JPH09124889A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition good in moldability and giving molded products good in impact resistance, chemical resistance and appearance by compounding two kinds of specific graft copolymers and a rigid copolymer. SOLUTION: Thus resin composition comprises (A) a graft copolymer the graft degree Gr% of the equation I [(x) is the weight of a sample; (y) is the weight of acetone insolubles at the ordinary temperature] satisfies the inequality II (R is the fraction of a dienic rubbery polymer)} produced by emulsion-grafting a monomer mixture (comprising 40-80wt.% of an aromatic vinyl monomer, 20-60wt.% of a vinyl cyanide monomer and 0-20wt.% of a vinylic comonomer) to the dienic rubber polymer having a weight-average particle diameter of 0.10-0.65μm, (B) a graft copolymer obtained by emulsion-polymerizing the above monomer mixture to an acrylic rubber polymer, and (C) a rigid copolymer produced by copolymerizing the above monomer mixture, in the composition ratios of the inequalities III and IV.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition. More specifically, two types of specific graft copolymers, or two types of specific graft copolymers and a copolymer, impact resistance, chemical resistance, good moldability,
And a thermoplastic resin composition which has a good appearance and is not only used as an impact resistant resin material itself but also useful for compounding this resin with other resins to form an impact resistant resin composition. Regarding things.

[0002]

BACKGROUND ART Graft copolymerization is well known as one of the methods for obtaining an impact resistant resin, and it is known that a resinous polymer is obtained in the presence of a rubbery polymer (for example, a latex of a conjugated diene polymer). A graft copolymerized thermoplastic resin composition produced by polymerizing a monomer (for example, styrene + acrylonitrile) to give a resin is praised as an impact resistant resin. Among them, the graft copolymer composed of polybutadiene / styrene / acrylonitrile is well known as an ABS resin.

However, ABS resins, for example, are inferior in chemical resistance and the like, such that when they are brought into contact with a specific chemical agent under a stress-loaded state, a crack is generated, and in a remarkable case, a phenomenon of breaking is observed. there were. To obtain a resin excellent in these properties, a method of increasing the compounding ratio of the acrylonitrile component in the ABS resin (for example, JP-A-47-5594), ABS resin and acrylic rubber / styrene / acrylonitrile (ASA resin) A (Japanese Patent Publication No. 54-40258, Japanese Patent Publication No. 63-28460), A
A method of adding an acrylic acid ester-based polymer to a BS resin (Japanese Patent Publication No. Sho 63-22222) and a method of mixing two characteristic graft copolymers (Japanese Examined Patent Publication No. 57-22064).
No. 2-175745) and the like are known.

[0004]

However, it can be said that these techniques are meaningful as a solution to the existing problems, but on the other hand, a defective phenomenon occurs in the appearance of the molded product, Injection moldability, extrusion moldability,
As far as the inventors of the present invention know, the sheet vacuum (pneumatic) formability and the like are not completely satisfactory.

That is, among the proposed methods, Japanese Patent Laid-Open No.
47-5594, JP 54-40258, JP 63-2222
No. 2, Japanese Patent Publication No. 63-28460, etc., a defective phenomenon is observed in the surface condition of the injection-molded product, for example, a surface appearance defect called a flow mark, or a surface peeling phenomenon is observed. In some cases, a die band or defective surface appearance called a pit mark may be observed on the surface of the extruded product, which is a serious problem in use. Further, in the one proposed in Japanese Patent Laid-Open No. 47-5594, the melt viscosity of the resin increases, so that not only the extrusion moldability decreases but also the corner portion of the box during the sheet vacuum (pressure) molding. For example, the portion having a high draw ratio tends to have a non-uniform wall thickness. In addition, Japanese Examined Sho 57-220
The ones proposed in Japanese Patent Laid-Open No. 64 and Japanese Patent Laid-Open No. 2-175745 have insufficient chemical resistance, and in the field where more chemical resistance is required, they still pose a problem in use.

In view of the above-mentioned circumstances, the present invention molds a sheet manufactured by an extrusion molding method with impact resistance, chemical resistance, a good appearance of a molded article, and a desired shape by a vacuum (compressed air) molding method. At the same time, it is an object of the present invention to provide a thermoplastic resin composition having excellent moldability such that a portion having a high draw ratio such as a corner portion of a box has a uniform wall thickness.

[0007]

The present inventors have arrived at the present invention as a result of intensive studies to solve the above problems. That is, a diene rubbery polymer having a specific average particle diameter, a monomer mixture comprising an aromatic vinyl monomer, a vinyl cyanide monomer, and a copolymerizable vinyl monomer in a specific ratio. A specific graft copolymer (A) obtained by a graft reaction of an emulsion polymerization method with an acrylic rubbery polymer in a specific ratio of an aromatic vinyl monomer, a vinyl cyanide monomer, and a copolymer. The graft copolymer (B) obtained by graft-reacting a monomer mixture composed of a polymerizable vinyl monomer by an emulsion polymerization method, and a hard copolymer (C) having an affinity for them are contained in a specific ratio. The present invention has been accomplished by discovering that a resin composition obtained by uniformly mixing with the above-mentioned compound has excellent chemical resistance, impact resistance, molding processability, and appearance that could not be obtained by conventional compositions.

That is, in order to solve the above problems, the present invention provides a graft copolymer A, a graft copolymer B and a hard copolymer C shown below with the following formulas (3) and (4): The present invention provides a thermoplastic resin composition characterized in that it is contained in a composition ratio. Graft Copolymer A: Graft Copolymer A is defined as follows.

(1) 40 to 80% by weight of an aromatic vinyl monomer, 20 to 60% by weight of a vinyl cyanide monomer, and a copolymerizable vinyl monomer in the presence of a diene rubbery polymer latex. Graft copolymer obtained by emulsion graft polymerization of a monomer mixture consisting of 0 to 20% by weight of the polymer, and (2) the weight average particle diameter of the diene rubber polymer is 0.1.
Have a particle size of 0 to 0.65 μm.

(3) The diene rubbery polymer fraction R is 0.
Must be 3 to 0.8. (4) The soluble content when the graft copolymer A is subjected to room temperature acetone extraction has a weight average molecular weight of 200,000 or more. (5) The graft ratio Gr represented by the following formula (1) of the graft copolymer A satisfies the following formula (2).

[0011]

(Equation 5)

[0012]

(Equation 6) (Here, the symbols have the following meanings: x: weight of graft copolymer composition sample, y: weight of acetone insoluble at room temperature in x, Gr: graft ratio%)

Graft Copolymer B: Graft Copolymer B
Is defined as follows. (1) In the presence of 100 parts by weight (based on the solid content) of the acrylic rubber polymer latex, 2 parts by weight or more of the vinyl monomer mixture with respect to the solid content of the latex are reacted by the emulsion polymerization method. Be united.

(2) The vinyl monomer mixture contains 40 to 80% by weight of an aromatic vinyl monomer and 20 vinyl cyanide monomers.
To 60% by weight and 0 to 20 copolymerizable vinyl monomers
Must consist of weight percent. (3) Acrylic rubbery polymer is an ester compound 7 of a monohydric alcohol having 2 to 12 carbon atoms and acrylic acid.
0-100% by weight, copolymerizable vinyl monomer 0-30
It should be obtained by emulsion-polymerizing a monomer mixture of 0 to 3% by weight and a polyfunctional vinyl monomer.

Hard Copolymer C: The hard copolymer C is defined as follows. (1) A monomer mixture comprising 40 to 80% by weight of an aromatic vinyl monomer, 20 to 60% by weight of a vinyl cyanide monomer, and 0 to 20% by weight of a copolymerizable vinyl monomer. Hard copolymer C obtained by polymerization.

[0016]

(Equation 7)

[0017]

(Equation 8)

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The thermoplastic resin composition according to the present invention comprises a graft copolymer A obtained by emulsion-polymerizing a specific monomer in the presence of a diene rubbery polymer latex.
A graft copolymer B obtained by emulsion-polymerizing a specific monomer in the presence of an acrylic rubbery polymer latex;
It is a mixture of a hard copolymer C composed of a specific monomer and having a substantially uniform composition.

I, Graft Copolymer (1) General Description As usual in graft copolymers, all the monomers that are to be "branches" are combined with a rubbery polymer having a "stem" to form "branches". However, the "graft copolymer" in the present invention is also a polymer derived from a "branch" monomer which is not such "branch" according to the commonly used place. It allows the coexistence of.

1) Rubber Polymer The graft copolymers A and B in the present invention can be obtained by emulsion graft polymerization of a monomer mixture to be “branches” in the presence of a rubber polymer latex described later. It is a thing.
The rubbery polymer, which is the “stem” of the graft copolymer, has a glass transition temperature lower than room temperature. Such a rubbery polymer can be produced by a conventionally known emulsion polymerization method. 2) Graft Polymerization The graft copolymerization thermoplastic resin composition according to the present invention comprises an aromatic vinyl monomer, a vinyl cyanide monomer and other copolymerizable other monomers in the presence of a latex of a rubber polymer described below. It is obtained by a graft polymerization reaction of a vinyl monomer mixture by an emulsion polymerization method. Graft copolymerization conditions are essentially the same as those conventionally used in the production of ABS resins, as long as they meet the requirements of the present invention. Further, the graft copolymerization conditions of the graft copolymers A and B do not have to be the same, and optimum conditions can be selected for each.

<Monomer> Examples of the aromatic vinyl monomer used in the present invention include styrene, and side-chain or / and nucleus-substituted styrene (substituents are a lower alkyl group, a lower alkoxy group, trifluoromethyl group). Group, halogen atom,
Others), for example, α-methylstyrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, nuclear halogenated styrene, α- or β-vinylnaphthalene, and the like. These may be used together within a group or between groups. The types of monomers used in the graft copolymers A and B (as well as the hard copolymer C) may be the same or different.

The vinyl cyanide monomer used in the present invention includes acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and the like. These are one or two
It may be a mixture of more than one species. As the monomer, a small amount of a comonomer copolymerizable therewith may be used in combination unless the purpose of the present invention is impaired. As such a monomer, an ester of acrylic acid or methacrylic acid and an alkanol having a carbon number of 1 to 10, particularly methyl acrylate and methyl methacrylate, a diene monomer, divinylbenzene, (poly) alkylene glycol dicarboxylic acid is used. There are (meth) acrylates and others.

<Graft Polymerization Reaction> Graft copolymerization is
It is carried out in the presence of a polymerization initiator. Initiators (or catalysts) that can be used include peracid catalysts such as persulfuric acid, peracetic acid, and perphthalic acid, persalt catalysts such as potassium persulfate and ammonium persulfate, hydrogen peroxide, benzoyl peroxide, and peroxides. Peroxide catalysts such as chlorobenzoyl oxide, naphthyl peroxide, acetyl peroxide, benzoylacetyl peroxide and lauryl peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, azobis compounds such as azobisisobutyronitrile There are catalysts, and these are used alone or in combination of two or more. They can also be used as redox catalysts in combination with reducing agents.

The graft copolymerization can be carried out in the presence of a chain transfer agent. The chain transfer agent used in the present invention is not particularly limited, but for example, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, etc., or terpinolene, α-methylstyrene linear dimer, etc. are used. The polymerization temperature condition in the graft copolymerization is 50 to 85 ° C, preferably 55 to 75 ° C.
The range of ° C is suitable. If the temperature is lower than 50 ° C, the polymerization reaction rate is too slow to be practical. On the other hand, if the temperature is higher than 85 ° C, the amount of coagulated substances or deposits increases at one time, which lowers the polymerization yield and quality of the final product. It is not preferable because it causes

Regarding the production of the graft copolymer, first, a graft copolymer latex specified in the range described below is produced, and an aromatic vinyl monomer, a vinyl cyanide monomer, and a copolymerizable vinyl monomer are added. The hard polymer latex obtained by copolymerizing the polymer may be mixed, or the graft copolymer may be directly produced without mixing the hard polymer latex. At this time, the weight ratio of the "branching" monomer of the graft copolymer latex to be mixed and the weight ratio of the hard polymer latex monomer may be the same or different.

The other graft copolymerization conditions are essentially the same as those conventionally used in the manufacture of ABS resins. The entire amount of the graft copolymerization monomer may be introduced into the polymerization system at once, or may be introduced stepwise. Further, the temperature during the polymerization can be changed with time.

(2) Graft Copolymer A 1) Rubbery Polymer The "trunk" rubbery polymer of the graft copolymer A is a diene rubbery polymer. Specifically, a homopolymer of a diene having 4 to 5 carbon atoms such as 1,3 butadiene, isoprene or chloroprene and a copolymer containing 50% by weight or more of such a conjugated diene are typical. The copolymer may be either a random copolymer or a block copolymer. Examples of the monomer that can be used for copolymerization with a conjugated diene, particularly butadiene include aromatic vinyl monomers such as styrene, α-methylstyrene and vinyltoluene, acrylic acid, methacrylic acid and their methyl, ethyl, propyl, n. -Acrylic monomers such as butyl and vinyl cyanide monomers such as acrylonitonyl and methacrylonitrile. Such a rubbery polymer latex can be produced by emulsion polymerization of a predetermined monomer or a mixture thereof in an aqueous medium at once or stepwise.

The "trunk" diene rubbery polymer of the graft copolymer A has an average particle size of 0.10 to 0.65 μm, preferably 0.15 to 0.45 μm.
When it is 0.10 μm or less, the impact resistance of the finally obtained resin is remarkably inferior and the molding processability is also insufficient.
When it is 0.65 μm or more, the appearance is deteriorated and only a resin having low impact resistance can be obtained. Further, in emulsion graft polymerization, destabilization of the latex is caused and problems such as an increase in scale amount occur during polymerization. It is not preferable.

The diene rubbery polymer latex having a relatively large particle size as described above can be directly obtained with a large particle size by selecting the production conditions, and the diene rubbery polymer having a small particle size can be obtained. It may be obtained by producing a latex and performing an operation of increasing the particle size. Particle size enlargement is a known method, for example,
Freezing the latex once and then re-dissolving it, adding mineral acid, organic acid, etc. to the latex to adjust the latex pH.
And a method of applying a shearing force to the latex (JP-A-54-133588, JP-A-59-202211).
Issue). In particular, the method of adding phosphoric acid or acetic anhydride to the latex is preferable because the particle size can be easily adjusted. The particle size distribution of the diene rubber polymer does not necessarily have to be monomodal, and may be multimodal, that is, a mixture of various particle sizes. The weight average particle diameter of the diene rubbery polymer latex in the present invention is measured by "N4S" manufactured by Coulter Co., USA.

2) Graft Polymerization and Graft Copolymer The monomer mixture used for producing the graft copolymer A is 40 to 80% by weight of an aromatic vinyl monomer and 20 to 20% of a vinyl cyanide monomer. 60% by weight and 0 to 20% by weight of a copolymerizable vinyl monomer, preferably 45
-80% by weight, 20-55% by weight, and 0-20% by weight. If the amount of the vinyl cyanide monomer exceeds the range of these weight ratios, the processability and the color tone decrease, and if it decreases, the chemical resistance decreases, which is not preferable. The fraction of the diene rubbery polymer in the graft copolymer A is 0.3 to
0.8, preferably 0.35 to 0.7. If the content of the rubbery polymer is less than this range, the composition of the present invention does not have sufficient impact resistance, and if it is higher than this range, sufficient rigidity cannot be obtained.

When the graft copolymer A is extracted with acetone at room temperature, the soluble component has a weight average molecular weight of 200,000 or more. If the molecular weight is lower than this value, the moldability decreases,
In addition, sufficient rigidity cannot be obtained. The graft copolymer having such a molecular weight extract has a polymerization temperature of graft polymerization,
It can be obtained by adjusting the amount of chain transfer agent, initiator and the like. The insoluble matter when the graft copolymer A is extracted with acetone at room temperature satisfies the following expressions (1) and (2).

[0032]

(Equation 9)

[0033]

(Equation 10)

(Here, the symbols have the following meanings: x: weight of graft copolymer composition sample, y: weight of insoluble acetone at room temperature in x, Gr: graft ratio%)

If the value is out of the range of the above equation, not only sufficient mechanical strength cannot be exhibited, but also molding processability is deteriorated.
The graft copolymer having such a value can be obtained by adjusting the amount of the monomer mixture, the polymerization temperature of the graft polymerization, the amount of the chain transfer agent, the amount of the initiator and the like.

(3) Graft Copolymer B 1) Rubber Polymer Latex The acrylic rubber polymer used in the graft copolymer B has a glass transition temperature lower than room temperature and has 2 to 10 carbon atoms. Twelve, preferably 4 to 8 ester compounds of monohydric alcohol and acrylic acid 70 to 100% by weight, copolymerizable vinyl monomers 0 to 30% by weight, and polyfunctional vinyl monomers 0 to It was obtained by emulsion-polymerizing a monomer mixture of 3% by weight, and is butyl acrylate, 2-ethylhexyl acrylate or the like. When the carbon number is out of the above range, sufficient rubber elasticity cannot be obtained, which is not preferable. These acrylic ester compounds may be used alone or in combination of two or more. Such a latex of a rubber polymer can be produced by emulsion polymerization of a predetermined monomer or a mixture thereof in an aqueous medium at once or stepwise.

The particle size of the rubber polymer is in the range of 0.05 to 0.50 μm, preferably 0.10 to 0.40 μm. If it is less than 0.05 μm, the impact resistance of the finally obtained resin will be remarkably inferior and the moldability will be insufficient. If it is 0.35 μm or more, the appearance may be deteriorated. The rubber-polymerized latex having a relatively large particle size as described above may be obtained by performing an operation of particle size enlargement in order to obtain a target particle size for a latex having a small particle size. It is similar to the case of A. The particle size distribution of the acrylic rubbery polymer is not necessarily monomodal, and may be multimodal, that is, a mixture of various particle sizes. The weight average particle size of the acrylic rubbery polymer latex is measured by "N4S" manufactured by Coulter Co., USA.

2) Graft Polymerization and Graft Copolymer The rubber polymer content is 200 parts by weight or more, preferably 200 to 550 parts by weight, based on 100 parts by weight of the acrylic rubbery polymer. Is. If the amount of the monomer mixture is less than this range, the composition of the present invention cannot obtain a good appearance, and if it is more than this range, sufficient chemical resistance cannot be obtained. The weight ratio of the "branching" monomer in the graft copolymer A is 40 to 80% by weight of the aromatic vinyl monomer, 20 to 60% by weight of the vinyl cyanide monomer, and the copolymerizable vinyl monomer. 0 to 20% by weight, preferably each,
45-80% by weight, 20-55% by weight, and 0-2
0% by weight. If the amount of the vinyl cyanide monomer exceeds the range of these weight ratios, the processability and the color tone decrease, and if it decreases, the chemical resistance decreases, which is not preferable.

II, Hard Copolymer C The hard copolymer C constituting the composition of the present invention means that the aromatic vinyl monomer is 40 to 80% by weight and the vinyl cyanide monomer is 20 to 60% by weight. , And copolymerizable vinyl monomer 0
-20% by weight, preferably 45-75% by weight, 25-55% by weight, and 0-20% by weight, respectively, a polymerization product of a monomer mixture. If the amount of the vinyl cyanide monomer exceeds the range of these weight ratios, the processability and the color tone decrease, and if it decreases, the chemical resistance decreases, which is not preferable.

The aromatic vinyl monomer, the vinyl cyanide monomer and the copolymerizable vinyl monomer, which are the constituents of the above-mentioned copolymer, are those exemplified above as the constituents of the graft copolymer. Is the same as. The polymerization method and polymerization conditions of the above-mentioned copolymer can be appropriately selected from a batch polymerization method and a continuous polymerization method such as a solution polymerization method, a bulk polymerization method and a suspension polymerization method. (See Japanese Laid-Open Patent Publication No. 62-1720).

The composition of the monomer components constituting the graft copolymers A and B and the hard copolymer C in the present invention may be within the ranges defined above, and it is said that the compositions of both are exactly the same. Does not necessarily mean that. However, even if both are selected within the above range and combined, if the compositions of both are remarkably different, the compatibility of both resins is deteriorated and the physical properties are deteriorated, which is not preferable.

"Thermoplastic Resin Composition" The thermoplastic resin composition according to the present invention is composed of the graft copolymers A and B and the hard copolymer C as described above,
The composition ratio is within the range shown by the equations (3) and (4). If the blending amount of each copolymer is out of the range of the formulas (3) and (4), the desired physical properties cannot be obtained, and a thermoplastic resin composition having good chemical resistance cannot be obtained. .

[0043]

[Equation 11]

[0044]

(Equation 12)

As shown in the formula (3), the rubber-like polymer contained in the thermoplastic resin composition according to the present invention is a rubber-like polymer obtained from the graft copolymer A. 20 to 20 per the total of the rubbery polymers of B and B
Must be 90% by weight. Further, as shown in the formula (4), the total amount of the rubber-like polymer obtained from the graft copolymers A and B is 5 to 50% by weight based on the total amount of the graft copolymers A and B and the hard copolymer C. Must.

A known mixing and kneading method may be used for blending and kneading the graft copolymer and the copolymer. At this time, the kneading temperature is preferably selected within a range from a temperature at which the composition melts to a temperature at which resin burning does not occur. The mixture of one or two kinds of these copolymers in the form of powder, beads, flakes or pellets can be used as a single-screw extruder, a twin-screw extruder, or a kneading machine such as a Banbury mixer, a pressure kneader, or a twin roll. A composition can be prepared by In some cases, one or two of these copolymers that have been polymerized may be mixed in an undried state, precipitated, washed, dried, and kneaded.

The composition according to the present invention contains a lubricant and a mold release agent, a mold release agent, a plasticizer, a colorant, an antistatic agent, a flame retardant, an ultraviolet absorber, and a light resistance which do not impair the properties as a resin. Various resin additives such as a stability stabilizer, a heat resistance stabilizer, and a filler can be appropriately combined and added. The composition according to the present invention includes an injection molding method, an extrusion molding method, a thermoforming method,
Formed by various processing methods such as press molding,
It can be used in applications where excellent chemical resistance, workability and impact resistance are required.

[0048]

EXAMPLES The following examples and comparative examples are intended to explain the present invention more specifically, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. In each of the following examples and comparative examples, the physical properties of the impact-resistant styrene resin were measured by the following methods.

(1) Izod impact strength Measured according to JIS K7110. (2) Melt flow rate Measured under the conditions of 220 ° C. and 10 kg in accordance with JIS K7210, and displayed as the number of g flowing out for 10 minutes. (3) Tensile Strength It was measured according to JIS K7113. (4) VICAT Softening Point It was measured according to JIS K7206. (5) Average particle size of latex The average particle size of latex is “N4” manufactured by Coulter, Inc. in the United States.
S ".

(6) Weight average molecular weight The weight average molecular weight of the soluble component obtained by subjecting the graft copolymer to extraction with acetone at room temperature is as follows.
GPC SYSTEM-11 ”was used for measurement and expressed in terms of polystyrene.

(7) Appearance Injection-molded test piece (thickness 2.5 mm, width 75 mm, length 160)
(mm) gloss and the degree of flow marks were visually determined as follows. ○: Decrease in gloss or no flow mark △: Decrease in gloss or slight flow mark ×: Decrease in gloss or considerable flow mark

(8) Chemical resistance Press-molded test pieces (thickness 2 mm, width 35 mm, length 230 m)
m) according to the bending foam method
The critical strain value of crack initiation for b is measured at a temperature of 23 ° C.,
It was determined as follows. ◎: Critical strain value of 0.8% or more, excellent chemical resistance ○: Critical strain value of 0.8 to 0.6%, good chemical resistance ×: Critical strain value of 0.6% or less, poor chemical resistance

[Manufacturing Example] 1. Manufacture of graft copolymer (A) A-1 (1) Manufacture of conjugated diene rubbery polymer 150 parts of 5 LSUS autoclave with deionized water and higher fatty acid soap (having 18 carbon atoms) (Sodium salt of fatty acid containing as main component) and 0.075 part of sodium hydroxide were charged, and the temperature was raised to 68 ° C. after nitrogen substitution. After 20% of a monomer mixture consisting of 90 parts of 1,3-butadiene (BD), 10 parts of styrene (ST) and 0.3 part of t-dodecyl mercaptan (TDM) was charged, potassium persulfate was added to 0.2%.
135 parts were added. Exothermic heat was generated in about several minutes, and the initiation of polymerization was confirmed. After 1 hour from the addition of potassium persulfate, continuous charging of 80% of the monomer mixture was started and completed at 6 hours. After adding the monomer mixture, the temperature is adjusted to 80
The temperature was raised to 0 ° C and the polymerization was further proceeded for 1 hour. The obtained diene rubbery polymer latex has a solid content concentration of 39.5.
%, The average particle size was 0.08 μm, and the gel content was 95.0%.

(2) Preparation of Graft Copolymer In a reactor having a capacity of 5 L equipped with a stirrer, a heating / cooling device, each raw material and an auxiliary charging device, the above-mentioned conjugated diene rubber latex was mixed with acetic anhydride to give a 0.1. 100 parts of solid content and 346 parts of deionized water (including water in the latex) were charged with the particle size enlarged to 30 μm, and the temperature was raised to 70 ° C. Styrene (ST) 73.
3 parts, acrylonitrile (AN) 48.9 parts, potassium persulfate 0.39 parts, disproportionated potassium rosinate soap 2.4
Parts, 0.45 parts potassium hydroxide, 41 parts deionized water 3 parts
Added over 30 minutes. In the middle of the process, 0.31 part of terpinolene (terpene compound) was added 30 minutes after the addition of the monomers and the like was started. 30 more after addition
The reaction was continued for a minute and then cooled to complete the reaction. After adding 2.5 parts of an antioxidant to this graft copolymer latex, it is added to an aqueous magnesium sulfate solution heated to 95 ° C. with stirring to coagulate, and the coagulated product is washed with water and dried to give a white powdery resin composition. I got A-1.

A-2 (1) Production of conjugated diene rubbery polymer It was carried out in the same manner as in A-1 (1). (2) Production of graft copolymer In a reactor having a capacity of 5 L equipped with a stirrer, a heating / cooling device, each raw material and an auxiliary charging device, the above conjugated diene rubber latex was 0.25 μm particles using acetic anhydride. The diameter-expanded product was charged with 100 parts as solid content and 451 parts of deionized water (including water in latex), and the temperature was raised to 70 ° C. 111.4 parts of styrene from the time of reaching 70 ° C,
Acrylonitrile 74.3 parts, potassium persulfate 0.59
Parts, terpinolene 0.46 parts, disproportionated potassium rosinate soap 3.7 parts, potassium hydroxide 0.45 parts, deionized water 41 parts were added over 5 hours and 30 minutes. After the addition was completed, the reaction was continued for another 30 minutes, cooled, and the reaction was completed.
After adding 2.5 parts of an antioxidant to this graft copolymer latex, it is added to an aqueous magnesium sulfate solution heated to 95 ° C. with stirring to coagulate, and the coagulated product is washed with water and dried to give a white powdery resin composition. I got A-2.

A-3 (1) Production of Conjugated Diene Rubber Polymer The same procedure as in A-1 (1) was carried out. (2) Production of graft copolymer In a reactor having a capacity of 5 L equipped with a stirrer, a heating / cooling device, raw materials, and an auxiliary charging device, the conjugated diene rubber latex was granulated to 0.30 μm using acetic anhydride. The diameter-enlarged product was charged with 100 parts as solid content and 218 parts of deionized water (including water in latex), and the temperature was raised to 70 ° C. During the heating, at 60 ° C., 0.43 part of sodium pyrophosphate, 0.11 part of dextrose and 0.004 part of ferrous sulfate dissolved in 14 parts of water were added. When the temperature reached 70 ° C., 25.7 parts of styrene, acrylonitrile 17.
1 part, terpinolene 0.11 part, cumene hydroperoxide 0.21 part, disproportionated potassium rosinate soap 0.9 part, potassium hydroxide 0.16 part, deionized water 14
Parts were added over 1 hour and 20 minutes. After the addition was completed, the reaction was continued for another 30 minutes, cooled, and the reaction was completed. After adding 5 parts of an anti-aging agent to this graft copolymer latex, it is added to an aqueous magnesium sulfate solution heated to 95 ° C. with stirring to coagulate, and the coagulated product is washed with water and dried to give a white powdery resin composition A- Got three.

A-4 (1) Production of Conjugated Diene Rubber Polymer The same procedure as in A-1 (1) was carried out. (2) Production of graft copolymer In a reactor having a capacity of 5 L equipped with a stirrer, a heating / cooling device, each raw material and an auxiliary charging device, the above conjugated diene rubber latex was granulated to 0.24 μm by using phosphoric acid. The diameter-expanded product was charged with 100 parts as solid content and 361 parts of deionized water, and the temperature was raised to 74 ° C. When reaching 74 ° C, 4
0.5 parts potassium persulfate dissolved in 4.6 parts deionized water
Simultaneously with the addition of 9 parts, a monomer mixture of 130 parts of styrene, 55.7 parts of acrylonitrile and 0.55 part of terpinolene was added over 4 hours and 30 minutes. On the way, 0.38 parts of potassium hydroxide was dissolved in 27.6 parts of deionized water after 1 hour and 2 hours and 30 minutes after the addition of the monomer mixture was started. Soap (carbon number 1
Sodium salt of fatty acid 8) was added.
After addition of the monomer mixture, continue the reaction for another 30 minutes,
The reaction was completed by cooling. After adding 4 parts of an antioxidant to this graft copolymer latex, the mixture is added to an aqueous magnesium sulfate solution heated to 95 ° C with stirring to coagulate, and the coagulated product is washed with water and dried to give a white powdery resin composition A- Four
I got

A-5 (1) Production of Conjugated Diene Rubber Polymer The same procedure as in A-1 (1) was carried out. (2) Production of graft copolymer In a reactor having a capacity of 5 L equipped with a stirrer, a heating / cooling device, each raw material, and an auxiliary charging device, the above conjugated diene rubber latex was granulated to 0.30 μm by using acetic anhydride. The diameter-enlarged product was charged with 100 parts as solid content and 712 parts of deionized water (including water in latex), and the temperature was raised to 70 ° C. From the time when the temperature reached 70 ° C., 540 parts of styrene, 360 parts of acrylonitrile, 2.88 parts of potassium persulfate, 2.25 parts of terpinolene, disproportionated potassium rosinate soap 1
8 parts, 3.33 parts of potassium hydroxide and 199 parts of deionized water were added over 7 hours and 30 minutes. 3 more after addition
The reaction was continued for 0 minutes and cooled to complete the reaction. After adding 2.5 parts of an antioxidant to this graft copolymer latex, it is added to an aqueous magnesium sulfate solution heated to 95 ° C. with stirring to coagulate, and the coagulated product is washed with water and dried to give a white powdery resin composition. Got A-5.

A-6 (1) Production of conjugated diene rubbery polymer It was carried out in the same manner as A-1 (1). (2) Production of graft copolymer In a reactor having a capacity of 5 L equipped with a stirrer, a heating / cooling device, each raw material, and an auxiliary charging device, the above conjugated diene rubber latex was granulated to 0.30 μm by using acetic anhydride. The diameter-enlarged product was charged with 100 parts as solid content and 10 parts of deionized water (including water in latex), and the temperature was raised to 70 ° C. From the time of reaching 70 ° C., 6.7 parts of styrene, 4.4 parts of acrylonitrile, 0.1 part of potassium persulfate, 0.05 part of terpinolene, 0.2 parts of disproportionated potassium rosinate soap.
Parts, 0.04 parts potassium hydroxide, 12 parts deionized water to 1 part
Added over time. After the addition was completed, the reaction was continued for another 30 minutes, cooled, and the reaction was completed. After adding 2.5 parts of anti-aging agent to this graft copolymer latex,
The mixture was added to an aqueous magnesium sulfate solution heated to while stirring to coagulate, and the coagulated product was washed with water and dried to obtain a white powdery resin composition A-6.

A-7 (1) Production of Conjugated Diene Rubber Polymer It was carried out in the same manner as in A-1 (1). (2) Production of Graft Copolymer A-1 (2) was used except that the conjugated diene rubber latex was used without increasing the particle size and the average particle size was 0.08 μm.
It carried out like -1 (2).

A-8 (1) Production of Conjugated Diene Rubber Polymer The same procedure as in A-1 (1) was carried out. (2) Production of Graft Copolymer A-1 (2) was used except that the particle size of the conjugated diene rubber latex was enlarged to 0.80 μm using acetic anhydride.
It carried out similarly to 1 (2).

A-9 (1) Production of conjugated diene rubber The same procedure as in A-1 (1) was carried out. (2) Production of graft copolymer In a reactor having a capacity of 5 L equipped with a stirrer, a heating and cooling device, each raw material, and an auxiliary charging device, the conjugated diene rubber latex was adjusted to 0.30 μm by using acetic anhydride. The enlarged particle size was charged with 100 parts as solid content and 241 parts of deionized water (including water in latex) and heated to 70 ° C. At 60 ° C. during the heating, 1 part of sodium pyrophosphate dissolved in 20 parts of water, 0.25 part of dextrose and 0.01 part of ferrous sulfate were added. When the temperature reached 70 ° C, 60 parts of styrene, 40 parts of acrylonitrile, 0.25 part of tododecyl mercaptan, 0.50 part of cumene hydroperoxide, and disproportionated potassium rosinate soap 2
Parts, potassium hydroxide 0.37 parts, deionized water 31 parts 3 parts
Added over 45 minutes. After the addition was completed, the reaction was continued for another 15 minutes and cooled to complete the reaction. After adding 5 parts of an antioxidant to the graft copolymer latex,
The mixture was added to an aqueous solution of magnesium sulfate heated to ° C with stirring to coagulate, and the coagulated product was washed with water and dried to obtain a resin composition A-9 in the form of a white powder. The results summarized above are shown in Table 1.

[0063]

[Table 1]

2. Production of Graft Copolymer (B) 2-1. Production Method of Acrylic Rubbery Polymer B1 B1-1 151 parts of water in a 5 L glass flask, higher fatty acid soap (mainly having 18 carbon atoms) Fatty acid sodium salt)
0.01 part, β-naphthalenesulfonic acid formalin condensate sodium salt 1 part and sodium hydrogen carbonate 1 part were charged, and the temperature was raised to 75 ° C. under a nitrogen stream. When the temperature reached 75 ° C., 0.07 part of potassium persulfate was added, and after 5 minutes,
Four parts of a monomer mixture consisting of 100 parts of butyl acrylate (BA) and 0.2 part of allyl methacrylate (AMA) was charged. Exothermic heat was generated in about several minutes, and the initiation of polymerization was confirmed. Twenty minutes after the initial charge of the monomer mixture, the continuous addition of the remaining monomer, 0.08 part of potassium persulfate and 1 part of disproportionated rosin acid soap was started, and the addition was started at 3 hours and 20 minutes. Finished. 8 after addition of monomer mixture
The temperature was raised to 0 ° C., and the polymerization was further advanced at the same temperature for 1 hour. The solid content concentration was 38.5% by weight, and the average particle size was 0.20 μm.

B1-2 151 parts of water in a 5 L glass flask, higher fatty acid soap (sodium salt of fatty acid containing 18 carbon as the main component)
0.12 parts and 1 part of sodium hydrogen carbonate were charged, and the temperature was raised to 75 ° C. under a nitrogen stream. When the temperature reached 75 ° C., 0.135 parts of potassium persulfate was added, and then 5 minutes later, 95 parts of butyl acrylate (BA), 5 parts of acrylonitrile (AN), 0.1 part of allyl methacrylate (AMA). Four parts of a monomer mixture consisting of parts were charged. Exothermic heat was generated in about several minutes, and the initiation of polymerization was confirmed. Twenty minutes after the first monomer mixture was charged, the continuous addition of the remaining monomers was started, and the addition was completed at 3 hours and 20 minutes.
At the time point, 1 part of fatty acid soap was added, and at the time point of 2 hours and 30 minutes, 0.015 part of potassium persulfate was added. After the addition of the monomer mixture was completed, the temperature was raised to 80 ° C., and the polymerization was further continued at the same temperature for 1 hour. The solid content concentration was 39.0% by weight, and the average particle size was 0.17 μm.

B1-3 B1-2 except for the following changes in B1-2
Was performed in the same manner as described above. Initial higher fatty acid soap 2 parts BA 90 parts ST 10 parts (styrene) AMA 0.5 parts TDM 1.2 parts Solid content concentration 39.6%, average particle size 0.10 μm.

B1-4 B1-1 was carried out in the same manner as B1-1 except that the composition of the monomer mixture was changed as follows. BA 50 parts ST 50 parts AMA 0.2 parts Solid content concentration 39.2%, average particle size 0.195 μm.

B1-5 B1-1 was carried out in the same manner as B1-1 except that the composition of the monomer mixture was changed as follows. BA 100 parts AMA 5 parts Solid content concentration 39.0%, average particle size 0.198 μm. The results summarized above are shown in Table 2.

[0069]

[Table 2]

2-2, Method for Producing Graft Copolymer B2 B2-1 In a reactor having a capacity of 5 L equipped with a stirrer, a heating and cooling device, each raw material and an auxiliary charging device, the above-mentioned acrylic rubber-like polymer was added. 100 parts of latex B1-1 as a solid content, 1.5 parts of sodium hydrogen carbonate and 372 parts of deionized water (including the water content of the latex) were charged, and the temperature was raised to 70 ° C. 2.2 parts of sodium pyrophosphate, 0.63 parts of dextrose and 0.022 parts of ferrous sulfate, which were dissolved in 50 parts of water at 60 ° C., were added during the temperature rise. When the temperature reached 70 ° C, 143 parts of styrene, 77 parts of acrylonitrile, 0.44 part of tododecyl mercaptan, 1.1 parts of cumene hydroperoxide, and 3.96 of disproportionated potassium rosinate soap.
Parts, and 88.2 parts of deionized water were added over 3 hours and 30 minutes. After the addition was completed, the reaction was continued for another 30 minutes, cooled, and the reaction was completed. After adding 2.5 parts of an antioxidant to this graft copolymer latex, it is added to an aqueous magnesium sulfate solution heated to 95 ° C with stirring to coagulate,
The solidified product was washed with water and dried to obtain a white powdery resin composition B2-1.

B2-2 The procedure of B2-1 was repeated, except that B1-2 was used as the acrylic rubbery polymer latex.

B2-3 The procedure of B2-1 was repeated, except that B1-3 was used as the acrylic rubbery polymer latex.

B2-4 The procedure of B2-1 was repeated, except that B1-4 was used as the acrylic rubbery polymer latex.

B2-5 The procedure of B2-1 was repeated, except that B1-5 was used as the acrylic rubbery polymer latex.

B2-6 B2-1 was carried out in the same manner as B2-1 except that the composition of the monomer mixture was changed as follows. ST 66 part AN 154 part TDM 0.44 part

B2-7 In B2-1, the same procedure as in B2-1 was carried out except that the composition of the monomer mixture was changed as follows. ST 198 copy AN 22 copy TDM 0.44 copy

B2-8 B2-1 was carried out in the same manner as B2-1 except that the composition of the monomer mixture was changed as follows. ST 65 parts AN 35 parts TDM 0.2 parts Table 3 shows the results summarized above.

[0078]

[Table 3]

3. Manufacturing Method of Hard Copolymer C C-1 A stainless steel autoclave equipped with a heating / cooling device, a curved turbine type stirring device, a thermometer, and a raw material auxiliary agent adding device,
The raw material auxiliary agent shown below was charged and the inside of the polymerization system was replaced with nitrogen gas. AN 45 parts ST 10 parts Terpene-based compound 0.657 parts Di-t-butyl-p-cresol 0.02 parts Acrylic acid / 2-ethylhexyl acrylate copolymer 0.03 parts Sodium bromide 0.4 parts Deionized water 70 Department

While stirring, the temperature in the polymerization tank was raised to 106 ° C., 0.15 parts of 1-t-azo-1-cyanocyclohexane dissolved in a small amount of styrene was added, and the polymerization reaction was started at the same temperature. Immediately after the polymerization was started, 36 parts of styrene was continuously added at a constant rate for 4 hours and 30 minutes, and at the same time, the temperature of the polymerization system was adjusted to 1 hour over 4 hours and 30 minutes.
The temperature was raised to 28 ° C. After 4 hours and 30 minutes from the start of the polymerization, continuous addition of styrene to the polymerization system was completed, and then the temperature of the polymerization system was raised to 145 ° C. over 45 minutes. 5 hours and 15 minutes after the start of the polymerization, the temperature of the polymerization system was adjusted to 14
Stripping was performed for an additional 1 hour while maintaining at 5 ° C. The suspension system that had undergone this stripping was cooled and cooled, filtered, washed with water and dried to obtain a bead-shaped copolymer. The AN% of the copolymer was 39.9%.

C-2 AS resin SAN-C (AN% = 30) manufactured by Mitsubishi Chemical Corporation
%) Was used as is.

C-3 In C-1, 3 parts of styrene charged in the autoclave were charged.
Parts, acrylonitrile 70 parts, terpene compound 0.6 parts, continuously added styrene 27 parts,
It carried out like C-1. AN% in the copolymer is
It was 69.9%. The results summarized above are shown in Table 4.

[0083]

[Table 4]

Examples 1 to 8 The above-mentioned graft copolymer A, graft copolymer B and hard copolymer C were mixed in the proportions shown in Table 5, kneaded with a Banbury mixer and pelletized. Using these pellets, a test piece for measuring physical properties and CFC resistance was molded by an injection molding machine. Table 5 shows the results.

[0085]

[Table 5]

[0086]

[Table 6]

Comparative Examples 1 to 14 The above-mentioned graft copolymer A, graft copolymer B and hard copolymer C were mixed in the proportions shown in Table 6, kneaded with a Banbury mixer and pelletized. Using these pellets, a test piece for measuring physical properties and CFC resistance was molded by an injection molding machine. Table 6 shows the results.

[0088]

[Table 7]

[0089]

[Table 8]

[0090]

[Table 9]

The following points will be apparent from Tables 5 and 6. (1) The thermoplastic resin composition obtained by the present invention has an excellent balance of impact strength and processability (Examples 1 to 1).
8, Comparative Examples 1 to 14). (2) The thermoplastic resin composition obtained by the present invention has excellent chemical resistance (Examples 1 to 18 and Comparative Examples 1 to 14).
reference). (3) The thermoplastic resin composition obtained by the present invention has an excellent appearance (see Examples 1 to 8 and Comparative Examples 1 to 14).

[0092]

INDUSTRIAL APPLICABILITY The thermoplastic resin composition of the present invention has the following particularly advantageous effects, and its industrial utility value is extremely large. That is, the thermoplastic resin composition of the present invention is composed of two specific graft copolymers, or two specific graft copolymers and a copolymer, and has good impact resistance, chemical resistance, and good molding processing. And the resulting molded article has a good appearance and can be used as an excellent impact-resistant thermoplastic resin composition.

Claims (1)

[Claims] 1. A graft copolymer A, a graft copolymer B and a hard copolymer C shown below are prepared according to the following formula (3):
A thermoplastic resin composition comprising the composition ratio of (4). Graft Copolymer A: Graft Copolymer A is defined as follows. (1) In the presence of a diene rubbery polymer latex, aromatic vinyl monomer 40 to 80% by weight, vinyl cyanide monomer 20 to 60% by weight, and copolymerizable vinyl monomer 0 to It is a graft copolymer obtained by emulsion graft polymerization of a monomer mixture of 20% by weight, and (2) the weight average particle diameter of the diene rubbery polymer is 0.1.
Have a particle size of 0 to 0.65 μm. (3) The diene rubber polymer fraction R is 0.3 to 0.8. (4) The soluble content when the graft copolymer A is subjected to room temperature acetone extraction has a weight average molecular weight of 200,000 or more. (5) The graft ratio Gr represented by the following formula (1) of the graft copolymer A satisfies the following formula (2). (Equation 1) (Equation 2) (Here, the symbols have the following meanings: x: weight of the graft copolymer composition sample, y: weight of insoluble acetone at room temperature in x, Gr: graft ratio%) Graft copolymer B: graft Copolymer B is defined as follows. (1) In the presence of 100 parts by weight (based on the solid content) of the acrylic rubber polymer latex, 2 parts by weight or more of the vinyl monomer mixture with respect to the solid content of the latex are reacted by the emulsion polymerization method. Be united. (2) The vinyl monomer mixture is the aromatic vinyl monomer 40.
-80% by weight, vinyl cyanide monomer 20-60% by weight, and copolymerizable vinyl monomer 0-20% by weight. (3) Acrylic rubbery polymer is an ester compound 7 of a monohydric alcohol having 2 to 12 carbon atoms and acrylic acid.
0-100% by weight, copolymerizable vinyl monomer 0-30
It should be obtained by emulsion-polymerizing a monomer mixture of 0 to 3% by weight and a polyfunctional vinyl monomer. Hard Copolymer C: Hard Copolymer C is defined as follows. (1) A monomer mixture comprising 40 to 80% by weight of an aromatic vinyl monomer, 20 to 60% by weight of a vinyl cyanide monomer, and 0 to 20% by weight of a copolymerizable vinyl monomer. Hard copolymer C obtained by polymerization. (Equation 3) (Equation 4)