JP3132040B2 - Powder composition and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a powder composition having improved powder properties of a graft copolymer powder represented by ABS resin, MBS resin and the like, and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, labor saving has been promoted due to automation of powder measurement and enlargement of a transportation system, and the problem of handling powder itself has been highlighted. In other words, blocking resistance, fluidity and bulk specific gravity can be applied to problems such as blocking phenomenon in which powders solidify during storage, bridging phenomenon in which powders stop in a hopper, and clogging of transport lines due to insufficient fluidity. There is a strong demand for improvements in powder characteristics represented by the above.

Various methods for improving the powder characteristics have been studied so far. For example, a method of directly spray-drying the graft copolymer latex, a method of coagulating the graft copolymer latex in the gas phase, and the like can be mentioned. However, these methods do not provide a sufficient effect of improving powder characteristics. On the other hand, there is also a method of adding an appropriate amount of an additive such as a lubricant. However, even this method does not provide an effect of sufficiently improving the powder characteristics, and particularly, a resin in a heated state after a drying step which is observed in a normal process. When the powder is tared and stored in a stack, there is a problem that heat fusion precedes and the anti-blocking effect is not sufficiently exhibited.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and has a blocking phenomenon,
A powder composition with improved powder properties of the graft copolymer, free of bridging phenomena and clogging phenomena in the transport line, resulting in automation of powder weighing and reduction of labor such as enlargement of the transport method. And a method for producing the same.

[0005]

According to the present invention, a glass transition temperature of 7 to 100 parts by weight of a graft copolymer (A) powder having a rubbery polymer content of 30 to 80% by weight is used.
0.1 to 10 parts by weight of a powder of a vinyl polymer (B) having a weight average molecular weight of 1,000,000 or less and 0 to 10 parts by weight of a lubricant (C) and a graft copolymer weight
Average particle diameter of powder of coalesced (A) / vinyl polymer (B)
The powder composition according to any one of claims 1 to 3, wherein the average particle diameter of the powder is 3 to 30 .

[0006] The graft copolymer (A) constituting the powder composition of the present invention can be obtained by graft-polymerizing a vinyl monomer in the presence of a rubbery polymer. This graft polymerization is preferably an emulsion polymerization. When emulsion polymerization is employed, among the rubbery polymers, those obtained by solution polymerization or bulk polymerization are emulsified by a known method and used in the form of a latex. Here, as the rubbery polymer, for example, polybutadiene, polyisoprene, styrene-butadiene random copolymer, acrylonitrile-butadiene copolymer, styrene-butadiene block copolymer, diene rubbery polymer such as polychloroprene, Examples include hydrogenated products of the diene rubbery polymer, ethylene-propylene- (diene) rubber, and acrylic rubber. The rubbery polymer is preferably a diene rubbery polymer obtained by an emulsion polymerization method, more preferably a polybutadiene obtained by an emulsion polymerization method,
It is a styrene-butadiene random copolymer. One or more of these rubbery polymers are used.

[0007] Examples of the vinyl monomer used for the graft polymerization include an aromatic vinyl compound, a vinyl cyanide compound, a (meth) acrylate and other copolymerizable monomers. The sale of these vinyl monomers <br/> Chi, the aromatic vinyl compound, styrene, t- butyl styrene, alpha-methyl styrene, p- methyl styrene, divinyl benzene, 1,1-diphenyl styrene,
N, N-diethyl-p-aminoethylstyrene, N, N
-Diethyl-p-aminoethylstyrene, vinylpyridine, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, fluorostyrene, ethylstyrene, vinylnaphthalene, etc., with styrene and α-methylstyrene being particularly preferred. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile, and these may be used alone or in combination of two or more. Acrylonitrile is particularly preferred as the vinyl cyanide compound.

Further, (meth) acrylic acid esters include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl Acrylic acid esters such as acrylate and benzyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate,
Examples thereof include butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, and benzyl methacrylate, and preferably methyl methacrylate.

Further, other copolymerizable monomers include unsaturated acid anhydrides such as maleic anhydride, itaconic anhydride and citraconic anhydride; unsaturated acids such as acrylic acid and methacrylic acid; maleimide, N -Methylmaleimide,
Maleimide compounds such as N-butylmaleimide, N- (p-methylphenyl) maleimide, N-phenylmaleimide and N-cyclohexylmaleimide; and epoxy compounds such as glycidyl methacrylate. The maleimide compound also includes, for example, a compound obtained by copolymerizing maleic anhydride and imidizing this with aniline or the like. The above vinyl monomers may be used alone or in combination of two or more.
More than one species can be used in combination.

Preferred vinyl monomers include any of the following combinations. Aromatic vinyl compound / vinyl cyanide compound = 40 to
95/5 to 60% by weight aromatic vinyl compound / (meth) acrylic acid ester =
10 to 95/5 to 90% by weight aromatic vinyl compound / (meth) acrylate /
Vinyl cyanide compound = 10-95 / 4-90 / 1-6
0% by weight

In order to produce the rubbery polymer and the graft copolymer (A) by an emulsion polymerization method, a vinyl monomer may be used in the presence of a monomer constituting the rubbery polymer or the rubbery polymer. It is usually obtained by emulsion polymerization at a temperature of 5 to 98 ° C. while stirring a mixture obtained by adding a polymerization initiator, a chain transfer agent, an emulsifier, and the like to the body. Here, as the polymerization initiator, a combination of an organic hydroperoxide such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, or paramenthane hydroperoxide with a reducing agent such as a sugar-containing pyrophosphate formulation or a sulfoxylate formulation. Or a peroxide such as persulfate, azobisisobutyronitrile and benzoyl peroxide.

Examples of the chain transfer agent include mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, t-octyl mercaptan, t-dodecyl mercaptan, n-dodecyl mercaptan, n-stearyl mercaptan, chloroform, bromoform, and quaternary mercaptan. Hydrocarbons such as carbon chloride and carbon tetrabromide; xanthogens such as dimethyl xanthogen disulfide and diisopropyl xanthogen disulfide; α-methylstyrene dimer; 9,10-dihydroanthracene;
Cyclohexadiene, 1,4-hexadiene, 2,5
Dihydrofuran and the like.

As the emulsifier, commonly used emulsifiers can be used. Examples of the emulsifier include sodium or potassium salts of fatty acids such as rosin acid, oleic acid, lauric acid, stearic acid and alkenylsuccinic acid, and sodium dodecylbenzenesulfonate. Anionic surfactants such as alkyl allyl sulfonates and dialkyl sulfosuccinic acids are preferred. In addition, the method of adding the monomer,
Commonly known emulsion polymerization methods such as batch addition polymerization, continuous addition polymerization, and multi-stage polymerization of monomers can be employed, and an emulsifier can be added in the same manner as the monomer.

The content of the rubbery polymer in the graft copolymer (A) thus obtained is 30 to 80% by weight, preferably 30 to 70% by weight. When the content of the rubbery polymer in the component (A) is less than 30% by weight, (A)
The components themselves have sufficient powder properties and it is not necessary to prepare the compositions of the present invention. On the other hand, if it exceeds 80% by weight, a composition having sufficient powder characteristics cannot be obtained even if the components (B) to (C) described below are added.

The graft ratio of the graft copolymer (A) is preferably at least 10% by weight, more preferably at least 20% by weight.
As described above, when the graft ratio is in this range, a further excellent object of the present invention can be obtained. Here, the graft ratio of the graft copolymer (A) is a value determined by the following method. That is, the graft copolymer (A) was put into 20 times by weight of methyl ethyl ketone, stirred at 25 ° C. for 48 hours, and then insoluble matter (dry weight =
W) and soluble matter (dry weight = X) were collected and determined by the following formula. Graft ratio (%) = [(WR) / R] × 100 (where R is the weight of the rubbery polymer before grafting determined from the polymerization recipe.)

Next, the vinyl polymer (B) constituting the powder composition of the present invention is the same as the vinyl monomer used for the graft polymerization of the graft copolymer (A). It is obtained by polymerization by an emulsion polymerization method, a suspension polymerization method, preferably an emulsion polymerization method. The emulsion polymerization method for producing the component (B) is the same as the emulsion polymerization method for preparing the component (A).

The type of the vinyl monomer constituting the vinyl polymer (B) is appropriately selected depending on the type of the vinyl monomer used for the graft polymerization of the graft copolymer (A). Is preferred. For example, when the vinyl monomer used to produce the graft copolymer (A) is an aromatic vinyl compound and a vinyl cyanide compound,
The vinyl monomer constituting the component (B) is at least two kinds of monomers selected from the group consisting of an aromatic vinyl compound, a vinyl cyanide compound and a (meth) acrylate. When the vinyl monomer used in producing the graft copolymer (A) is an aromatic vinyl compound and a (meth) acrylate, the vinyl monomer constituting the component (B) is used as the vinyl monomer. Is preferably a (meth) acrylate or a (meth) acrylate and an aromatic vinyl compound. Among these vinyl monomers, aromatic vinyl compounds include styrene, t
-Butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N, N-diethyl-p-aminoethylstyrene, vinylpyridine, vinylxylene, monochlorostyrene,
Examples thereof include dichlorostyrene, monobromostyrene, fluorostyrene, ethylstyrene, and vinylnaphthalene, which are used alone or in combination of two or more. Among them, styrene and α-methylstyrene are particularly preferred. Examples of the vinyl cyanide compound include, for example, acrylonitrile, methacrylonitrile, and the like, and one or more of these may be used. Acrylonitrile is particularly preferred as the vinyl cyanide compound. Furthermore, examples of the (meth) acrylate include methyl methacrylate, t-butyl methacrylate, sec-butyl methacrylate, 2-hydroxyethyl methacrylate, isobornyl acrylate, 2-naphthyl acrylate, and the like. Used in more than species. As the (meth) acrylate, methyl methacrylate is preferred.

The glass transition temperature of the vinyl polymer (B) is from 70 to 170 ° C., preferably from 80 to 120 ° C. If the glass transition temperature is less than 70 ° C., sufficient powder properties cannot be obtained, while if it exceeds 170 ° C., coagulation becomes difficult and the generation of ultrafine powder or coagulation may be insufficient. Here, the adjustment of the glass transition temperature of the vinyl polymer (B) can be easily achieved by appropriately selecting the type and amount of the vinyl monomer used. Further, the measurement of the glass transition temperature of the vinyl polymer (B) can be performed, for example, using D
SC measuring device [Seiko Electronics Co., Ltd., SSC / 580
DS].

The weight average molecular weight of the vinyl polymer (B) is 1,000,000 or less, preferably 30,000 to 900,000.
If it exceeds 1,000,000, fish eyes are formed when molded using the obtained composition, which is not preferable. The adjustment of the weight average molecular weight can be easily achieved by adjusting the amount of a chain transfer agent or a polymerization initiator. Here, the weight average molecular weight is a value determined in terms of polystyrene using, for example, a high performance liquid chromatograph HLC-802A (carrier liquid = tetrahydrofuran) manufactured by Tosoh Corporation.

The amount of the vinyl polymer (B) in the powder composition of the present invention is 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, per 100 parts by weight of the component (A). Parts, more preferably 0.5 to 3 parts by weight. 0.1
If the amount is less than 10 parts by weight, sufficient powder characteristics cannot be obtained.
Exceeding the weight part is not preferred because the impact resistance is reduced.

Next, the kind of the lubricant (C) used in the powder composition of the present invention is not particularly limited.
Conventional resins used in combination with S resins, MBS resins and the like may be used. For example, higher fatty acids such as stearic acid and palmitic acid and esters thereof, higher alcohols such as stearyl alcohol and palmityl alcohol, glycerin monostearate, glycerin monoester Fatty acid esters such as oleate, silicone oil and the like can be mentioned.
As the lubricant (C), a plasticizer, an antioxidant, an antistatic agent, and the like can be appropriately added in addition to what is generally called a lubricant. These lubricants may be used alone or in combination of two or more.

The amount of the lubricant (C) is from 0 to 10 parts by weight, preferably from 0.1 to 5 parts by weight, more preferably from 0.2 to 5 parts by weight, based on 100 parts by weight of the graft copolymer (A). Parts, and if it exceeds 10 parts by weight, it may cause a decrease in impact resistance, which is not preferable. Thus, the powder composition of the present invention comprises a vinyl copolymer (B) having a glass transition temperature and a weight average molecular weight in a specific range per 100 parts by weight of the powder of the graft copolymer (A). Further, since the lubricant (C) is further blended, the powder characteristics are greatly improved.

The method for producing the powder composition of the present invention is not particularly limited. For example, any one of the following (A) to (C)
It can be easily manufactured by the method described above. (A) A slurry obtained by coagulating 100 parts by weight (in terms of solid content) of latex of the graft copolymer (A) is mixed with a vinyl polymer (B) in an amount of 0.1 to 10 parts by weight (in terms of solid content) of latex. , And 0 to 10 parts by weight of a lubricant (C)
A method of obtaining a powder composition through dehydration and drying steps after mixing.

(B) 0.1 to 10 parts by weight of a vinyl polymer (B) (in terms of solids) is added to a slurry obtained by coagulating 100 parts by weight (in terms of solids) of a latex of the graft copolymer (A). )) A slurry obtained by coagulating the latex and / or a powder after drying the slurry and 0 to 10 parts by weight of a lubricant (C) are added and mixed, and then a powder composition is obtained through a dehydration and drying step. Method. (C) 100 parts by weight of the powder of the graft copolymer (A)
A method of adding and mixing 0.1 to 10 parts by weight of a powder of a vinyl polymer (B) and 0 to 10 parts by weight of a lubricant (C) to obtain a powder composition. Among the methods for producing the powder composition, a preferred method is
(A) and / or (b). According to this method, a composition having more excellent powder characteristics can be obtained.

In the above-mentioned production method, the latex of the graft copolymer (A) and the vinyl polymer (B)
Examples of the coagulant for coagulating latex include sulfuric acid, hydrochloric acid, phosphoric acid, inorganic acids such as nitric acid, organic acids such as acetic acid,
Alternatively, so-called alkali metal halides such as sodium and potassium, alkali metal salts with inorganic acids, and alkali metal salts with organic acids are used. These coagulants are used alone or in combination of two or more. These coagulants are used as an aqueous solution, and the amount of the coagulant added is not particularly limited, but an amount that sufficiently coagulates the latex is used.

In the powder composition of the present invention, the average particle size of the powder of the graft copolymer (A) is preferably 50 to 800 μm, more preferably 100 to 600 μm.
m, particularly preferably 150 to 400 μm, while the average particle diameter of the powder of the vinyl polymer (B) is preferably 15 to 200 μm, more preferably 20 to 150 μm.
m, particularly preferably 20 to 100 μm. further,
The ratio of the average particle diameter of (A) / (B) is 3 to 30, preferably
It is 4.5 to 25, more preferably 5 to 20.
When the average particle size is in the above range, a powder composition having more excellent powder characteristics can be obtained. Here, the measurement of the average particle size is performed by a robot shifter R manufactured by Seishin Enterprise Co.
Using PS-85, 20 g of powder was shaken for 5 minutes to form a sphere, and the average particle size was determined by a standard sieve.

The powder composition of the present invention, injection molding, extrusion molding, vacuum molding, profile molding, automobile parts and the like foam molding, electrical parts, household goods, various industrial products to such <br/> be molded Can be. At that time, usual additives, such as antioxidants, ultraviolet absorbers, flame retardants, antistatic agents, foaming agents, glass fibers, other polymers, such as polyamides,
Polycarbonate, thermoplastic polyester, polyphenylene ether, polyvinylidene fluoride resin, diene rubber, ethylene-propylene rubber, acrylic rubber, and the like can be blended.

[0028]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. In the examples, parts and% are based on weight unless otherwise specified.
Various measurements in the examples were based on the following methods.

Measurement of bulk specific gravity The bulk specific gravity (unit = g / ml) was measured based on JIS K6721. Measurement of flow index "Chemical Engineering" (Chemical Engineering)
Engineering, published Jan. 18, 1965, pp. 163-168, the four angles of repose, compression, spacherer angle and uniformity (or cohesion).
Two measured values were obtained for the obtained powder composition, points were scored from the values in accordance with the integration table, and evaluated by an index represented by the sum of these points. The larger the measured value, the better the fluidity.

The average particle diameter sun Electronic Co. latex, a laser particle size analyzer LPA-30
It was measured at 00/3100. A fixed load (3 kg / c) was applied to 25 g of the obtained powder composition.
m ² ) for 30 minutes in the form of a block (shape; cylindrical shape, dimensions;
4 cm × 2 cm), and the block is subjected to a constant vibration (frequency: 60 Hz) for 200 seconds to be collapsed. Of the collapsed powder, the weight of the powder of the 16 mesh pass is determined by the weight of the original block. Expressed as a percentage of the total weight. The numerical value of the percentage is called a disintegration rate, and the larger the numerical value, the harder it is to block. In addition, the disintegration rate was measured immediately after the powder composition was dried, and about 10 minutes after the drying, and then left. In addition, for the powder composition immediately after drying, the disintegration rate was measured in the same manner also for the blocks prepared for a load application time of one month. 100 parts of a vinyl chloride resin having an Izod impact strength average polymerization degree of 700,
15 parts of graft copolymer powder or its composition, 2 parts of dibutyltin malate-based stabilizer, dioctyl phthalate 3
Part and butane glycol montanate 0.5
Part of the mixture into a Henschel mixer,
After heating and stirring to 20 ° C, the mixture was cooled to 50 ° C, kneaded with a 165 ° C roll for 7 minutes, and then pressed at 180 ° C into a 1/2 inch x 1/4 inch x 2.5 inch test piece. Molded. Using these ten test pieces, Izod impact strength was measured according to ASTM D256 at a measurement temperature of 23 ° C. The unit is kg · cm / cm. 100 parts of vinyl chloride resin having a fisheye number average polymerization degree of 700,
15 parts of graft copolymer powder or its composition, 2 parts of dibutyltin malate-based stabilizer, dioctyl phthalate 3
Part and butane glycol montanate 0.5
Part of the mixture into a Henschel mixer,
After heating to 20 ° C. and stirring, the mixture was cooled to 50 ° C., and a T-die sheet having a thickness of 0.2 mm was prepared using an extruder, and the number of fish eyes in 50 × 1,000 mm was measured. The Fischer Interview number of eye was observed in the 20 side, it was average.

Example 1 Preparation of latex of graft copolymer (A) 150 parts of deionized water, 66 parts of 1,3-butadiene, 34 parts of styrene, 2.0 parts of potassium laurate, 0.6 parts of potassium phosphate 0.06 part of diisopropylbenzene hydroperoxide, and 0.01 part of ferrous sulfate, 0.025 part of disodium ethylenediaminetetraacetate,
A mixture of 0.04 parts of sodium formaldehyde sulfoxylate was charged into a nitrogen-substituted autoclave, and polymerized at 5 ° C. for 6 hours with stirring.
% Emulsified the emulsion polymerization. Next, steam was blown into the obtained rubbery polymer latex to remove unreacted monomers.

Next, in a nitrogen-substituted flask, 60 parts of the rubbery polymer latex produced as described above in terms of solid content and 150 parts of deionized water (including water in the rubbery polymer latex) And the temperature is raised to 7
When the temperature reached 0 ° C., a mixture of 0.2 part of cumene hydroperoxide, 14 parts of styrene and 26 parts of methyl methacrylate, and a solution obtained by dissolving 0.10 part of sodium formaldehyde sulfoxylate in 20 parts of deionized water Were simultaneously dropped continuously from different supply ports over 4 hours, and stirring was further continued for 1 hour to complete the graft polymerization. The obtained graft copolymer latex was designated as A-1. The average particle diameter of latex A-1 was 1,500 °.

Preparation of latex of vinyl polymer (B) 180 parts of deionized water, 2 parts of potassium laurate, 100 parts of methyl methacrylate, 0.12 parts of diisopropylbenzene hydroperoxide, 0.02 parts of ferrous sulfate
Parts, disodium ethylenediaminetetraacetate 0.05
Parts, sodium formaldehyde sulfoxylate 0.0
Eight parts of the mixed aqueous solution was charged into a nitrogen-substituted autoclave, and polymerized at 60 ° C. for 2 hours with stirring to complete the polymerization at a polymerization conversion of 100%, thereby obtaining a vinyl polymer latex B-1. This vinyl polymer latex B-1
Of the latex had a glass transition temperature of 100 ° C. and a weight average molecular weight of 800,000.

Preparation of powder composition Latex A of graft copolymer (A) obtained above
After adding 1 part of butylated hydroxytoluene as an antioxidant to 100 parts in terms of solid content,
Coagulation was performed with a 0.5% aqueous sulfuric acid solution at ℃. The resulting slurry was heated to 90 ° C. and held for 5 minutes. Then, 3 parts of the latex B-1 of the vinyl polymer (B) obtained above was converted to a solid content, and glycerin monostearate was used as a lubricant. One part was added and held for 5 minutes with further mixing. Thereafter, dehydration and drying were performed to obtain a powder composition. The average particle size of the particles of A-1 in the powder composition is about 240 μm
Met. Table 1 shows the results.

Examples 2 to 5 Except that the amount of the latex B-1 of the vinyl polymer (B) or the amount of glycerin monostearate as the lubricant (C) was changed as shown in Table 1, In the same manner as in Example 1, a powder composition was obtained. The average particle size of A-1 in the powder composition was about 240 μm. Table 1 shows the results.

Example 6 Latex A-1 and Latex B-1 used in Example 1
Were coagulated with a 0.5% aqueous sulfuric acid solution at 40 ° C. and kept at 90 ° C. for 5 minutes to obtain slurries. Then, 100 parts of the slurry obtained from latex A-1 in terms of solid content, 3 parts of the slurry obtained from latex B-1 in terms of solid content, and 1 part of glycerin monostearate, which is a lubricant, were mixed. Dehydration and drying were performed to obtain a powder composition. Table 2 shows the results.

Example 7 The slurry obtained from the latex A-1 prepared in Example 6 was obtained by dehydrating and drying the slurry obtained from the latex B-1 prepared in Example 6 to 100 parts in terms of solid content. Powder 3 parts, and glycerin monostearate 1 part,
Thereafter, dehydration and drying were performed to obtain a powder composition. Table 2 shows the results
Shown in

Example 8 In the polymerization recipe of latex B-1 in Example 1, 100 parts of methyl methacrylate was added to methyl methacrylate 9
Latex B-2 of vinyl polymer (B) was obtained by the same polymerization recipe as in Example 1 except that 5 parts and 5 parts of butyl acrylate were used, and 0.5 part of t-dodecyl mercaptan was used as a molecular weight regulator. . This latex B-
2 had an average particle diameter of 650 °, a polymer constituting the latex had a glass transition temperature of 87 ° C., and a weight average molecular weight of 400,000. This vinyl polymer latex B-2
Except for using, a powder composition was obtained in the same manner as in Example 1. Table 2 shows the results.

Example 9 A powder composition was obtained in the same manner as in Example 1 except that glycerin monostearate as the lubricant (C) was changed to epoxidized soybean oil. Table 2 shows the results. Example 10 As a lubricant (C), glycerin monostearate 0.5
And a powder composition was obtained in the same manner as in Example 1, except that 0.5 part by weight and epoxidized soybean oil were used. Table 3 shows the results. Example 11 A powder composition was obtained in the same manner as in Example 1 except that the lubricant (C) was not used. Table 3 shows the results. Example 12 A powder obtained by coagulating, dehydrating, and drying latex A-1 in the same manner as in Example 1 and a powder obtained by coagulating, dehydrating, and drying latex B- 1 in the same manner as in Example 1 were shown in Table 1. A powder composition was obtained by mixing according to the formulation shown in FIG. Table 3 shows the results.

Comparative Examples 1 to 3 Whether the amount of latex B-1 exceeds the upper limit of the present invention (Comparative Example 1), is not used (Comparative Example 2), or the amount of the lubricant (C) is determined according to the present invention. A powder composition was obtained in the same manner as in Example 1 except that the powder composition was used beyond the upper limit (Comparative Example 3). Table 4 shows the results.

Comparative Example 4 Latex A-1 of Graft Copolymer (A) of Example 1
A graft copolymer latex A-2 was obtained in the same manner as in Example 1 except that the rubbery polymer latex was used in an amount of 20 parts in terms of solids, 28 parts of styrene, and 52 parts of methyl methacrylate. . This latex A-
The average particle size of No. 2 was 1,450 °. A powder composition was obtained in the same manner as in Example 1, except that this graft copolymer latex A-2 was used instead of the graft copolymer latex A-1. Table 5 shows the results.

Comparative Example 5 Latex A-1 of Graft Copolymer (A) of Example 1
The graft copolymer latex A- was prepared in the same manner as in Example 1 except that the rubbery polymer latex was used in an amount of 90 parts, 3.5 parts of styrene, and 6.5 parts of methyl methacrylate. 3 was obtained. The average particle size of this latex A-3 was 1,500 °. A powder composition was obtained in the same manner as in Example 1, except that this graft copolymer latex A-3 was used instead of the graft copolymer latex A-1. Table 5 shows the results.

Comparative Example 6 In the polymerization recipe of latex B-1 of Example 1, diisopropylbenzene hydroperoxide was added in an amount of 0.06.
Parts, a mixture of ferrous sulfate 0.01 part, disodium ethylenediaminetetraacetate 0.025 part, and sodium formaldehyde sulfoxylate 0.04 part, except that the polymerization temperature is 40 ° C. and polymerization is performed for 3 hours. Example 1
A latex B-3 of a vinyl polymer (B) was obtained by the same polymerization recipe as described above. The latex B-3 had an average particle size of 720 °, a polymer constituting the latex had a glass transition temperature of 100 ° C., and a weight average molecular weight of 1.5 million. A powder composition was obtained in the same manner as in Example 1, except that this vinyl polymer latex B-3 was used. Table 5 shows the results.

Comparative Example 7 In the polymerization recipe of latex B-1 in Example 1, 100 parts of methyl methacrylate were added to methyl methacrylate 3
Latex B-4 of vinyl polymer (B) was obtained by the same polymerization recipe as in Example 1 except that 0 part and 70 parts of butyl acrylate were used. The average particle diameter of this latex B-4 was 700 °, the glass transition temperature of the polymer constituting the latex was 31 ° C, and the weight average molecular weight was 750,000. A powder composition was obtained in the same manner as in Example 1, except that this vinyl polymer latex B-4 was used. Table 5 shows the results. In the powder compositions of Comparative Examples 1 to 7, the powder average particle diameter of the component (A) was about 240 μm.

As apparent from Tables 1 to 3, Examples 1 to
11 is the powder composition of the present invention, and the powder composition intended for the present invention has been obtained. In contrast, as apparent from Table 4, Comparative Example 1 is an example in which the amount of the vinyl polymer (B) used exceeds the range of the present invention, and is inferior in impact resistance. Comparative Example 2 is an example in which the vinyl polymer (B) was not used, and the powder characteristics were not improved.

As is clear from Table 4, Comparative Example 4
Is an example in which the content of the rubbery polymer in the graft copolymer (A) is less than the range of the present invention, and a powder having excellent powder properties can be obtained without using the powder composition of the present invention. It is understood that it can be done. Comparative Example 5 is an example in which the content of the rubbery polymer in the graft copolymer (A) exceeded the range of the present invention, and a powder composition having improved powder characteristics could not be obtained. Comparative Example 6
Is an example in which the weight average molecular weight of the vinyl polymer (B) exceeds the range of the present invention, and the fish eyes are increased. Comparative Example 7 is an example in which the glass transition temperature of the vinyl polymer (B) is less than the range of the present invention, and the powder properties are inferior.

[0047]

[Table 1]

[0048]

[Table 2]

[0049]

[Table 3]

[0050]

[Table 4]

[0051]

[Table 5]

[0052]

EFFECT OF THE INVENTION The powder composition of the present invention has no blocking phenomenon, bridging phenomenon, clogging phenomenon in the transportation line, etc., and as a result, it is possible to automate powder measurement and to save labor such as enlarging the transportation system. It is.

──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Yoshiaki Kawamura 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (56) References JP-A-4-306252 (JP, A) JP-A JP-A-4-94908 (JP, A) JP-A-3-119030 (JP, A) JP-A-64-87612 (JP, A) JP-A-61-192736 (JP, A) JP-A-58-1742 (JP) (A) JP-A-4-300947 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 51/04 C08L 55/02 C08K 5/10 C08L 57/00

Claims (3)

(57) [Claims] 1. A glass transition temperature of 70 to 170 ° C. and a weight average molecular weight of 100 parts by weight of a graft copolymer (A) powder having a rubbery polymer content of 30 to 80% by weight. Average particle size of the graft copolymer (A) powder containing 0.1 to 10 parts by weight of the powder of the vinyl polymer (B) of 1,000,000 or less and 0 to 10 parts by weight of the lubricant (C)
Particle diameter / average particle diameter of powder of vinyl polymer (B) is 3 to
30. A powder composition, which is 30 . 2. Average particle size of the powder of the graft copolymer (A)
Powder of vinyl polymer (B) having a diameter of 50 to 800 μm
2. The composition according to claim 1, which has an average particle size of 15 to 200 μm.
Powder composition. 3. The process for producing a powder composition according to claim 1 , wherein the process (a), (b) or (c) is as follows. (A) A slurry obtained by coagulating 100 parts by weight (in terms of solid content) of latex of the graft copolymer (A) is mixed with a vinyl polymer (B) in an amount of 0.1 to 10 parts by weight (in terms of solid content) of latex. , And 0 to 10 parts by weight of a lubricant (C)
A method of obtaining a powder composition through dehydration and drying steps after mixing. (B) A slurry obtained by coagulating 100 parts by weight (in terms of solid content) of a latex of a graft copolymer (A) is mixed with a vinyl polymer (B) in an amount of 0.1 to 10 parts by weight (in terms of solid content) of latex. And / or powder after drying the slurry, and lubricants (C)
A method of obtaining a powder composition through dehydration and drying steps after adding and mixing parts by weight. (C) 100 parts by weight of the powder of the graft copolymer (A)
A method of adding and mixing 0.1 to 10 parts by weight of a powder of a vinyl polymer (B) and 0 to 10 parts by weight of a lubricant (C) to obtain a powder composition.