density of 00 dl / g. 4. The thermoplastic resin composition according to claim 3, wherein the weight ratio of (A) / [(B) + (C)] is 95/5 to 30/70. 5. The (B) aromatic copolyester resin is
The thermoplastic resin composition according to claim 1, which has an alkylene terephthalate unit of 60% by weight or more. 6. A compound in which the branching unit having at least 3 ester-forming groups contained in (B) has 3 or more —OH groups and / or —COOH groups in the molecule. Alternatively, the thermoplastic resin composition according to any one of claims 1 to 5, which is an ester-forming derivative thereof. 7. The thermoplastic resin composition according to claim 3, wherein the linear aromatic polyester resin (C) has an alkylene terephthalate unit of 80% by weight or more. 8. A thermoplastic resin composition (D) according to claim 1, which is 100 parts by weight,
(E) A thermoplastic resin composition containing 0.01 to 25 parts by weight of a rubber-like elastic material. 9. (E) The rubber-like elastic body is the rubber-like elastic body 1.
0 to 90 parts by weight of at least one monomer selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds, and (meth) acrylic acid alkyl ester,
The thermoplastic resin composition according to claim 8, which is a copolymer obtained by polymerizing 90 to 10 parts by weight of a monomer mixture consisting of another vinyl compound copolymerizable therewith.