JP3538491B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] 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 hard copolymer, impact resistance, chemical resistance, good moldability,
And a thermoplastic resin composition having a good appearance, which itself is used not only as an impact-resistant resin material, but also useful for blending it with other resins to form an impact-resistant resin composition About.

[0002]

2. Description of the Related Art Graft copolymerization is a well-known method for obtaining an impact-resistant resin, and a resinous polymer is prepared in the presence of a rubbery polymer (for example, a latex of a conjugated diene polymer). The graft copolymerized thermoplastic resin composition produced by polymerizing a monomer (for example, styrene + acrylonitrile) to give a resin is awarded as an impact-resistant resin. Among them, the graft copolymer composed of polybutadiene / styrene / acrylonitrile is famous as an ABS resin. However,
For example, in the case of ABS resin, when it comes into contact with a specific chemical under a stress-loaded state, cracks are generated, and if it is severe, a phenomenon of breakage is observed, and properties such as chemical resistance are inferior.

In order to obtain a resin excellent in these properties, a method of increasing the blending ratio of an acrylonitrile component in an ABS resin (for example, JP-A-47-5594)
A method of mixing BS resin and acrylic rubber / styrene / acrylonitrile (ASA resin) (Japanese Patent Publication No. 54-40258, Japanese Patent Publication No. 63-28460), a method of adding an acrylate polymer to the ABS resin Japanese Patent Publication No. Sho 63-22222), a method of mixing two characteristic graft copolymers (Japanese Patent Publication No. 57-22064, Japanese Patent Application Laid-Open No. 2-175745) and the like are known.

[0004]

However, it can be said that these techniques are significant as having given a reasonable solution to the existing problems, but as far as the present inventors know, they are completely effective. Not to be satisfied.
That is, among these methods, JP-A-47-5594, JP-B-54-40258, JP-B-63-22222, and JP-B-63-28460 disclose the surface condition of an injection molded product. Defective phenomena, for example, surface appearance defects called flow marks, or peeling phenomena may be observed,
A surface appearance defect called a die band is sometimes observed in the surface state of the extruded product, which has been a major problem in use. Also, Japanese Patent Publication No. 57-22064, JP-A-2-175745
In the publication, the chemical resistance is insufficient, and in fields where more chemical resistance is required, there is still a problem in use.

[0005]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and have reached the present invention. That is, a monomer mixture comprising a specific ratio of an aromatic vinyl monomer, a vinyl cyanide monomer, and a copolymerizable vinyl monomer to a diene rubber polymer having a specific average particle size To a graft copolymer (A) obtained by a graft reaction by an emulsion polymerization method and an acrylic rubbery polymer having a specific average particle size and a gel content, with a specific ratio of an aromatic vinyl monomer and cyan A graft copolymer (B) obtained by a graft reaction of a monomer mixture of a vinylated monomer and a copolymerizable vinyl monomer by an emulsion polymerization method;
A resin composition obtained by uniformly mixing a hard polymer (C) having an affinity with them has excellent chemical resistance, impact resistance, molding processability, and appearance which cannot be obtained by a conventional composition. This has led to the present invention.

In order to solve the above-mentioned problems, the present invention provides a graft copolymer A, a graft copolymer B and a hard copolymer C defined below by the following formulas (1) and (2).
The present invention provides a thermoplastic resin composition characterized by comprising the following composition ratio: Graft copolymer A: weight average particle size 0.10 to 0.6
In the presence of 100 parts by weight (based on solid content) of a diene rubbery polymer latex of 5 μm, an aromatic vinyl monomer 4
0 to 80% by weight, 20 to 60% by weight of a vinyl cyanide monomer, and 0 to 2 of another vinyl monomer copolymerizable therewith.
A graft copolymer obtained by emulsion-polymerizing 40 to 450 parts by weight of a monomer mixture consisting of 0% by weight.

Graft copolymer B: In the presence of 100 parts by weight (based on solid content) of an acrylic rubbery polymer latex, a vinyl monomer mixture at least 2 times the solid content of this latex is emulsified. A graft copolymer B reacted by a synthetic method, wherein the vinyl monomer mixture contains 40 to 80% by weight of an aromatic vinyl monomer, 20 to 60% by weight of a vinyl cyanide monomer, and is copolymerizable. Vinyl monomer 0
-20% by weight, and the acrylic rubbery polymer is
70 to 100% by weight of an ester compound of a monohydric alcohol having 2 to 12 carbon atoms and acrylic acid, 0 to 30% by weight of a copolymerizable vinyl monomer, and 0 to 3% by weight of a polyfunctional vinyl monomer % Of a monomer mixture obtained by emulsion polymerization, wherein the weight-average particle diameter and the gel content of the acrylic rubbery polymer are within the compartments indicated by oblique lines in FIG.

Hard copolymer C: aromatic vinyl monomer 40
A hard copolymer obtained by polymerizing a monomer mixture consisting of 〜80% by weight, vinyl cyanide monomer 20 ビ ニ ル 60% by weight, and copolymerizable vinyl monomer 0０〜20% by weight.

[0009]

[Equation 3]

[0010]

(Equation 4)

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The thermoplastic resin composition according to the present invention comprises a graft copolymer A obtained by emulsion polymerization of a specific monomer in the presence of a diene rubbery polymer latex,
A graft copolymer B obtained by emulsion polymerization of a specific monomer in the presence of an acrylic rubbery polymer latex,
Hard polymer C consisting of specific monomer and having substantially uniform composition
Is blended.

I. Graft Copolymer (1) General Description As in the case of the graft copolymer, it is assumed that all the monomers to be "branched" are combined with the rubbery polymer which is the "backbone" to form "branches". Although not limited, the term "graft copolymer" as used in the present invention also permits the coexistence of a polymer derived from a monomer for a "branch" that is not a "branch" according to a commonly used place. Things.

1) Rubbery Polymer The graft copolymers A and B in the present invention can be obtained by emulsion graft polymerization of a monomer mixture to be a "branch" in the presence of a rubbery polymer latex described below. 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 copolymer resin composition according to the present invention can be prepared by copolymerizing an aromatic vinyl monomer, a vinyl cyanide monomer and a copolymerizable polymer in the presence of a rubbery polymer latex described below. It is obtained by performing a graft polymerization reaction of another vinyl monomer mixture by an emulsion polymerization method. The graft copolymerization conditions are not essentially different from those commonly used in the production of ABS resins, as long as the requirements of the present invention are satisfied. Further, the graft copolymerization conditions for the graft copolymers A and B do not need to be the same, and optimal conditions can be selected for each.

<Monomer> Examples of the aromatic vinyl monomer used in the present invention include styrene and styrene substituted with side chains or (and) nuclei (substituents are lower alkyl groups, lower alkoxy groups, trifluoromethyl Group, halogen atom,
Other), for example, α-methylstyrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, nuclear halogenated styrene, α- or β-vinylnaphthalene,
Others are listed. These may be used within or between counties. The types of monomers used for the graft copolymers A and B (and 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 as long as the gist of the present invention is not impaired. Such monomers include esters of acrylic acid or methacrylic acid with alkanols having 1 to 10 carbon atoms, especially methyl acrylate and methyl methacrylate, diene monomers, divinylbenzene, (poly) alkylene glycol diesters. (Meth) acrylate and others.

<Graft polymerization reaction>
Performed in the presence of a polymerization initiator. Examples of the initiator (or catalyst) that can be used include a peracid catalyst such as persulfuric acid, peracetic acid, and perphthalic acid; a persalt catalyst such as potassium persulfate and ammonium persulfate; hydrogen peroxide; benzoyl peroxide; Peroxide catalysts such as chlorobenzoyl oxide, naphthyl peroxide, acetyl peroxide, benzoylacetyl peroxide, lauryl peroxide, alkyl peroxides such as t-butyl hydroperoxide, and azo catalysts such as azobisisobutyronitrile There is
These can be used alone or in combination of two or more. These can also be used as a redox catalyst in combination with a reducing agent.

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. For example, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, etc., 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.
° C. If the temperature is lower than 50 ° C., the polymerization reaction rate is low and it is not practical. Is not preferred.

Regarding the production of the graft copolymer, first, a graft copolymer latex specified in the range described later is produced, and an aromatic vinyl monomer, a vinyl cyanide monomer, and a copolymerizable vinyl monomer are prepared. A hard polymer latex obtained by copolymerizing the polymer may be mixed, or a graft copolymer may be directly produced without mixing the hard polymer latex. At this time, the weight ratio of the monomer for the “branch” monomer of the graft copolymer latex to be mixed and the weight ratio of the monomer of the hard polymer latex may be the same or different. Other graft copolymerization conditions are:
It is not essentially different from what is commonly used in the production of ABS resins. The entire amount of the monomer for graft copolymerization may be introduced with the polymerization system at a time, or may be introduced stepwise. Further, the temperature during the polymerization can be changed over time.

(2) Graft copolymer A 1) Rubbery polymer The rubbery polymer of the "backbone" 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 any of a random copolymer and a block copolymer. Monomers that can be used to copolymerize with conjugated dienes, especially butadiene, include aromatic vinyl monomers such as styrene, α-methylstyrene, vinyltoluene, acrylic acid, methacrylic acid and their methyl, ethyl, propyl, n -Acrylic monomers such as -butyl and the like, and vinyl cyanide monomers such as acrylonitrile and methacrylonitrile. Such a rubbery polymer latex can be produced by subjecting a predetermined monomer or a mixture thereof to emulsion polymerization in an aqueous medium either temporarily or stepwise.

The "stem" rubbery polymer of the graft copolymer A has a weight average particle diameter of 0.10 to 0.65 μm, preferably 0.15 to 0.65 μm.
The range of the particle size is 0.45 μm. If it is less than 0.10 μm, the impact resistance of the finally obtained resin will be extremely poor, and the moldability will be insufficient. If it exceeds 0.65 μm, the appearance is reduced and only a resin with low impact resistance is obtained.In addition, during emulsion graft polymerization, the latex becomes unstable, causing problems such as an increase in the amount of scale during polymerization. It is not preferred.

The diene rubbery polymer latex having a relatively large particle diameter as described above can be directly obtained in a large particle diameter by selecting the production conditions, and a diene rubbery polymer having a small particle diameter can be obtained. A latex may be produced and obtained by performing an operation of enlarging the particle size. Particle size enlargement is a known method, for example, a method in which a latex is frozen and then redissolved, a method in which a mineral acid, an organic acid, or the like is added to the latex to temporarily lower the pH of the latex, and a method in which the latex is sheared. Method of applying force (JP-A-54-133588, JP-A-59-133588)
202211). In particular, a method of adding phosphoric acid or acetic anhydride to the latex is preferable because the particle diameter can be easily adjusted.

The particle size distribution of the diene rubbery polymer does not necessarily have to be monomodal, but may be multimodal, that is, a mixture of rubbery polymers of various particle sizes. The weight average particle diameter of the diene rubber-based polymer latex is measured by "N4S" manufactured by Coulter, USA.

2) The monomer mixture used for the graft polymerization and the production of the graft copolymer A is 40 to 80% by weight of an aromatic vinyl monomer and 20 to 20% by weight of a vinyl cyanide monomer. 60% by weight and 0-20% by weight of copolymerizable vinyl monomer, preferably 4% each.
5 to 80% by weight, 20 to 55% by weight, and 0 to 20%
% By weight. From these weight ratio ranges, when the amount of the vinyl cyanide monomer increases, the processability and the color tone decrease,
If the amount is small, the chemical resistance is undesirably reduced. The amount of the monomer mixture used is 40 to 450 parts by weight based on 100 parts by weight of the rubber solid content in the rubbery polymer latex.

The weight fraction R of the diene rubbery polymer in the graft copolymer A is preferably from 0.3 to 0.8, more preferably from 0.35 to 0.7. If the content of the rubbery polymer is less than this range, the composition of the present invention is difficult to maintain sufficient impact resistance, and if it is higher than this range, it tends to be difficult to obtain sufficient rigidity.

When the graft copolymer A is extracted with acetone at room temperature, the weight average molecular weight of the soluble component is preferably 1
It is 50,000 or more, more preferably 200,000 or more. If the molecular weight is lower than this value, the moldability tends to decrease, and it is difficult to obtain sufficient rigidity. A graft copolymer having an extract having such a molecular weight can be obtained by adjusting the polymerization temperature of the graft polymerization, the amounts of the chain transfer agent, the initiator, and the like. As for the insoluble content when the graft copolymer A is extracted with acetone at room temperature, the graft ratio Gr (expressed in% by weight) represented by the following formula (3) preferably satisfies the following formula (4).

[0027]

(Equation 5)

[0028]

(Equation 6)

(Where the symbols have the following meanings: x: weight of the graft copolymer sample, y: weight of the insoluble portion of acetone at room temperature in x, R: diene rubber in the graft copolymer Weight fraction of polymer, Gr: graft ratio, weight%)

When the value is outside the range of the above formula, not only is it difficult to exhibit sufficient mechanical strength, but also the moldability tends to decrease. A graft copolymer having such a value is
It 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 rubbery polymer used in the graft copolymer B has a glass transition temperature lower than room temperature and has 2 to 2 carbon atoms. Twelve, preferably 4 to 8, 70 to 100% by weight of an ester compound of a monohydric alcohol and acrylic acid, 0 to 30% by weight of a copolymerizable vinyl monomer, and 0 to 30% of a polyfunctional vinyl monomer. It is obtained by emulsion polymerization of a 3% by weight monomer mixture, such as butyl acrylate and 2-ethylhexyl acrylate. If the carbon number is outside the above range, sufficient rubber elasticity cannot be obtained, which is not preferable. These esters may be used alone or in combination of two or more. Such a rubber polymer latex can be produced by subjecting a predetermined monomer or a mixture thereof to emulsion polymerization in an aqueous medium, either temporarily or stepwise.

The weight-average particle size and the gel content of the acrylic rubbery polymer are in the section shown in FIG. When it is out of this section, the moldability and appearance of the resin composition of the present invention are reduced. In the section of FIG. 1, in the graph of the relationship between the weight average particle size and the gel content, [weight average particle size (μm) and gel content (%)] are each [0.4 , 0], [0.3,0], [0.15,2
0], [0.15,100], [0.4,100]
It is a range defined as an interior surrounded by connecting points.

The fact that such a rubber latex having a relatively large particle size may be obtained by performing an operation of enlarging the particle size in order to obtain a target particle size for a latex having a small particle size means that the graft copolymer The same as in the case of A.
The particle size distribution of the acrylic rubbery polymer does not necessarily have to be monomodal, but may be multimodal, that is, a mixture of rubbery polymers having various weight average particle diameters. It is sufficient that the weight average particle size of the rubbery polymer satisfies a specified range. The average particle size of the acrylic rubbery polymer latex is measured by “N4S” manufactured by Coulter Inc. of the United States.

2) Graft polymerization and graft copolymer The rubbery polymer content is at least 200 parts by weight, preferably 200 to 550 parts by weight, based on 100 parts by weight of the acrylic rubbery polymer. It is. If the amount of the monomer mixture is less than this range, the composition of the present invention cannot have a good appearance, and if it is more than this range, sufficient chemical resistance cannot be obtained. The weight ratio of the “branch” monomer in the graft copolymer A is 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. 0-20% by weight, preferably
45-80% by weight, 20-55% by weight, and 0-2
0% by weight. If the amount of the vinyl cyanide monomer is larger than the above range, the processability and the color tone are reduced. If the amount is smaller, the chemical resistance is undesirably reduced.

II Hard Copolymer C The hard copolymer C constituting the composition of the present invention is composed of 40 to 80% by weight of an aromatic vinyl monomer, 20 to 60% by weight of a vinyl cyanide monomer, And copolymerizable vinyl monomer 0
To 20% by weight, preferably 45 to 75% by weight, 25 to 55% by weight, and 0 to 20% by weight, respectively. If the amount of the vinyl cyanide monomer is larger than the above range, the processability and the color tone are reduced. If the amount is smaller, the chemical resistance is undesirably reduced.

The aromatic vinyl monomer, vinyl cyanide monomer and copolymerizable vinyl monomer which are constituents of the copolymer are those exemplified above as constituents of the graft copolymer. Is the same as The polymerization method and polymerization conditions for the above copolymer can be appropriately selected from batch or continuous methods such as a solution polymerization method, a bulk polymerization method, and a suspension polymerization method. 1962-1720
Reference). Graft copolymers A and B in the present invention
The composition of the monomer component constituting the hard polymer C may be within the above-defined range, and does not necessarily mean that the two compositions are completely the same. However, even if both are selected within the above range and combined, if the compositions of both are significantly different, the compatibility of both resins is inferior and the physical properties are undesirably reduced.

"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 weight composition ratio is in the range shown by the formulas (1) and (2). The blending amount (weight ratio) of each copolymer is
Outside the range of the formulas (1) and (2), the desired physical properties cannot be obtained, and a thermoplastic resin composition having good chemical resistance cannot be obtained.

[0038]

(Equation 7)

[0039]

(Equation 8)

As shown in the formula (1), the rubbery polymer contained in the thermoplastic resin composition according to the present invention is obtained by converting the rubbery polymer derived from the graft copolymer A into the graft copolymer A. 20 to 20 per total of the rubbery polymers of
Must be 90% by weight. Further, as shown in the formula (2), the total amount of the rubbery polymers derived 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.

The blending and kneading of the graft copolymer and the copolymer may be performed by a known mixing and kneading method. At this time, the temperature for kneading is preferably selected within a range in which the composition does not cause resin burn due to heat. One or two kinds of mixtures of these copolymers in the form of powder, beads, flakes, or pellets are mixed with a single-screw extruder, a twin-screw extruder, or a kneader such as a Banbury mixer, a pressure kneader, or a two-roll machine. Thus, a composition can be obtained. In some cases, one or two of these copolymers after polymerization may be mixed without drying, precipitated, washed, dried and kneaded.

The composition according to the present invention contains lubricants, mold release agents, plasticizers, coloring agents, antistatic agents, flame retardants, ultraviolet absorbers, and light fastnesses which do not impair the properties as a resin. Various resin additives such as a heat stabilizer, a heat resistance stabilizer and a filler can be added in an appropriate combination. The composition according to the present invention is formed into a molded product by various processing methods such as an injection molding method, an extrusion molding method, and a press molding method, and is used for applications requiring excellent chemical resistance, workability and impact resistance. be able to.

[0043]

The following examples and comparative examples are provided to explain the present invention more specifically, but the present invention is not limited to the following examples unless it exceeds the gist. 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 expressed by the number of grams of outflow for 10 minutes.

(3) Tensile strength Measured according to JIS K7113. (4) VICAT softening point Measured according to JIS K7206. (5) Weight average particle size of latex (μm) The average particle size of latex is “N4
S ".

(6) Gel Content (%) of Acrylic Rubbery Polymer A certain amount (weight: a) of an acrylic rubbery polymer is weighed, put into tetrahydrofuran, and allowed to stand at room temperature overnight. Then, the free copolymer was completely dispersed and dissolved in an ultrasonic cleaner for 15 minutes. This solution was centrifuged at 20000 rpm for 1 hour to remove soluble components. Further, the precipitate was re-dispersed in tetrahydrofuran, centrifuged, and this operation was repeated three times to sufficiently remove soluble components, and then dried overnight at 60 ° C. using a vacuum dryer,
An insoluble matter (weight: b) was obtained. The gel content (% by weight)
It was calculated by the following equation. Gel content (%) = b / a × 100

(7) Weight-Average Molecular Weight The weight-average molecular weight of the soluble component when the graft copolymer was subjected to extraction with acetone at room temperature was determined by the Shodex GPC SYS manufactured by Showa Denko.
TEM-11 "and expressed in terms of polystyrene.

(8) Appearance injection molded test piece (2.5 mm thick, 75 mm wide, 160 mm long)
mm) and the degree of flow mark were visually determined as follows. ：: Deterioration of gloss or no flow mark is observed △: Deterioration of gloss or flow mark is slightly observed ×: Deterioration of gloss or flow mark is considerably observed

(9) Chemical resistant press-formed test piece (2 mm thick, 35 mm wide, 230 m long)
m) was changed to Freon 141 by the bending form method.
The critical strain value of crack initiation for b was measured at a temperature of 23 ° C.
It was determined as follows. ◎: Critical strain value of 0.8% or more, very good 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

[Production Example] 1. Production of Graft Copolymer (A) A-1 (1) Production of Conjugated Diene Rubber Polymer In a 5LSUS autoclave, 150 parts of deionized water, a higher fatty acid soap (18 carbon atoms) (A sodium salt of a fatty acid whose main component is 4.0%) and 0.075 part of sodium hydroxide. After charging 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), potassium persulfate was added to 0.1 part.
135 parts were added. An exotherm occurred in about several minutes, confirming the start of polymerization. One hour after the addition of potassium persulfate, continuous charging of 80% of the monomer mixture was started and ended at 6 hours. After the addition of the monomer mixture, the temperature is raised to 80.
C., and the polymerization was further proceeded for 1 hour. The resulting diene rubbery polymer latex had a solids concentration of 39.5.
%, The average particle size was 0.08 μm, and the gel content was 95.0%.

(2) Production of Graft Copolymer The above conjugated diene rubbery polymer latex was prepared by using acetic anhydride in a 5 L capacity reactor equipped with a stirrer, a heating / cooling device, each raw material, and an auxiliary charge device. 100 parts as a solid content and deionized water 3
Charge 46 parts (including moisture in latex), 70 ° C
The temperature rose. When the temperature reaches 70 ° C., 73.3 styrene
Parts, acrylonitrile 48.9 parts, potassium persulfate 0.
39 parts, 2.4 parts of disproportionated potassium soap, 0.45 parts of potassium hydroxide and 41 parts of deionized water were added over 3 hours and 30 minutes. In the middle, 0.31 part of terpinolene (terpene mixture mainly composed of terpinolene) was added 30 minutes after the addition of monomers and the like was started. After completion of the addition, the reaction was continued for another 30 minutes, cooled, and the reaction was terminated. After adding 2.5 parts of an antioxidant to this graft copolymer latex, the mixture is added to an aqueous magnesium sulfate solution heated to 95 ° C. while stirring to coagulate, and the coagulated product is washed with water and dried to obtain a white powdery resin composition. A-1 was obtained.

A-2 (1) Preparation of conjugated diene rubbery polymer The same procedure as in A-1 (1) was carried out. (2) Production of graft copolymer The above conjugated diene-based rubber latex was granulated to 0.25 μm using acetic anhydride in a reactor having a capacity of 5 L equipped with a stirrer, a heating / cooling device, each raw material, and an auxiliary agent charging device. The diameter-expanded material was charged with 100 parts as solids and 451 parts of deionized water (including the water content in latex), and the temperature was raised to 70 ° C. When the temperature reached 70 ° C., 111.4 parts of styrene,
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, and deionized water 41 parts were added over 5 hours and 30 minutes. After completion of the addition, the reaction was continued for another 30 minutes, cooled, and the reaction was terminated.
After adding 2.5 parts of an antioxidant to this graft copolymer latex, the mixture is added to an aqueous magnesium sulfate solution heated to 95 ° C. while stirring to coagulate, and the coagulated product is washed with water and dried to obtain a white powdery resin composition. A-2 was obtained.

A-3 (1) Preparation of conjugated diene rubbery polymer The same procedure as in A-1 (1) was carried out. (2) Production of graft copolymer The above conjugated diene rubber latex was reduced to 0.30 μm using acetic anhydride in a reactor having a capacity of 5 L equipped with a stirrer, a heating / cooling device, each raw material, and an auxiliary agent charging device. 100 parts as solids and 218 parts of deionized water (including the water content in latex) were added to the expanded particle size, and the temperature was raised to 70 ° C. At 60 ° C. during the heating, 0.43 part of sodium pyrophosphate dissolved in 14 parts of water, 0.11 part of dextrose and 0.004 part of ferrous sulfate were added. When the temperature reached 70 ° C., 25.7 parts of styrene and acrylonitrile 1
7.1 parts, terpinolene 0.11 parts and cumene hydroperoxide 0.21 parts, disproportionated potassium rosinate soap 0.9 parts, potassium hydroxide 0.16 parts, deionized water 1
4 parts were added over 1 hour and 20 minutes. After completion of the addition, the reaction was continued for another 30 minutes, cooled, and the reaction was terminated. After adding 5 parts of an antioxidant to the graft copolymer latex, the mixture is added to an aqueous magnesium sulfate solution heated to 95 ° C. while stirring to coagulate, and the coagulated product is washed with water and dried to obtain a white powdery resin composition A-. Got three.

A-4 (1) Production of conjugated diene rubbery polymer The same procedure as in A-1 (1) was carried out. (2) Production of graft copolymer The above conjugated diene-based rubber latex was granulated to 0.24 μm in a 5 L reactor equipped with a stirrer, a heating / cooling device, each raw material and an auxiliary agent charging device using phosphoric acid. 100 parts and 361 parts of deionized water were charged as a solid content and heated to 74 ° C. When the temperature reaches 74 ° C, 4
0.5 parts potassium persulfate dissolved in 4.6 parts deionized water
At the same time as adding 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, 2.0 parts of a higher fatty acid obtained by dissolving 0.38 part of potassium hydroxide in 27.6 parts of deionized water after 1 hour and 2 hours and 30 minutes after 30 minutes from the start of addition of the monomer mixture. Soap (carbon number 1
8 as a main component).
After the addition of the monomer mixture, the reaction was continued for another 30 minutes,
Upon cooling, the reaction was terminated. 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. while stirring to coagulate, and the coagulated product is washed with water and dried to obtain a white powdery resin composition A-. Four
Got.

A-5 (1) Preparation of conjugated diene rubbery polymer The same procedure as in A-1 (1) was carried out. (2) Production of graft copolymer The above conjugated diene-based rubber latex was granulated to 0.30 μm in a 5 L reactor equipped with a stirrer, a heating / cooling device, each raw material, and an auxiliary agent charging device using acetic anhydride. The diameter-enlarged product was charged with 100 parts as solid content and 712 parts of deionized water (including the water content in latex), and the temperature was raised to 70 ° C. When the temperature reaches 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
Eight parts, 3.33 parts of potassium hydroxide and 199 parts of deionized water were added over 7 hours and 30 minutes. After the addition is complete,
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, the mixture is added to an aqueous magnesium sulfate solution heated to 95 ° C. while stirring to coagulate, and the coagulated product is washed with water and dried to obtain a white powdery resin composition. A-5 was obtained.

A-6 (1) Preparation of conjugated diene rubbery polymer The same procedure as in A-1 (1) was carried out. (2) Production of graft copolymer The above conjugated diene-based rubber latex was granulated to 0.30 μm in a 5 L reactor equipped with a stirrer, a heating / cooling device, each raw material, and an auxiliary agent charging device using acetic anhydride. The diameter-enlarged product was charged with 100 parts as solids and 10 parts of deionized water (including the water content in latex), and the temperature was raised to 70 ° C. When the temperature reaches 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 soap of rosin acid are used.
Parts, 0.04 parts of potassium hydroxide and 12 parts of deionized water
Added over time. After completion of the addition, the reaction was continued for another 30 minutes, cooled, and the reaction was terminated. After adding 2.5 parts of an antioxidant to this graft copolymer latex, 95 ° C.
The mixture was added to a heated aqueous magnesium sulfate solution with 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) Preparation of conjugated diene rubbery polymer The same procedure as in A-1 (1) was carried out. (2) Preparation of graft copolymer In A-1 (2), except that conjugated diene rubber latex (average particle size 0.08 μm) was used as it was,
This was performed in the same manner as in 1 (2).

A-8 (1) Preparation of conjugated diene rubbery polymer The same procedure as in A-1 (1) was carried out. (2) Production of graft copolymer In A-1 (2), except that the particle size of the conjugated diene rubber latex was increased to 0.80 μm using acetic anhydride,
-1 (2).

A-9 (1) Production of Conjugated Diene Rubber This was carried out in the same manner as in A-1 (1). (2) Production of graft copolymer The above conjugated diene rubber latex was reduced to 0.30 μm using acetic anhydride in a reactor having a capacity of 5 L equipped with a stirrer, a heating / cooling device, each raw material, and an auxiliary agent charging device. 100 parts as solids and 241 parts of deionized water (including the water content in latex) were added to the expanded particle size, and the temperature was raised to 70 ° C. At 60 ° C. during the temperature rise, 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, 0.50 part of cumene hydroperoxide, 2 parts of disproportionated potassium soap, 0.37 part of potassium hydroxide, and 31 parts of deionized water were added to 3 parts. It was added over a period of 45 minutes. After the addition,
The reaction was continued for another 15 minutes, cooled, and the reaction was terminated. After adding 5 parts of an antioxidant to the graft copolymer latex, the mixture is added to an aqueous magnesium sulfate solution heated to 95 ° C. while stirring to coagulate, and the coagulated product is washed with water and dried to obtain a white powdery resin composition A-. I got 9. Table 1 shows the results summarized above.

[0060]

[Table 1]

2. Production of Graft Copolymer (B) 2-1. Production Method of Acrylic Rubbery Polymer B1 B1-1 A 5-L glass flask was charged with 151 parts of water and a higher fatty acid soap (having 18 carbon atoms as a main component). Fatty acid sodium salt)
0.01 part and 1 part of sodium hydrogen carbonate were charged, and the temperature was raised to 80 ° C. under a nitrogen stream. When the temperature reached 80 ° C., 0.05 parts of potassium persulfate was added, and then 5 minutes, a monomer mixture consisting of 100 parts of butyl acrylate (BA) and 0.2 part of allyl methacrylate (AMA) , And 0.1 part of potassium persulfate and 1 part of disproportionated rosin acid soap were continuously added, and the addition was completed at 3 hours and 20 minutes. The polymerization was further proceeded at the same temperature for 1 hour. The solid concentration was 39.5% by weight, and the average particle size was 0.21 μm.

B1-2 In a 5 L glass flask, 151 parts of water and a higher fatty acid soap (sodium salt of a fatty acid having 18 carbon atoms as a main component)
0.1 part and 1 part of sodium hydrogen carbonate were charged, and the temperature was raised to 80 ° C. under a nitrogen stream. When the temperature reached 80 ° C., 0.12 parts of potassium persulfate was added.
Continuous addition of the monomer mixture consisting of 0.1 part was started and ended at 3 hours and 20 minutes, but 1 part of fatty acid soap was added at 2 hours and 2 hours and 30 minutes after the addition. 0.01 parts of potassium sulfate was added. After the addition of the monomer mixture, the polymerization was further continued at the same temperature for 1 hour. Solids concentration 39.8% by weight, average particle size 0.17 μm, gel content 6
It was 0%.

B1-3 Into a 5 L glass flask were charged 151 parts of water, 1 part of disproportionated potassium soap and 1 part of sodium hydrogen carbonate, and the temperature was raised to 75 ° C. in a nitrogen stream. When the temperature reached 75 ° C., 0.135 parts of potassium persulfate was added, and after 5 minutes, BA
Four of the 100 parts were charged. An exotherm occurred in about several minutes, confirming the start of polymerization. 20 minutes after the initial BA preparation, continuous addition of the remaining BA was started, and the addition was completed at the time of 3 hours and 20 minutes. One part of the fatty acid soap was added at the time of 2 hours, and at the time of 2 hours and 30 minutes. With potassium persulfate 0.0
15 parts were added. After completion of the addition of the monomer mixture, the temperature was raised to 80 ° C., and polymerization was continued at the same temperature for 1 hour. The solid concentration was 39.0% by weight, and the average particle size was 0.32 μm.

B1-4 Except for changing B1-1 as described below, B1-1
Was performed in the same manner as described above. Initial higher fatty acid soap 2 parts BA 100 parts AMA 0.5 part Solids concentration 39.6%, average particle size 0.10 μm.

B1-5 B1-1 is the same as B1-1 except for the following changes.
Was performed in the same manner as described above. BA 100 parts, AMA 0 parts, the solid content concentration was 39.6%, and the average particle size was 0.20 μm.

B1-6 The procedure of B1-1 was repeated, except that the composition of the monomer mixture was changed as follows. BA 50 parts ST 50 parts AMA 0.2 parts Solid concentration 39.2%, average particle size 0.195 μm. Table 2 shows the results summarized above.

[0067]

[Table 2]

2-2, Method B2-1 for Producing Graft Copolymer B2-1 Acrylic rubbery polymer was placed in a 5 L reactor equipped with a stirrer, a heating / cooling device, each raw material, and an auxiliary agent charging device. 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 latex) were charged, and the temperature was raised to 70 ° C. During the heating, 2.2 parts of sodium pyrophosphate dissolved in 50 parts of water at 60 ° C., 0.63 parts of dextrose and 0.022 parts of ferrous sulfate were added. When the temperature reaches 70 ° C., 143 parts of styrene, 77 parts of acrylonitrile, 0.44 parts of t-decyl mercaptan and 1.1 parts of cumene hydroperoxide, 3.96 of disproportionated potassium rosinate soap.
Parts and 88.2 parts of deionized water were added over 3 hours and 30 minutes. After completion of the addition, the reaction was continued for another 30 minutes, cooled, and the reaction was terminated. After adding 2.5 parts of an antioxidant to the graft copolymer latex, the mixture is added to an aqueous solution of magnesium sulfate heated to 95 ° C. with stirring to coagulate,
The coagulated product was washed with water and dried to obtain a white powdery resin composition B2-1.

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

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

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

B2-5 The same procedure as in B2-1 was carried out except that B1-5 was used as the acrylic rubbery polymer latex.

B2-6 The procedure was the same as B2-1, except that B1-6 was used as the acrylic rubbery polymer latex.

B2-7 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 parts AN 154 parts TDM 0.44 parts

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 198 part AN 22 part TDM 0.44 part

B2-9 B2-1 was carried out in the same manner as B2-1, except that the composition of the monomer mixture was changed as follows. Table 3 shows the results obtained by summarizing ST 65 parts, AN 35 parts, and TDM 0.2 parts or more.

[0077]

[Table 3]

3. Production Method C-1 of Hard Copolymer C A stainless steel autoclave equipped with a heating / cooling device, a curved turbine-type stirrer, a thermometer, and a raw material assistant adding device was prepared.
The following raw material auxiliaries were charged, and the inside of the polymerization system was replaced with nitrogen gas. AN 45 parts ST 10 parts Terpene mixture 0.657 parts Di-tert-butyl-p-cresol 0.02 parts Acrylic acid / 2-ethylhexyl acrylate copolymer
0.03 parts Sodium bromide 0.4 parts Deionized water 70 parts

The temperature in the polymerization tank was raised to 106 ° C. while stirring, and 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 start of the polymerization, 36 parts of styrene were continuously added at a constant rate for 4 hours and 30 minutes, and at the same time, the temperature of the polymerization system was raised over 1 hour 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 terminated, and then the temperature of the polymerization system was raised to 145 ° C over 45 minutes. Five hours and fifteen minutes after the start of the polymerization, the temperature of the polymerization system was raised to 14
Stripping was performed for an additional hour while maintaining at 5 ° C. The suspension after completion of the stripping was cooled down, cooled, filtered, washed with water and dried to obtain a beaded copolymer. The AN% of the copolymer was 39.9%.

C-2 SAN-C (AN% = 27%) manufactured by Mitsubishi Chemical Corporation was used as it was.

C-3 The styrene charged in the autoclave in C-1 was 3
Parts, 70 parts of acrylonitrile and 0.1 part of terpene mixture.
6 parts and 27 parts of styrene added continuously.
-1. The AN% of the copolymer is 6
It was 9.9%. Table 4 shows the results summarized above.

[0082]

[Table 4]

Examples 1 to 9 The above 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 the pellets, test pieces for measuring physical properties and for measuring CFC resistance were molded by an injection molding machine. Table 5 shows the results.

[0084]

[Table 5]

[0085]

[Table 6]

Comparative Examples 1 to 14 The above 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 the pellets, test pieces for measuring physical properties and for measuring CFC resistance were molded by an injection molding machine. Table 6 shows the results.

[0087]

[Table 7]

[0088]

[Table 8]

[0089]

[Table 9]

[0090]

【The invention's effect】

(1) The thermoplastic resin composition obtained by the present invention has an excellent balance between impact strength and processability. (2) The thermoplastic resin composition obtained by the present invention has excellent chemical resistance. (3) The thermoplastic resin composition obtained according to the present invention has an excellent appearance. (4) The thermoplastic resin composition of the present invention has no surface appearance defect called a flow mark on the surface of the obtained injection-molded product, and substantially no peeling phenomenon is observed. An excellent effect that a surface state called a die band does not substantially occur is exhibited.

[Brief description of the drawings]

FIG. 1 is a graph showing the relationship between the weight average particle size and the gel content of the acrylic rubbery polymer of the present invention.

Continuation of front page (56) References JP-A-55-60547 (JP, A) JP-A-62-101647 (JP, A) JP-A-60-36553 (JP, A) JP-A-4-170460 (JP) , A) JP-A-6-240100 (JP, A) JP-A-7-11096 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 55/02 C08L 25/12 C08L 51/04 C08L 51/06

Claims (2)

(57) [Claims] A graft copolymer A, a graft copolymer B and a hard copolymer C defined below are combined with the following formula (1):
A thermoplastic resin composition comprising the composition in the composition ratio of (2). Graft copolymer A: weight average particle size 0.10 to 0.6
In the presence of 100 parts by weight (based on solid content) of a diene rubbery polymer latex of 5 μm, an aromatic vinyl monomer 4
0 to 80% by weight, 20 to 60% by weight of a vinyl cyanide monomer, and 0 to 2 of another vinyl monomer copolymerizable therewith.
A graft copolymer obtained by emulsion-polymerizing 40 to 450 parts by weight of a monomer mixture consisting of 0% by weight. Graft copolymer B: In the presence of 100 parts by weight (based on solid content) of an acrylic rubbery polymer latex, a vinyl monomer mixture at least 2 times the solid content of this latex is reacted by an emulsion polymerization method. Graft copolymer B, wherein the vinyl monomer mixture is an aromatic vinyl monomer 40 to 8
0% by weight, 20 to 60% by weight of a vinyl cyanide monomer, and 0 to 20% by weight of a copolymerizable vinyl monomer, wherein the acrylic rubbery polymer has 2 to 12 carbon atoms. Ester compound of monohydric alcohol and acrylic acid 70-
A monomer mixture obtained by emulsion polymerization of 100% by weight, 0 to 30% by weight of a copolymerizable vinyl monomer, and 0 to 3% by weight of a polyfunctional vinyl monomer, 1. The weight average particle size and the gel content of the acrylic rubbery polymer are within the hatched area in FIG. Hard copolymer C: a monomer mixture consisting of 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 A hard copolymer obtained by polymerizing (Equation 1) (Equation 2)