JP2005264060A - Noncrystalline polyester resin composition and molded product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a noncrystalline polyester resin composition yielding a molded product exerting physical properties including weatherability, impact resistance and stress whitening resistance in a highly well-balanced manner. <P>SOLUTION: The noncrystalline polyester resin composition as a thermoplastic resin composition comprises (A) a thermoplastic resin component comprising a noncrystalline polyester resin and (B) a composite rubber-based graft copolymer comprising a polyorganosiloxane and a polyalkyl (meth)acrylate, wherein the component (B) contains composite rubber particles 30-140 nm in average size. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an amorphous polyester resin composition and a molded article thereof.

Amorphous polyester resins are excellent in transparency, mechanical properties, and gas barrier properties, and are widely used mainly for packaging materials such as bottles and sheets.
However, due to the recent increase in size and complexity of containers, higher impact resistance and workability have been demanded. Further, depending on the application (for example, sheet, film, bottle, pipe), stress whitening resistance as well as impact resistance is required at the same time.

Therefore, as a means to improve the impact resistance of amorphous polyester resins, many attempts have been made to improve impact resistance by adding rubber-like polymers and rubber-containing polymers to amorphous polyethylene terephthalate resins. It is done. In particular, it is known that the addition of a core-shell type graft polymer having a structure in which rubber-like polymer particles are surrounded by a glass-like polymer is effective in improving impact resistance. For example, Patent Document 1 describes a core-shell type impact resistance improver comprising a shell having a specific composition and a diene rubber as a core. Patent Document 2 describes a composition in which an acrylic silicone rubber modifier and a lubricant are blended with an amorphous polyester resin.
JP-A-6-65331 JP 2001-200166 A

  However, although the above method has a certain effect in improving the impact resistance, the weather resistance tends to decrease when MBS resin is used. Further, when an acrylic silicon rubber modifier is used, there is a problem that although it is excellent in weather resistance and impact resistance, stress whitening resistance is inferior to that of MBS resin.

  The present invention has been made to solve the above problems, and provides an amorphous polyester resin composition that realizes a molded product that exhibits various physical properties such as weather resistance, impact resistance and stress whitening resistance in a highly balanced manner. Objective.

The amorphous polyester resin composition of the present invention comprises (A) a thermoplastic resin component containing an amorphous polyester resin, and (B) a composite rubber graft copolymer comprising polyorganosiloxane and polyalkyl (meth) acrylate. A thermoplastic resin composition containing a polymer,
(B) The composite rubber-based graft copolymer is characterized by having a particulate composite rubber having an average particle size of 30 to 140 nm.
Here, (B) the polyorganosiloxane of the composite rubber-based graft copolymer is desirably particles having an average particle diameter of 25 to 100 nm.
The molded article of the present invention is obtained by molding the amorphous polyester resin composition.

  ADVANTAGE OF THE INVENTION According to this invention, the molded article which exhibits various physical properties, such as a weather resistance, impact resistance, and stress whitening resistance, with high balance is realizable. Therefore, it is suitable for various uses such as various molded products, in particular, resin sheets, films, wallpaper, various parts, surface cosmetics, containers, bottles, foams and the like.

Hereinafter, the present invention will be described in detail.
The amorphous polyester resin composition of the present invention contains (A) a thermoplastic resin component and (B) a composite rubber-based graft copolymer.
(A) The thermoplastic resin component contains an amorphous polyester resin. Here, the amorphous polyester resin refers to a resin in which crystallinity is not substantially recognized. For example, a homopolymer, a copolymer, or a mixture thereof obtained by condensation polymerization of a diol having 50 mol% or more of ethylene glycol and a dicarboxylic acid having 50 mol% or more of terephthalic acid or an alkyl ester thereof can be given. Examples of the copolymer include those obtained by copolymerizing other dicarboxylic acids such as isophthalic acid or halogenated terephthalic acid in a range of 50 mol% or less of the total carboxylic acids, and poly ( (Alkylene glycol) Specifically, a copolymer of diethylene glycol or a copolymer of alkylene glycol having 3 to 12 carbon atoms, for example, 1,4-cyclohexanedimethanol.
For example, trade name “PETG 6763” manufactured by Eastman Chemical Co., Ltd. (a copolymer of a dicarboxylic acid component comprising terephthalic acid and a diol component comprising 30 mol% 1,4-cyclohexanedimethanol and 70 mol% ethylene glycol) Copolyester), and the trade name “Provista” (a dicarboxylic acid component comprising terephthalic acid, a diol component comprising 30 mol% 1,4-cyclohexanedimethanol and 70 mol% ethylene glycol, and a very small amount of third It is commercially available as a copolyester having a high melt viscosity obtained by copolymerizing the components.
Such an amorphous polyester resin has good transparency.
(A) The thermoplastic resin component can be blended with other thermoplastic resin as necessary, with an amorphous polyester resin as a main component. Examples thereof include polyethylene, polypropylene, acrylic resin, polyamide, polyphenylene sulfide resin, polyether ether ketone resin, polyester, polysulfone, polyphenylene oxide, polyacetal, polyimide, and polyetherimide.

  (B) The composite rubber-based graft copolymer is a composite rubber-based graft copolymer containing polyorganosiloxane and polyalkyl (meth) acrylate, and has a particulate composite rubber having an average particle size of 30 to 140 nm. It is.

  The polyorganosiloxane contained in the composite rubber is not particularly limited, but polyorganosiloxane having a vinyl polymerizable functional group is preferably used. Moreover, as a dimethylsiloxane used for preparation of polyorganosiloxane, a 3 or more membered ring dimethylsiloxane type cyclic body is mentioned, A 3-7 membered ring thing is preferable. Specific examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and the like. These may be used alone or in combination of two or more.

  When preparing the polyorganosiloxane having a vinyl polymerizable functional group, a siloxane that contains a vinyl polymerizable functional group and can be bonded via a bond with dimethylsiloxane is used together with dimethylsiloxane. As such a siloxane, considering the reactivity with dimethylsiloxane, various alkoxysilane compounds having a vinyl polymerizable functional group are preferable. Specifically, β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, γ-methacryloyloxypropylethoxydiethoxymethylsilane and δ-methacryloyloxybutyldiethoxymethylsilane, etc., methacryloyloxysilane, vinylsiloxanes such as tetramethyltetravinylcyclotetrasiloxane, vinyl such as p-vinylphenyldimethoxymethylsilane Mels such as phenylsilane, γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropyltrimethoxysilane Script siloxane, and the like. In addition, the siloxane which has these vinyl polymerizable functional groups can be used individually or in mixture of 2 or more types.

  The polyalkyl (meth) acrylate contained in the composite rubber is obtained by polymerizing an alkyl (meth) acrylate component. The alkyl (meth) acrylate component includes an alkyl (meth) acrylate and a polyfunctional alkyl. (Meth) acrylate is included. Examples of the alkyl (meth) acrylate include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate, and alkyl methacrylates such as hexyl methacrylate, 2-ethylhexyl methacrylate, and n-lauryl methacrylate. These can be used alone or in combination of two or more. In consideration of the impact resistance and stress whitening resistance of the amorphous polyester resin composition of the present invention, n-butyl acrylate and 2-ethylhexyl acrylate are particularly preferable.

  Examples of the polyfunctional alkyl (meth) acrylate include allyl methacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, triallyl cyanurate, and triallyl. An isocyanurate etc. are mentioned, These can be used individually or in combination of 2 or more types. Of these polyfunctional alkyl (meth) acrylates, allyl methacrylate is preferable in consideration of the graft structure of the composite rubber-based graft copolymer (B) (the amount of acetone-insoluble components and the solution viscosity of acetone-soluble components).

  Although there is no restriction | limiting in particular as a manufacturing method of composite rubber, As mentioned later, the alkyl (meth) acrylate which contains alkyl (meth) acrylate and polyfunctional alkyl (meth) acrylate in the manufactured polyorganosiloxane latex. A method of manufacturing by impregnating the components and then polymerizing is preferable. Hereinafter, the manufacturing method will be sequentially described.

  Examples of the method for producing the polyorganosiloxane latex include water, an emulsifier, a mixture of dimethylsiloxane and a siloxane having a vinyl polymerizable functional group (hereinafter referred to as a siloxane mixture), and, if necessary, a siloxane crosslinking agent. The latex containing is mixed and micronized. As a method of mixing a latex containing a siloxane mixture, an emulsifier, water, etc., there are a mixing method by high-speed stirring using a homomixer and the like, a mixing method by a high-pressure emulsifier using a homogenizer, etc., but mixing using a homogenizer This method is preferable because the particle size distribution of the polyorganosiloxane latex becomes small.

Next, the finely divided latex is dropped at a constant rate into an aqueous solution of a high-temperature acid catalyst and polymerized at a high temperature. In addition, as a method of allowing the aqueous solution of the acid catalyst and the latex to act, there is a method of mixing a latex containing a siloxane mixture, an emulsifier and water, and an aqueous solution of the acid catalyst, but the particle size of the polyorganosiloxane is controlled. In consideration of easiness, a method of dropping the micronized latex into an aqueous solution of a high-temperature acid catalyst at a constant rate is preferable.
The polymerization temperature of the polyorganosiloxane is preferably 50 ° C. or higher, more preferably 80 ° C. or higher. The polymerization time of the polyorganosiloxane is preferably maintained for about 1 hour after the completion of the dropping of the latex in the method of dropping the latex in which the siloxane mixture is finely divided into the aqueous solution of the acid catalyst. In the case of mixing with a latex containing a mixture, an emulsifier, water, and the like, and polymerizing the mixture by micronization, it is 2 hours or longer, more preferably 5 hours or longer. When the polymerization of polyorganosiloxane carried out in this way is stopped, the reaction solution can be cooled, and the polyorganosiloxane latex can be further neutralized with an alkaline substance such as caustic soda, caustic potash or sodium carbonate.
The emulsifier is preferably an anionic emulsifier, and examples thereof include sodium alkylbenzene sulfonate, sodium polyoxyethylene nonylphenyl ether sulfate, sodium lauryl sulfate, and the like, and particularly sodium alkylbenzene sulfonate and sodium lauryl sulfate are preferable.
As the siloxane crosslinking agent, trifunctional or tetrafunctional silane crosslinking agents such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane are used.
Examples of the acid catalyst used for polymerization of polyorganosiloxane include aliphatic sulfonic acid, aliphatic substituted benzene sulfonic acid such as n-dodecylbenzene sulfonic acid, sulfonic acid such as aliphatic substituted naphthalene sulfonic acid, and sulfuric acid, hydrochloric acid, nitric acid, etc. Examples include mineral acids. These acid catalysts may be used alone or in combination of two or more. Among these, aliphatic substituted benzenesulfonic acid is preferable and n-dodecylbenzenesulfonic acid is particularly preferable in that it is excellent in stabilizing action of the polyorganosiloxane latex.

  The particle diameter of the polyorganosiloxane latex is preferably in the range of 10 to 140 nm, and more preferably 25 to 100 nm. If it is less than 10 nm, impact resistance may be reduced. On the other hand, if the particle size exceeds 140 nm, it is difficult to control the particle size of the composite rubber within the range of 30 to 140 nm.

A composite rubber latex can be obtained by adding an alkyl (meth) acrylate component to the polyorganosiloxane latex produced as described above and allowing the radical polymerization initiator to act on the polyorganosiloxane latex. Moreover, as a method of adding an alkyl (meth) acrylate component, there are a method of batch mixing with a polyorganosiloxane latex and a method of dropping at a constant rate into the polyorganosiloxane latex. In view of the impact resistance of the amorphous polyester resin composition of the present invention, a method of batch mixing with the polyorganosiloxane latex is preferred.
Further, as the radical polymerization initiator used for polymerization, a peroxide, an azo initiator, or a redox initiator combined with an oxidizing agent / reducing agent is used. Among these, a redox initiator is preferable, and a system in which ferrous sulfate, ethylenediaminetetraacetic acid disodium salt, Rongalite, and hydroperoxide are combined is particularly preferable.

The composite rubber produced in this way has a structure in which the polyorganosiloxane and the polyalkyl (meth) acrylate rubber are entangled with each other so as not to separate.
The average particle size of the composite rubber is 30 to 140 nm. Furthermore, 60-120 nm is more preferable. If the average particle size of the composite rubber is less than 30 nm, the impact resistance may be lowered. If a large amount of emulsifier is used, the appearance and other physical properties may be impaired. When the average particle size of the composite rubber exceeds 140 nm, the stress whitening resistance decreases.

  Examples of vinyl monomers to be graft-polymerized on a composite rubber containing polyorganosiloxane and polyalkyl (meth) acrylate include aromatic alkenyl compounds such as styrene, α-methylstyrene, vinyltoluene; methyl methacrylate, 2-ethylhexyl methacrylate Methacrylic acid esters such as methyl acrylate, ethyl acrylate, n-butyl acrylate, etc., and various vinyl monomers such as vinyl cyanide compounds such as acrylonitrile and methacrylonitrile. Or you may use 2 or more types together. In addition, if necessary, the vinyl monomer may have ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene having two or more unsaturated bonds in the molecule. Addition of a crosslinking agent such as glycol dimethacrylate, divinylbenzene, polyfunctional methacrylic group-modified silicone and the like, and a graft crossing agent such as allyl methacrylate, triallyl cyanurate, triallyl isocyanurate in the range of 20% by mass or less. May be used. In order to improve the dispersibility with the amorphous polyester resin composition, it is preferable to use 70 to 100% by mass of alkyl (meth) acrylate, particularly methyl methacrylate as the main component per 100% by mass of the graft monomer.

  The ratio of the organosiloxane rubber and the alkyl (meth) acrylate rubber in the composite rubber-based graft copolymer is not particularly limited, but the polyorganosiloxane is 0.1 to 90% by mass in 100% by mass of the composite rubber. It is preferably 0.5 to 30% by mass. When the polyorganosiloxane is less than 0.1% by mass, the effect of the organosiloxane is reduced and the impact resistance may be lowered. If the polyorganosiloxane exceeds 90% by mass, the compatibility with the graft component may be lowered, and the impact resistance may be lowered.

  The composite rubber-based graft copolymer is obtained by adding a vinyl monomer to the composite rubber latex and polymerizing it in one or more stages by radical polymerization. The composite rubber-based graft copolymer is prepared by adding the graft copolymer latex into hot water in which an acid such as sulfuric acid or hydrochloric acid, a metal salt such as calcium chloride, calcium acetate, or magnesium sulfate is dissolved, and salting out. It is obtained as particles by solidifying, separating and collecting. At this time, salts such as sodium carbonate and sodium sulfate may be used in combination. It can also be obtained by a direct drying method such as a spray drying method. The composite rubber-based graft copolymer thus obtained is blended and used in an amorphous polyester resin as an impact modifier.

  The ratio of the composite rubber and the vinyl monomer in the composite rubber-based graft copolymer is not particularly limited, but the composite rubber is 30 to 99% by mass and the vinyl monomer is 70 to 1% by mass. More preferably, the composite rubber is 51 to 90% by mass. When the vinyl monomer is less than 1% by mass, the dispersibility of the obtained composite rubber-based graft copolymer in the resin is lowered, and the processability of the amorphous polyester resin composition obtained by blending it is reduced. May decrease. On the other hand, if it exceeds 90% by mass, the impact resistance of the composite rubber-based graft copolymer may be lowered.

  In the amorphous polyester resin composition of the present invention, 1 to 50 parts by mass of (B) composite rubber-based graft copolymer may be blended with 99 to 50 parts by mass of (A) amorphous polyester resin. preferable. When the composite rubber-based graft copolymer is less than 1 part by mass, the impact resistance may not be improved. On the other hand, when the amorphous polyester resin composition contains 50 parts by mass or more of the (B) composite rubber-based graft copolymer, the original characteristics of the amorphous polyester resin may be impaired.

  Furthermore, workability and other physical properties can be improved by adding appropriate amounts of various lubricants to the resin composition as required. In particular, when an acrylic polymer lubricant is used, there is an effect of suppressing bleed-out during roll shaping.

As a method for producing the resin composition of the present invention, components (A) and (B) are separately produced in advance and then mixed using a conventional blending method such as a Henschel mixer, a tumbler, etc., and then single screw extrusion It is possible to adopt a method of forming a resin composition by shaping with an apparatus used for ordinary shaping, such as a machine or a twin screw extruder Banbury mixer.
In addition, antioxidants, heat stabilizers, light resistance improvers, ultraviolet absorbers, plasticizers, mold release agents, antistatic agents, and sliding properties that are commonly used as additives in the resin composition of the present invention are improved. An agent, a coloring agent, etc. may be added.

  The amorphous polyester resin composition of the present invention can be molded into various molded articles, and the resulting molded articles exhibit various physical properties such as weather resistance, impact resistance and stress whitening resistance in a highly balanced manner. It will be a thing. Examples of such molded products include resin sheets, films, wallpaper, and various parts, surface cosmetics, containers, bottles, foams, and the like, and are particularly suitable for sheets.

  The composition of the present invention will be described below with reference to examples, but these are illustrative only and do not limit the contents of the present invention.

Measurement of average particle size and particle size distribution The particle size of the rubber latex produced below was measured as follows. The obtained rubber latex was diluted with distilled water, and 0.1 ml of diluted latex having a concentration of about 3% was used as a sample, using a CHDF2000 type particle size distribution meter manufactured by MATEC USA, flow rate of 1.4 ml / min, pressure of about 2.76 MPa. (Approximately 4000 psi) and temperature 35 ° C. In the measurement, a capillary cartridge for particle separation and a carrier liquid were used, and the liquidity was made almost neutral. Before the measurement, a standard curve was prepared by measuring a total of 12 particle diameters from 0.02 μm to 0.8 μm, using monodisperse polystyrene with a known particle diameter manufactured by DUKE of the United States as a standard particle size substance. .

Manufacture of polyorganosiloxane latex (S-1) 2 parts by mass of tetraethoxysilane, 0.5 part by mass of γ-methacryloyloxypropyldimethoxymethylsilane and 97.5 parts by mass of octamethylcyclotetrasiloxane are mixed to obtain a siloxane-based mixture. 100 parts by mass were obtained. To this was added 300 parts by weight of distilled water in which 0.67 parts by weight of sodium dodecylbenzenesulfonate was dissolved, and the mixture was stirred for 2 minutes at 10,000 rpm with a homomixer and then passed twice through the homogenizer at a pressure of 300 kg / cm ² to stabilize. A premixed organosiloxane latex was obtained.
On the other hand, 10 parts by mass of dodecylbenzenesulfonic acid and 90 parts by mass of distilled water were injected into a separable flask equipped with a cooling condenser to prepare a 10% by mass aqueous solution of dodecylbenzenesulfonic acid.
While this aqueous solution was heated to 85 ° C., the premixed organosiloxane latex was added dropwise over 2 hours, and the temperature was maintained for 3 hours after the completion of the addition, followed by cooling. The reaction product was then neutralized with an aqueous caustic soda solution to obtain a latex.
The latex thus obtained was dried at 170 ° C. for 30 minutes and the solid content was determined to be 18.2% by mass. The degree of swelling of this latex was 15.6, the gel content was 87.6% by mass, and the number average particle size was 40 nm.

Production of polyorganosiloxane latex (S-2) to (S-5) Except for changing the type and amount of each raw material as shown in Table 1, in the same manner as the polyorganosiloxane latex (S-1), A latex was produced, and the particle size of the obtained latex is shown in Table 1.

Production of Silicone Latex (S-6) 2 parts by mass of tetraethoxysilane, 0.5 part by mass of γ-methacryloyloxypropyldimethoxymethylsilane and 97.5 parts by mass of octamethylcyclotetrasiloxane were mixed to obtain 100 parts by mass of a siloxane-based mixture. Got. 100 parts by mass of this siloxane-based mixture was added to 200 parts by mass of distilled water in which 1 part by mass of dodecylbenzenesulfonic acid and 1 part by mass of sodium dodecylbenzenesulfonate were dissolved, and preliminary dispersion with a homomixer and emulsification / dispersion with a homogenizer were performed. The premixed organosiloxane latex was heated at 80 ° C. for 5 hours, then cooled, and then allowed to stand at 20 ° C. for 48 hours, and then neutralized with an aqueous sodium hydroxide solution to 7.0 to complete the polymerization. A polyorganosiloxane latex was obtained. The polymerization rate of this organosiloxane was 87.6%, and the mass average particle diameter of the polyorganosiloxane rubber was 134 nm.

Production of composite rubber-based graft copolymer (G-1) 4 parts by mass of the above-prepared polyorganosiloxane latex (S-1) was collected in a separable flask, and 1 part by mass of sodium dodecylbenzenesulfonate and After adding 200 parts by mass of distilled water, a mixture of 66 parts by mass of butyl acrylate containing 2% allyl methacrylate and 0.33 parts by mass of tert-butyl hydroperoxide was added.
The atmosphere in the flask was replaced with nitrogen by passing a nitrogen stream through the separable flask, and the temperature was raised to 60 ° C. When the liquid temperature reached 60 ° C., an aqueous solution in which 0.003 parts by mass of ferrous sulfate, 0.009 parts by mass of disodium ethylenediaminetetraacetate and 0.4 parts by mass of Rongalite were dissolved in 10 parts by mass of distilled water. Addition to initiate radical polymerization. This state was maintained for 1 hour to complete the polymerization of the acrylate component to obtain a latex of a composite rubber of polyorganosiloxane and butyl acrylate. The mass average particle diameter of the composite rubber was 75 nm.
After the liquid temperature of the latex dropped to 60 ° C., a mixed solution of 0.15 parts by mass of tert-butyl hydroperoxide, 29 parts by mass of methyl methacrylate and 1 part by mass of butyl acrylate was dropped over 60 minutes, and then at 70 ° C. Hold for 2 hours to complete the graft polymerization. The obtained acrylic rubber-based graft copolymer latex is dropped into 200 parts by mass of hot water of 1.5% calcium chloride, solidified, separated, washed, dried at 65 ° C. for 24 hours, and powdered acrylic rubber-based A graft copolymer (G-1) was obtained.

Production of composite rubber-based graft copolymers (G-2) to (G-10) The composite rubber-based graft copolymer (G-1) except that the type and amount of each raw material were changed as shown in Table 2. ) To produce composite rubber-based graft copolymers (G-2) to (G-10). The particle diameter is also shown in Table 2.

Production of acrylic rubber-based graft copolymer (G-11) 195 parts by mass of distilled water and 0.3 part by mass of sodium lauryl sulfate were added to a separable flask equipped with a stirrer, followed by nitrogen substitution, and the temperature was raised to 50 ° C. . Next, a mixed liquid of 0.002 parts by mass of ferrous sulfate, 0.006 parts by mass of disodium ethylenediaminetetraacetate, 0.26 parts by mass of Rongalite and 5 parts by mass of distilled water was added, and 2% of nitrogen-substituted 2% A mixture of 70 parts by mass of n-butyl acrylate containing allyl methacrylate and 0.35 parts by mass of t-butyl hydroperoxide was added to initiate radical polymerization. Thereafter, the polymerization was completed by maintaining the liquid temperature at 70 ° C. for 2 hours to obtain a rubber latex.
To this rubber latex, a mixed solution of 0.3 part by weight of sodium lauryl sulfate, 0.30 part by weight of t-butyl hydroperoxide, 29 parts by weight of methyl methacrylate and 1 part by weight of butyl acrylate was added dropwise at 65 ° C. over 30 minutes. Thereafter, the mixture was held at 70 ° C. for 1 hour to complete the graft polymerization to the rubber latex, and an acrylic graft copolymer latex was obtained. A part of this graft copolymer latex was sampled and the mass average particle diameter was measured. The polymerization rate of methyl methacrylate was 99.2%.
Then, the powdery acrylic rubber-type graft copolymer was obtained by the method similar to the said composite rubber-type graft copolymer (G-1).

Production of butadiene-based graft copolymer (G-12) In a pressure-resistant autoclave, 150 parts by mass of deionized water, 60 parts by mass of 1,3-butadiene, 40 parts by mass of styrene, 0.5 part by mass of t-dodecyl mercaptan, diisopropyl Benzene hydroperoxide 0.4 parts by mass, sodium pyrophosphate 1.5 parts by mass, ferrous sulfate 0.02 parts by mass, dextrose 1.0 parts by mass, and potassium oleate 1.0 parts by mass were stirred. Then, the reaction was carried out at 50 ° C. for 15 hours to produce a butadiene rubber polymerized latex. The particle size of this rubber latex was 80 nm.
70 parts by mass (as a solid content) of this butadiene-based rubber polymerization latex was charged into a flask and purged with nitrogen. Then, 1.2 parts by mass of NaHCO ₃ was added to a 10% aqueous solution and stirred for 30 minutes. To this solution, 1 part by mass of potassium oleate was added as a 7% aqueous solution and stabilized. Thereafter, 0.6 parts by mass of Rongalite was added and the liquid temperature was maintained at 70 ° C., and a mixed liquid of 29 parts by mass of methyl methacrylate, 1 part by mass of butyl acrylate and 0.2 part by mass of cumene hydroperoxide was added to butadiene. Graft polymerization was carried out on the rubber-based latex polymer.
After adding 0.5 parts by mass of dibutylhydroxytoluene (BHT) to the obtained graft copolymer latex, 0.2% sulfuric acid aqueous solution is added to coagulate the graft copolymer and heat treatment at 90 ° C. Solidified. Thereafter, the coagulated product was washed with warm water and further dried to obtain MBS resin-based graft copolymer (G-12) powder.

After blending (A) amorphous polyester resin (Easter 6863 manufactured by Eastman Kodak Co.), (B) graft copolymer, and (C) lubricant in the ratios shown in Tables 3 and 4, they were premixed and manufactured by Kansai Roll. It was melt-kneaded with an 8-inch heating roll to obtain a resin composition.
Subsequently, a molded product of about 1 mm sheet was obtained.
Impact Resistance Three sheets of each obtained sheet were stacked using a press machine, and the test piece obtained by cutting was used to evaluate the impact strength at 23 ° C. according to ASTM D-256. .

Stress whitening resistance A sheet with a thickness of 1 mm was formed in the same manner as described above, and a 1 cm tip diameter was used with a DuPont impact strength measuring device, and the weight was dropped from a height of 50 cm with a 200 g load. It was deformed, and the degree of whitening of the deformed portion was visually evaluated in five stages from A (good) to E (bad).

Weather resistance Eye super UV manufactured by Dainippon Plastics Co., Ltd., which was prepared by adjusting the temperature of a 3.2 mm sheet specimen prepared by the same composition and method as described above except that 0.3 part by mass of carbon black was added. After 8 hours on the tester, the operation of placing in a constant temperature and humidity controlled at 60 ° C. and 95% for 16 hours was repeated 5 times, and the appearance of the sheet test piece was A (good) to E (bad). Visual evaluation was performed in five stages.

(A) Amorphous polyester resin: PETG Easter 6763 (manufactured by Eastman Kodak Company)
(B) Graft copolymer: (G-1) to (G-12)
(C) Lubricant: (C-1) Montanate ester wax: Licowax (manufactured by Clariant Japan), (C-2) Metabrene L-1000 (manufactured by Mitsubishi Rayon Co., Ltd.)

As is clear from the results of Tables 3 and 4, the resin compositions of Examples 1 to 10 which are the resin compositions of the present invention were excellent in weather resistance, impact resistance and stress whitening resistance in a high balance. .
On the other hand, it is clear that Comparative Examples 1 to 8 do not have performances such as weather resistance, impact resistance, and stress whitening resistance that are the object of the present invention.

  The amorphous polyester resin composition of the present invention is useful for various molded articles such as resin sheets, films, wallpaper, various parts, surface cosmetics, containers, bottles, foams and the like.

Claims (4)

(A) A thermoplastic resin composition containing a thermoplastic resin component containing an amorphous polyester resin, and (B) a composite rubber-based graft copolymer containing a polyorganosiloxane and a polyalkyl (meth) acrylate. There,
(B) An amorphous polyester resin composition, wherein the composite rubber-based graft copolymer has a particulate composite rubber having an average particle size of 30 to 140 nm.   2. The amorphous polyester resin composition according to claim 1, wherein the polyorganosiloxane (B) is a particle having an average particle size of 25 to 100 nm.   A molded product obtained by molding the amorphous polyester resin composition according to claim 1. The molded article according to claim 3, which is a resin sheet.