JPH037711A - Core-shell polymer, resin composition containing the same and molded resin article composed thereof - Google Patents

Abstract

PURPOSE:To obtain a resin composition giving a molded article having excellent impact resistance and high luster. etc., by using a core-shell polymer containing specific core, intermediate layer and shell at specific ratios as an impact resistance improver. CONSTITUTION:A core-shell polymer composed of 50-90wt.% of a core, 5-30wt.% of an intermediate layer and 5-30wt.% of a shell is produced e.g. by (1) polymerizing an elastic polymer (preferably polybutadiene, etc.) having a glass transition point of <=-30 deg.C by consecutive three-stage emulsion polymerization process to form a core, (2) polymerizing a polymer (preferably polymethyl methacrylate) having a glass transition point of >=60 deg.C to form an intermediate layer covering the core and (3) polymerizing an aromatic vinyl polymer (preferably polystyrene) to form a shell covering the intermediate layer. The objective resin composition having improved impact resistance can be produced by adding 5-40 pts.wt. of the polymer obtained by the above process to 100 pts.wt. of a resin composed of 10-90wt.% of a polyphenylene ether resin and 90-10wt.% of a styrene resin.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to core-shell polymers, resin compositions containing such core-shell polymers as impact modifiers, particularly polyphenylene ether resin compositions, and The present invention relates to a resin molded product formed by molding such a resin composition.

Polyphenylene ether resin is known as a high-performance thermoplastic engineering plastic. However, this resin has a relatively high melt viscosity and softening point,
Furthermore, since the impact resistance is inferior to that of certain resins, it is commercially inappropriate to mold this resin alone.

This is because high temperatures are required to melt the resin, which causes various undesirable problems such as discoloration and oxidative deterioration.

In order to solve the second problem, U.S. Patent No. 3;38
No. 3,435 discloses a resin composition comprising a polyphenylene ether resin and an impact-resistant styrene resin rubber-modified with a styrene-acrylonitrile copolymer, a styrene-acrylonitrile-butadiene copolymer, etc. . In this resin composition, moldability is as follows:
Although the impact resistance has been improved to some extent,
Still not enough.

Therefore, in order to improve impact resistance, resin compositions containing an elastic body or a rubber polymer in addition to a polyphenylene ether resin and a rubber-modified styrene resin as described above are also known. For example, British Patent No. 1,477,7
In the specification of No. 06, in addition to polyphenylene ether resin and rubber-modified polystyrene, A is composed of a polymerized monoalkenyl aromatic hydrocarbon block, and B is a polymerized conjugate whose degree of unsaturation is reduced to 10% or less of the initial degree of unsaturation. A resin composition containing an ABA type hydrogenated block copolymer consisting of a diene block is disclosed. Although this resin composition has improved impact resistance to some extent,
Even so, it cannot be said that it has sufficient impact resistance to withstand practical use, and its fluidity is also insufficient.

Generally, in order to improve the impact resistance of a resin, as is well known, a core-shell polymer having a core made of an elastic body and a shell made of a glassy polymer is used as an impact resistance modifier. A method of blending it into resin is known. Such a core-shell polymer is melt-mixed with a resin, and has the advantage that it can be dispersed in the resin regardless of the melt-mixing conditions with the resin. However, hitherto, no impact modifier has been known that can impart satisfactory impact resistance to polyphenylene ether resins.

For example, even if a core-shell polymer having a shell made of a polymer of methacrylic acid ester and/or acrylic acid ester is blended into polyphenylene ether resin, sufficient impact resistance cannot be imparted.

On the other hand, as described in U.S. Pat. No. 4,684,696, polyphenylene ether resins are formulated with a core-shell polymer having a shell made of an aromatic vinyl polymer as an impact modifier. Compositions are also known. In this core-shell polymer, the shell is made of crosslinked styrene resin, the core is made of acrylate polymer, and the styrene resin shell surrounds the core and penetrates into the shell. .

However, according to the present inventors, when styrene was emulsion polymerized in the presence of crosslinked acrylate elastomer particles according to the description in the above-mentioned literature, a two-phase polymer in which styrene resin was dispersed in the acrylate elastomer was obtained. It has been found that particles are generated to form a so-called salami structure. That is, the resulting polymer particles are substantially free of styrene resin on their surfaces, and therefore the polymer particles are very likely to stick to each other and are very difficult to handle. Moreover,
Such core-shell polymers do not impart satisfactory impact resistance to polyphenylene ether resins.

By the time the polymer particles have styrene resin on their surface,
If the amount of styrene used is increased, the resulting polymer particles no longer have much effect as an impact modifier.

As a result of intensive research to solve the above-mentioned problems and improve the impact resistance of polyphenylene ether resin, the present inventors have developed a core made of an elastic polymer. By providing an intermediate layer of polymethyl methacrylate with a glass transition point of 60° C. or higher between the shell of styrene resin, the above-mentioned rough structure is not generated in the core-shell polymer. Thus, it has been discovered that by blending such a core-shell polymer into polyphenylene ether resin as an impact modifier, it is possible to impart satisfactory impact resistance to polyphenylene ether resin, leading to the present invention. be.

That is, the present invention relates to a novel core-shell polymer, a resin composition containing such a core-shell polymer as an impact modifier, particularly a polyphenylene ether resin composition, and a product obtained by molding such a resin composition. The purpose is to provide resin molded products.

The core-shell polymer according to the present invention for "I" comprises: (a) 50 to 90% by weight of a core comprising an elastomeric polymer having a glass transition point of 130° C. or lower; (b) a core with a glass transition point of 60° C. C) an intermediate layer containing a polymer having a temperature of 5 to 30% by weight, and (c) a shell containing an aromatic vinyl polymer of 5 to 30% by weight. The total weight is 100% by weight.

The core-shell polymer according to the present invention has a core comprising an elastomeric polymer having a glass transition temperature of 130° C. or less. Such elastic polymers include organosiloxane rubber, ethylene-propylene rubber, urethane rubber, diene rubber, acrylate rubber, or mixtures thereof.

The core-shell polymers according to the invention are advantageously obtained by a three-stage sequential seeded emulsion polymerization, in which the polymer produced in an earlier stage is successively coated with the polymer produced in a subsequent stage. be able to.

If necessary, the elastomeric polymer may be prepared separately first by a method other than emulsion polymerization and then emulsified for use as a seed. For example, a small amount of linear isocyanate group-terminated urethane prepolymer (usually 0.
1 to 10% by weight) of a branched isocyanate group-terminated urethane prepolymer in a hydrophobic organic solvent such as toluene or xylene. to obtain a urethane prepolymer emulsion. This emulsion is aged for several hours to several days to polymerize the prepolymer using water as a chain extender, and then the solvent is distilled off, for example under reduced pressure, to obtain a urethane rubber seed latex.

By carrying out two consecutive stages of seed emulsion polymerization using this seed latex, a core-shell polymer having a core made of urethane rubber can be obtained.

As another example, an organosiloxane rubber seed latex can be obtained as follows. Contains cycloorganosiloxanes such as hexamethylcyclohexatrisiloxane and octamethylcyclotetrasiloxane, and small amounts (usually 0.1 to 10% by weight) of polyalkoxysilanes such as trimethoxymethylsilane and triethoxyphenylsilane. The solution is dispersed in an aqueous solution of an emulsifier such as alkylbenzenesulfonic acid, alkylsulfonic acid, etc. to obtain an emulsion. Next, by aging this emulsion for several hours to several days to polymerize the organosiloxane, a seed latex of organosiloxane rubber can be obtained. By carrying out two consecutive stages of seed emulsion polymerization using this seed latex, a core-shell polymer having a core made of organosiloxane rubber can be obtained.

However, the core-shell polymers according to the invention can most advantageously be obtained by a three-stage sequential seeded emulsion polymerization as described below. That is, in the first step, a conjugated diene monomer, an alkyl acrylate whose alkyl group has 2 to 8 carbon atoms, or a mixture thereof is emulsion polymerized to form an elastic polymer with a glass transition temperature of 130°C or less. form a core consisting of

In this first step, the conjugated diene monomer used is, for example, butadiene, isoprene, chloroprene, etc., but butadiene is particularly preferably used. As the alkyl acrylate in which the alkyl group has 2 to 8 carbon atoms, for example, ethyl acrylate, propyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate-1, etc. are used, but in particular, butyl acrylate Or 2-ethylhexyl acrylate is preferably used.

Therefore, in the core-shell polymer according to the present invention,
Preferably, the core is polybutadiene or poly(n-
butyl acrylate) and polyalkyl acrylate in which the alkyl group has 2 to 8 carbon atoms, such as poly(2ethylhexyl acrylate-1.), or a mixture thereof.

In the first step, a third monomer having copolymerizability with these conjugated diene monomers and/or alkyl acrylates may be copolymerized. Such third monomers include, for example, styrene, vinyltoluene, α
- Aromatic vinyl monomers such as methylstyrene, vinyl cyanide monomers such as acrylonitrile and meccrylonitrile, alkyl methacrylates such as methyl methacrylate and butyl methacrylate, and the like.

In the first step, if a conjugated diene monomer is not used, or if it is used but it is less than 20% by weight of the total monomer amount, it is added to the polyphenylene ether resin as an impact modifier. Sometimes crosslinking monomers and/or grafting monomers are added to obtain core-shell polymers that can impart particularly low-temperature impact resistance to the resulting resin composition. It is preferable to use a small amount of.

Examples of such crosslinkable monomers include aromatic divinyl monomers such as divinylbenzene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, butylene glycol diacrylate, hexanediol diacrylate, hexanediol dimethacrylate, and oligoediling. Alkane polyol polyacrylates or alkane polyol polyols such as recall diacrylate, oligoethylene glycol dimethacrylate, trimethylolpropane diacrylate-1, trimethylolpropane triacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, etc. Mention may be made of methacrylates.

Among these, butylene glycol diacrylate or hexanediol diacrylate is particularly preferably used.

Examples of the grafting monomer include unsaturated carboxylic acid allyl esters such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, and diallylitaconate, with allyl methacrylate being particularly preferred. used.

Such crosslinking monomers or grafting monomers, respectively, can be used in amounts of 0.00000000000000000000000000000000000000000000000000000000000000000 type type type type type type type type type type type type type type type type type type type type type type type type type type type type type type type type type type type type type in type type what to type where by
It is used in a range of 0.01 to 5% by weight, preferably 0.1 to 2% by weight.

The core-shell polymer according to the present invention has a core composed of such an elastic polymer in an amount of 50 to 90% by weight, preferably 6% by weight.
It is contained in a range of 0 to 80% by weight. When the core-shell polymer contains core in an amount outside the above range,
The impact resistance of the resulting resin composition cannot be sufficiently improved. Furthermore, when the glass transition temperature of the core is higher than 130°C, it is not possible to improve the impact resistance, especially at low temperatures.

In the second step, the core made of the elastic polymer described above is covered with an intermediate layer made of a glassy 3 4 polymer having a glass transition temperature of 60° C. or more. For this purpose, monomers such as methacrylic esters, acrylic esters, vinyl carboxylic esters, vinyl cyanide, and mixtures thereof are used, and methyl methacrylate is particularly preferably used. .

If necessary, ethyl acrylate is copolymerized with methyl methacrylate.

Also in the second stage, if necessary, the crosslinking monomer and grafting monomer as described above are added in amounts of 0.01 to 5.0%, respectively, based on the total monomers used in the second stage. It is used in a range of 0.1 to 2% by weight, preferably 0.1 to 2% by weight.

The core-shell polymers according to the invention preferably contain 5 to 30% by weight of an intermediate layer as described above consisting of polymethyl methacrylate or optionally polymethyl methacrylate copolymerized with ethyl acrylate as described above. %, preferably in the range of 10 to 25% by weight. In the core-shell polymer, if the intermediate layer is outside the above range, the impact resistance of the resin composition obtained by blending the core-shell polymer cannot be sufficiently improved.

In the third step, an aromatic vinyl monomer is polymerized on top of the intermediate layer to form a shell.

In this third step, the aromatic vinyl monomer used is, for example, styrene, vinyltoluene, α-methylstyrene, chlorostyrene, etc., and styrene is particularly preferably used.

The core-shell polymers according to the invention contain such shells in a range from 5 to 30% by weight, preferably from 10 to 25% by weight. When the shell is outside this range,
The impact resistance of a resin composition obtained by blending such a core-shell polymer cannot be sufficiently improved.

After the completion of the third stage emulsion polymerization, the obtained solid polymer product is salted out from the latex as a precipitate, centrifugally dehydrated,
By drying, the core-shell polymer according to the invention can be obtained in the form of granules, flakes or powder. Spray drying of latex is also a preferred method for removing core-shell polymers.

The core-shell polymer according to the present invention thus obtained consists of a core, an intermediate layer and a shell, with the intermediate layer clearly separating the core and the shell. Therefore, such a core-shell polymer has only styrene resin on its surface and is not mutually adhesive, so that it is very easy to handle.

The core-shell polymer according to the present invention may be used as an impact modifier as it is, or may be used as an impact modifier using an extruder and a pelletizer, if necessary. It may be processed into pellets and used.

Further, according to the present invention, there is provided a polyphenylene ether resin composition in which such a core-shell polymer is melt-mixed as an impact modifier.

The resin composition according to the present invention contains (i) 10 to 90% by weight of a polyphenylene ether resin, (ii) 90 to 10% by weight of a styrene resin, and (ii)
i) 5 to 100 parts by weight of the total amount of these resins
40 parts by weight of a core-shell polymer, wherein the core-shell polymer comprises (a) 50 to 90% by weight of a core comprising an elastomeric polymer having a glass transition point of -30"C or less; (b) a glass transition point; (c) 5 to 30% by weight of an intermediate layer containing a polymer having a point of 60''C or more; and (c) 5 to 30% by weight of a shell containing an aromatic vinyl polymer.

Preferably, the resin composition according to the present invention contains 20 to 60 fi 1% polyphenylene ether resin and 8 % styrene resin.
0 to 20% by weight, and 10 to 30 parts by weight of the core/shell polymer based on 100 parts by weight of the total amount of these resins.

The polyphenylene ether resin used in the resin composition according to the present invention is already known, and preferably has the general formula (wherein R represents an alkyl group having 1 to 3 carbon atoms, R
2 and R3 are each independently a hydrogen atom or a carbon number 1
~3 alkyl group is shown. ) A polymer having a structural unit represented by the following in its main chain, which may be a homopolymer or a copolymer.

More specifically, such polyphenylene ether resins include, for example, poly(2,6-dimethyl-1,4-phenylene) ether, poly(2,6-ethyl-1,4-phenylene) ether, and poly(2,6-dipropyl-1,4-phenylene) ether. L4-
phenylene) ether, poly(2-methyl-6-ethyl-1,4-phenylene) ether, poly(2-methyl-
6-broby-14-phenylene) ether, 2.6
-dimethylphenol/2,3.6-1-limethylphenol copolymer and the like. Among these, in particular poly(2,6-dimethyl-1,4-phenylene) ether or 2,6-dimethylphenol/2,
3.6-Dolimethylphenol copolymer is preferably used.

The styrenic resin used in the resin composition of the present invention has the general formula (wherein R4 is a hydrogen atom or a lower alkyl group such as a methyl group or an ethyl group, and Z is a halogen atom such as chlorine or It represents a hydrogen atom or a lower alkyl group such as a methyl group or an ethyl group, and p is 0 or an integer of 1 to 3.

) is a resin containing at least 25% by weight of the structural unit represented by the following formula based on the styrenic resin.

Therefore, such styrenic resins include, for example, polystyrene, high-impact polystyrene, styrene-butadiene copolymer, styrene-butadiene acrylonitrile copolymer, styrene-α-methylstyrene copolymer, and styrene-maleic anhydride copolymer. Polymers such as styrene-bukjene-maleic anhydride copolymer, styrene-methyl methacrylate copolymer, ethylene-styrene copolymer, ethylene brobylene-bukjene-styrene copolymer, and the like can be mentioned. Here, the impact-resistant polystyrene includes rubber-modified polystyrene modified with a rubber component such as polybutadiene, butadiene-styrene rubber, and EPDM rubber.

The styrenic resin used in the present invention preferably has a weight average molecular weight of 3,000 to 500,000, preferably 3,000 to 200,000, as measured by gel permeation chromatography.

In the resin composition according to the present invention, in addition to the above-mentioned core-shell polymer, -C is combined with an elastomeric polymer used in a resin composition containing a polyphenylene ether resin, a styrene resin, or both. can do. As such an elastic polymer, for example, a block polymer of a conjugated diene and an alkenyl aromatic compound, an ABA type hydrogenated block copolymer as described above, etc. are suitably used. These elastomeric polymers are commercially available from Shell Chemical Company under the trade names "Krayton D" and "Krayton G", respectively, and are readily available.

When the above-described elastic body is blended into a resin composition together with a core-shell polymer, the resin composition contains the above-mentioned elastic body and core based on 100 parts by weight of the total amount of polyphenylene ether resin and styrene resin. - A shell polymer is designed to be contained in a total amount of 5 to 40 parts by weight, preferably 10 to 30 parts by weight.

The resin composition according to the present invention may contain commonly known additives such as pigments, heat stabilizers, ultraviolet absorbers, flame retardants, fillers, and the like. The resin composition according to the present invention can be manufactured by a generally known method. For example, a polyphenylene ether resin, a styrene resin, and a core/shell polymer are kneaded together with the above-mentioned additives and fillers using, for example, an extruder and a Berekizer, as necessary, to form a material with suitable dimensions. It may be extruded into pellets 1 2 .

The core-shell polymer according to the present invention consists of a core, an intermediate layer, and a shell, and the core and shell are clearly separated by the intermediate layer interposed therebetween. Therefore, such a core-shell polymer has only styrene resin on its surface and is not mutually adhesive, so it is very easy to handle.

Furthermore, by melt-blending such a core-shell polymer with a polyphenylene ether resin as an impact modifier, a resin composition having satisfactory impact resistance can be obtained. That is, the resin composition of the present invention exhibits high impact resistance in the low temperature range from room temperature to -40°C, which could not be achieved by using conventionally known core-shell polymers. has.

Further, the resin molded article according to the present invention is suitable for a wide variety of uses because of its excellent properties. For example, the resin molded product according to the present invention can be made into various molded products or films by extrusion molding, injection molding, calendar molding, or the like. It can also be processed with other resins such as polyolefins. Furthermore, the resin molding according to the present invention can be applied as a coating composition to any substrate in the form of a solution or suspension.

In particular, the resin molded product obtained by molding the polyphenylene ether resin composition according to the present invention has excellent impact resistance and high gloss in appearance, as described above, and has no tackiness at all. .

The present invention will be explained below with reference to Examples and Comparative Examples.
The present invention is not limited in any way by these Examples.

In the following examples and comparative examples, the glass transition temperature is
Dynamic viscoelasticity in tensile mode at 10Hz (Iwamoto Seisakusho■
The peak temperature of tan δ was measured using a VEF-3 model manufactured by Co., Ltd. In addition, the weight average particle diameter of the core-shell polymer was determined by Coulter Co.
34 measurements were made using model N-4.

Furthermore, in Examples and Comparative Examples, parts mean parts by weight.

Example 1 (Production of impact modifier A) 51 1540 g of deionized water was placed in a polymerization vessel equipped with a reflux condenser;
Dodecyl biphenyl ether sulfonic acid sodium salt 1
10g of 0% aqueous solution and 1% of sodium bicarbonate aqueous solution
00g was charged, and the temperature was raised to 70°C while stirring under a nitrogen stream.

Next, add 1 2-ethylhexyl acrylate to the above mixture.
992 g of allyl methacrylate, 4 g of 1,4-butylene glycol diacrylate, and 100 g of the first stage monomer emulsion mixture consisting of 992 g of allyl methacrylate and 4 g of 1,4-butylene glycol diacrylate were added and allowed to disperse for 10 minutes. Seed polymerization was started by adding 200 g of aqueous solution.

Subsequently, the remainder of the first stage monomer mixture 19 is added to this mixture.
00 g, 140 g of a 10% aqueous solution of sodium dodecyl biphenyl ether sulfonate, 100 g of a 1% aqueous solution of sodium bicarbonate, and 610 g of deionized water were continuously added over a period of 3 hours. After that, the temperature was raised to 80° C., and the mixture was aged for 1 hour to carry out the first stage of emulsion polymerization.

After this, the mixture was cooled to 70°C, 25 g of 2% sodium persulfate aqueous solution was added thereto, and then 249 g of methyl methacrylate, 0.5 g of 1,4-butylene glycol diacrylate, 0.5 g of allyl methacrylate,
Dodecyl biphenyl ether sulfonic acid sodium salt 1
Add over 30 minutes 412.5 g of the second stage monomer emulsion consisting of 17.5 g of 0% aqueous solution, 25 g of 1% aqueous sodium bicarbonate solution and 120 g of deionized water;
A second stage of emulsion polymerization was carried out by aging at 80° C. for 1 hour.

Next, the mixture was cooled to 70°C, 25 g of a 2% aqueous solution of sodium persulfate was added thereto, and 250 g of styrene was added.
g, 17.5 g of a 10% aqueous solution of sodium dodecyl biphenyl ether sulfonate, 25 g of a 1% aqueous solution of sodium bicarbonate and 120 g of deionized 56 water.
12.5g was added over 30 minutes, the temperature was raised to 90°C, and 1
After aging for a period of time, the third stage of emulsion polymerization was carried out.

After the reaction was completed, the reaction mixture was cooled and filtered through a 3°O mesh stainless wire mesh to obtain a solid content of 44.5%.
A core-shell polymer latex with a weight average particle diameter of 250 nm was obtained. This latex was spray-dried at an inlet temperature of 140°C and an outlet temperature of 70°C, with a particle size of 50 to 100 μm.
Impact modifier A was obtained.

Example 2 (Production of Impact Modifier B) Each dodecyl of the polymerization preaddition and monomer emulsion in the first stage, the monomer emulsion in the second stage, and the monomer emulsion in the third stage Biphenyl ether sulfonic acid sodium salt 10%
A core-shell polymer latex having a solid content of 44.3% and a weight average particle diameter of 500 nm was obtained by the same polymerization operation as in Example 1, except that the amount of the aqueous solution was halved. This latex was spray dried under the same conditions as in Example 1 to obtain impact modifier B.

Example 3 (Production of impact modifier C) 2! In a polymerization vessel with a reflux condenser, 560 g of deionized water, 1% aqueous solution of dioctyl sulfosuccinate sodium salt 2
g and 40 g of 1% aqueous sodium hydrogen carbonate solution,
The temperature was raised to 70°C while stirring under a nitrogen stream.

To this mixture was added 4 g of the first stage monomer mixture consisting of 796.4 g of n-butyl acrylate (2.0 g of allylmaleny) and 1.6 g of 1,6-hexanediol diacrylate and after dispersion for 10 minutes. , 80 g of a 2% aqueous solution of sodium persulfate was added to initiate seed polymerization.

Subsequently, the remaining 796 g of the monomer mixture from the first stage
A monomer emulsion consisting of 298 g of a 1% aqueous solution of dioctyl sulfosuccinate sodium salt, 40 g of a 1% aqueous solution of sodium bicarbonate, and 40 g of deionized water was added continuously over 3 hours, and then the temperature was raised to 8780°C. The mixture was heated and aged for 1 hour to carry out the first stage of emulsion polymerization.

After this, the mixture was cooled to 70°C, and a 2% aqueous solution of sodium persulfate (Log) was added thereto, followed by 99.5 g of methylmeccryle-1, 0.3 g of allylmalenyi, and 1
．． 6-hexanethiol diacrylate) 0.2g, dioctyl sulfosuccinate 1% aqueous solution of Lium salt 3
5 g of a second stage monomer emulsion consisting of 1% aqueous sodium bicarbonate solution Log and 20 g of deionized water.
65 g was added over 30 minutes and aged at 80° C. for 1 hour to carry out the second stage of emulsion polymerization.

Thereafter, the mixture was cooled to 70°C, a 2% aqueous solution of sodium persulfate (Log) was added thereto, and styrene 100%
g, dioctyl sulfosuccine-1-sodium salt 1%
Of the third stage monomer emulsion consisting of 35 g of aqueous solution, 1% sodium bicarbonate aqueous solution Log and 20 g of deionized water, 165 g was added over 30 minutes and then heated to 90°C for 1 hour. It was aged and thus the third stage of emulsion polymerization was carried out.

After the reaction was completed, the resulting reaction mixture was cooled and filtered through a 300-mesh stainless wire mesh to reduce the solid content to 45.1%.
A core-shell polymer latex having a weight average particle diameter of 510 nm was obtained. This latex was spray-dried under the same conditions as in Example 1 to obtain impact modifier C.

Example 4 (Production of impact modifier) The polymerization procedure was exactly the same as in Example 1, except that the amounts of the first stage polymerization front monomer and 1% aqueous solution of dioctyl sulfosuccinate sodium salt were increased by 10 times. Depending on the solid content 4
A core-shell polymer latex with a weight average particle size of 4.7% and a weight average particle diameter of 290 nm was obtained.

This latex was spray-dried under the same conditions as in Example 1 to obtain an impact modifier.

Example 5 (Production of impact modifier E) 4! Using a polymerization vessel equipped with a reflux condenser, each of the dioctyl sulfonate prepolymerization and monomer emulsion liquid in the first stage, the monomer milk 90 conversion method in the second stage, and the monomer emulsion liquid in the third stage was added. The polymerization procedure was exactly the same as in Example 3, except that the aqueous solution of succinate sodium salt was 4%, and the amount of deionized water added before polymerization in the first stage was increased by 4 times.
A core-shell polymer latex with a solid content of 144.8% and a weight average particle diameter of 160 nm was obtained. This latex was spray-dried under the same conditions as in Example 1 to obtain impact modifier E.
I got it.

Comparative Example 1 (Production of impact modifier F) The following solutions were prepared.

Pot A n-butyl acrylate 826.5 g
l,3-butylene glycol diacrylate 1.4 g 1 Sodium metabisulfite deionized water 1.9 g 30.1 g Ammonium persulfate deionized water 5.3 g 82.6 g Kajindan styrene 275.7 g5
5% divinylbenzene 2.9 g Sodium lauryl sulfate 2.3 g Dioctylsulfosuccinate sodium salt 4.6 g Deionized water 3806.0
g51 The entire amount of solution E and 816.1 g of the solution were placed in a polymerization container equipped with a reflux condenser, stirred for 30 minutes under a nitrogen stream, and then 165.6 g of solution A was added thereto.
The temperature was raised to 5°C. Then add 4.9 g of solution CI,
After keeping the mixture at 55°C for 1.5 hours, 1 2 of the remaining solution A, the remaining solution B, and 44.4 g of solution C were added thereto, and the mixture was reacted at 55°C for 2.5 hours. After this, 35
Cooled to ℃.

Next, a solution was added to the resulting mixture and heated at 35°C for 15 minutes.
After mixing for a minute, the temperature was raised to 60"C. The remainder of the solution was added thereto, and after reacting for 1.25 hours, the temperature was raised to 75°C and maintained at this temperature for 45 minutes.

After cooling, the reaction mixture was filtered through a 300-mesh stainless wire mesh to obtain a solid content of 22.1% and a weight average particle size of 19.
A latex of 0 nm was obtained. This latex is 0.25
It was added to 10ffi of a weight % calcium chloride-methatul solution with stirring to cause agglomeration. The aggregate was filtered, washed with methanol, and then dried at 60°C to obtain impact modifier F as a lump.

Comparative Example 2 (Production of Impact Modifier G) Impact modifier G was obtained in exactly the same manner as Comparative Example 1, except that divinylbenzene was removed from the solution.

The obtained latex had a solid content of 21.9% and a weight average particle diameter of 185 nm. Impact modifier G according to this comparative example was also lumpy and could not be obtained as a powder.

Comparative Example 3 (Production of Impact Modifier H) 21 560 g of deionized water 1 1% aqueous solution of dioctyl sulfosuccinate sodium salt 2 in a polymerization vessel equipped with a reflux condenser
0g and 40g of a 1% aqueous solution of sodium hydrogen carbonate were charged, and the temperature was raised to 70°C while stirring under a nitrogen stream.

Next, n-butyl acrylate 796.
4 g of the first stage monomer mixture consisting of 4 g allyl methacrylate 2,0 g and 1.6 g 1°4-butylene glycol diacrylate were added and allowed to disperse for 10 minutes, followed by 2% sodium persulfate. Seed polymerization was started by adding 80 g of aqueous solution.

Subsequently, the remaining 760 g of the monomer mixture from the first stage,
A monomer emulsion consisting of 280 g of a 1% aqueous solution of sodium dioctyl sulfosuccinate 3 4 , 40 g of a 1% aqueous sodium bicarbonate solution, and 40 g of deionized water was added continuously over 3 hours, and then the temperature was raised to 80°C. warm, 1
After aging for a period of time, the first stage of emulsion polymerization was carried out.

After this, the mixture was cooled to 70°C, and 20 g of a 2% aqueous solution of sodium persulfate was added thereto, followed by 200.0 g of methyl methacrylate, 60.0 g of a 1% aqueous solution of dioctyl sulfosuccinate sodium salt, and 1% aqueous solution of sodium bicarbonate. After adding 320 g of the second stage monomer emulsion consisting of 20.0 g of aqueous solution and 40.0 g of deionized water over 30 minutes, the temperature was raised to 90°C, aged for 1 hour, and the third stage was completed. emulsion polymerization was carried out.

After the reaction was completed, the resulting reaction mixture was cooled and filtered through a 300-mesh stainless wire mesh to reduce the solid content to 44.9%.
A core-shell polymer latex having a weight average particle diameter of 290 nm was obtained.

This latex has an inlet temperature of 140°C and an outlet temperature of 70°C.
The resulting product was spray-dried to obtain an impact modifier H having a particle size of 50 to 100 μm.

The properties of the impact modifiers A to H obtained in Examples 1 to 5 and Comparative Examples 1 to 3 are summarized in Table 1.

Example 6 Intrinsic viscosity measured in chloroform at 25°C is 0.50
dl/g of poly(2,6-dimethyl-1,4 phenylene) ether powder and impact-resistant polystyrene (
Product name made by Mitsubishi Monsando ■ “Dialex, YH-4”
7,854 parts and 10 parts of the impact modifier A of Example 1 were put into a tumbler, stirred for 10 minutes, and then heated at 290°C using a twin screw extruder (PCM-30 manufactured by Ikegu Iron Works). Melt kneading and extrusion were performed to obtain pellets. The pellets were injection molded to form various test pieces. Table 2 shows the physical property values measured using this test piece.

5 6 7 Examples 7 to 10 The same procedure as in Example 6 was carried out except that in Example 6, impact modifiers BE of Examples 2 to 5 were used in place of impact modifier A. A test piece was obtained. Table 2 shows the physical property values measured using this test piece.

Example 11 Intrinsic viscosity measured in chloroform at 25°C is 0.50
36 parts of poly(2,6-dimethyl-1,4 phenylene) ether powder with a
HF-77) 54 parts and impact modifier A10 of Example 1
After stirring for 10 minutes, 290 parts were added to a tumbler and stirred for 10 minutes.
The mixture was melt-kneaded and extruded at C to obtain pellets. The pellets were injection molded to form various test pieces. Table 2 shows the physical property values measured using this test piece.

Example 12 The same procedure as in Example 11 was carried out, except that in place of impact modifier A, 15 parts of impact modifier A and 5 parts of Kraton G1651J were used. Table 2 shows the physical property values of the obtained test piece.

Comparative Examples 4 to 6 The same procedure as in Example 6 was carried out, except that impact modifiers F to H produced in Comparative Examples 1 to 3 were used in place of impact modifier A. Ta. Table 2 shows each physical property value of the obtained test piece.

Claims (3)

[Claims] (1) (a) 50 to 90% by weight core containing an elastic polymer with a glass transition point of -30°C or lower; (b) 5 to 30% by weight of an intermediate layer containing a polymer having a glass transition point of 60°C or higher. %, and (c) 5 to 30% by weight of a shell containing an aromatic vinyl polymer. (2) (i) 10 to 90% by weight of polyphenylene ether resin, (ii) 90 to 10% by weight of styrene resin, and (iii) based on 100 parts by weight of the total amount of these resins,
5 to 40 parts by weight of a core-shell polymer, the core-shell polymer comprising (a) 50 to 90% by weight of a core containing an elastic polymer having a glass transition point of -30°C or lower; (b) glass; A resin composition comprising: 5 to 30% by weight of an intermediate layer containing a polymer having a transition point of 60° C. or higher; and (c) 5 to 30% by weight of a shell containing an aromatic vinyl polymer. (3) (i) 10 to 90% by weight of polyphenylene ether resin, (ii) 90 to 10% by weight of styrene resin, and (iii) based on 100 parts by weight of the total amount of these resins,
5 to 40 parts by weight of a core-shell polymer, the core-shell polymer comprising (a) 50 to 90% by weight of a core containing an elastic polymer having a glass transition point of -30°C or lower; (b) glass; It is characterized by being formed by molding a resin composition consisting of 5 to 30% by weight of an intermediate layer containing a polymer having a transition point of 60°C or higher, and (c) 5 to 30% by weight of a shell containing an aromatic vinyl polymer. A resin molded product.