JP2001040167A - Acrylic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an acrylic resin composition useful as a resin modifier which improves the impact resistance without deteriorating the physical properties of a target thermoplastic resin. SOLUTION: An acrylic resin composition comprises 100 pts.wt. multistage polymer (I) consisting of an elastomer layer mainly comprising an acrylic ester monomer having a 1-8C alkyl and a resin layer mainly comprising a methacrylic ester monomer having a 1-8C alkyl which is crosslinked and/or grafted to the elastomer layer, from 0.005 to 1 pts.wt. antifoaming nonionic surfactant (II) and from 0.01 to 1 pts.wt. at least one compound (III) chosen from a salt or ester of a fatty acid, an ester of a polyhydric alcohol, an inorganic salt and an inorganic oxide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an acrylic resin composition, and more particularly to an acrylic resin composition useful for improving impact resistance without causing deterioration in physical properties of a thermoplastic resin to be modified.

[0002]

2. Description of the Related Art Hitherto, polybutadiene or methyl methacrylate-butadiene-styrene (MBS) resin (US Pat.
No. 4 specification) and the like. Further, an impact resistance improver using an acrylic rubber having excellent weather resistance has been developed, and an acrylic resin (JP-B-55-27576),
Polyvinyl chloride resin (U.S. Pat. No. 4,145,380) and polyalkylene terephthalate resin (JP-B-6060)
It is known that resin has an effect of improving the impact resistance of the resin. Japanese Patent Publication No. 55-27576, U.S. Pat. No. 4,145,380 and Japanese Patent Publication No. Sho.
The impact modifier using an acrylic rubber disclosed in Japanese Patent Publication No. 0-3101 is a submicron multi-stage polymer produced by emulsion polymerization, and the multi-stage polymer is usually several tens to several hundreds. Supplied in agglomerate powder of size μm. In general, the production is carried out by aggregating the polymer from a multi-stage polymer emulsion obtained by emulsion polymerization to tens to hundreds of μm by an agglomeration step, and washing and drying to form a powder. It is.

In removing resin from an emulsion polymerization emulsion in such a production method, a slurry of an aggregated polymer is formed in an aggregation step. The slurry of the agglomerated polymer is
Coalesced by the temperature conditions and agitation conditions after aggregation to produce coarse particles, sedimentation at a relatively low flow velocity in the transfer line, causing clogging of piping, and polymerization in the aqueous phase of the slurry Since some of the emulsifier components used sometimes exist, foaming may occur due to stirring or the like, and the aggregated polymer may float. In particular, the formation of coarse particles and floating polymer
This is not preferable because the effect of washing the polymer is low and impurities are likely to be contained. Further, the obtained impact modifier may cause blocking when subjected to temperature or pressure. Therefore, it is known to add an inorganic salt or a lubricant as a method for improving the powder properties. It is preferable that such an antiblocking agent is uniformly mixed, and therefore, it is necessary to devise a method of adding the antiblocking agent.

[0004]

DISCLOSURE OF THE INVENTION The present invention is useful for a resin modifier which has a small amount of coarse particles and contained impurities and which imparts impact resistance without impairing the properties of a thermoplastic resin as a base material. An acrylic resin composition is provided.

[0005]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, have found that the above object can be solved by a specific acrylic resin composition, which has led to the achievement of the present invention. Was. That is, the present invention provides a method for preparing an elastic body (A) layer mainly composed of an acrylate monomer unit having an alkyl group having 1 to 8 carbon atoms, in the presence of an elastic body (A) layer.
Methacrylate monomer 6 having an alkyl group of 8
Multi-stage polymer (I) obtained by polymerizing resin (B) consisting of 0% by weight or more and 40% by weight or less of other copolymerizable monomer.
100 parts by weight, 0.005 to 1 part by weight of a nonionic surfactant (II) having an antifoaming action and at least one compound of a salt or ester of a fatty acid, an ester of a polyhydric alcohol, an inorganic salt, and an inorganic oxide (III) An acrylic resin composition comprising 0.01 to 1 part by weight.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The multi-stage polymer (I) used in the present invention has a "soft" elastic layer mainly composed of an acrylate monomer having an alkyl group having 1 to 8 carbon atoms. Having 1 carbon atom cross-linked and / or grafted to
When a resin layer composed of 60% by weight or more of a methacrylate monomer having an alkyl group of from 8 to 40% by weight and another monomer copolymerizable with 40% by weight or less is "hard", soft-hard or hard-soft Two-stage polymer of soft-hard-soft or hard-soft-hard 3
Step polymers, and four-step polymers of soft-hard-soft-hard are included.

Hereinafter, the present invention will be described in more detail by taking a soft-hard two-stage polymer as an example. In the two-stage polymer, first, the elastic body (A) is emulsion-polymerized. The elastic body (A) is composed of 70 to 99.95% by weight of an acrylate monomer having an alkyl group having 1 to 8 carbon atoms, 0.05 to 5% by weight of a graft-binding monomer, and copolymerizable therewith. It is preferably obtained by emulsion polymerization of 29.95% by weight or less of a monomer unit. Here, the alkyl group may be any of a linear alkyl group, a branched alkyl group, and an alicyclic alkyl group. Specific examples of the acrylate monomer having an alkyl group having 1 to 8 carbon atoms in the present invention include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and the like. Further, the graft-linking monomer is introduced into the elastic body (A) of the multi-stage polymer (I) by introducing a crosslinked structure, and the thermoplastic polymer (B) which is subsequently polymerized in the presence of the elastic body (A) layer and the layer. ) Used for the purpose of graft bonding with the layer. Examples of the graft-binding monomer include allyl esters and crotyl esters of α and β unsaturated carboxylic acids, and specific examples thereof include allyl methacrylate and diallyl maleate.

In the polymerization of the elastic body (A), the number of carbon atoms is 1
If the proportion of the acrylate monomer having an alkyl group of 8 is less than 70% by weight, the effect of improving the impact resistance as a resin modifier is unpreferably small. On the other hand, when the ratio of the acrylate monomer exceeds 99.95% by weight,
As a result, the ratio of the graft-linking monomer is less than 0.05% by weight, and the cross-linking structure is too small or the graft bonding with the thermoplastic resin polymerized in the next stage becomes insufficient, so that the elasticity is lowered, which is not preferable. . On the other hand, if the proportion of the graft-linking monomer exceeds 5% by weight, the crosslinked structure is increased, so that the resin becomes hard and the effect of improving the impact resistance as a resin modifier is undesirably reduced.

Specific examples of the copolymerizable monomer in the polymerization of the elastic body (A) include methacrylate monomers such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, and styrene.
aromatic vinyl monomers such as p-methylstyrene and o-methylstyrene, maleimide monomers such as N-propylmaleimide, N-cyclohexylmaleimide and No-chlorophenylmaleimide, ethylene glycol dimethacrylate, propylene glycol di Multifunctionality such as methacrylate, triethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, triethylene glycol diacrylate, 1,6-hexanediol diacrylate triallyl isocyanurate Monomers.

[0010] The emulsion polymerization of the elastic body (A) is generally carried out using an aqueous medium under a nitrogen atmosphere. The emulsifier used in the emulsion polymerization is a carboxylate such as sodium stearate as an anionic emulsifier, a dialkyl sulfosuccinate such as sodium dioctyl sulfosuccinate, sodium dilauryl sulfosuccinate, or an alkylbenzene sulfonate such as sodium dodecylbenzene sulfonate. , Alkyl sulfates such as sodium dodecyl sulfate,
Examples of the nonionic emulsifier include polyoxyethylene alkyl ether, polyoxyethylene nonylphenyl ether and the like. Examples of nonionic anionic emulsifiers include polyoxyethylene nonyl phenyl ether sulfates such as sodium polyoxyethylene nonyl phenyl ether sulfate, polyoxyethylene alkyl ether sulfates such as sodium polyoxyethylene alkyl ether sulfate, and polyoxyethylene. Examples thereof include alkyl ether carboxylate such as sodium tridecyl ether acetate. When the addition mole number of ethylene oxide in the nonionic emulsifier and the nonionic anionic emulsifier is too large, the foaming property increases, which is not preferable. The number of moles of ethylene oxide added is 30 mol or less,
Preferably it is 20 mol or less, more preferably 10 mol or less. Two or more of these emulsifiers can be used in combination.

Examples of the polymerization initiator include any of persulfate initiators such as potassium persulfate and ammonium persulfate, and redox initiators such as persulfoxylate / organic peroxide and persulfate / sulfite. May be used. The polymerization temperature is usually in the range of 40 to 95 ° C. Further, the monomer mixture of the elastic body (A) is supplied to the polymerization system by a method such as divided addition or continuous dropping.

When the polymerization of the elastic body (A) is completed, as the next step, the resin (B) is emulsion-polymerized in the presence of the elastic body (A). At this time, after replenishing the polymerization initiator to the polymerization system and adding an emulsifier as required, a methacrylate monomer having an alkyl group having 1 to 8 carbon atoms is 60 to 100% by weight.
A monomer mixture comprising 40% by weight or less of another monomer copolymerizable with the above is continuously added to the polymerization system to polymerize the resin (B).

Here, the alkyl group in the methacrylic acid ester monomer may be any of a linear alkyl group, a branched alkyl group and an alicyclic alkyl group as long as it has 1 to 8 carbon atoms. Examples of the methacrylate having an alkyl group having 1 to 8 carbon atoms include methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate,
Examples thereof include cyclohexyl methacrylate, and among them, methyl methacrylate is preferably used.

Examples of other monomers copolymerizable in the polymerization of the resin (B) include methyl acrylate, ethyl acrylate, butyl acrylate, propyl acrylate and the like.
Acrylate monomers such as hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate and benzyl acrylate, vinyl acetate, styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, α-methylstyrene, aromatic vinyl monomers such as vinyl naphthalene, acrylonitrile, nitriles such as methacrylonitrile, acrylic acid,
Α, β unsaturated carboxylic acids such as methacrylic acid and crotonic acid; maleimide compounds such as N-ethylmaleimide and N-cyclohexylmaleimide;
More than one species can be used in combination. If necessary, a chain transfer agent such as octyl mercaptan and lauryl mercaptan can be added.

Upon completion of the polymerization of the resin, the polymerization of the multi-stage polymer (I) is completed. The latex of the multi-stage polymer (I) is cooled and taken out, filtered through a wire mesh of 100 mesh or more, preferably 200 mesh or more to remove aggregates generated during polymerization, and then subjected to salting out or freeze-thawing. A slurry containing an aggregate of the multi-stage polymer (I) is obtained. The solid content of the slurry is usually 5 to 40% by weight, preferably 10 to 30% by weight.

The salting out can be performed by a known salting out agent and method. Specific examples of the salting-out agent include magnesium sulfate, aluminum sulfate, and aluminum chloride, and the salting-out temperature is about 20 to 60 ° C. Freezing-thawing can also be performed by a known method, and the latex is frozen at a temperature of -5 ° C or less, preferably -20 ° C or less,
Melts at a temperature of 5-60 ° C.

The resin composition of the present invention comprises a nonionic surfactant (II) having a defoaming effect on a coagulated product of the multistage polymer (I) obtained by the above-mentioned method, and a salt or ester of a fatty acid. It comprises at least one compound (III) of an ester of a polyhydric alcohol, an inorganic salt and an inorganic oxide inhibitor.

The nonionic surfactant (I) used in the present invention
I) is a nonionic surfactant having an antifoaming action,
Examples of such a nonionic surfactant include a low HLB nonionic surfactant and an adduct of propylene oxide. Low HLB nonionic surfactants are available from HL
B is a nonionic surfactant of 10 or less, preferably 5 or less, and specific examples thereof include sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate, and ethylene oxide addition moles of 5 to 5. Polyoxyethylene alkyl ether and polyoxyethylene nonyl phenyl ether which are 10, and adducts of alkylene oxides. The alkylene oxide adducts include polyoxypropylene ether and polyoxypropylene polyoxyethylene ether obtained by adding ethylene oxide to propylene oxide and derivatives thereof, and polyoxypropylene oxyethylene alkyl ether. Express.

[0019]

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[0020]

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[0021]

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[0022]

Embedded image Here, m is 3 to 30, and n is 20 to 60.

The nonionic surfactant is added in the form of a slurry of a coagulated product of the multi-stage polymer (I) obtained by salting out or freeze-thawing the latex of the multi-stage polymer (I). In this case, the nonionic surfactants can be used alone or in combination. The amount of addition is 0.005 to 1 part by weight, preferably 0.01 to 0.6 part by weight, more preferably 0.1 to 100 parts by weight based on 100 parts by weight of the multistage polymer (I).
05 to 0.4 parts by weight. If the added amount of the nonionic surfactant exceeds 1 part by weight, a large amount of the nonionic surfactant remains in the finally obtained resin modifier, causing coloration and deterioration in the properties of the thermoplastic resin as the base material. Is often not preferred. On the other hand, if the addition amount is less than 0.005 parts by weight, the effect of addition is small and blocking of the coagulates, blockage of the slurry transport pipe, bubbling of the slurry, and the like tend to occur, which is not preferable.

In the present invention, the nonionic surfactant (II) having a defoaming effect can be added at any stage in the production of the acrylic resin composition. The addition method is preferred.
According to this addition method, not only can the stability of the slurry be increased and clogging of the slurry transport pipe can be significantly reduced, but also a particle having a stable particle size of the solidified particles can be obtained.

Also, at least one compound (III) selected from the group consisting of fatty acid salts or esters, polyhydric alcohol esters, inorganic salts and inorganic oxides used in the present invention.
In general, those having a large anti-sticking effect are preferable. Specific examples thereof include calcium stearate, calcium carbonate, calcium sulfate, magnesium sulfate, barium sulfate, and silicon dioxide. These compounds improve dispersibility with the multi-stage polymer (I) by being combined with the above-mentioned nonionic surfactant (II) having an antifoaming action, and thereby improve the impact resistance more effectively. Can be The amount used is the multi-stage polymer (I)
The amount is usually 0.01 to 1 part by weight, preferably 0.1 to 0.5 part by weight based on 100 parts by weight. The amount added is 0.01
If the amount is less than 1 part by weight, it is not preferable because the effect of preventing sticking is small, while if it exceeds 1 part by weight, no further improvement is observed in the prevention of sticking, the effect of improving the impact resistance is reduced, the mold becomes dirty during molding, and This is not preferable because out-of-work and the like are likely to occur.

Dehydration of the coagulated slurry of the multi-stage polymer (I) can be performed by a known bucket type or decanter type centrifugal separator or the like, and drying can be performed by a known fluidized drier, vibration drier, hot air drier. It can be dried by a machine or the like.

The acrylic resin composition of the present invention can contain additives such as an ultraviolet absorber, a lubricant, an antioxidant, and a dye, if necessary. The obtained acrylic resin composition includes polyvinyl chloride resin, polyethylene terephthalate (PET) resin, polybutylene terephthalate (PBT) resin, polyvinylidene fluoride resin, polyamide resin, styrene resin, acrylonitrile-styrene (AS) resin, ABS It is effectively used for imparting impact resistance, solvent resistance, and the like of resins and methacrylic resins.

[0028]

The present invention will be described below with reference to specific examples and comparative examples, but the present invention is not limited to these examples. “Parts” and “%” used in Examples and Comparative Examples are all “parts by weight” and “% by weight”. The evaluation of the examples and comparative examples was performed by the following method. (1) Particle size measurement The particle size was measured using a light scattering photometer DLS-600 manufactured by Otsuka Electronics Co., Ltd. (2) Particle Size Measurement 200 g of the acrylic resin composition powder was classified by a standard sieve, and the weight average particle size was defined as the average particle size. (3) Izod impact strength Measured using a 30 kg hammer under conditions of edgewise and notch according to ASTM D256. Ten pieces were evaluated and the number of test pieces that did not break (NB) (NB / NB)
The number of tests was used to evaluate the effect of improving the impact resistance. (4) Falling ball impact test A horizontally fixed test plate (100 mm x 100 mm x 1 m
A steel ball of 2 kg was dropped vertically from a height of 40 cm at the center of the mt) to check for cracks. The number of tests per sample was set to 10, and the impact resistance improving effect was evaluated by NB / test number, where NB was the number of cracks that did not occur.

Example 1 33.4 kg of ion-exchanged water was placed in a 75-liter glass-lined reaction tank equipped with a condenser, a thermometer, and a stirrer.
And 40 g of Nikkor OTP-100 (manufactured by Nikko Chemical Co., Ltd .: sodium dioctylsulfosuccinate) and 10 g of sodium carbonate are dissolved.
The temperature was raised to ° C. Separately, 8.87 kg of butyl acrylate, 135 g of allyl methacrylate and 90 g of Nikkor OTP-100 are dissolved in a 30-liter stainless steel container to prepare an emulsifier-dissolved monomer mixture (1). After 9 g of potassium persulfate was charged as a polymerization initiator, the emulsifier-dissolved monomer mixture (1) was continuously supplied at a supply rate of 1.7% by weight / minute to carry out polymerization. When the supply of the emulsifier-dissolved monomer mixture (1) is completed, the mixture is heated to 80 ° C. with stirring.
After holding for 9 minutes, 9 g of potassium persulfate was added, and 8.87 kg of butyl acrylate and 135 g of allyl methacrylate were added.
And an emulsifier-dissolved monomer mixture (2) consisting of 45 g of Nikkor OTP-100 are continuously fed at a feed rate of 2.0% by weight / minute for polymerization. When the supply of the emulsifier-dissolved monomer mixture (2) is completed, the temperature is raised to 80 ° C. while stirring.
And then charged with 2.0 g of potassium persulfate, 1.88 kg of methyl methacrylate and 120 g of methyl acrylate
g and 10 g of Nikkor OTP-100 are continuously fed at a feed rate of 5.0% by weight / minute for polymerization. When the supply of the monomer mixture was completed, the mixture was maintained at 80 ° C. for 60 minutes with stirring to complete the polymerization.
After completion of the polymerization, the mixture was cooled to 40 ° C., and filtered through a 325-mesh wire net to take out an emulsion containing 37% of a two-stage polymer having a particle diameter of 0.14 μm.

1 with stirrer, thermometer and jacket
3 liters of ion exchange water in a 00 liter stainless steel tank
8.6 kg of Defomax 702 (manufactured by Toho Chemical Industry Co., Ltd .: nonionic surfactant of polymer containing propylene oxide as a main component, HLB = 7) 8.6 with 3 kg charged and stirred.
g, and the temperature was raised to 30 ° C. 2 frozen at -30 ° C
10 kg of a frozen emulsion of the step polymer is introduced while crushing. After confirming that all the frozen emulsions were completely melted and the temperature was constant, an aggregated polymer slurry was obtained. Next, the aggregated polymer slurry is fed to a centrifugal separator for washing,
After dehydration, 11.1 g of calcium stearate was added, followed by drying with a vibration drier to obtain a powder of an acrylic resin composition having an average particle size of 235 μm and a uniform particle size. The properties of the agglomerated slurry are shown in Table 1. As a result, the agglomerated material could be fed to the centrifugal separator very stably without floating, and coarse particles were not generated by coalescence of the agglomerated polymer. 10 parts by weight of the obtained acrylic resin composition was blended with 100 parts by weight of polyvinyl chloride resin (PVC) by a mixer and melt-kneaded by a twin-screw extruder having a screw diameter of 30 mm to obtain an impact-resistant PVC. A pellet was obtained. The pellets were subjected to Izo under the conditions of a cylinder temperature of 180 ° C. and a mold temperature of 40 ° C. using an SG-100 type injection molding machine manufactured by Sumitomo Heavy Industries, Ltd.
d Test pieces were molded and evaluated. Table 1 shows the evaluation results.

Comparative Example 1 33 kg of ion-exchanged water was charged into a 100-liter stainless steel tank equipped with a stirrer, thermometer and jacket, and the temperature was raised to 30 ° C. 10 kg of a frozen emulsion of the two-stage polymer of Example 1 frozen at −30 ° C. is added while crushing. After confirming that all the frozen emulsions were completely melted and the temperature was constant, an aggregated polymer slurry was obtained. However, most of the aggregate slurry floated and clogging of the piping occurred during the transfer of the slurry, so the amount of aggregate that could be fed to the centrifugal separator for washing and dewatering was 1/4 of the total charge in a dry state. Was. The polymer obtained by drying was a non-uniform powder in which powder of coarse particles of 1000 μm or more was mixed. The obtained polymer was evaluated in the same manner as in Example 1, but the impact resistance improving effect was lower than that of Example 1. It is considered that poor dispersion of the impact modifier occurred due to the mixture of coarse particles.

Comparative Example 2 The agglomerated polymer slurry of Comparative Example 1 was fed to a centrifuge for washing and dehydration.
After adding 1 g, the mixture was dried with a vibration drier to obtain a powder having an average particle size of 395 μm of the polymer. This was evaluated in the same manner as in Example 1. Although the addition of calcium stearate had an effect of suppressing the formation of coarse particles to some extent, it was not sufficient, and the effect of improving impact resistance was lower than that of Example 1.

Example 2 33 kg of ion-exchanged water was charged into a 100-liter stainless steel tank equipped with a stirrer, a thermometer and a jacket, 40 g of magnesium sulfate were charged, and the temperature was raised to 40 ° C. The salting out was performed by continuously feeding 10 kg of the two-stage polymer emulsion of Example 1. Then, after stirring, 8.6 g of Defomax 702 was added thereto while stirring, and then 80 ° C.
And kept for 60 minutes to obtain an aggregated polymer slurry.
Next, the aggregated polymer slurry is fed to a centrifugal separator, washed and dehydrated, and after adding 5.6 g of calcium stearate and drying with a vibration drier, an average particle size of 2 is obtained.
An acrylic resin composition powder having a uniform particle size of 72 μm was obtained. The properties of the agglomerated slurry are shown in Table 1. As a result, the agglomerated material could be fed to the centrifugal separator very stably without floating, and coarse particles were not generated by coalescence of the agglomerated polymer. The obtained acrylic resin composition was molded into an Izod test piece in the same manner as in Example 1 and evaluated. Table 1 shows the evaluation results.

Comparative Example 3 33 kg of ion-exchanged water was charged into a 100-liter stainless steel tank equipped with a stirrer, a thermometer and a jacket, 40 g of magnesium sulfate were charged, and the temperature was raised to 40 ° C. After salting out by continuously feeding 10 kg of the two-stage polymer emulsion of Example 1, the temperature was raised to 80 ° C.
After holding for 0 minutes, an aggregated polymer slurry was obtained. However, coalescence of the aggregate slurry produced coarse particles and clogging of the piping during the transfer of the slurry. Therefore, the amount of aggregate that could be fed to the centrifuge for washing and dewatering was 1/100 of the total charge in a dry state. It was 2. The resin modifier obtained by drying was a non-uniform powder in which powder of coarse particles of 1000 μm or more was mixed. The obtained impact modifier was evaluated in the same manner as in Example 1, but the impact resistance improving effect was lower than that of Example 2.

Example 3 33.4 k of ion-exchanged water was placed in a 75-liter glass-lined reaction tank equipped with a condenser, a thermometer and a stirrer.
g, and 2 g of Nikkor OTP-100 (manufactured by Nikko Chemical: sodium dioctylsulfosuccinate) and 10 g of sodium carbonate are dissolved.
The temperature rose. Separately, 8.9 kg of butyl acrylate, 90 g of allyl methacrylate and 36 g of 1,6-hexanediol diacrylate were placed in a 30-liter stainless steel container.
g and 45 g of Nikkor OTP-100 to prepare an emulsifier-dissolved monomer mixture (3). After 9 g of potassium persulfate was charged as a polymerization initiator, the emulsifier-dissolved monomer mixture (3) was continuously supplied at a supply rate of 1.7% by weight / minute to carry out polymerization. Emulsifier-soluble monomer mixture (3)
Is completed, the mixture is kept at 80 ° C. for 30 minutes with stirring, 8.8 g of potassium persulfate is added, 8.9 kg of butyl acrylate, 90 g of allyl methacrylate,
An emulsifier-dissolved monomer mixture (4) comprising 36 g of 6-hexanediol diacrylate and 27 g of Nikkor OTP-100 is continuously fed at a feed rate of 2.0% by weight / minute for polymerization. When the supply of the emulsifier-dissolved monomer mixture (4) is completed, the mixture is maintained at 80 ° C. for 60 minutes with stirring.
After charging 2.0 g of potassium persulfate, a monomer mixture consisting of 1.9 kg of methyl methacrylate, 100 g of methyl acrylate and 4 g of Nikkor OTP-100 is continuously supplied at a supply rate of 5.0% by weight / minute. And polymerize. When the supply of the monomer mixture is completed, stir 8
It was kept at 0 ° C. for 60 minutes to complete the polymerization. After polymerization 4
After cooling to 0 ° C., the mixture was filtered through a 325 mesh wire net and taken out to obtain an emulsion containing 37% of a two-stage polymer having a particle diameter of 0.35 μm.

1 with stirrer, thermometer and jacket
3 liters of ion exchange water in a 00 liter stainless steel tank
3 kg was charged, and 8.6 g of Defomax 702 was charged with stirring, and the temperature was raised to 30 ° C. 10 kg of a frozen emulsion of a two-stage polymer frozen at −30 ° C. is introduced while crushing. After confirming that all the frozen emulsions were completely melted and the temperature was constant, an aggregated polymer slurry was obtained. Next, the aggregated polymer slurry is fed to a centrifugal separator, washed and dehydrated, and then aerosil (silicon dioxide powder) is added to the slurry.
By adding 0 g and drying with a vibration dryer, a powder of an acrylic resin composition having an average particle size of 205 μm and a uniform particle size was obtained. The properties of the agglomerated slurry are shown in Table 1. As a result, the agglomerated material could be fed to the centrifugal separator very stably without floating, and coarse particles were not generated by coalescence of the agglomerated polymer. 10 parts by weight of the obtained impact modifier was added to 100 parts by weight.
Parts by weight of polyethylene terephthalate resin (PET:
KS750RC manufactured by Kuraray Co., Ltd.) and melt-kneaded at a cylinder temperature of 280 ° C. with a twin-screw extruder having a screw diameter of 30 mm to obtain a master pellet of PET with improved impact resistance. After uniformly mixing 5 parts of this master pellet and 95 parts by weight of polyethylene terephthalate resin pellets, a cylinder temperature of 270 ° C. and a mold temperature of 40 ° C. were obtained using an SG-100 type injection molding machine manufactured by Sumitomo Heavy Industries, Ltd.
Ball impact test specimen (100 mm x 100 mm x 1)
mmt) was molded and evaluated. Table 1 shows the evaluation results.

Comparative Example 4 33 kg of ion-exchanged water was charged into a 100-liter stainless steel tank equipped with a stirrer, thermometer and jacket, and the temperature was raised to 30 ° C. 10 kg of a frozen emulsion of the two-stage polymer of Example 1 frozen at −30 ° C. is added while crushing. After confirming that all the frozen emulsions were completely melted and the temperature was constant, an aggregated polymer slurry was obtained. However, most of the aggregate slurry floated and clogging of the piping occurred during the transfer of the slurry, so the amount of aggregate that could be fed to the centrifugal separator for washing and dewatering was 1/4 of the total charge in a dry state. Was. The resin modifier obtained by drying was a non-uniform powder in which powder of coarse particles of 1000 μm or more was mixed. The obtained impact modifier was evaluated in the same manner as in Example 3, but the effect of improving the impact resistance was lower than that of Example 3.

Comparative Example 5 The amount of Defomax 702, which is a nonionic surfactant, added when preparing an aggregated polymer slurry was 3
A resin modifier was prepared and evaluated in the same manner as in Example 3 except that the amount was changed to 2.3 g. Although the properties and powder particle size of the agglomerated polymer slurry were good, the effect of improving impact resistance was lower than that of Example 3.

Example 4 Nonal 204 (manufactured by Toho Chemical Industry Co., Ltd .: polyoxyethylene nonyl phenyl ether, HLB =) was used instead of Defomax 702 as a nonionic surfactant to be added when preparing an agglomerated polymer slurry. The same operation as in Example 3 was performed except that 8.9) was used.

Example 5 Sorbone S-60 (manufactured by Toho Chemical Industry Co., Ltd .: sorbitan monostearate, HLB =) instead of Defomax 702 as a nonionic surfactant to be added when preparing an aggregated polymer slurry 4.7) The same operation as in Example 3 was performed, except that 10 g was added.

Example 6 Pegnol O-6 (manufactured by Toho Chemical Industry Co., Ltd .: polyoxyethylene oleyl ether, HLB) was used in place of Defomax 702 as a nonionic surfactant to be added when preparing an aggregated polymer slurry. = 9.6) The same operation as in Example 3 was performed except that 8 g was added.

[0042]

[Table 1]

[0043]

Industrial Applicability The acrylic resin composition of the present invention is extremely useful as a resin modifier useful for improving impact resistance without lowering the physical properties of the thermoplastic resin to be modified.

Continued on the front page F-term (reference) 4J002 BG04W BG05X BN12W CH023 CH053 DE237 DG047 DG057 DJ017 EG007 EH007 EH016 EH156 FD207 FD313 FD313 FD316 4J100 AB00T AB02R AB02T AB03T AB04R AB04T AG04T AJ03T AJT AL04 AL08 AL AM02T AM45R AM45T AM47R AM47T AQ21R BA02R BB01R BC04R BC04S BC04T BC43R CA03 CA29 DA52 EA07 FA20 FA35 JA00

Claims (3)

[Claims] 1. A methacrylic acid ester having an alkyl group having 1 to 8 carbon atoms in the presence of an elastic body (A) layer mainly comprising an acrylate monomer unit having an alkyl group having 1 to 8 carbon atoms. 100 parts by weight of a multi-stage polymer (I) obtained by polymerizing a resin (B) comprising at least 60% by weight of a monomer and at most 40% by weight of another monomer copolymerizable with a monomer, a nonionic type having an antifoaming action 0.005 to 1 part by weight of a surfactant (II) and at least one compound of a salt or ester of a fatty acid, an ester of a polyhydric alcohol, an inorganic salt, and an inorganic oxide (II
I) An acrylic resin composition comprising 0.01 to 1 part by weight. 2. The acrylate monomer having an alkyl group having 1 to 8 carbon atoms, wherein the elastic body (A) has 70 to 99.9.
The composition according to claim 1, which is obtained by emulsion polymerization of 5% by weight, 0.05 to 5% by weight of a graft-linking monomer and 0 to 29.95% by weight of a monomer copolymerizable therewith. Acrylic resin composition. 3. The nonionic surfactant (II) having an antifoaming action is an adduct of a nonionic surfactant and / or propylene oxide having an HLB of 10 or less. Or the acrylic resin composition according to 2.