JPH04335052A - Powder composition and its production - Google Patents

Abstract

PURPOSE:To provide a powder composition having powder properties better than those of the contained graft copolymer, not undergoing blocking, bridging and stoppage of a transfer line and being capable of labor reduction such as the automated weighing of a powder and the use of a large-sized transportation system. CONSTITUTION:A powder composition mainly consisting of 100 pts.wt. powder of a graft copolymer having a rubbery polymer content of 30-80wt.%, 0.1-10 pts.wt. powder of a vinyl polymer of a glass transition temperature of 70-170 deg.C and a weight-average molecular weight of 1000000 or below, and 0-10 pts.wt. lubricant.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a powder composition with improved powder characteristics of a graft copolymer powder typified by ABS resin, MBS resin, etc., and a method for producing the same.

0002

2. Description of the Related Art In recent years, efforts have been made to save labor by automating powder weighing and increasing the size of transportation methods, and with this, the problem of handling the powder itself has been brought into focus. In other words, we have improved blocking resistance, fluidity, and bulk specific gravity to prevent problems such as blocking phenomenon where powders solidify together during storage, bridging phenomenon where powders get stuck in the hopper, and clogging of transportation lines due to lack of fluidity. There is a strong demand for improvements in the powder properties represented by .

[0003] Various methods have been studied to improve the powder properties. Examples include a method of directly spray drying the graft copolymer latex, a method of coagulating the graft copolymer latex in a vapor phase, and the like. However, these methods do not show a sufficient effect of improving powder properties. On the other hand, there is also a method of adding an appropriate amount of additives such as lubricants, but even this method does not have the effect of sufficiently improving the powder properties, especially when the resin is heated after the drying process that is seen in normal processes. When the powder is tared and stored in stacks, there is a problem that heat fusion occurs first and the anti-blocking effect is not sufficiently developed.

0004

SUMMARY OF THE INVENTION The present invention has been made against the background of the above-mentioned problems of the prior art, and solves the problem of blocking phenomenon,
A powder composition with improved powder characteristics of a graft copolymer that does not cause bridging phenomena or clogging phenomena in transportation lines, and as a result, can automate powder weighing and save labor such as increasing the size of transportation methods. The purpose is to provide a method for producing the same.

[0005]

[Means for Solving the Problems] The present invention provides a graft copolymer (
For 100 parts by weight of powder A), the glass transition temperature is 70%.
A powder composition containing as main components 0.1 to 10 parts by weight of a vinyl polymer (B) powder at ~170°C and a weight average molecular weight of 1 million or less, and 0 to 10 parts by weight of a lubricant (C). It provides:

The graft copolymer (A) constituting the powder composition of the present invention is obtained by graft polymerizing a vinyl monomer in the presence of a rubbery polymer. This graft polymerization is preferably emulsion polymerization. When employing emulsion polymerization, among the rubbery polymers, those obtained by solution polymerization or bulk polymerization are emulsified by a known method and used in the form of latex. Here, examples of the rubbery polymer include diene rubbery polymers such as polybutadiene, polyisoprene, styrene-butadiene random copolymer, acrylonitrile-butadiene copolymer, styrene-butadiene block copolymer, and polychloroprene; Hydrogenated product of the diene rubbery polymer, ethylene-
Examples include propylene (diene) rubber and acrylic rubber. The rubbery polymer is preferably a diene-based rubbery polymer obtained by emulsion polymerization, and more preferably polybutadiene or styrene-butadiene random copolymer obtained by emulsion polymerization. These rubbery polymers may be used alone or in combination of two or more.

[0007] Vinyl monomers to be subjected to graft polymerization include aromatic vinyl compounds, vinyl cyanide compounds, (meth)acrylic acid esters, and other copolymerizable monomers. Among these vinyl monomers, aromatic vinyl compounds include styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene,
Divinylbenzene, 1,1-diphenylstyrene, N,
N-diethyl-p-aminoethylstyrene, N,N-diethyl-p-aminoethylstyrene, vinylpyridine,
Examples include vinylxylene, monochlorostyrene, dichlorostyrene, monobromstyrene, fluorostyrene, ethylstyrene, vinylnaphthalene, and styrene and α-methylstyrene are particularly preferred. Examples of the cyanated vinyl compound include acrylonitrile and methacrylonitrile, which may be used alone or in combination of two or more. Acrylonitrile is particularly preferred as the vinyl cyanide compound.

Furthermore, (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, and phenyl acrylate. Acrylic acid esters such as acrylate and benzyl acrylate; methyl methacrylate,
Examples include ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, and benzyl methacrylate, with methyl methacrylate being preferred.

Furthermore, 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,
Examples include maleimide compounds such as N-butylmaleimide, N-(p-methylphenyl)maleimide, N-phenylmaleimide, and N-cyclohexylmaleimide; and epoxy compounds such as glycidyl methacrylate. Note that the maleimide compound includes, for example, one obtained by copolymerizing maleic anhydride and imidizing this with aniline or the like. The above vinyl monomers may be used alone or in combination.
More than one species can be used together.

[0010] Preferred vinyl monomers include any of the following combinations (1) to (2). ■Aromatic vinyl compound/vinyl cyanide compound = 40~
95/5 to 60% by weight ■Aromatic vinyl compound/(meth)acrylic acid ester=
10-95/5-90% by weight ■Aromatic vinyl compound/(meth)acrylic acid ester/
Vinyl cyanide compound = 10-95/4-90/1-6
0% by weight

[0011] In order to produce the rubbery polymer and graft copolymer (A) by an emulsion polymerization method, monomers constituting the rubbery polymer or vinyl monomers are added in the presence of the rubbery polymer. It is usually obtained by emulsion polymerization at 5 to 98°C while stirring a mixture of a polymerization initiator, a chain transfer agent, an emulsifier, and the like. Here, the polymerization initiator is a combination of organic hydroperoxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, and paramenthane hydroperoxide, and a reducing agent such as a sugar-containing pyrophosphate formulation or a sulfoxylate formulation. redox systems, or peroxides such as persulfates, azobisisobutyronitrile, and benzoyl peroxide are used.

As chain transfer agents, mercaptans such as n-hexylmercaptan, n-octylmercaptan, t-octylmercaptan, t-dodecylmercaptan, n-dodecylmercaptan, and n-stearylmercaptan, chloroform, bromoform, and Hydrocarbons such as carbon chloride and carbon tetrabromide, xanthogens such as dimethylxanthogen disulfide and diisopropylxanthogen disulfide, α-methylstyrene dimer, 9,10-dihydroanthracene, 1,4-
Examples include cyclohexadiene, 1,4-hexadiene, 2,5-dihydrofuran, and the like.

Further, as the emulsifier, commonly used emulsifiers can be used, but sodium salts or potassium salts of fatty acids such as rosin acid, oleic acid, lauric acid, stearic acid or alkenylsuccinic acid, sodium dodecylbenzenesulfonate, etc. Anionic surfactants are preferred, such as alkylaryl sulfonates, dialkyl sulfosuccinic acids, and the like. The method of adding the monomer is as follows:
Generally known emulsion polymerization methods such as bulk addition polymerization, continuous addition polymerization, and multistage polymerization of monomers can be employed, and the emulsifier can also be added in the same manner as the monomers.

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 component (A) is less than 30% by weight, component (A) itself has sufficient powder properties and there is no need to prepare the composition of the present invention. On the other hand, if it exceeds 80% by weight,
Even if components (B) to (C) described below are added, a composition with sufficient powder characteristics cannot be obtained.

[0015] The preferable graft ratio of the graft copolymer (A) is 10% by weight or more, preferably 20% by weight.
This is the above, and when the grafting ratio is within this range, even more excellent objects 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 added to 20 times the weight of methyl ethyl ketone, stirred at 25°C for 48 hours, and then centrifuged to remove the insoluble matter (dry weight =
W) and soluble content (dry weight = X) were collected and determined from the following formula. Grafting rate (%) = [(WR)/R] x 100 (wherein, 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 a vinyl monomer similar to the vinyl monomer used in the graft polymerization of the graft copolymer (A). , emulsion polymerization, suspension polymerization, preferably emulsion polymerization. The emulsion polymerization method used to produce component (B) is the same as the emulsion polymerization method used to prepare component (A).

[0017] The type of vinyl monomer constituting the vinyl polymer (B) is appropriately selected depending on the type of vinyl monomer used in the graft polymerization of the graft copolymer (A). It is preferable. For example, when the vinyl monomers used to produce the graft copolymer (A) are an aromatic vinyl compound and a vinyl cyanide compound, (
The vinyl monomers constituting component B) are at least two monomers selected from the group of aromatic vinyl compounds, vinyl cyanide compounds, and (meth)acrylic acid esters. Furthermore, the vinyl monomer used in producing the graft copolymer (A) is an aromatic vinyl compound and (meth)
In the case of an acrylic ester, the vinyl monomer constituting component (B) is preferably a (meth)acrylic ester or a (meth)acrylic ester 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, dichlorostyrene, monobromustyrene, fluorostyrene, ethylstyrene, vinylnaphthalene, etc.
These may be used alone or in combination of two or more. Among them,
Particularly preferred are styrene and α-methylstyrene. Also,
Examples of vinyl cyanide compounds include acrylonitrile and methacrylonitrile, which may be used alone or in combination of two or more. Acrylonitrile is particularly preferred as the vinyl cyanide compound. moreover,(
Examples of the meth)acrylic acid ester include methyl methacrylate, t-butyl methacrylate, sec-butyl methacrylate, 2-hydroxyethyl methacrylate, isobornyl acrylate, and 2-naphthyl acrylate, and these may be used alone or in combination of two or more. used. As the (meth)acrylic acid ester, methyl methacrylate is preferred.

The glass transition temperature of the vinyl polymer (B) is 70 to 170°C, preferably 80 to 120°C. If the glass transition temperature is less than 70°C, sufficient powder characteristics cannot be obtained, while if it exceeds 170°C, coagulation becomes difficult and ultrafine powder may be generated or coagulation may be insufficient. Here, 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. Furthermore, the glass transition temperature of the vinyl polymer (B) can be measured using, for example, DS
C measurement device [Seiko Electronics Co., Ltd., SSC/580D
S].

Furthermore, the weight average molecular weight of the vinyl polymer (B) is 1 million or less, preferably 30,000 to 900,000,
If it exceeds 1 million, fish eyes will occur when the resulting composition is molded, which is not preferable. Adjustment of the weight average molecular weight can be easily achieved by adjusting the amount of chain transfer agent or 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 manufactured by Tosoh Corporation (carrier liquid = tetrahydrofuran).

The blending 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 component (A). Department,
More preferably, it is 0.5 to 3 parts by weight. If it is less than 0.1 part by weight, sufficient powder properties cannot be obtained, while if it exceeds 10 parts by weight, impact resistance is undesirably reduced.

Next, the type of lubricant (C) used in the powder composition of the present invention is not particularly limited, but AB
Those commonly used in combination with S resin, MBS resin, etc. may be used, such as higher fatty acids and their esters such as stearic acid and palmitic acid, higher alcohols such as stearyl alcohol and palmityl alcohol, glycerin monostearate, and glycerin monostearate. Examples include fatty acid esters such as oleate, silicone oil, and the like. Moreover, as the lubricant (C), in addition to what is generally called a lubricant, a plasticizer, an antioxidant, an antistatic agent, etc. can also be appropriately added. These lubricants may be used alone or in combination of two or more.

The blending amount of the lubricant (C) is 0 to 10 parts by weight, preferably 0.1 to 5 parts by weight, more preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the graft copolymer (A). parts by weight, and if it exceeds 10 parts by weight, it is not preferable because it causes a decrease in impact resistance. As described above, the powder composition of the present invention includes 100 parts by weight of the graft copolymer (A), a vinyl polymer (B) having a glass transition temperature and a weight average molecular weight within a specific range, and optionally a vinyl polymer (B) having a glass transition temperature and a weight average molecular weight within a specific range. Furthermore, lubricant (C
), the powder properties are significantly improved.

The method for producing the powder composition of the present invention is not particularly limited, but it can be easily produced, for example, by any one of the following methods (a) to (c), or a combination of these methods. (B) Graft copolymer (A) 0.1 to 10 parts by weight (in terms of solid content) of latex is added to a slurry obtained by coagulating 100 parts by weight (in terms of solid content) of latex of vinyl polymer (B). , and 0 to 10 parts by weight of lubricant (C) are added.
After mixing, a powder composition is obtained through dehydration and drying steps.

(b) Graft copolymer (A) 0.1 to 10 parts by weight (in terms of solid content) of vinyl polymer (B) is added to the slurry obtained by coagulating 100 parts by weight (in terms of solid content) of latex. A slurry obtained by coagulating the latex of ) and/or a powder after drying the slurry, and a lubricant (
C) A method of obtaining a powder composition by adding and mixing 0 to 10 parts by weight, followed by dehydration and drying steps. (c) 100 parts by weight of the powder of the graft copolymer (A),
A method of obtaining a powder composition by adding and mixing 0.1 to 10 parts by weight of a vinyl polymer (B) powder and 0 to 10 parts by weight of a lubricant (C). Among the methods for producing the powder composition described above, a preferred method is:
(a) and/or (b). According to this method, a composition with even better powder properties can be obtained.

[0025] In the above manufacturing method, the latex of the graft copolymer (A) and the vinyl polymer (B)
Coagulants for coagulating latex include inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, and nitric acid, organic acids such as acetic acid,
Alternatively, halides of so-called alkali metals such as sodium and potassium, alkali metal salts with inorganic acids, alkali metal salts with organic acids, etc. are used. These coagulants may be used alone or in combination of two or more. These coagulants are used in the form of an aqueous solution, and the amount added is not particularly limited, but is used in an amount that sufficiently coagulates the latex.

Further, in the powder composition of the present invention, the average particle diameter of the powder of the graft copolymer (A) is usually 30
~1,000 μm, preferably 50 to 800 μm, more preferably 100 to 600 μm, particularly preferably 15
0 to 400 μm, while the average particle diameter of the vinyl polymer (B) powder is usually 10 to 300 μm, preferably 15 to 200 μm, and more preferably 20 to 150 μm.
m, particularly preferably 20 to 100 μm. moreover,
The average particle diameter ratio of (A)/(B) is preferably 3 to 3.
0, more preferably 4.5 to 25, particularly preferably 5
~20. When the average particle diameter is within the above range, a powder composition having even better powder properties can be obtained. Here, the average particle diameter was measured using a robot shifter RPS-85 manufactured by Seishin Enterprise Co., Ltd., by shaking 20 g of powder for 5 minutes and dividing it into spheres, and the average particle diameter was determined using a standard sieve. It is.

The powder composition of the present invention can be molded into automobile parts, electrical parts, household goods, various industrial goods, etc. by injection molding, extrusion molding, vacuum forming, irregular molding, foam molding, and the like. In this case, the usual additives such as antioxidants, UV absorbers, flame retardants, antistatic agents, blowing agents, glass fibers, other polymers such as polyamides,
Polycarbonate, thermoplastic polyester, polyphenylene ether, polyvinylidene fluoride resin, diene rubber, ethylene-propylene rubber, acrylic rubber, etc. can be blended.

[0028]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples in any way as long as the gist thereof is not exceeded. In the examples, parts and percentages are based on weight unless otherwise specified. Moreover, various measurements in the examples were based on the following methods.

Measurement of bulk specific gravity Bulk specific gravity (unit = g/ml) is determined according to JIS K6721.
Measured based on. Measurement of flow index "Chemical Engineering"
Engineering), January 18, 1965, pages 163-168, the angle of repose, degree of compaction, Spatella angle, and degree of uniformity (or degree of cohesion)
Two measured values were obtained for the obtained powder composition, and scores were assigned based on these values according to an integration table, and evaluation was made using an index represented by the sum of these scores. The larger the measured value, the better the fluidity.

Average particle size of latex Laser particle size analyzer LPA-30 manufactured by Taiyodenshi Co., Ltd.
Measured at 00/3100. Measurement of disintegration rate A constant load (3 kg/c) was applied to 25 g of the obtained powder composition.
m2) for 30 minutes to produce a block (shape: cylindrical, dimensions: 4 cm x 2 cm), and this block was given constant vibration (frequency: 60 Hz) for 200 seconds to collapse.
Among the disintegrated powders, the weight of the powder of 16 mesh passes was expressed as a percentage of the total weight of the original block. The percentage value is called the decay rate, and the larger the value, the more difficult it is to block. Note that the disintegration rate was measured immediately after drying the powder composition and after drying for 10 hours. In addition, the disintegration rate was similarly measured for a block prepared by applying a load for one month using the powder composition immediately after drying. 100 parts of a vinyl chloride resin having an Izod impact strength average degree of polymerization of 700;
15 parts of graft copolymer powder or its composition, 2 parts of dibutyltin malate stabilizer, 3 parts of dioctyl phthalate
part and montanic acid butylene glycol ester 0.5
Place the mixture with 1 part into a Henschel type mixer, and
The temperature was raised to 20°C and stirred, then 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 10 test pieces, Izod impact strength was measured at a measurement temperature of 23° C. according to ASTM D256. The unit is kg·cm/cm. 100 parts of a vinyl chloride resin having a fisheye number average degree of polymerization of 700;
15 parts of graft copolymer powder or its composition, 2 parts of dibutyltin malate stabilizer, 3 parts of dioctyl phthalate
part and montanic acid butylene glycol ester 0.5
Place the mixture with 1 part into a Henschel type mixer, and
After the temperature was raised to 20° C. and stirred, it was cooled to 50° C., and a T-die sheet with a thickness of 0.2 mm was produced using an extruder, and the number of fish eyes in 50×1,000 mm was measured. The number of fisheyes observed in the 20 sheets was averaged.

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.
parts, diisopropylbenzene hydroperoxide 0
．． A mixture of 0.06 parts of ferrous sulfate, 0.01 part of ferrous sulfate, 0.025 parts of disodium ethylenediaminetetraacetate, and 0.04 parts of sodium formaldehyde sulfoxylate was placed in a nitrogen-substituted autoclave, and heated at 5°C with stirring. Polymerization was carried out for 6 hours, and emulsion polymerization was concentrated at a polymerization conversion rate of 90%. Next, water vapor 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) were added. Prepare and raise the temperature until the internal temperature is 7.
When the temperature reaches 0℃, cumene hydroperoxide is 0.
．． 2 parts, 14 parts of styrene and 2 parts of methyl methacrylate
A mixture of 6 parts of sodium formaldehyde sulfoxylate and a solution of 0.10 parts of sodium formaldehyde sulfoxylate dissolved in 20 parts of deionized water were simultaneously added dropwise from separate feed ports over a period of 4 hours, and stirring was continued for an additional hour. Graft polymerization was completed. The obtained graft copolymer latex was designated as A-1. The average particle diameter of latex A-1 was 1,500 Å.

Production 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, Disodium ethylenediaminetetraacetate 0.05 part, sodium formaldehyde sulfoxylate 0.08
A mixed aqueous solution of 1 part was charged into a nitrogen-substituted autoclave, and polymerized with stirring at 60°C for 2 hours to complete the polymerization at a polymerization conversion rate of 100% to obtain vinyl polymer latex B-1. The average particle diameter of this vinyl polymer latex B-1 is 700 Å, the glass transition temperature of the polymer constituting the latex is 100°C, and the weight average molecular weight is 8
It was 0,000.

Production of powder composition Latex A of the graft copolymer (A) obtained above
After adding 1 part of butylated hydroxytoluene as an anti-aging agent to 100 parts of -1 in terms of solid content, 40 parts of
Coagulation was performed with a 0.5% aqueous sulfuric acid solution at °C. The temperature of the obtained slurry was raised to 90°C and held for 5 minutes, and then 3 parts of latex B-1 of the vinyl polymer (B) obtained above was added in terms of solid content, and glycerin monostearate was added as a lubricant. 1 part was added and held for 5 minutes with further mixing. Thereafter, it was dehydrated and dried to obtain a powder composition. The average particle diameter of the particles of A-1 in the powder composition is approximately 240 μm
Met. The results are shown in Table 1.

Examples 2 to 5 Examples 2 to 5 except that the amount of 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. A powder composition was obtained in the same manner as in Example 1. The average particle size of A-1 in the powder composition was about 240 μm. The results are shown in Table 1.

Example 6 Latex A-1 and Latex B-1 used in Example 1
Each of these was coagulated with a 0.5% sulfuric acid aqueous solution at 40°C and held at 90°C for 5 minutes to obtain each slurry. Next, the slurry obtained from latex A-1 was reduced to 1 in terms of solid content.
00 parts, 3 parts in terms of solid content of the slurry obtained from Latex B-1, and 1 part of glycerin monostearate as a lubricant were mixed, followed by dehydration and drying to obtain a powder composition. The results are shown in Table 2.

Example 7 The slurry obtained from latex A-1 prepared in Example 6 was reduced to 100 parts in terms of solid content, and the slurry obtained from latex B-1 prepared in Example 6 was dehydrated and dried. Mix 3 parts of powder and 1 part of glycerin monostearate,
Thereafter, it was dehydrated and dried to obtain a powder composition. Table 2 shows the results.
Shown below.

Example 8 In the polymerization recipe of latex B-1 in Example 1, 100 parts of methyl methacrylate was replaced with 9 parts of methyl methacrylate.
A vinyl polymer (
Latex B-2 of B) was obtained. This latex B-2
The average particle diameter of the latex is 650 Å, the glass transition temperature of the polymer constituting the latex is 87°C, and the weight average molecular weight is 4.
It was 0,000. A powder composition was obtained in the same manner as in Example 1 except for using this vinyl polymer latex B-2. The results are shown in Table 2.

Example 9 A powder composition was obtained in the same manner as in Example 1, except that the lubricant (C), glycerin monostearate, was changed to epoxidized soybean oil. The results are shown in Table 2. Example 10 Glycerin monostearate 0.5 as lubricant (C)
A powder composition was obtained in the same manner as in Example 1, except that 0.5 parts of epoxidized soybean oil and 0.5 parts of epoxidized soybean oil were used. The results are shown in Table 3. Example 11 A powder composition was obtained in the same manner as in Example 1 except that the lubricant (C) was not used. The results are shown in Table 3. 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 latex BBA1 in the same manner as in Example 1.
The powder obtained by dehydration and drying was mixed with the formulation shown in Table 2 to obtain a powder composition. The results are shown in Table 3.

Comparative Examples 1 to 3 The amount of latex B-1 is used in an amount exceeding the upper limit of the present invention (Comparative Example 1) or not (Comparative Example 2), or the amount of lubricant (C) is Powder compositions were obtained in the same manner as in Example 1, except that the upper limit was used (Comparative Example 3). The results are shown in Table 4.

Comparative Example 4 Latex A-1 of the graft copolymer (A) of Example 1
Graft copolymer latex A-2 was obtained in the same manner as in Example 1, except that in the polymerization recipe, 20 parts of rubbery polymer latex, 28 parts of styrene, and 52 parts of methyl methacrylate were used in terms of solid content. . This latex A-
The average particle diameter of No. 2 was 1,450 Å. 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 graft copolymer latex A-1. The results are shown in Table 5.

Comparative Example 5 Latex A-1 of the graft copolymer (A) of Example 1
Graft copolymer latex A- I got 3. The average particle diameter of this latex A-3 was 1,500 Å. 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 graft copolymer latex A-1. The results are shown in Table 5.

Comparative Example 6 In the polymerization recipe of Latex B-1 of Example 1, 0.06 part of diisopropylbenzene hydroperoxide, 0.01 part of ferrous sulfate, 0.025 part of disodium ethylenediaminetetraacetate, and formaldehyde sulfonate were added. Latex B-3 of vinyl polymer (B) was prepared using the same polymerization recipe as in Example 1, except that a mixture of 0.04 parts of sodium xylate was used and the polymerization temperature was 40°C for 3 hours. Obtained. The average particle diameter of this latex B-3 was 720 Å, the glass transition temperature of the polymer constituting the latex was 100° C., and the weight average molecular weight was 1.5 million. A powder composition was obtained in the same manner as in Example 1 except for using this vinyl polymer latex B-3. The results are shown in Table 5.

Comparative Example 7 In the polymerization recipe of latex B-1 of Example 1, 100 parts of methyl methacrylate was replaced with 3 parts of methyl methacrylate.
Latex B-4 of vinyl polymer (B) was obtained using the same polymerization recipe as in Example 1, except that 0 parts and 70 parts of butyl acrylate were used. The average particle diameter of this latex B-4 was 700 Å, 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 for using this vinyl polymer latex B-4. The results are shown in Table 5. In addition, in the powder compositions of Comparative Examples 1 to 7, the powder average particle diameter of component (A) was about 240 μm.

As is clear from Tables 1 to 3, Examples 1 to 3
No. 11 is the powder composition of the present invention, and the powder composition targeted by the present invention has been obtained. On the other hand, as is clear from Table 4, Comparative Example 1 is an example in which the amount of vinyl polymer (B) used exceeds the range of the present invention, and the impact resistance is poor. Comparative Example 2 is an example in which the vinyl polymer (B) was not used, and the powder properties were not improved. is inferior.

Furthermore, 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 below the range of the present invention, and the powder composition of the present invention is It can be seen that powder with excellent properties can be obtained regardless of the material used. Comparative Example 5 is an example in which the content of the rubbery polymer in the graft copolymer (A) exceeds the range of the present invention, and a powder composition with improved powder properties cannot be obtained. Comparative example 6 is
This is an example in which the weight average molecular weight of the vinyl polymer (B) exceeds the range of the present invention, resulting in increased fish eyes. Comparative Example 7 is an example in which the glass transition temperature of the vinyl polymer (B) is lower than the range of the present invention, and the powder properties are poor.

[0047]

[Table 1]

[0048]

[Table 2]

[0049]

[Table 3]

[0050]

[Table 4]

[0051]

[Table 5]

[0052]

[Effects of the Invention] The powder composition of the present invention does not cause blocking phenomena, bridging phenomena, clogging phenomena in transportation lines, etc., and as a result, it is possible to automate powder weighing and save labor by increasing the size of transportation methods. It is.

Claims (2)

[Claims] Claim 1: For 100 parts by weight of a powder of graft copolymer (A) having a rubbery polymer content of 30 to 80% by weight, a powder having a glass transition temperature of 70 to 170°C and a weight average molecular weight of A powder composition whose main components are 0.1 to 10 parts by weight of a vinyl polymer (B) having a weight of 1 million or less, and 0 to 10 parts by weight of a lubricant (C). 2. A method for producing the powder composition according to claim 1, using at least one of the following methods (a) to (c). (B) Graft copolymer (A) 0.1 to 10 parts by weight (in terms of solid content) of latex is added to a slurry obtained by coagulating 100 parts by weight (in terms of solid content) of latex of vinyl polymer (B). , and 0 to 10 parts by weight of lubricant (C) are added.
After mixing, a powder composition is obtained through dehydration and drying steps. (B) Graft copolymer (A) 100 parts by weight (in terms of solid content) of latex is coagulated into a slurry obtained, and vinyl polymer (B) 0.1 to 10 parts by weight (in terms of solid content) of latex is added to the slurry. A slurry obtained by coagulating and/or a powder after drying the slurry, and a lubricant (C) 0 to 10
After adding and mixing parts by weight, a powder composition is obtained through dehydration and drying steps. (c) 100 parts by weight of the powder of the graft copolymer (A),
A method of obtaining a powder composition by adding and mixing 0.1 to 10 parts by weight of a vinyl polymer (B) powder and 0 to 10 parts by weight of a lubricant (C).