JPH06299044A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin compsn. which is resistant to impact and chemicals and has a good moldability by compounding two specific graft copolymers and a rigid copolymer in a specified ratio. CONSTITUTION:The compsn. comprises the following copolymers in a specified ratio: a graft copolymer (A) comprising a graft copolymer (A1) which is produced by grafting monomers onto a diene rubber latex, a graft copolymer (A2) which is produced by grafting monomers onto a diene rubber latex and has chemical bonds to a specific monomer and secondary particles in a form of grapes, and a graft copolymer (A3) which contains grafted rubbery polymer particles dispersed therein; a graft copolymer (B) which is produced by grafting monomers onto an acrylic rubber; and a rigid copolymer (C) made from an arom. vinyl monomer, a vinyl cyanide monomer, and another vinyl monomer copolymerizable with the foregoing monomers.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thermoplastic resin composition. More specifically, the present invention provides two types of specific graft copolymers (A and B), or two types of specific graft copolymers and a hard copolymer C, which are impact resistance, chemical resistance, and A thermoplastic resin composition that has good moldability and is useful not only as an impact resistant material itself but also as a compounded with another resin to form an impact resistant resin composition. Regarding things.

[0002]

2. Description of the Related Art A graft copolymerization method is well known as one of methods for obtaining an impact resistant resin, and it is known that a resinous resin is prepared in the presence of a rubbery polymer (for example, a latex of a conjugated diene polymer). A graft copolymer resin composition produced by polymerizing a monomer (for example, styrene + acrylonitrile) to give a polymer is widely used as an impact resistant resin. Of these, the graft copolymer consisting of polybutadiene / styrene / acrylonitrile is well known as an ABS resin. However,
For example, ABS resins 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.

In order to obtain a resin excellent in these properties, a method of increasing the content ratio of the acrylonitrile component in the ABS resin (for example, JP-A-47-5594), ABS resin and acrylic rubber / styrene / acrylonitrile ( Method of mixing (ASA resin) (Japanese Patent Publication No.
No. 40258), a method of mixing an acrylic acid ester-based polymer with an ABS resin (Japanese Patent Publication No. 63-22222), and a method of mixing two kinds of characteristic graft copolymers (Japanese Patent Publication No. 57-22064). JP-A-2-1757
No. 45) has been proposed. However, although these techniques can be said to be meaningful as a solution to the existing problems, they are not completely satisfactory as far as the present inventors know. That is, among the proposed methods, in JP-A-47-5594, JP-B-54-40258, etc., a defective phenomenon in the surface condition of an injection-molded article, for example, a defective surface appearance called flow mark, or However, a surface peeling phenomenon may be observed, and a surface appearance defect called a die band may be observed in the surface state of the extruded product, which is a big problem in use. Further, the ones proposed in Japanese Patent Publication No. 57-22064 and Japanese Unexamined Patent Publication No. 2-175745 have insufficient chemical resistance, and are still used in the field where more chemical resistance is required. It was a problem.

[0004]

DISCLOSURE OF THE INVENTION The present invention is intended to solve the above-mentioned problems, and a diene rubbery polymer having a specific average particle diameter is used in a specific ratio of an aromatic vinyl monomer. And a graft copolymer (A1) obtained by carrying out a graft polymerization reaction of a monomer mixture comprising a vinyl cyanide monomer and another vinyl monomer copolymerizable therewith by an emulsion polymerization method. A diene rubbery polymer having an average particle size, aromatic vinyl monomer, vinyl cyanide monomer in a specific ratio so as to have a specific graft ratio, and other vinyl monomers copolymerizable therewith. Monomer mixture consisting of a body, graft-copolymerized by emulsion polymerization method, formed by agglomeration of the primary particles of the rubbery polymer graft-copolymerized, secondary showing a grape-bundle-like particle shape Graph containing particles From the copolymer (A2) and a solid diene rubbery polymer, a specific proportion of aromatic vinyl monomer, vinyl cyanide monomer and other vinyl monomer copolymerizable with these A graft copolymer (A3) having a specific average particle diameter, which is subjected to a graft polymerization reaction by a bulk-suspension two-step polymerization method, and an acrylic rubber-based polymer having a specific average particle diameter. The mixture is subjected to a graft polymerization reaction by a emulsion polymerization method with a specific mixture of an aromatic vinyl monomer, a vinyl cyanide monomer, and another vinyl monomer copolymerizable therewith. It is intended to achieve this object by uniformly mixing the graft copolymer (B) thus obtained and the hard copolymer (C) having an affinity with them.

[0005]

However, the gist of the present invention lies in that the graft copolymer A, the graft copolymer B and the hard polymer C shown below are prepared from the following (1) to
A thermoplastic resin composition is characterized by comprising a composition ratio (weight basis) represented by the formula (5). Graft Copolymer A: Graft Copolymer A is composed of Graft Copolymer A1, Graft Copolymer A2 and Graft Copolymer A3 defined as follows. Graft Copolymer A1: (1) Aromatic vinyl monomer 40 in the presence of 100 parts by weight (based on solid content) of diene rubbery polymer latex having a weight average particle size of 0.10 to 0.65 μm. Emulsion polymerization of 45 to 550 parts by weight of a monomer mixture consisting of ˜80% by weight, 20 to 60% by weight of vinyl cyanide monomer, and 0 to 20% by weight of another vinyl monomer copolymerizable therewith. Graft copolymer A2: (1) 100 parts by weight (based on solid content) of a diene rubbery polymer latex having a weight average particle diameter of 0.05 to 0.20 μm. Amount of aromatic vinyl monomer in the presence of 40 to 80% by weight, vinyl cyanide monomer 20 to 60% by weight, and 0 to 20% by weight of other vinyl monomer copolymerizable therewith. Emulsify 25-200 parts by weight of body mixture It is a graft copolymer obtained by polymerizing, (2) 10 to 80 parts by weight of an aromatic vinyl monomer, a cyanide vinyl monomer, and 100 parts by weight of a rubbery polymer, and That other copolymerizable vinyl monomers are chemically bonded,
(3) Graft copolymer containing primary particles of the graft-copolymerized rubbery polymer aggregated and containing grape tuft-shaped secondary particles having an average particle diameter of 0.4 to 3.0 μm. A3: (1) 100 parts by weight of a solid diene rubbery polymer,
A monomer mixture 4 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 another vinyl monomer copolymerizable therewith.
It was obtained by dissolving in 100 to 900 parts by weight, polymerizing by the bulk polymerization method until the polymerization rate of the monomer mixture reached 15 to 45% by weight, and then substantially completing the polymerization reaction by the suspension polymerization method. The weight average particle diameter of the graft copolymer rubber-like polymer is 0.60 to 2.
Dispersed as 5 μm particles. 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 an acrylic rubbery polymer latex having a weight average particle diameter of 0.05 to 0.50 μm, 40 to 80% by weight of an aromatic vinyl monomer and cyan Graft copolymer obtained by emulsion polymerization of 200 parts by weight or more of a monomer mixture comprising 20 to 60% by weight of a vinyl chloride monomer and 0 to 20% by weight of another vinyl monomer copolymerizable therewith. (2) the acrylic rubbery polymer is an ester compound of a monohydric alcohol having 2 to 12 carbon atoms and acrylic acid, 70 to 100% by weight,
A polymer obtained by emulsion-polymerizing a monomer mixture consisting of 0 to 30% by weight of another vinyl monomer copolymerizable with these and 0 to 3% by weight of a polyfunctional vinyl monomer. Rigid Copolymer C: Rigid Copolymer C is defined as follows. (1) A monomer 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 another vinyl monomer copolymerizable therewith. A hard copolymer obtained by polymerizing a mixture.

[0006]

[Equation 6]

[0007]

[Equation 7]

[0008]

[Equation 8]

[0009]

[Equation 9]

[0010]

[Equation 10]

DETAILED DESCRIPTION OF THE INVENTION The thermoplastic resin composition according to the present invention is a graft copolymer obtained by emulsion polymerization of a specific monomer mixture in the presence of a diene rubbery polymer latex. Graft polymer obtained by dissolving solid diene rubbery polymer in the combination of A1 and A2 and a specific monomer mixture and subjecting the obtained solution to a graft polymerization reaction by a bulk-suspension two-stage polymerization method. A3 and a graft copolymer B obtained by emulsion polymerization of a specific monomer mixture in the presence of an acrylic rubbery polymer latex, and a substantially uniform composition of the specific monomer mixture. And a hard copolymer C.

[I] Graft Copolymer (1) General Description As a usual graft copolymer, all of the monomers to be “branches” are combined with a rubbery polymer which becomes a “stem” to form a “copolymer”. branch"
However, the “graft copolymer” in the present invention is also a polymer derived from a monomer for “branch” which is not “branch” according to a commonly used condition. It permits the coexistence of coalescence.

1) Rubber Polymer Among the graft copolymers of the present invention, the graft copolymers A1, A2 and B are "branches" in the presence of the rubber polymer (latex) which becomes the "trunk". It is a monomer mixture obtained by graft polymerization by an emulsion polymerization method. Further, the graft copolymer A3 is obtained by dissolving a solid rubbery polymer which becomes a “stem” in a monomer mixture which becomes a “branch”, and subjecting this solution to a polymerization reaction to obtain a lump-suspension mixture. It is obtained by a graft polymerization reaction by a step polymerization method. The rubbery polymer, which is the “stem” of each graft copolymer, has a glass transition temperature lower than room temperature. Such a rubbery polymer can be produced by a conventionally known production method.

2) Graft Polymerization Among the graft copolymers used in the present invention, the graft copolymers A1, A2 and B are aromatic vinyl monomers, cyan and cyan, in the presence of a rubbery polymer latex described below. It is obtained by carrying out a graft polymerization reaction of a monomer mixture of a vinyl chloride monomer and another vinyl monomer copolymerizable therewith by an emulsion polymerization method. Further, the graft copolymer A3 is obtained by adding a solid rubber material described below to a monomer mixture composed of an aromatic vinyl monomer, a vinyl cyanide monomer, and another vinyl monomer copolymerizable therewith. It is obtained by dissolving a polymer and subjecting the resulting solution to a graft polymerization reaction by a two-step polymerization of bulk-suspension. The conditions for the graft polymerization reaction are A as long as they meet the requirements specified in the present invention.
It is essentially the same as is commonly used in the manufacture of BS resins. The conditions for the graft polymerization reaction of the graft copolymers A1, A2, and B do not have to be the same, and the optimum conditions can be selected according to the particle size of each.

<Monomer> The aromatic vinyl monomer used in the present invention includes styrene, and side-chain or / and nucleus-substituted styrene (substituents are a lower alkyl group, a lower alkoxy group, trifluoromethyl). Groups, halogen atoms, etc.), for example, α-methylstyrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, nuclear halogenated styrene, α- or β-vinylnaphthalene,
There are others. These may be used in combination 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 may be one kind or a mixture of two or more kinds. As the monomer, a small amount of another monomer copolymerizable with the above-mentioned monomer may be used in combination as long as the gist of the present invention is not impaired. Examples of such monomers include esters of acrylic acid and methacrylic acid with monohydric alcohols having 1 to 10 carbon atoms, especially methyl methacrylate, and the like.

<Graft Polymerization Reaction> The graft polymerization reaction is carried out in the presence of a polymerization initiator. As the initiator (or catalyst) that can be used, persulfuric acid, peracetic acid, perphthalic acid and other peracid catalysts, potassium persulfate and other peracid catalysts, hydrogen peroxide, benzoyl peroxide, chlorobenzoyl peroxide, etc. , Naphthyl peroxide, acetyl peroxide, octanoyl peroxide,
Decanoyl peroxide, benzoyl acetyl peroxide, lauroyl peroxide, stearoyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, dicumyl peroxide,
Peroxide catalysts such as t-butyl peracetate, t-butyl perpivalate, t-butyl hydroperoxide, alkyl hydroperoxides such as hydroperoxide cumene, azobisisobutyronitrile, phenylazotriphenylmethane And the like, and these can be used alone or in combination of two or more. They can also be used as redox catalysts in combination with reducing agents.

The graft polymerization reaction 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 temperature when the graft polymerization reaction is carried out by the emulsion polymerization method is 50 to 85 ° C., preferably 5
A range of 5 to 75 ° C is suitable. When the temperature is lower than 50 ° C, the polymerization reaction rate is low and not practical, and when the temperature is higher than 85 ° C, the reaction occurs at once, and the solidified product is generated in the reaction product or the deposit on the reaction vessel (can). (Scale) increases, resulting in a decrease in polymerization yield and a deterioration in quality of the final product, which is not preferable.

The temperature at which the graft polymerization reaction is carried out in two steps of bulk-suspension is carried out in the bulk polymerization step of the first stage (previous stage).
A temperature in the range of 0 to 150 ° C., preferably 80 to 130 ° C. is suitable, and 100 to 2 in the second (second) suspension polymerization step.
A range of 00 ° C, preferably 110 to 160 ° C is suitable. The other graft polymerization reaction conditions are essentially the same as those conventionally used in the production of ABS resins. The total amount of the graft copolymerization monomer may be added to the polymerization system at once, or may be added stepwise. Further, the polymerization initiator and the chain transfer agent may be added to the polymerization system all at once, or may be added stepwise. Further, the temperature of the polymerization system can be changed with time during the polymerization.

<Production of Resin Composition> In producing the thermoplastic resin composition (graft copolymer resin composition) according to the present invention, first, the specific rubbery polymer latex or solid rubbery material is used. Using a polymer as a starting material, a latex-like or solid graft copolymer obtained by copolymerizing a monomer mixture defined in the present invention with these rubber-like polymers is produced, and then these latex-like or A method of mixing or blending the solid graft copolymer and, if necessary, the latex or solid hard polymer in such a proportion that the specific composition ratio defined in the present invention can be adopted.

(2) Graft Copolymer A1 The graft copolymer A1 used in the present invention is a limited graft copolymer resin satisfying the above-mentioned specific conditions. 1) Rubbery Polymer The rubbery polymer used in the production of the graft copolymer A1 and serving as the “stem” of the graft copolymer A1 is a diene rubbery polymer. Specifically, typical are dienes having 4 to 5 carbon atoms, for example, homopolymers of 1,3-butadiene, isoprene or chloroprene and copolymers thereof containing 50% by weight or more of such conjugated dienes. Is. The copolymer may be either a random copolymer or a block copolymer. In the case of a copolymer, examples of the monomer that can be used for copolymerization with conjugated dienes, particularly butadiene include aromatic vinyl monomers such as styrene, α-methylstyrene and vinyltoluene, acrylic acid, and methacrylic acid. Examples thereof include acrylic monomers such as acid and its methyl ester, ethyl ester, propyl ester, n-butyl ester, and vinyl cyanide monomers such as acrylonitrile and methacrylonitrile. This diene-based rubbery polymer may be used alone or as a mixture of two or more kinds.

The above-mentioned "trunk" rubbery polymer has a weight average particle diameter of 0.10 to 0.65 μm. 0.
When it is less than 10 μm, the impact resistance of the finally obtained resin composition is poor and the moldability is insufficient, which is not preferable. 0.
If the average particle size exceeds 65 μm, it is not preferable because not only the instability of the latex and the increase in the scale amount occur during emulsion polymerization, but also the appearance of the molded product obtained from the resin composition is poor. . Particularly preferable range is 0.15 to 0.45 μm. The diene rubbery polymer latex having a relatively large average particle diameter as described above can be directly obtained to have a large particle diameter by selecting the production conditions, and a rubbery polymer latex having a small particle diameter can be produced. It can also be obtained via an operation of enlarging the particle size. The operation of enlarging the particle size is a known method,
For example, a method of freezing the latex once and then re-thawing it, or adding a mineral acid to the latex to adjust the pH of the latex
And a method of applying a shearing force to the latex (Japanese Patent Laid-Open No. 54-133588, Japanese Patent Laid-Open No. 5-133588).
9-202121)). 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 weight average particle size distribution of the diene rubbery polymer latex does not need to be unimodal (single peak distribution), but is multimodal (bimodal distribution, trimodal distribution), that is, of the average particle size. It may be a mixture of different latexes. The weight average particle diameter of the diene rubbery polymer latex is measured by "Nanosizer" manufactured by Coulter, Inc., USA.

2) Graft Polymerization Graft copolymer A1 is an aromatic vinyl monomer, a vinyl cyanide monomer, and these with 100 parts by weight of diene rubbery polymer latex (based on solid content). Emulsified by adding 45 to 550 parts by weight, preferably 55 to 400 parts by weight, of a monomer mixture (“branching” monomer) obtained by mixing another copolymerizable vinyl monomer in a specific ratio. It is produced by graft polymerization by polymerization. When the grafting monomer mixture is more than the above range, sufficient impact resistance is not expressed in the obtained resin composition, and when the monomer mixture is less than the above range, sufficient rigidity is not expressed, Neither is preferable. The ratio of each monomer component of the above monomer mixture is 40 to 80% by weight of an aromatic vinyl monomer, 20 to 60% by weight of a vinyl cyanide monomer, and another vinyl monomer copolymerizable therewith. 0 to 20% by weight, preferably 45 to 80% by weight, 20 to 55% by weight, 0 to 2 respectively
It is 0% by weight. If the amount of the vinyl cyanide monomer is more than the above range, the processability and color tone of the obtained resin composition will be lowered, and if it is less, the chemical resistance will be lowered, which is not preferable.

The reaction temperature in the graft polymerization is 50 to 50.
The temperature is preferably 85 ° C, preferably 55 to 75 ° C. If it is lower than 50 ° C, the polymerization reaction rate is slow and not practical, while if it is higher than 85 ° C, the coagulation or deposits increase at one time, resulting in a decrease in the polymerization yield, or the final product. This is because inconvenience such as deterioration of quality is likely to occur. Graft copolymer A1 produced as described above
The composition is in the range of 45 to 550 parts by weight, preferably 55 to 400 parts by weight, based on 100 parts by weight (solid content) of the diene rubber polymer.

(3) Graft Copolymer A2 The graft copolymer A2 used in the present invention is a limited graft copolymer resin as in the case of the graft copolymer A1. 1) Rubbery Polymer The rubbery polymer used for producing the graft copolymer A2 is the same diene rubbery polymer as used for producing the graft copolymer A1. However, the weight average particle diameter of the rubber-like polymer which is to be the “stem” of the graft copolymer A2 is in the range of 0.05 to 0.2 μm.
The weight average particle diameter of the rubbery polymer that becomes the "trunk" is 0.05
If it is in the range of 0.2 μm to 0.2 μm, the particle form of the graft copolymerized rubbery polymer dispersed and present in the resulting graft copolymer A2 is 0. It is suitable because it is a secondary particle in the form of grape clusters (also referred to as clusters; detailed later) of 4 to 3.0 μm.

2) Graft Polymerization Graft copolymer A2 is an aromatic vinyl monomer, a vinyl cyanide monomer, and these with 100 parts by weight of diene rubbery polymer latex (based on solid content). Emulsifying a monomer mixture (“branching” monomer), which is a mixture of other copolymerizable vinyl monomers in a specific ratio, in an amount of 25 to 200 parts by weight, preferably 30 to 150 parts by weight. It is produced by graft polymerization by polymerization. When the grafting monomer mixture is more than the above range, sufficient impact resistance is not expressed in the obtained resin composition, and when the monomer mixture is less than the above range, sufficient rigidity is not expressed, Neither is preferable. The ratio of each monomer component of the above monomer mixture is 40 to 80% by weight of an aromatic vinyl monomer, 20 to 60% by weight of a vinyl cyanide monomer, and another vinyl monomer copolymerizable therewith. 0 to 20% by weight, preferably 45 to 80% by weight, 20 to 55% by weight, 0 to 2 respectively
It is 0% by weight. When the amount of vinyl cyanide monomer is more than these ratio ranges, the processability and color tone of the obtained resin composition deteriorates, and when it is less, the chemical resistance of the molded product obtained from this resin composition decreases, which is not preferable. .

The composition of the graft copolymer A2 produced as described above is such that the monomer mixture component is 25 to 200 relative to 100 parts by weight (solid content) of the diene rubber polymer.
In the range of 30 parts by weight, preferably in the range of 30 to 150 parts by weight, and the amount of the "branching" monomer component chemically bonded to the rubbery polymer as the "trunk" (grafting ratio). ) Is relatively low as follows. That is, the graft ratio of the graft copolymer A2 is the "trunk" rubbery polymer 1
It is necessary that the amount of the "branch" monomer component is 10 to 80 parts by weight, preferably 20 to 70 parts by weight, with respect to 00 parts by weight. If the graft ratio is lower than this range, the resulting resin composition will not exhibit impact resistance, while if it is higher than this range, the processability and chemical resistance will decrease. The above graft ratio is closely related to the dispersion form of the graft copolymerized rubbery polymer particles in this graft copolymer A2, and when the graft ratio is within the above range, it is a feature of grape bunch shape. It is easy to satisfactorily form the agglomerated structure of.

The above graft ratio is measured by the following method. That is, after a certain amount (X) of the graft copolymer was put into acetonitrile and left overnight,
Sonicate for 15 minutes to completely dissolve free copolymer, then centrifuge at 2000 rpm for 1 minute.
Centrifuge for hours to obtain insoluble matter. This is dried at 60 ° C. overnight using a vacuum dryer to obtain an insoluble matter (Y). Then, the graft ratio was calculated by the following formula.

[0029]

[Equation 11] Here, the rubber fraction (R) of the graft copolymer is calculated from the rubbery polymer and the graft copolymer used.

The graft copolymer A2 is as described above.
It is characterized by the dispersion form of the rubber-like polymer particles that are graft-copolymerized. That is, the rubber-like polymer particles in the rubber-like polymer latex used as a starting material for the graft copolymer A2 (as described above, a weight average particle of 0.05 to 0.20 μm, preferably 0.07 to 0.18 μm). Glue particles; hereinafter also referred to as primary particles) are agglomerated while undergoing a graft copolymerization reaction to give a graft copolymerized rubbery polymer having an average particle diameter of 0.4 to 3.0 μm. By including the secondary particles in the graft copolymer A2, good chemical resistance is imparted to the composition of the present invention. The average particle size of the grape bunch-shaped secondary particles is 0.4.
If it is smaller than μm, this effect is small, and if it is larger than 3.0 μm, the agglomerates are adversely affected and the rigidity is lowered.

The grape tufted secondary particles are rubbery polymer primary particles in the rubbery polymer latex (in the case of the graft copolymer A2, the particle size is 0.05 to 0.20 μm).
However, while substantially maintaining its particle morphology, after undergoing post-treatments such as graft polymerization, subsequent salting-out, aciding-out, and drying, and processing operations such as extrusion and molding, several or more aggregated grape bunches. It exists in a dispersed form.
The grape bunch-shaped secondary particles are considered to be those in which the primary particles are physically or chemically relatively strongly associated with each other, and are linked to each other. It does not dissociate. The particle size of such secondary particles can be measured by an electron microscope with respect to a slice of an ultrathin layer cut from a test piece molded by an injection molding machine. This measurement is based on the graft copolymer A2
The sample itself may be used as the measurement sample, but normally the rubber content is about 1
It is preferable to use, as a measurement sample, a composition diluted with a compatible styrene-based resin containing no rubber component such as “hard copolymer C” described later so that the content becomes about 0 to 20% by weight. In addition, in this invention, the average particle diameter of this grape bunch secondary particle means the average value of each maximum direction dimension measured about several secondary particles.

(4) Graft Copolymer A3 The graft copolymer A3 used in the present invention is a limited graft copolymer as in the case of the graft copolymers A1 and A2. 1) Rubbery Polymer The rubbery polymer used for producing the graft copolymer A3 is a diene rubbery polymer of the same kind as the rubbery polymer used for producing the graft copolymer A1, and is a latex. It is not solid but solid. 2) Graft Polymerization Graft copolymer A3 comprises 100 parts by weight of the above-mentioned solid diene rubbery polymer, aromatic vinyl monomer, vinyl cyanide monomer, and other vinyl copolymerizable with these. Monomer mixture (monomers for "branch") 400-
It is dissolved in 900 parts by weight, preferably 450 to 800 parts by weight, and this solution is first polymerized by a bulk polymerization method until the polymerization rate of the monomer mixture reaches 15 to 45% by weight (first step), and then this solution is added. It was obtained by converting the polymerization reaction system into a suspension polymerization system and substantially completing the polymerization reaction by the suspension polymerization method (second step).

If the proportion of the monomer mixture is less than this range, the solution viscosity becomes too high in the bulk polymerization step, and if the proportion of the monomer mixture is more than this range, sufficient impact resistance cannot be obtained. Neither is preferable. In addition, the ratio of each monomer component of the monomer mixture is from the aromatic vinyl monomer 40 to
80% by weight, vinyl cyanide monomer 20-60% by weight,
And 0 to 20% by weight of other vinyl monomers copolymerizable therewith, preferably 45 to 80% by weight, and 20 to 20% by weight, respectively.
It is 55% by weight and 0 to 20% by weight. If the amount of the vinyl cyanide monomer is more than the above range, the processability and color tone of the obtained resin composition are deteriorated, and if it is less, the chemical resistance is deteriorated, which is not preferable. In the production of the graft copolymer A3, if the polymerization rate in the bulk polymerization step of the first step is less than 15% by weight, micro-dispersion of the rubber-like polymer is not favorably carried out, and it is obtained from the resin composition finally obtained. The molded product has a glossy and textured appearance, and the polymerization rate is 4
If it exceeds 5% by weight, not only the solution viscosity becomes too high in the bulk polymerization step, but also the micro-dispersion of the rubber-like polymer proceeds too much, and the impact resistance of the finally obtained resin composition becomes poor. Conspicuous and not preferable.

Some inert solvent may be present in the first stage bulk polymerization process, and a suspending agent may be used in the second stage suspension polymerization process. Specific examples of the suspending agent that can be used in the second step include polyvinyl alcohol, gelatin, agar, starch, glycerin, polyacrylic acid or its sodium salt, ethylene glycol, polyacrylamide, and a copolymer of acrylic acid and 2-ethylhexyl acrylate. Dispersion stabilizers for polymers such as methyl cellulose, hydroxymethyl cellulose, carboxymethyl cellulose,
Surfactants such as rosin soap, sodium glycolate, sodium dodecylbenzene sulfonate, sodium stearate, polyoxyethylene distearate, lauryl trimethyl ammonium chloride; carbonates such as calcium, magnesium and barium as so-called anti-adhesive agents, silica Examples thereof include acid salts, alumina and bentonite. The amount of these suspending agents used depends on the type thereof and the ratio of the polymerization reaction mixture and water, but the dispersion stabilizer, the surfactant and the anti-tacking agent are used alone or in combination, and the polymerization reaction is performed. It can be appropriately selected within the range of 0.01 to 1.5% by weight with respect to the mixture. The ratio of the polymerization reaction mixture and water is 60 to 100 parts by weight of the polymerization reaction mixture, although it depends on the structure of the stirring blade of the suspension polymerization vessel and the stirring force.
It can be appropriately selected within the range of 200 parts by weight.

The graft copolymer A3 is produced by the bulk-suspension two-stage polymerization method as described above, but the weight average particles of the graft copolymerized rubbery polymer dispersed in the graft copolymer A3. The diameter needs to be 0.60 to 2.5 μm. When it is less than 0.60 μm, the impact resistance of the finally obtained resin composition becomes poor,
If it exceeds 2.5 μm, the impact resistance is poor and only a molded product having an inferior appearance is obtained, which is not preferable. The particle size of the rubbery polymer is controlled by the structure of the stirring blade used in the bulk polymerization reaction,
It is possible by appropriately selecting the stirring strength and the polymerization rate.

(5) Graft Copolymer B As in the case of the graft copolymer A, the graft copolymer B used in the present invention is a limited graft copolymer. 1) Rubber-like polymer The rubber-like polymer which is the "stem" of the graft copolymer B is an acrylic rubber-like polymer. Specifically, the number of carbon atoms is 2 to
70 to 100% by weight of an ester compound of 12 monohydric alcohols and acrylic acid, 0 to 30% by weight of another vinyl monomer copolymerizable therewith, and 0 to 3% by weight of a polyfunctional vinyl monomer. % Is a polymer obtained by emulsion-polymerizing a monomer mixture of 100% by weight. When the carbon number is out of the above range, sufficient rubber elasticity cannot be obtained, which is not preferable. More specifically, ethyl acrylate, propyl acrylate, butyl acrylate, especially n-butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate,
Examples thereof include alkyl acrylates such as dodecyl acrylate. Particularly preferred is an ester compound of a monohydric alcohol having 4 to 8 carbon atoms and acrylic acid. These ester compounds may be one kind or a mixture of two or more kinds.

The acrylic rubbery polymer comprises 70 to 100% by weight of the above ester compound, 0 to 30% by weight of another vinyl monomer copolymerizable therewith, and 0 to 3% by weight of a polyfunctional vinyl monomer. It is obtained by emulsion-polymerizing a monomer mixture of 100%. When the amount of the ester compound is less than 70% by weight, the acrylic rubber polymer does not exhibit sufficient rubber elasticity, which is not preferable. Other vinyl monomers copolymerizable with the above ester compound include aromatic vinyl monomers, vinyl cyanide monomers, acrylic amides, methacryloamides, vinylidene chloride, alkyls (having 1 to 6 carbon atoms). degree)
Vinyl ether and the like can be mentioned, and these may be one kind,
It may be a mixture of two or more kinds.

A polyfunctional vinyl monomer can be used in the production of the acrylic rubbery polymer. This polyfunctional vinyl monomer has a function of cross-linking the acrylic rubbery polymer and is a monomer having two or more vinyl groups in one molecule of the monomer. Specific examples of the polyfunctional vinyl monomer include aromatic polyfunctional vinyl monomers such as divinylbenzene and divinyltoluene, ethylene glycol dimethacrylate, and methacrylates and acrylates of polyhydric alcohols such as trimethylolpropane triacrylate. , Diallyl malate, diallyl fumarate,
Triallyl isofumanurate, allyl methacrylate,
Examples thereof include allyl acrylate and the like, and these may be one kind or a mixture of two or more kinds.

The amount of the polyfunctional vinyl monomer that can be used when producing the acrylic rubbery polymer is determined by the composition of the monomer for producing the acrylic rubbery polymer and the kind of the polyfunctional vinyl monomer. It can be changed depending on the conditions, but it should be selected within the range of 3% by weight or less. If it exceeds 3% by weight, the elasticity of the acrylic rubbery polymer is lowered and the graft ratio becomes poor, which is not preferable. The acrylic rubber-like polymer that is to be the “trunk” of the graft copolymer B has a weight average particle diameter of 0.05 to
The range is 0.50 μm. When it is less than 0.05 μm, the impact resistance of the finally obtained resin composition is poor and the moldability is insufficient, which is not preferable. If it exceeds 0.50 μm, the appearance of the molded article obtained from the resin composition is not good,
Etc. are not preferable. Particularly preferred in the above range is 0.
It is in the range of 07 to 0.40 μm.

The acrylic rubbery polymer latex having a relatively large average particle size as described above can be directly obtained with a large particle size by selecting the production conditions, and the rubbery polymer latex having a small particle size can be obtained. It is the same as in the case of the above-mentioned diene rubbery polymer, which can also be obtained through an operation of producing a polymer and enlarging the particle size. The weight average particle size of acrylic rubbery polymer latex is unimodal (single peak distribution)
It does not have to be, and may be multimodal (bimodal distribution, trimodal distribution), that is, a mixture of various latexes having different average particle diameters. The weight average particle diameter of the acrylic rubbery polymer latex is measured by "Nanosizer" manufactured by Coulter, Inc., USA.

2) Graft Polymerization Graft copolymer B is an acrylic rubbery polymer 100.
A monomer mixture in which an aromatic vinyl monomer, a vinyl cyanide monomer, and another vinyl monomer copolymerizable with these are mixed in a specific ratio with respect to parts by weight (solid content). (Monomer for "branch") 200 parts by weight or more, preferably 2
It is produced by emulsion polymerization with 100 to 550 parts by weight. If the ratio of the monomer mixture is less than this range,
A molded product having a good appearance cannot be obtained from the resin composition of the present invention, and if it exceeds this range, a molded product having sufficient chemical resistance cannot be obtained. The ratio of each monomer component of the above monomer mixture is 40 to 80% by weight of an aromatic vinyl monomer, 20 to 60% by weight of a vinyl cyanide monomer, and another vinyl monomer copolymerizable therewith. 0 to 20% by weight, preferably 45 to 85% by weight, 20 to 55% by weight, respectively, and
0 to 20% by weight. When the amount of the vinyl cyanide monomer is more than the above range, the processability and color tone of the obtained resin composition are deteriorated, and when the amount is less, the chemical resistance is deteriorated, which is not preferable.

[II] Hard Copolymer C The hard copolymer C constituting the resin composition according to the present invention is
30 to 80% by weight of aromatic vinyl monomer, 20 to 70% by weight of vinyl cyanide monomer, and 0 to 20% by weight of other vinyl monomer copolymerizable therewith, preferably, respectively,
It is a polymerization product of a monomer mixture consisting of 40 to 80% by weight, 20 to 60% by weight, and 0 to 20% by weight. From these weight ranges, if the amount of vinyl cyanide monomer increases,
If the processability and color tone of the resulting resin composition deteriorate, and if it decreases, the chemical resistance decreases, which is not preferable.

Specific examples of the aromatic vinyl monomer, the vinyl cyanide monomer, and other vinyl monomers copolymerizable with these, which are the constituents of the above copolymer, are mentioned above in the graft copolymer. It can be found among those exemplified as the constituents of A and B. The polymerization method and polymerization conditions of 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 (details of the production method are described in (See Japanese Patent Laid-Open No. 62-1720). Graft copolymer A1, A2, A in the present invention
The compositions of 3 and B and the monomer components constituting the hard copolymer C may be within the ranges defined above, and do not necessarily mean that the respective compositions are exactly the same. However, even if both are selected within the above range and combined, if the compositions of both are remarkably different, the compatibility of both graft copolymers deteriorates and the physical properties decrease, which is not preferable.

[III] Thermoplastic Resin Composition The thermoplastic resin composition according to the present invention is composed of the graft copolymers A1, A2 and B and the hard copolymer C as described above, The composition ratio is within the range represented by the formulas (1) to (5). If the blending amount of each copolymer is out of the range defined by the formulas (1) to (5), the desired physical properties cannot be obtained, and a thermoplastic resin composition having good moldability cannot be obtained. .

[0045]

[Equation 12]

[0046]

[Equation 13]

[0047]

[Equation 14]

[0048]

[Equation 15]

[0049]

[Equation 16]

In the thermoplastic resin composition according to the present invention, as shown by the above formula (1), the graft copolymer A (A1 relative to the total amount of the rubbery polymer from the graft copolymers A and B). , A2 and A3) must be in the range of 20 to 90% by weight. Further, as shown in the above formula (2), the graft copolymer A from the graft copolymer A to the rubbery polymer is obtained.
The proportion of rubbery polymer from 1 should be 5 to 90% by weight. Further, as shown in the above formula (3), the ratio of the rubber-like polymer from the graft copolymer A2 to the rubber-like polymer from the graft copolymer A must be 5 to 90% by weight. Further, as shown in the above formula (4), the ratio of the rubber-like polymer from the graft copolymer A3 to the rubber-like polymer from the graft copolymer A is:
It should be between 2 and 30% by weight. Furthermore, the above (5)
As shown in the formula, in the thermoplastic resin composition according to the present invention, the amount of the rubbery polymer from the graft copolymers A and B relative to the total amount of the graft copolymers A and B and the hard copolymer C is as follows. The proportion should be between 5 and 50% by weight.

When out of the range of the above equations (1) to (5),
The finally obtained thermoplastic resin composition has difficulty in exhibiting desired physical properties and cannot exhibit excellent impact resistance and chemical resistance. Further, when the finally obtained thermoplastic resin composition is molded, the processability is deteriorated and the gloss of the molded product is impaired. Graft copolymer A (A1, A2, and A
3), the graft copolymer B and the hard copolymer C may be blended and mixed and kneaded by a known mixing and kneading method. At this time, the kneading temperature is preferably selected in the range where the resin composition does not cause resin burning. The mixture of two or three kinds of these copolymers in the form of powder, beads, flakes, or pellets can be obtained by a single-screw extruder, a twin-screw extruder, or a kneading machine such as a Banbury mixer, a pressure kneader, or a twin roll. Can be a resin composition. In some cases, two types (A and B) of these copolymers that have been polymerized, or three types including hard copolymers are mixed while still undried, precipitated, washed, and dried. Then, a method of kneading can be adopted.

The resin composition according to the present invention contains a lubricant, a plasticizer, an antistatic agent, a flame retardant, an ultraviolet absorber, a light resistance stabilizer, and a heat resistance stabilizer in the types and amounts that do not impair the properties of the resin. Various resin additives such as a filler, etc. can be added in an appropriate combination. The resin composition according to the present invention is formed into a molded article by various processing methods such as an injection molding method, an extrusion molding method, a compression molding method, and a thermoforming method, and is required to have excellent chemical resistance, workability and impact resistance. For example, it can be used as an electric part such as an inner box material of an electric refrigerator and an industrial part.

[0053]

The thermoplastic resin composition according to the present invention comprises a graft copolymer A consisting of three kinds of graft copolymers starting from a diene rubber and a graft copolymer starting from an acrylic rubber. Combined B, and hard copolymer C
Which is a novel composition in which these components are blended in a specific composition ratio, and has excellent impact resistance, processability, and chemical resistance that cannot be obtained by conventional resin compositions. It has various characteristics and its industrial utility value is extremely high.

[0054]

EXAMPLES The following examples and comparative examples are for more specifically explaining the present invention, and the present invention is not limited to the following examples as long as the gist thereof is not exceeded.
In the following examples, "part" means part by weight. In the following respective production examples, examples and comparative examples, each measurement and evaluation was carried out by the following methods.

(1) Weight average particle diameter of latex It was measured by "Nanosizer" manufactured by Coulter Co., USA. Unit: μm (2) Average diameter of agglomerated particles (graft copolymer A2) An electron micrograph is taken of a test piece molded by an injection molding method, and the maximum of 200 secondary particles in which agglomeration is observed is observed from the photograph. The diameter was measured, and the average value was used as the average diameter of the aggregated particles. Unit: μm (3) Tensile strength Measured according to JIS K7113. Unit: Kg / cm2 (4) Izod impact strength Measured according to JIS K7110. Unit: Kg-cm /
cm (5) Vicat softening point Measured in accordance with JIS K7206. Unit: ° C (6) Melt flow rate (MFR) According to JIS K7210, temperature 220 ° C, load 10
The outflow rate for 10 minutes was measured under the condition of kg. unit:
g / 10 minutes (7) Appearance Injection molded test piece (thickness 2.5 mm, width 75 mm, length 160)
mm) was visually observed and judged. The judgment result is displayed as follows.

[Table 1] Good: No decrease in gloss or no flow mark is observed. Δ: A decrease in gloss or a slight flow mark is recognized. X: A decrease in gloss or a considerable flow mark is recognized. (8) Chemical resistance Compression molded test pieces (thickness 2 mm, width 35 mm, length 230
(mm) was measured by a bending foam method at 23 ° C. to determine the critical strain value for crack initiation with respect to Freon 123. The measurement results are displayed as follows.

Table 2 ⊚: Critical strain value of 0.8% or more (extremely good) ◯: Critical strain value of 0.6% or more and less than 0.8% (good) ×: Critical strain value of 0 Less than 6% (poor)

[Production Example] 1. Production of Graft Copolymer A 1-1. Production of Graft Copolymer A1 Nine types were produced as follows. A1-1; (1) Production of diene-based rubbery polymer Deionized in a reactor (a stainless steel autoclave with a capacity of 5 liters) equipped with a stirrer, a heating and cooling device, each raw material, an auxiliary additive device, etc. 150 parts of water, 4 parts of higher fatty acid soap (sodium salt of fatty acid having 18 carbon atoms as a main component), and 0.075 part of sodium hydroxide were charged, and after substituting with nitrogen gas, the mixture was heated to 68 ° C. Next, 90 parts of 1,3-butadiene (BD) and styrene (S
T) 10 parts with t-dodecyl mercaptan (TDM) 0.
A monomer mixture containing 3 parts was prepared, 20% of the mixture was charged into the reactor, and 0.135 parts of potassium persulfate was added. Exothermic heat was generated in about several minutes, and the start of the polymerization reaction was confirmed. One hour after the addition of potassium persulfate, the continuous addition of the remaining 80% of the above monomer mixture was started, and the addition was completed over 6 hours. After the continuous addition was completed, the temperature was raised to 80 ° C. over 1 hour, and the polymerization reaction was continued at this temperature for 1 hour. Immediately thereafter, the mixture was cooled to room temperature to stop the polymerization reaction, and a butadiene-styrene diene rubber polymer latex was obtained. The obtained rubber polymer latex had a solid content concentration of 40.2% by weight and a weight average particle diameter of the rubber polymer of 0.08 μm. (2) Particle size enlargement treatment The rubbery polymer latex obtained above was divided into two. Deionized water in which acetic anhydride was added and forcibly mixed was added to each of them, and the rubbery polymer particles dispersed therein were enlarged by stirring to have a weight average particle diameter of 0.25 each.
μm (Latex A1-1-a) and 0.65μ
m latex (Latex A1-1-b) was obtained.

(3) Preparation of Graft Copolymer In the same reactor as used in the preparation of the rubbery polymer latex, 80 parts of the above-mentioned latex A1-1-a (based on solid content) and latex A1-1- b 20 parts (solid content basis) and mixed latex (rubber polymer particles,
Particle size: Two peak distribution, weight average particle size: 0.33 μm) 1
00 parts and 347 parts deionized water (including water in the mixed latex) were charged. Then, the heating of the reactor contents was started, and when the temperature reached 60 ° C., 1.0 part of sodium pyrophosphate, 0.5 part of dextrose and ferrous sulfate of 0.
An aqueous solution of 01 parts dissolved in 20 parts deionized water was added. From the time of reaching 70 ℃, while maintaining this temperature,
To 70 parts of styrene and 30 parts of acrylonitrile (AN)
A monomer mixture containing 1.1 parts of dodecyl mercaptan, 0.5 parts of cumene hydroperoxide, 1.8 parts of disproportionated potassium rosinate soap, 0.37 potassium hydroxide
Parts of water with 35 parts of deionized water for 3 hours
It was added continuously over 0 minutes. After the continuous addition was completed, while maintaining the temperature at 70 ° C., the polymerization reaction was continued for another 30 minutes and then cooled to stop the polymerization reaction to obtain a copolymer latex. Next, 5 parts of an antioxidant was added to the obtained copolymer latex, and then this was added to a previously prepared 95 ° C. magnesium sulfate aqueous solution with stirring to coagulate. This coagulated product is washed with water by a conventional method,
It was filtered and dried to obtain a powdery graft copolymer A1-1.

A1-2; (1) Manufacture of diene rubbery polymer By the same procedure as in A1-1 (1), the solid content concentration was 40.2% by weight, and the weight average particle diameter of the rubbery polymer was 0. ．
A 08-μm butadiene-styrene rubbery polymer latex was obtained. (2) Particle size enlargement treatment To the rubbery polymer latex obtained above, deionized water in which acetic anhydride was added and forcibly mixed was added, and the particles were dispersed by stirring. The diameter was enlarged to obtain a latex having a weight average particle diameter of 0.30 μm.

(3) Production of Graft Copolymer 100 parts of the rubbery polymer latex subjected to the particle size enlargement treatment (on a solid content basis) in the same reactor used for producing the rubbery polymer latex. ) And deionized water 34
7 parts (including water in the mixed latex) were charged.
Thereafter, heating of the reactor contents was started, and a powdery graft copolymer A1-2 was obtained by the same procedure as in A1-1 (3).

A1-3; (1) Manufacture of diene rubbery polymer By the same procedure as in A1-1 (1), the solid content concentration was 40.2% by weight, and the weight average particle diameter of the rubbery polymer was 0. ．
A 08-μm butadiene-styrene rubbery polymer latex was obtained. (2) Particle size enlargement treatment By the same procedure as in A1-1 (1), the weight average particle size of the dispersed rubbery polymer is 0.25 μm.
Two types of latex were obtained, one of which is latex (Atex-3-1) and the other of which is 0.65 μm (latex A1-3-b).

(3) Preparation of Graft Copolymer In the same reactor as used for the preparation of the rubbery polymer latex, 60 parts of the above-mentioned latex A1-3-a (based on solid content) and the latex A1-3- b 40 parts (based on solid content) mixed latex (rubber polymer particles are
Particle size: Two peak distribution, weight average particle size: 0.40 μm) 1
00 parts and 347 parts deionized water (including water in the mixed latex) were charged. Thereafter, in the example described in A1-1 (3), the monomer mixture added when the temperature reached 70 ° C. was calculated from 57.3 parts of styrene containing no t-dodecyl mercaptan and 24.5 parts of acrylonitrile. In the same manner as in the example, except that the continuous addition time was changed to 2 hours to obtain a powdery graft copolymer A1-3.

A1-4; (1) Manufacture of diene rubbery polymer By the same procedure as in A1-1 (1), the solid content concentration was 40.2% by weight, and the weight average particle diameter of the rubbery polymer was 0. ．
A 08-μm butadiene-styrene rubbery polymer latex was obtained. (2) Particle size enlargement treatment In the example described in A1-2 (2), a rubbery polymer dispersed by the same procedure as in the same example except that phosphoric acid is used instead of acetic anhydride. Has a weight average particle diameter of 0.
25 μm latex was obtained.

(3) Preparation of Graft Copolymer 100 parts of rubber polymer latex subjected to the above-mentioned particle size enlargement treatment (solid content) was added to the same reactor used for the production of the rubber polymer latex. Standard) and deionized water 3
61 parts (including water in the latex) were charged. Then, the heating of the reactor contents was started, and when it reached 74 ° C., an aqueous solution of 0.59 parts of potassium persulfate dissolved in 44.6 parts of deionized water was added. While continuing to maintain this temperature, 130 parts of styrene and 55.
The monomer mixture obtained by adding 0.55 parts of the terpene mixture to 7 parts was continuously added over 4 hours and 30 minutes. During the process, 30 minutes after starting the addition of the monomer mixture,
0.38 parts of potassium hydroxide as a 0% aqueous solution, and deionized water of 27.
An aqueous solution in which 6 parts of 2.0 parts of higher fatty acid soap (sodium salt of fatty acid having 18 carbon atoms as a main component) was dissolved was added to each reactor. After the continuous addition of the monomer mixture was completed, the polymerization reaction was continued for another 30 minutes while maintaining the temperature at 74 ° C, and then the polymerization reaction was stopped by cooling to obtain a copolymer latex. Next, 5 parts of an antioxidant was added to the obtained copolymer latex, and then this was added to a previously prepared 95 ° C. magnesium sulfate aqueous solution with stirring to coagulate. This coagulated product was washed with water, filtered and dried by a conventional method to obtain a powdery graft copolymer A1-4.

A1-5; (1) Production of diene rubbery polymer By the same procedure as in A1-1 (1), the solid content concentration was 40.2% by weight, and the weight average particle diameter of the rubbery polymer was 0. ．
A 08-μm butadiene-styrene rubbery polymer latex was obtained. (2) Particle Size Enlargement Treatment By the same procedure as in A1-2 (2), a latex having a weight average particle diameter of the dispersed rubbery polymer of 0.18 μm was obtained.

(3) Preparation of Graft Copolymer 100 parts of rubbery polymer latex subjected to the above-mentioned particle size enlargement treatment (solid content) was added to the same reactor used in the production of the above rubbery polymer latex. Standard) and deionized water 3
47 parts (including water in the latex) were charged. Then, heating of the reactor contents was started, and when the temperature reached 60 ° C, 1.0 part of sodium pyrophosphate, 1.0 part of dextrose and 0.01 part of ferrous sulfate were dissolved in 20 parts of deionized water. Aqueous solution was added. From when it reached 65 ℃,
While maintaining this temperature, a monomer mixture obtained by adding 50 parts of styrene and 50 parts of acrylonitrile with 1.5 parts of t-dodecyl mercaptan, 0.5 part of cumene hydroperoxide, and disproportionated potassium rosinate soap 1. An aqueous solution prepared by dissolving 8 parts and 0.37 part of potassium hydroxide in 35 parts of deionized water was continuously added to the reaction system over 3 hours and 30 minutes. After the continuous addition was completed, the polymerization reaction was continued for another 30 minutes while maintaining the temperature at 65 ° C., and then the polymerization reaction was stopped by cooling to obtain a copolymer latex. Then
After adding 5 parts of an antioxidant to the obtained copolymer latex, this was added to a previously prepared 95 ° C. magnesium sulfate aqueous solution with stirring to coagulate. This coagulated product was washed with water, filtered, and dried by a conventional method to obtain a powdery graft copolymer A1-5.

A1-6; (1) Production of diene-based rubbery polymer By the same procedure as in A1-1 (1), the solid content concentration was 40.2% by weight, and the weight average particle diameter of the rubbery polymer was 0. ．
A 08-μm butadiene-styrene rubbery polymer latex was obtained. (2) Particle size enlargement treatment By the same procedure as in A1-1 (2), a latex having a weight average particle size of the dispersed rubbery polymer of 0.33 µm was obtained. (3) Production of Graft Copolymer In the example described in A1-1 (3), the monomer mixture continuously added from the time when the temperature of the reactor contents reached 70 ° C. was mixed with 90 parts of styrene. 10 parts of acrylonitrile
-A powdery graft copolymer A1-6 was obtained by the same procedure as in the same example except that 0.2 part of dodecyl mercaptan was added.

A1-7; (1) Production of diene rubbery polymer By the same procedure as in A1-1 (1), the solid content concentration was 40.2% by weight, and the weight average particle diameter of the rubbery polymer was 0. ．
A 08-μm butadiene-styrene rubbery polymer latex was obtained. (2) Particle size enlargement treatment By the same procedure as in A1-1 (2), a latex having a weight average particle size of the dispersed rubbery polymer of 0.33 µm was obtained. (3) Production of Graft Copolymer In the example described in A1-1 (3), the monomer mixture continuously added from the time when the temperature of the reactor contents reached 70 ° C., was added with 20 parts of styrene. 80 parts of acrylonitrile
-A powdery graft copolymer A1-7 was obtained by the same procedure as in the same example except that 1.5 parts of dodecyl mercaptan was added.

A1-8; (1) Production of diene rubbery polymer By the same procedure as in A1-1 (1), the solid content concentration was 40.2% by weight, and the weight average particle diameter of the rubbery polymer was 0. ．
A 08-μm butadiene-styrene rubbery polymer latex was obtained. (2) Particle Size Enlargement Treatment By the same procedure as in A1-2 (2), a latex having a weight average particle diameter of the dispersed rubbery polymer of 0.80 μm was obtained. (3) Production of Graft Copolymer A powdery graft copolymer A1-8 was obtained by the same procedure as in A1-1 (3).

A1-9; (1) Production of diene rubbery polymer By the same procedure as in A1-1 (1), the solid content concentration was 40.2% by weight, and the weight average particle diameter of the rubbery polymer was 0. ．
A 08-μm butadiene-styrene rubbery polymer latex was obtained. (2) Particle size enlargement treatment The particle size enlargement treatment was not performed. (3) Production of Graft Copolymer The rubber polymer latex of (1) above, in which the weight average particle diameter of the dispersed rubber polymer before particle size enlargement treatment is 0.08 μm, is used. Is the same as in A1-1 (3), but is in the form of powdery graft copolymer A1.
-9 was obtained.

The amount of the rubbery polymer used in the above-mentioned production examples of the respective graft copolymers A1, the weight average particle diameter, the amount of the monomers used for the graft polymerization to these rubbery polymers, and the composition ratio. Etc. are summarized in Table-1.

[0071]

[Table 3]

1-2. Production of Graft Copolymer A2 (1) Production of Mixing Copolymer Latex (A21) Two types of copolymer latexes were produced as follows. A21-1: A reactor (a stainless steel autoclave with a capacity of 5 liters) equipped with a stirrer, a heating and cooling device, each raw material, an auxiliary additive device, etc., 165 parts of deionized water, a higher fatty acid soap (having 18 carbon atoms) 2 parts of a sodium salt of a fatty acid containing as a main component, 0.2 part of potassium chloride, 0.3 part of sodium carbonate, and 0.15 part of potassium persulfate were charged, and the mixture was heated to 80 ° C. Next, while maintaining the temperature at 80 ° C., a monomer mixture obtained by adding 0.20 part of t-dodecyl mercaptan to 70 parts of styrene and 30 parts of acrylonitrile, 0.4 parts of potassium persulfate, and a higher fatty acid soap (carbon number) Sodium salt of fatty acid consisting mainly of 18)
An aqueous solution prepared by dissolving 2 parts in 16 parts of deionized water was continuously added over 4 hours. After the continuous addition is completed, the temperature is changed to 80
The polymerization reaction was continued for another 30 minutes while maintaining the temperature at 0 ° C., and then the polymerization reaction was stopped by cooling to obtain a copolymer latex for mixing A21-1.

A21-2: In the example described in A21-1, the monomer mixture continuously added was replaced with 60 parts of styrene and 40 parts of acrylonitrile to which 0.25 part of t-dodecyl mercaptan was added. Others were the same as in the example, and a copolymer latex for mixing A21-2 was obtained.

(2) Production of Graft Copolymer A2 Five types of products were produced as follows. A2-1; (a) Production of rubbery polymer latex A22-1 The reactor was equipped with a stirrer, a heating / cooling device, each raw material, an auxiliary additive device, etc. (a stainless steel autoclave with a capacity of 5 liter) 165 parts of deionized water, 6 parts of higher fatty acid soap (sodium salt of fatty acid having 18 carbon atoms as a main component), and 0.60 parts of potassium chloride were charged, replaced with nitrogen gas, and heated to 53 ° C. Then 1,3-
A monomer mixture was prepared by adding 0.4 part of t-dodecyl mercaptan to 90 parts of butadiene and 10 parts of styrene, and after charging the whole amount in the autoclave, 0.15 parts of potassium persulfate was added, and the temperature was adjusted. The polymerization reaction was initiated while maintaining the temperature at 53 ° C. On the way, when 5 hours passed from the start of the polymerization reaction, 0.80 part of ethylene glycol dimethacrylate was added, and then the polymerization reaction was continued for another 5 hours to obtain a rubbery polymer latex A22-1 (this latex Was subjected to the production of the following graft copolymer A2-1 as the whole reaction system). The obtained rubbery polymer latex had a solid content concentration of 39.0% by weight and a weight average particle diameter of the rubbery polymer of 0.09 μm.

(B) Preparation of Graft Copolymer A2-1 Subsequent to the above, graft copolymer A2-1 was prepared as follows. To 100 parts (based on solid content) of the rubbery polymer latex obtained in the above b), 0.21 part of potassium persulfate and 14 parts of deionized water were added, and then the temperature was adjusted to 5
While maintaining at 3 ° C, a monomer mixture consisting of 34.3 parts of styrene and 8.6 parts of acrylonitrile was continuously added over 4 hours. After the continuous addition was completed, the polymerization reaction was continued for another hour while maintaining the temperature at 53 ° C.
The polymerization reaction was stopped by cooling. Then, the copolymer latex for mixing A21-1 produced in the above (1) so that the content of the rubbery polymer is 35% by weight based on the solid content.
Was added and mixed, and 1 part of the antioxidant was further added, and then the latex in the reactor was added to a previously prepared 95 ° C. magnesium sulfate aqueous solution with stirring to coagulate. This coagulated product is washed with water and dried by a conventional method, and then Table-2
A powdery graft copolymer A2-1 containing agglomerated particles of the graft copolymerized rubbery polymer listed in 1. was obtained.

A2-2; a) Production of rubbery polymer latex By the same procedure as in A2-1-b), a rubbery polymer latex was obtained (this latex is substantially A
Since it is the same quality as 22-1, this is also called A22-1 for convenience. The total amount of this latex was used for the next production of the graft copolymer A2-2). B) Production of graft copolymer A2-2 In the example described in A2-1-b), the monomer mixture continuously added is made of styrene 30.0 parts and acrylonitrile 12.9 parts. A graft polymerization reaction was carried out in the same manner as in the same example except that it was replaced. Then
The mixing copolymer latex A21-1 produced in the above (1) was added and mixed so that the content of the rubbery polymer was 50% by weight based on the solid content, and the subsequent procedure was the same as in the same example. Then, the powdery graft copolymer A containing the agglomerated particles of the rubbery polymer obtained by the graft copolymerization listed in Table 2 is obtained.
2-2 was obtained.

A2-3; a) Production of rubbery polymer latex By the same procedure as in A2-1-a), a rubbery polymer latex was obtained.
Since it is the same quality as 22-1, this is also called A22-1 for convenience. The total amount of this latex was used for the next production of the graft copolymer A2-2). B) Production of graft copolymer A2-3 In the example described in A2-1-b), 25.7 parts of styrene and 17.2 parts of acrylonitrile were added to t-dodecylmercaptan. The graft polymerization reaction was carried out in the same manner as in the example except that 0.3 part was added. Then, the content of the rubbery polymer is adjusted to 50% by weight based on the solid content, and the above (1)
The copolymer latex A21-2 for mixing produced in 1. was added and mixed.
A powdery graft copolymer A2-3 containing the rubbery polymer agglomerated particles obtained by graft copolymerization listed in 2 was obtained.

A2-4; a) Production of rubbery polymer latex By the same procedure as in A2-1-a), a rubbery polymer latex was obtained (this latex is substantially A
Since it is the same quality as 22-1, this is also called A22-1 for convenience. The total amount of this latex was used for the next production of the graft copolymer A2-2). B) Production of Graft Copolymer A2-4 In the example described in A2-2-b), the monomer mixture continuously added is made of 163.0 parts of styrene and 70.0 parts of acrylonitrile. Instead, the graft polymerization reaction was performed in the same manner as in the same example except that the continuous addition time was 5 hours. Subsequent procedures were the same as in the same example except that the addition and mixing of the copolymer latex for mixing was omitted and the rubbery polymer content of the resulting graft copolymer was not adjusted. Graft copolymer A2-4 was obtained. No aggregated particles were observed in this graft copolymer.

A2-5; a) Production of rubbery polymer latex A22-2 In the example described in A2-1-a), 3.0 parts of higher fatty acid soap and potassium chloride to be initially charged, respectively. 10
The polymerization reaction was initiated in the same manner as in the example except that the parts were replaced. On the way, when 10 hours passed from the start of the polymerization reaction, 0.80 part of ethylene glycol dimethacrylate was added and the polymerization reaction was continued for further 20 hours to obtain a rubbery polymer latex A22-2 (this latex Was used for the production of the following graft copolymer A2-5). As a result of analysis, the obtained rubbery polymer latex had a solid content concentration of 38.9% by weight and a weight average particle diameter of the rubbery polymer of 0.30 μm. B) Production of graft copolymer A2-5 The same as the example described in A2-2-b) except that the rubber polymer latex A22-2 is used instead of the rubber polymer latex A22-1. As in the example,
Graft polymerization reaction was performed. Then, the copolymer latex for mixing A21-1 produced in the above (1) so that the content of the rubbery polymer is 50% by weight based on the solid content.
Was added and mixed, and the subsequent procedure was performed in the same manner as in the same example to obtain a powdery graft copolymer A2-5 containing the graft copolymerized rubbery polymer agglomerated particles listed in Table 2. No aggregated particles were observed in this graft copolymer.

The amount of the rubbery polymer used in the above-mentioned production examples of the respective graft copolymers A2, the weight average particle diameter, the amount of the monomers used for the graft polymerization to these rubbery polymers, and the composition ratio. Table 2 collectively shows the content of the rubbery polymer in the obtained graft copolymer A2.

[0081]

[Table 4]

1-3. Production of Graft Copolymer A3 Five types were produced as follows. A3-1; (1) Bulk polymerization In a reactor (stainless steel autoclave with a capacity of 5 liters) equipped with an anchor type stirring device, a heating / cooling device, and each raw material, auxiliary agent adding device, etc., 441 parts of styrene and acrylonitrile 159 parts of a monomer mixture and 100 parts of solid polybutadiene were charged and replaced with nitrogen gas,
The mixture was heated to 60 ° C. with stirring and maintained at this temperature for 3 hours to dissolve the solid polybutadiene in the monomer mixture. Then, di-t-butyl peroxide 0.37
Parts, 0.12 parts of t-butyl peracetate, and 4.9 parts of the terpene mixture were added, and the mixture was heated to 100 ° C. with stirring under a nitrogen gas atmosphere so that the polymerization rate of the monomer mixture was about 30.
The bulk polymerization reaction was continued until the weight% was reached to obtain a syrupy reaction product.

(2) Suspension Polymerization Curved turbine type stirring device, heating / cooling device, and each raw material,
A reactor equipped with an auxiliary agent adding device (stainless steel autoclave with a capacity of 10 liters) was charged with deionized water 615.
Parts, 1.7 parts of sodium alkylnaphthalene sulfonate-formaldehyde condensate and 5 parts of a suspending agent consisting of a copolymer of 2-ethylhexyl acrylate and acrylic acid.
% Aqueous solution (36.4 parts) was charged, the atmosphere was replaced with nitrogen gas, and then the mixture was heated to 100 ° C. with stirring and waited. The reactor in standby was charged with the entire amount of the syrup-like reaction product obtained in the bulk polymerization reaction, and heated to 135 ° C. over 2 hours while stirring. Then 140 ° C over 3 hours
After warming up to, an antifoam was added. The internal temperature of the reactor is 1
At 40 ° C., when the internal pressure reached 6.5 Kg / cm 2, the gas was gradually exhausted through the condenser to start stripping of unreacted monomers, and this was continued for about 3 hours. During this period, about 96 parts of water and 54 parts of unreacted monomer were recovered. After completion of stripping, the contents of the reactor were cooled to stop the polymerization reaction, and then the suspension was taken out from the reactor, dehydrated, washed,
After drying, a bead-shaped graft copolymer A3-1 was obtained. The graft copolymer A3-1 had a rubbery polymer content of 15.5% by weight, and the rubbery polymer had a weight average particle diameter of 1.5 μm measured by an electron microscope method.

A3-2; (1) Bulk polymerization In the example described in A3-1 (1), the charged amounts of styrene, acrylonitrile, and polybutadiene were each 37
The procedure was the same as in the example except that 8 parts, 222 parts, and 100 parts were replaced. (2) Suspension Polymerization A procedure similar to that in the example described in A3-1 (2) was followed.

A3-3; (1) Bulk Polymerization In the example described in A3-1 (1), the charged amounts of styrene, acrylonitrile, and polybutadiene were each 90%.
The procedure was the same as in the example, except that 0 copy, 0 copy, and 100 copy were used. (2) Suspension Polymerization A procedure similar to that in the example described in A3-1 (2) was followed.

A3-4; (1) Bulk polymerization In the example described in A3-1 (1), the addition amount of the terpene mixture was changed to 7.4 parts, and the polymerization rate of the monomer mixture was about 25% by weight. The procedure was the same as in the same example except that the polymerization reaction was continued until (2) Suspension Polymerization A procedure similar to that in the example described in A3-1 (2) was followed.

A3-5; (1) Bulk polymerization In the example described in A3-1 (1), the addition amount of the terpene mixture was changed to 3.5 parts, and the polymerization rate of the monomer mixture was about 40% by weight. The procedure was the same as in the same example except that the polymerization reaction was continued until (2) Suspension Polymerization A procedure similar to that in the example described in A3-1 (2) was followed.

Table 3 shows the composition ratios of the polybutadiene and the monomers used in the polymerization reaction, the content ratio of the rubbery polymer, and the average particle diameter in the production of each of the above graft copolymers A3. .

[0089]

[Table 5]

2. Production of Graft Copolymer B 2-1. Production of rubbery polymer (B1) B1-1: Into a reactor (stainless steel autoclave with a capacity of 5 liters) equipped with a retreating blade type stirring device, a heating and cooling device, and each raw material, auxiliary agent adding device, etc. Ion water 151
Parts, 2 parts of higher fatty acid soap (sodium salt of fatty acid having 18 carbon atoms as a main component), and 1 part of sodium hydrogencarbonate were charged, the atmosphere was replaced with nitrogen gas, and the mixture was heated to 75 ° C. Next, 0.135 parts of potassium persulfate was added, and immediately, 1.2 parts of t-dodecyl mercaptan was added to 95 parts of butyl acrylate (BA), 5 parts of acrylonitrile, and 0.5 parts of allyl methacrylate (AMA). 4 parts of the above monomer mixture were charged. After a few minutes a fever occurred,
The start of the polymerization reaction was confirmed. 20 minutes after the monomer mixture is charged, the rest of the monomer mixture is mixed for 3 hours and 20 hours.
Added continuously over minutes. In addition, after 2 hours from the start of continuous addition, 1 part of the higher fatty acid soap,
Potassium persulfate 0.015 after 2 hours and 30 minutes
Parts were additionally added. 80 ° C after continuous addition
The mixture was heated up to this temperature, and the polymerization reaction was continued at this temperature for another 30 minutes, and then the polymerization reaction was stopped by cooling to obtain an acrylic rubbery polymer latex B1-1. The obtained latex had a solid content concentration of 39.5% by weight and a rubbery polymer having a weight average particle diameter of 0.10 μm.

B1-2; In the example described in B1-1,
Acrylic rubbery polymer latex B was obtained by carrying out the polymerization reaction in the same manner as in the same example except that the monomer mixture used in the same example was changed to one consisting only of 100 parts of butyl acrylate.
1-2 was obtained. The obtained latex has a solid content of 3
It had a weight average particle diameter of 0.095 μm.

B1-3; In the example described in B1-1,
The monomer mixture used in the same example was mixed with butyl acrylate 100.
Part, except that 0.3 part of allyl methacrylate (AMA) was added with 0.9 part of t-dodecyl mercaptan,
A polymerization reaction was carried out in the same manner as in the example to obtain an acrylic rubbery polymer latex B1-3. The obtained latex had a solid content concentration of 38.6% by weight and a weight average particle diameter of 0.
It was of 096 μm.

B1-4; In the example described in B1-1,
90 parts of butyl acrylate were added to the monomer mixture used in the same example,
Acrylic rubbery polymer latex B1-4 was obtained by carrying out the polymerization reaction in the same manner as in the same example except that 10 parts of styrene was added with 0.6 part of t-dodecyl mercaptan.
Got The obtained latex had a solid content concentration of 39.0% by weight and a weight average particle diameter of 0.090 μm.

B1-5; In the example described in B1-1,
70 parts of butyl acrylate was added to the monomer mixture used in the same example,
Acrylic rubbery polymer latex B1-5 was obtained by carrying out the polymerization reaction in the same manner as in the example except that it was replaced with the one consisting of 3O parts of methyl methacrylate (MMA). The obtained latex had a solid content concentration of 39.0% by weight and a weight average particle diameter of 0.078 μm.

B1-6; In the example described in B1-1,
50 parts of butyl acrylate was added to the monomer mixture used in the same example,
Acrylic rubbery polymer latex B1-5 was obtained by carrying out the polymerization reaction in the same manner as in the same example except that 50 parts of styrene was used. The obtained latex had a solid content concentration of 39.9% by weight and a weight average particle diameter of 0.102 μm.
It was the one.

Rubbery polymer (latex) B1-1 to B
Monomer composition of 1-6, physical properties (average particle size, solid content concentration)
These are summarized in Table-4.

[0097]

[Table 6]

2-2. Production of Graft Copolymer B B-1; Acrylic rubber was added to a reactor (stainless steel autoclave with a capacity of 5 liters) equipped with a receding blade type stirring device, heating / cooling device, each raw material, auxiliary agent adding device and the like. 100 parts of the solid polymer latex B1-1 as a solid content, 1 part of sodium hydrogen carbonate, and 402 parts of deionized water (including water in the latex) were charged, and the atmosphere was replaced with nitrogen gas, and then heated to 80 ° C. Next, while maintaining this temperature, over 3 hours and 30 minutes, 154 parts of styrene, a monomer mixture of 0.44 parts of t-dodecyl mercaptan and 66 parts of acrylonitrile, 1.1 parts of potassium persulfate, and Disproportionated potassium rosinate soap 3.96 parts with deionized water 8
The aqueous solution dissolved in 8.2 parts was continuously added. After the continuous addition was completed, the polymerization reaction was continued for another 30 minutes while maintaining the temperature at 80 ° C., and then the polymerization reaction was stopped by cooling to obtain a graft copolymer latex.
Next, after adding 5 parts of an antioxidant to the above graft copolymer latex, this was added to the previously prepared 95 ° C.
Was added to the aqueous solution of magnesium sulfate with stirring to solidify. This coagulated product was washed with water, filtered and dried by a conventional method to obtain a white powdery graft copolymer B-1.

B-2; In the example described in B-1, a white powdery graft copolymer was prepared by the same procedure as described in the same example except that the acrylic rubbery polymer latex was changed to B1-2. Polymer B-2 was obtained. B-3; In the example described in B-1, a white powdery graft copolymer B was prepared by the same procedure as described in the same example except that the acrylic rubbery polymer latex was replaced with B1-3. -3 was obtained. B-4; In the example described in B-1, a white powdery graft copolymer B was prepared by the same procedure as described in the same example except that the acrylic rubbery polymer latex was replaced with B1-4. -4 was obtained. B-5; In the example described in B-1, a white powdery graft copolymer B was prepared by the same procedure as described in the same example except that the acrylic rubbery polymer latex was replaced with B1-5. -5 was obtained.

B-6: In the same reactor as used in the example described in B-1, 100 parts of acrylic rubbery polymer latex B1-1 as solid content, 1 part of sodium hydrogen carbonate, deionized water. 440 parts (including water in the latex) were charged, the atmosphere was replaced with nitrogen gas, and then the mixture was heated to 80 ° C. Next, while maintaining this temperature, t-type was added to 175 parts of styrene and 75 parts of acrylonitrile over 3 hours and 30 minutes.
A monomer mixture containing 0.5 part of dodecyl mercaptan and an aqueous solution prepared by dissolving 1.25 parts of potassium persulfate and 4.5 parts of disproportionated potassium rosinate soap in 93.8 parts of deionized water, respectively. Added continuously. After the continuous addition was completed, while maintaining the temperature at 80 ° C., the polymerization reaction was continued for another 30 minutes and then cooled to stop the polymerization reaction,
A graft copolymer latex was obtained. Next, after adding 5 parts of an antioxidant to the above graft copolymer latex, this was added to a previously prepared 95 ° C. magnesium sulfate aqueous solution with stirring to coagulate. This coagulated product was washed with water, filtered and dried by a conventional method to obtain a white powdery graft copolymer B-6.

B-7: In the same reactor as used in the example described in B-1, 100 parts of acrylic rubbery polymer latex B1-1 as solid content, 1 part of sodium hydrogen carbonate, deionized water. After charging 505 parts (including water in the latex) and substituting with nitrogen gas, the mixture was heated to 80 ° C. Next, while maintaining this temperature, t-type was added to 210 parts of styrene and 90 parts of acrylonitrile over 3 hours and 30 minutes.
A monomer mixture containing 0.6 part of dodecyl mercaptan and an aqueous solution prepared by dissolving 1.43 parts of potassium persulfate and 5.4 parts of disproportionated potassium rosinate soap in 105 parts of deionized water were continuously prepared. Was added to. After continuous addition,
While maintaining the temperature at 80 ° C., the polymerization reaction was continued for another 30 minutes and then cooled to stop the polymerization reaction to obtain a graft copolymer latex. Next, after adding 5 parts of an antioxidant to the above graft copolymer latex, this was added to a previously prepared 95 ° C. magnesium sulfate aqueous solution with stirring to coagulate. This coagulated product was washed with water, filtered, and dried by a conventional method to obtain a white powdery graft copolymer B-7.

B-8: In the example described in B-1, the monomer mixture used in the same example was added to 143 parts of styrene and 77 parts of acrylonitrile in t-dodecyl mercaptan.
A white powder-like graft copolymer B-8 was prepared by the same procedure as described in the same example except that 44 parts were added.
Got B-9; In the example described in B-1, except that the monomer mixture used in the same example was replaced with one in which 0.44 parts of t-dodecylmercaptan was added to 132 parts of styrene and 88 parts of acrylonitrile, By the same procedure as described in the same example, a white powdery graft copolymer B-9 was obtained. B-10; In the example described in B-1, the monomer mixture used in the same example was added with 0.44 parts of t-dodecyl mercaptan to 110 parts of styrene, 66 parts of acrylonitrile, 44 parts of methyl methacrylate. In the same procedure as described in the same example except that the above was used, a white powdery graft copolymer B-9 was obtained.

B-11; 100 parts of acrylic rubbery polymer latex B1-1 as solid content, 1 part of sodium hydrogen carbonate, deionized water were added to the same reactor as used in the example described in B-1. After charging 204 parts (including water in the latex) and purging with nitrogen gas, the mixture was heated to 80 ° C. Next, while maintaining this temperature, over 3 hours and 30 minutes, a monomer mixture obtained by adding 0.1 part of t-dodecyl mercaptan to 35 parts of styrene and 15 parts of acrylonitrile,
An aqueous solution prepared by dissolving 0.25 part of potassium persulfate and 0.9 part of disproportionated potassium rosinate soap in 22.2 parts of deionized water was continuously added. After the continuous addition was completed, the reaction was continued for 30 minutes while maintaining the temperature at 80 ° C., and then the polymerization reaction was stopped by cooling to obtain a graft copolymer latex. Next, after adding 5 parts of an antioxidant to the above graft copolymer latex,
It was added to a previously prepared 95 ° C. magnesium sulfate aqueous solution with stirring to coagulate. This coagulated product was washed with water, filtered, and dried by a conventional method to obtain a white powdery graft copolymer B-11.

B-12; In the same reactor used in the example described in B-1, 100 parts of acrylic rubbery polymer latex B1-1 as solid content, 1 part of sodium hydrogen carbonate, deionized water. 258 parts (containing water in the latex) were charged, the atmosphere was replaced with nitrogen gas, and then the mixture was heated to 80 ° C. Next, while maintaining at this temperature, a monomer mixture obtained by adding 70 parts of styrene, 30 parts of acrylonitrile and 0.2 part of t-dodecyl mercaptan over 3 hours and 30 minutes,
An aqueous solution prepared by dissolving 0.5 parts of potassium persulfate and 1.8 parts of disproportionated potassium rosinate soap in 47.7 parts of deionized water were continuously added. After the addition is complete, increase the temperature to 8
While maintaining the temperature at 0 ° C., the polymerization reaction was continued for another 30 minutes and then cooled to stop the polymerization reaction to obtain a graft copolymer latex. Next, after adding 5 parts of an antioxidant to the above graft copolymer latex, this was added to a previously prepared 95 ° C. magnesium sulfate aqueous solution with stirring to coagulate. This coagulated product was washed with water, filtered and dried by a conventional method to obtain a white powdery graft copolymer B-12.

B-13: In the same reactor as used in the example described in B-1, 100 parts of acrylic rubbery polymer latex B1-1 as solid content, 1 part of sodium hydrogen carbonate, deionized water. After charging 307 parts (containing water in the latex) and substituting with nitrogen gas, the mixture was heated to 80 ° C. Next, while maintaining this temperature, t-type was added to 105 parts of styrene and 45 parts of acrylonitrile over 3 hours and 30 minutes.
A monomer mixture containing 0.31 part of dodecyl mercaptan and an aqueous solution prepared by dissolving 0.75 part of potassium persulfate and 2.7 parts of disproportionated potassium rosinate soap in 72.7 parts of deionized water were prepared. Added continuously. After the addition was completed, the polymerization reaction was continued for another 30 minutes while maintaining the temperature at 80 ° C., and then the polymerization reaction was stopped by cooling to obtain a graft copolymer latex. Next, after adding 5 parts of an antioxidant to the above graft copolymer latex, this was added to a previously prepared 95 ° C. magnesium sulfate aqueous solution with stirring to coagulate. This coagulated product was washed with water, filtered and dried by a conventional method to obtain a white powdery graft copolymer B-13.

B-14; In the example described in B-1, the monomer mixture used in the same example was replaced with 44 parts of styrene and 176 parts of acrylonitrile to which 1.5 parts of t-dodecyl mercaptan was added. Otherwise, by the same procedure as described in the same example, the white powdery graft copolymer B-
I got 14. B-15; In the example described in B-1, except that the monomer mixture used in the same example was replaced with 198 parts of styrene, 22 parts of acrylonitrile and 0.2 part of t-dodecyl mercaptan, By the same procedure as described in the same example, a white powdery graft copolymer B-15 was obtained.

B-16; In the example described in B-1, the acrylic rubbery polymer latex B1-1 is not used as it is, and the weight average particle diameter is increased to 0.50 μm by the particle diameter enlargement treatment using acetic anhydride. A white powdery graft copolymer B-16 was obtained by the same procedure as described in the same example except that the enlarged one was used. B-17; In the example described in B-1, a white powdery graft copolymer B was prepared by the same procedure as described in the same example except that the acrylic rubbery polymer latex was replaced with B1-6. -17 was obtained.

The rubbery polymers, graft monomers and the like used in the production examples of the graft copolymers B-1 to B-17 are collectively shown in Tables 5- (1) and (2).

[0109]

[Table 7]

[0110]

[Table 8]

3. Production of hard copolymer (C) C-1; 70 parts of deionized water in a reactor (stainless steel autoclave) equipped with a curved turbine stirrer, heating and cooling device, each raw material, auxiliary agent addition device, etc. , Acrylonitrile 45 parts, styrene (# 1) 10 parts, di-t-butyl-p-cresol 0.02 parts, acrylic acid / 2-ethylhexyl acrylate copolymer (suspension stabilizer) 0.03
Parts and 0.4 parts of sodium bromide were charged and replaced with nitrogen gas. Next, the mixture was heated to 106 ° C. with stirring, 0.15 parts of 1-t-azo-cyanocyclohexane dissolved in a small amount of styrene was added, and the polymerization reaction was initiated while maintaining the same temperature. Immediately after the start of the polymerization reaction, additional addition of styrene was started, and 36 parts of styrene (# 2) was continuously added at a constant rate over 4 hours and 30 minutes. The temperature was raised to ° C. Furthermore, after the continuous addition of styrene is completed, 45
Warmed to 145 ° C over a period of minutes. After 5 hours and 15 minutes have passed since the initiation of the polymerization reaction, stripping was carried out for 1 hour while maintaining the temperature at 145 ° C. to recover the unreacted monomer. After completion of this stripping, the mixture was cooled and the temperature was lowered, washed with water, filtered and then dried by a conventional method to obtain a bead-shaped hard copolymer C-1. This rigid copolymer C-1
The acrylonitrile content rate (AN%) was 39.9%.

C-2: SAN manufactured by Monsanto Kasei Co., Ltd.
-L (AN% = 30%) was used as is. C-3; in the example described in C-1, 70 parts of acrylonitrile, 3 parts of styrene (# 1) and styrene (#
A bead-shaped hard copolymer C-3 was obtained by the same procedure as described in the same example except that 2) was replaced with 27 parts. Acrylonitrile content of hard copolymer C-3 (AN%)
Was 69.9%.

4. Production of thermoplastic resin composition Examples 1 to 22 Graft copolymer A obtained by the method described in the above production example
1, the graft copolymer A2, the graft copolymer A3, the graft copolymer B and the hard copolymer C were blended according to the blending ratio (parts) shown in Table 6 and kneaded using a Banbury mixer. , Pellets of the thermoplastic resin composition were produced. From the pellets of the thermoplastic resin composition, test pieces for measuring physical properties and for chemical resistance were molded by injection molding and compression molding. Melt flow rate (MFR) for pellets, Izod impact strength for injection molded test pieces, chemical resistance for compression molded test pieces,
Each was measured. The results are as shown in Tables 6- (1) to (3).

[0114]

[Table 9]

[0115]

[Table 10]

[0116]

[Table 11]

Comparative Examples 1 to 22 Each of the graft copolymer A, the graft copolymer B and the hard copolymer C obtained by the method described in the above Production Example was mixed in proportions (parts) shown in Table-7. In the same manner as in Example 1, kneading was performed using a Banbury mixer to prepare pellets of the thermoplastic resin composition. The melt flow rate (MFR) of the pellet, the Izod impact strength of the injection molded test piece, and the chemical resistance of the compression molded test piece were measured. The results are shown in Table-7.
-It is as shown in (1) to (3).

[0118]

[Table 12]

[0119]

[Table 13]

[0120]

[Table 14]

In Tables 1 to 7, the meanings of the respective abbreviations are as follows.

[0122]

Table 15 ST: Styrene AN: Acrylonitrile MMA: Methyl methacrylate BA: Butyl acrylate AMA: Allyl methacrylate TDM: t-Dodecyl mercaptan

From Table-6 and Table-7, the following will become clear. (1) The thermoplastic resin composition according to the present invention is excellent in both impact strength and processability and is well balanced in properties (Examples 1 to 22 and Comparative Examples 1 to 22). (2) When the thermoplastic resin composition according to the present invention is molded using the same, molded products having excellent appearance and chemical resistance are obtained (Examples 1 to 22 and Comparative Examples 1 to 22).

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takeshi Watanabe 1 Toho-cho, Yokkaichi-shi, Mie Monsanto Kasei Co., Ltd. (72) Inventor Yuichi Kanayama 1 Toho-cho, Yokkaichi-shi, Mie Monsanto Kasei Co., Ltd.

Claims (1)

[Claims] 1. A graft copolymer A, a graft copolymer B, and a hard polymer C shown below are prepared from the following (1) to
A thermoplastic resin composition comprising a composition ratio (weight basis) represented by the formula (5). Graft Copolymer A: Graft Copolymer A is composed of Graft Copolymer A1, Graft Copolymer A2 and Graft Copolymer A3 defined as follows. Graft Copolymer A1: (1) Aromatic vinyl monomer 40 in the presence of 100 parts by weight (based on solid content) of diene rubbery polymer latex having a weight average particle size of 0.10 to 0.65 μm. Emulsion polymerization of 45 to 550 parts by weight of a monomer mixture consisting of ˜80% by weight, 20 to 60% by weight of vinyl cyanide monomer, and 0 to 20% by weight of another vinyl monomer copolymerizable therewith. Graft copolymer A2: (1) 100 parts by weight (based on solid content) of a diene rubbery polymer latex having a weight average particle diameter of 0.05 to 0.20 μm. Amount of aromatic vinyl monomer in the presence of 40 to 80% by weight, vinyl cyanide monomer 20 to 60% by weight, and 0 to 20% by weight of other vinyl monomer copolymerizable therewith. Emulsify 25-200 parts by weight of body mixture It is a graft copolymer obtained by polymerizing, (2) 10 to 80 parts by weight of an aromatic vinyl monomer, a cyanide vinyl monomer, and 100 parts by weight of a rubbery polymer, and That other copolymerizable vinyl monomers are chemically bonded,
(3) Graft copolymer containing primary particles of the graft-copolymerized rubbery polymer aggregated and containing grape tuft-shaped secondary particles having an average particle diameter of 0.4 to 3.0 μm. A3: (1) 100 parts by weight of a solid diene rubbery polymer,
A monomer mixture 4 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 another vinyl monomer copolymerizable therewith.
It was obtained by dissolving in 100 to 900 parts by weight, polymerizing by the bulk polymerization method until the polymerization rate of the monomer mixture reached 15 to 45% by weight, and then substantially completing the polymerization reaction by the suspension polymerization method. The weight average particle diameter of the graft copolymer rubber-like polymer is 0.60 to 2.
Dispersed as 5 μm particles. 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 an acrylic rubbery polymer latex having a weight average particle diameter of 0.05 to 0.50 μm, 40 to 80% by weight of an aromatic vinyl monomer and cyan Graft copolymer obtained by emulsion polymerization of 200 parts by weight or more of a monomer mixture comprising 20 to 60% by weight of a vinyl chloride monomer and 0 to 20% by weight of another vinyl monomer copolymerizable therewith. (2) the acrylic rubbery polymer is an ester compound of a monohydric alcohol having 2 to 12 carbon atoms and acrylic acid, 70 to 100% by weight,
A polymer obtained by emulsion-polymerizing a monomer mixture consisting of 0 to 30% by weight of another vinyl monomer copolymerizable with these and 0 to 3% by weight of a polyfunctional vinyl monomer. Rigid Copolymer C: Rigid Copolymer C is defined as follows. (1) A monomer 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 another vinyl monomer copolymerizable therewith. A hard copolymer obtained by polymerizing a mixture. [Equation 1] [Equation 2] [Equation 3] [Equation 4] [Equation 5]