JP2002348335A - Acrylic elastomer graft copolymer, impact strength improving agent, resin composition, and method for producing acrylic elastomer graft copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an impact strength improving agent which is added a little to a resin to furnish it with improved impact resistance and better workability, and can provide a molded product with adequate discoloration resistance. SOLUTION: The impact strength improving agent is an acrylic elastomer graft copolymer having an acid group and obtained by graft copolymerizing (B) a vinyl monomer to (A) a polyalkyl(meth)acrylate composite elastomer, wherein the polyalkyl(meth)acrylate composite elastomer contains two or more acrylic elastomer components which have their different glass transition temperatures (Tg).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an impact strength modifier which imparts impact resistance such as Charpy impact strength, surface impact strength and the like, which is excellent in weatherability, especially fading resistance, and which is excellent in workability. The present invention relates to an impact strength modifier, a method for producing the same, and a resin composition using the same.

[0002]

2. Description of the Related Art Impact strength modifiers (also referred to as impact modifiers) are used in many resins. In particular, vinyl chloride resins have insufficient impact resistance despite being highly versatile resins. In some cases, various impact strength modifiers are added. In addition, poor workability of the vinyl chloride resin is generally cited as a conventional problem.

[0003] The addition of a processing aid is effective in improving the processability. However, due to the cost and the need for simplification of the compounding process, etc.
Studies have been made to reduce the number of added parts as much as possible.

[0004] Many proposals have been made on methods for improving impact resistance. For example, an MBS resin comprising an MBS resin obtained by graft-polymerizing methyl methacrylate, styrene or acrylonitrile on a butadiene rubber-like polymer. There is a method in which an agent is used by adding it to a vinyl chloride resin.

However, when an MBS-based modifier is used in combination with a vinyl chloride resin, the impact resistance is improved but the weather resistance may be reduced. When the molded product is used outdoors, the color may fade. is there.

[0006] The main cause of the decrease in weather resistance is MBS.
It is thought to be based on UV degradation of the butadiene units that make up the resin.

Accordingly, methyl methacrylate, styrene, acrylonitrile, or the like is graft-polymerized to a crosslinked alkyl (meth) acrylate rubber polymer composed of an alkyl (meth) acrylate and a crosslinker to improve the weather resistance of the MBS resin, and A method of imparting impact resistance is proposed in Japanese Patent Publication No. 51-28117.

There are also many known techniques for improving the impact resistance of general-purpose thermoplastic resins such as methacrylic resins, polystyrene resins, acrylonitrile / styrene resins, and polycarbonates.

For example, Japanese Patent Publication No. 4-325542 discloses a method for improving the appearance of a product while maintaining impact resistance by adding a specific alcohol to a rubber-like polymer latex. Further, Japanese Patent Application Laid-Open No. 10-10
No. 1869 discloses a method for improving the impact resistance of a composite rubber having a structure in which an isobutylene-based polymer segment and a vinyl polymer segment cannot be separated from each other by a graft copolymer obtained by graft-polymerizing a vinyl-based monomer. Proposed. Japanese Patent No. 3083515 proposes an impact resistance modifier using a specific acrylic rubber.

[0010]

However, when such an acrylic graft copolymer is used, the molded article produced is excellent in weather resistance and has a small decrease in impact resistance. In terms of workability, MB
S was sometimes inferior to S.

[0011] Against this background, there is a strong demand for improving the processability of vinyl chloride resins in particular, and processing aids containing methacrylic resin as a main component have been proposed to compensate for this. Although it has an effect on improvement, further improvement has been demanded in terms of balance with impact resistance. Further, since the addition of a processing aid leads to an increase in cost, a material that can improve the processability by adding only an impact modifier has been desired.

In view of the above situation, the present invention improves the impact resistance of a resin by adding a small amount thereof, imparts good workability, and realizes a sufficient fading resistance of a molded product obtained. It is intended to provide a modifier. It is another object of the present invention to provide a thermoplastic resin composition having excellent impact strength and weather resistance, which is used for a profile extrusion molded product such as a pipe, a window frame, and a flat plate, which require surface impact strength and Charpy impact strength. .

[0013]

According to the present invention for achieving the above object, a vinyl monomer (B) is graft-polymerized onto a polyalkyl (meth) acrylate-based composite rubber (A). Wherein the polyalkyl (meth) acrylate-based composite rubber (A) contains two or more acrylic rubber components having different glass transition temperatures (Tg) from each other. A graft copolymer is provided.

Such an acrylic rubber-based graft copolymer is prepared by a process of preparing a polyalkyl (meth) acrylate-based composite rubber (A) by an emulsion polymerization method and a method of preparing the polyalkyl (meth) acrylate-based composite rubber (A). And a step of graft-polymerizing the vinyl monomer (B) by an emulsion polymerization method.

Since the acrylic rubber-based graft copolymer of the present invention contains an acid group, it is excellent in miscibility with a matrix resin such as a vinyl chloride resin. For this reason, workability can be improved.

Further, since the composition contains a polyalkyl (meth) acrylate-based composite rubber (A) component having two or more different glass transition temperatures (Tg), impact resistance particularly at low temperatures is improved.

As a result, by using the acrylic rubber-based graft copolymer of the present invention as an impact strength modifier, the impact resistance of the resin can be improved with a small amount of addition, good processability can be imparted, and the resulting molding can be obtained. Good fading resistance of the product can be realized. In addition, it can be used for molded extrusion products such as pipes, window frames, and flat plates that require surface impact strength, Charpy impact strength, and the like, and can realize a thermoplastic resin composition excellent in impact strength and weather resistance.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION As the alkyl (meth) acrylate used in the polyalkyl (meth) acrylate-based composite rubber (A), for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2- Examples include ethylhexyl acrylate, ethoxyethoxyethyl acrylate, methoxytripropylene glycol acrylate, 4-hydroxybutyl acrylate, lauryl methacrylate, and stearyl methacrylate. These alkyl (meth)
Acrylates are used alone or in combination of two or more.

Further, in this monomer, styrene, α-
Aromatic alkenyl compounds such as methylstyrene and vinyltoluene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; various vinyl monomers other than alkyl (meth) acrylates such as methacrylic acid-modified silicone and fluorine-containing vinyl compounds. It may be contained as a copolymer component in a range of 30% by mass or less.

As the cross-linking agent or the graft cross-linking agent, for example, monomers having two or more unsaturated bonds in the molecule can be used alone or as a mixture. Examples of the crosslinking agent include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, divinylbenzene, and a polyfunctional methacryl group-modified silicone. Further, examples of the graft crosslinking agent include allyl methacrylate, triallyl cyanurate, triallyl isocyanurate and the like. Allyl methacrylate can also be used as a crosslinking agent.

The polyalkyl (meth) acrylate-based composite rubber (A) is a rubber containing two or more types of acrylic rubber components having different glass transition temperatures (Tg), and at least one of the rubber components contains an acid group. Each acrylic rubber component is obtained by polymerizing a monomer containing one or more alkyl (meth) acrylates.

In this monomer, a monomer having two or more unsaturated bonds in the molecule can be used, but preferably 0.1% by mass or more and 20% by mass or less, more preferably Is used in a range of 18% by mass or less.

The glass transition temperature of at least one of the acrylic rubber components of the polyalkyl (meth) acrylate rubber (A) is preferably 10 ° C. or less.
Further, it is preferable that at least one glass transition temperature is lower than the glass transition temperature of the n-butyl acrylate homopolymer. When the glass transition temperature of the acrylic rubber component of the polyalkyl (meth) acrylate-based composite rubber (A) is in such a range, the obtained impact strength modifier can impart more impact resistance.

The glass transition temperature of the acrylic rubber component is measured as a Tan δ transition point measured by a dynamic mechanical property analyzer (hereinafter abbreviated as DMA). In general, polymers obtained from monomers have a unique glass transition temperature,
One transition point is observed in a homopolymer (single component or a random copolymer of multiple components), but a unique transition point is observed in each of a mixture of multiple polymers or a composite polymer. Is done.

For example, in the case of two components, two transition points are observed. In the Tan δ curve measured by DMA, two peaks are observed. However, when there is a bias in the composition ratio or when the transition temperature is close, the respective peaks may approach each other. Although it may be observed, it can be distinguished from a simple one-peak curve seen in the case of a homopolymer.

The glass transition temperature of an n-butyl acrylate homopolymer varies depending on the presence or absence and degree of crosslinking. Therefore, the expression herein lower than the glass transition temperature of n-butyl acrylate homopolymer is:
N-butyl acrylate is used in the component, and the glass transition temperature of this component alone is compared with the glass transition temperature of the other component alone, and the glass transition temperature of the other component is n-butyl acrylate. Means lower than the glass transition temperature of the component used.

The acrylic rubber component of the polyalkyl (meth) acrylate-based composite rubber (A) is not particularly limited as long as it is at least two kinds having different glass transition temperatures, but is not limited to 2-ethylhexyl acrylate, ethoxyethoxyethyl acrylate, and methoxytrimethyl acrylate. Acrylic rubber (A) obtained by polymerizing at least one monomer component selected from the group consisting of propylene glycol acrylate, 4-hydroxybutyl acrylate, lauryl methacrylate, tridecyl methacrylate and stearyl methacrylate
1) Component and acrylic rubber (A2) obtained by polymerizing at least n-butyl acrylate as a monomer component
Those containing the components are preferred because they have excellent impact resistance.

In this case, the glass transition temperature (Tg1) derived from the acrylic rubber (A1) component of the polyalkyl (meth) acrylate-based composite rubber (A) is the same as that of the acrylic rubber (A2).
If it is lower than the glass transition temperature (Tg2) derived from the component,
It is preferable because it has excellent low-temperature impact resistance.

From the same viewpoint, the glass transition temperature (Tg2) derived from the acrylic rubber (A2) component is preferably 10 ° C. or less.

From the viewpoint of impact resistance, at least 1
One or more acrylic rubber components are preferably copolymerized with 0.01% by mass or more, more preferably 0.05% by mass or more, preferably 20% by mass or less, more preferably 10% by mass or less of an allyl methacrylate component. Is preferred.

When stearyl methacrylate or the like having crystallinity near room temperature is used, it is preferable to use it by mixing it with a monomer that dissolves it.

Although the particle size distribution of the polyalkyl (meth) acrylate-based composite rubber (A) is not particularly limited, it is more preferable that the particle size distribution be bidisperse.

Further, as one desirable form of particle size distribution, polyalkyl (meth) acrylate-based composite rubber (A) has a particle size distribution of 0.05 μm to 0.4 μm.
a bidisperse distribution having at least two peaks in μm, and 70% by mass or more of the polyalkyl (meth) acrylate-based composite rubber (A) is 0.05 μm or more.
The particles preferably have a particle diameter of 0.4 μm. Polyalkyl (meth) showing such particle distribution
If the acrylate-based composite rubber (A) is used as an impact strength modifier, excellent impact resistance, particularly high surface impact, can be realized with a small amount of addition. The distribution of the particle diameter of the polyalkyl (meth) acrylate rubber (A) is 0.05 to 0.1.
When there is at least one peak at each of 15 μm and 0.15 to 0.4 μm, an impact strength modifier exhibiting more excellent impact resistance can be obtained.

Another preferred form of the particle-based distribution is a bidisperse distribution in which a plurality of peaks are observed in the mass distribution, and has at least one peak in the range of 0.05 μm to 0.4 μm. The mass ratio in that range is 50 to 9
9.9% by mass, and a bidisperse distribution having at least one peak in the range of 0.4 μm to 1.0 μm and a mass ratio of 0.1 to 50% by mass in that range. Preferably, 7 in the range of 0.05 μm to 0.4 μm.
From the viewpoint of impact strength, a bidisperse distribution of 0 to 99.9% by mass and 0.1 to 30% by mass in 0.4 to 1.0 μm is preferable.

The mass distribution refers to a certain particle diameter dp and d
5 is a distribution in which the mass ratio of particles within a minute interval from p + Δdp to all particles is expressed as a percentage.

When an acrylic rubber-based graft copolymer using the polyalkyl (meth) acrylate-based composite rubber (A) having the above-described particle size distribution is used as an impact strength modifier, such a particle size distribution can be obtained. This is preferable because the impact resistance when blended with a resin is further improved as compared with those having no resin.

As a method for producing the polyalkyl (meth) acrylate-based composite rubber (A), for example, when it is produced from two kinds of acrylic rubber components, first, a monomer containing at least one kind of alkyl (meth) acrylate Polymerized into the first
Acrylic rubber (A1) component latex is obtained, and then the monomer constituting the second acrylic rubber (A2) component is added to the acrylic rubber component latex and impregnated, and then the presence of a radical polymerization initiator Examples include a method of performing lower polymerization. As the polymerization proceeds, a latex of a polyalkyl (meth) acrylate-based composite rubber (A) in which two types of acrylic rubber components are composited is obtained.

Alternatively, the second rubber may be produced by a method such as drop polymerization in the presence of the first rubber, or a method of enlarging a composite rubber with an acid or a salt.

Further, there is a method of preparing two kinds of seed particles having different particle diameters, mixing them, and then carrying out polymerization in the presence of those.

More specifically, an acrylic rubber containing at least one of 2-ethylhexyl acrylate, ethoxyethoxyethyl acrylate, methoxytripropylene glycol acrylate, 4-hydroxybutyl acrylate, lauryl methacrylate and stearyl methacrylate as a constituent component ( In the presence of the component (A1), it is more preferable to obtain a polyalkyl (meth) acrylate-based composite rubber (A) by emulsion polymerization of a monomer containing n-butyl acrylate constituting the acrylic rubber (A2) component. .

Here, the polymerization method is not particularly limited.
Usually, emulsion polymerization and, if necessary, forced emulsion polymerization may be used. For polymerization of the acrylic rubber (A1) component, forced emulsion polymerization is preferably used.

In particular, since 2-ethyl acrylate, lauryl methacrylate and stearyl methacrylate are poorly water-soluble as monomers constituting the acrylic rubber (A1) component, the acrylic rubber (A1) component is produced by forced emulsion polymerization. Is preferred.

The compound (E) is preferably used as the emulsifier and the dispersion stabilizer, but any known surfactant such as anionic, nonionic or cationic may be used in combination. When these mixtures are used as necessary, it is preferable to use an emulsifier having a large micelle-forming ability in combination with a small emulsifier.

Vinyl monomer (B) graft-polymerized to polyalkyl (meth) acrylate composite rubber (A)
As aromatic alkenyl compounds such as styrene, α-methylstyrene and vinyltoluene; methacrylic esters such as methyl methacrylate and 2-ethylhexyl methacrylate; acrylic esters such as methyl acrylate, ethyl acrylate and n-butyl acrylate;
Various vinyl monomers such as vinyl cyanide compounds such as acrylonitrile and methacrylonitrile can be exemplified, and these may be used alone or in combination of two or more.

If necessary, the vinyl monomer (B) may have ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate having two or more unsaturated bonds in the molecule. , A crosslinking agent such as 1,4-butylene glycol dimethacrylate, divinylbenzene, a polyfunctional methacryl group-modified silicone, and a graft crosslinking agent such as allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, preferably 0.1% by mass. As described above, it is used in an amount of 20% by mass or less, more preferably 18% by mass or less.

The ratio of the polyalkyl (meth) acrylate-based composite rubber (A) to the vinyl monomer (B) in the acrylic rubber-based graft copolymer is preferably such that the polyalkyl (meth) acrylate-based composite rubber ( A) is preferably 60 parts by mass or more, more preferably 70 parts by mass or more, still more preferably 80 parts by mass or more, and most preferably 85 parts by mass or more, while 99.9 parts by mass or less is preferable, and 95 parts by mass or less. More preferred. Further, the vinyl monomer (B) is preferably at least 0.1 part by mass, more preferably at least 5 parts by mass, and on the other hand, preferably at most 40 parts by mass,
It is more preferably at most 30 parts by mass, more preferably at most 20 parts by mass, most preferably at most 15 parts by mass. When the amount of the vinyl monomer (B) is 0.1 parts by mass or more, sufficient dispersibility of the obtained acrylic rubber-based graft copolymer in the resin can be realized, and a resin composition obtained by blending the same. Workability of the product is improved. On the other hand, if it is 40 parts by mass or less, sufficient impact strength of the acrylic rubber-based graft copolymer can be realized.

Examples of the acid group contained in the acrylic rubber-based graft copolymer include a carboxyl group and a sulfonyl group. Among them, a carboxyl group is preferable.
Further, it is preferably a carboxyl group derived from (meth) acrylic acid.

(Meth) acrylic acid is a vinyl-based monomer, which is convenient because it is incorporated into the polymer chain by mixing with other rubber components at the polymerization stage. However, the present invention is not limited to such an embodiment, and an acid group may be introduced into the polyalkyl (meth) acrylate-based composite rubber after polymerization. However, it is preferable that the acid group is not in a state of being mixed alone, but at least chemically bonded, for example, copolymerized with a poly (meth) acrylate component.

When the acrylic rubber-based graft copolymer is directly incorporated into the acrylic rubber-based graft copolymer or the like, the acid group-containing portion may be a polyalkyl (meth) acrylate-based composite rubber (A). Vinyl monomer (B)
Either, or both.

When (meth) acrylic acid is used for introducing an acid group, the amount of the (meth) acrylic acid is 0.1 to 100 parts by mass of the polyalkyl (meth) acrylate-based composite rubber (A).
001 parts by mass or more is preferable, 0.01 parts by mass or more is more preferable, 20 parts by mass or less is preferable, 10 parts by mass or less is more preferable, and 7 parts by mass or less is further preferable. If it is 0.001 part by mass or more, workability is sufficiently improved, and if it is 20 parts by mass or less, sufficient impact resistance can be realized.

As a method for producing an acrylic rubber-based graft copolymer, a vinyl monomer (B) is added to a latex of a polyalkyl (meth) acrylate-based composite rubber (A), and the graft is carried out in one or more stages by radical polymerization. The polymerized and graft-copolymerized latex is put into hot water in which an acid such as sulfuric acid or hydrochloric acid or a metal salt such as calcium chloride, calcium acetate or magnesium sulfate is dissolved, salted out, coagulated, separated and recovered. Thereby, there can be mentioned a method of obtaining particles of an acrylic rubber-based graft copolymer. At this time, salts such as sodium carbonate and sodium sulfate may be used in combination. Further, it can be obtained by a direct drying method such as a spray drying method.

As a more preferred form of the acrylic rubber-based graft copolymer, a compound containing a sulfonic acid or a sulfuric acid group and having a benzene ring skeleton (E) may be used. Is a compound containing a sulfonyl group or a sulfate group and having a benzene ring skeleton. The sulfonic acid or sulfate group may remain unneutralized, or may take the form of a salt with an alkali metal or the like.

The compound (E) may have a nonionic polyoxyethylene chain in the molecule, irrespective of its skeleton structure such as alkylphenyl type or alkylphenyl ether type as long as it has a benzene ring skeleton. Absent.

The compound (E) or a salt thereof is preferably a compound having a sulfonic acid group or a salt thereof, and is preferably a compound having two or more benzene rings in one molecule and having a sulfonic acid group or a salt thereof. Is more preferable because the thermal stability during molding is improved.

Specific examples of compound (E) or a salt thereof include linear or branched alkylbenzene sulfonic acids such as sodium dodecylbenzenesulfonate and salts thereof, sodium polyoxyethylene nonyl phenyl ether sulfate, polyoxyethylene octyl phenyl ether Polyoxyethylene alkyl phenyl ether sulfuric acid such as sodium sulfate and salts thereof, and diphenyl ether disulfonic acid such as sodium alkyl diphenyl ether disulfonate (sodium alkyl phenoxybenzene sulfonate) and the like, and salts thereof are particularly preferred. Those are the salts of alkyl diphenyl ether disulphonic acid.

The content of the compound (E) or a salt thereof is 0.1 to 100000 in the acrylic rubber-based graft copolymer.
Preferably, it is contained in the range of ppm by mass. Within this range, sufficient impact resistance can be realized.

When the compound (E) or a salt thereof has an emulsifying ability, it can be used as an emulsifier for producing an acrylic rubber-based graft copolymer.
Alternatively, the preferable content of the salt can be adjusted by washing or coagulating the acrylic rubber-based graft copolymer using a known coagulant and washing it when coagulating and recovering the acrylic rubber-based graft copolymer.

In the case where a coagulant is used, the counter ion of the compound (E) may be different from the original one, but this is not a problem.

The amount of compound (E) or a salt thereof used as an emulsifier is preferably at least 0.2 part by mass, more preferably at least 0.3 part by mass, based on 100 parts by mass of the acrylic rubber-based graft copolymer. It is preferably 15 parts by mass or less,
It is more preferably at most 12 parts by mass. When it is 0.2 parts by mass or more, stable polymerization can be realized, and when it is 15 parts by mass or less, a desired particle size distribution can be obtained.

The acrylic rubber-based graft copolymer obtained as described above is preferably blended with a thermoplastic resin, particularly a hard vinyl chloride-based resin (PVC-based resin), as an impact strength modifier. It can be used by being blended with resins such as polycarbonate, polystyrene and polyester resin.

Specific examples of the resin in which the impact strength modifier is blended include hard vinyl chloride resin (PVC resin), semi-hard and soft vinyl chloride resin (PVC resin), polypropylene (PP), and polyethylene. Olefinic resins such as (PE), polystyrene (PS), high impact polystyrene (HIPS), (meth) acrylate / styrene copolymer (MS), styrene / acrylonitrile copolymer (SAN), styrene / maleic anhydride Styrene resin (St resin) such as acid copolymer (SMA), ABS, ASA, AES, etc., acrylic resin (Ac resin) such as polymethyl methacrylate (PMMA), polycarbonate resin (PC resin) ), Polyamide resin (PA resin), polyethylene terephthalate (PE
T) and polyester resins (PEs resins) such as polybutylene terephthalate (PBT), (modified) polyphenylene ether resins (PPE resins), polyoxymethylene resins (POM resins), polysulfone resins (PSO) Plastics), engineering plastics such as polyarylate resin (PAr resin), polyphenylene resin (PPS resin), thermoplastic polyurethane resin (PU resin), styrene elastomer, olefin elastomer, vinyl chloride Elastomers, urethane elastomers, polyester elastomers,
Polyamide-based elastomer, fluorine-based elastomer,
Thermoplastic elastomer (TPE) such as 1,2-polybutadiene, trans 1,4-polyisoprene, PC / A
PC resin such as BS / St resin alloy, PVC / A
PVC resin such as BS / St resin alloy, PA / A
PA resin such as BS / St resin alloy, PA resin / TPE alloy, PA resin such as PA / PP / Polyolefin resin alloy, PBT resin / TPE, PC /
Allo-PPE / HIPS, PPE / PB between PC-based resin such as PBT / PEs-based resin alloy, polyolefin-based resin / TPE, olefin-based resin such as PP / PE
T, PPE resin alloys such as PPE / PA, PVC /
Examples include polymer alloys such as a PVC resin / Ac resin alloy such as PMMA, and hard, semi-hard, and soft vinyl chloride resins.

The amount of the acrylic rubber-based graft copolymer is preferably at least 0.1 part by mass, based on 100 parts by mass of the thermoplastic resin, from the viewpoint of the performance of the obtained thermoplastic resin composition. It is more preferably at least part by mass, while
It is preferably at most 30 parts by mass, more preferably at most 20 parts by mass.

To the thermoplastic resin composition of the present invention, conventional stabilizers and fillers are added at the time of compounding, kneading, molding and the like of the resin according to the purpose, as long as the physical properties are not impaired. be able to.

As the stabilizer, for example, tribasic lead sulfate,
Lead-based stabilizers such as dibasic lead phosphite, basic lead sulfite, and lead silicate; metals such as potassium, magnesium, barium, zinc, cadmium, and lead; and 2-ethylhexanoic acid;
Metallic soap-based stabilizers derived from fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, oleic acid, ricinoleic acid, linoleic acid, behenic acid, alkyl groups, ester groups and fatty acids Organotin stabilizer derived from salt, maleate, sulfide-containing, Ba-Zn-based, Ca-Zn
System, Ba-Ca-Sn system, Ca-Mg-Sn system, Ca-
Composite metal soap stabilizers such as Zn-Sn, Pb-Sn, and Pb-Ba-Ca, metal groups such as barium and zinc, and branched fatty acids such as 2-ethylhexanoic acid, isodecanoic acid, and trialkylacetic acid, and oleic acid Metals derived from two or more organic acids, usually unsaturated fatty acids such as ricinoleic acid and linoleic acid, aliphatic acids such as naphthenic acid, aromatic acids such as carboxylic acid, benzoic acid, salicylic acid, and their substituted derivatives Salt-based stabilizers, these stabilizers are dissolved in organic solvents such as petroleum hydrocarbons, alcohols, and glycerin derivatives, and phosphites, epoxy compounds, color inhibitors, transparency improvers, light stabilizers, and antioxidants Metal stabilizers, such as metal salt liquid stabilizers, which contain stabilizing aids such as antioxidants, plate-out inhibitors, and lubricants, as well as epoxy resins and epoxy resins. Soybean oil, epoxidized vegetable oils, epoxy compounds such as epoxidized fatty acid alkyl esters,
Organic phosphites in which phosphorus is substituted with an alkyl group, an aryl group, a cycloalkyl group, an alkoxyl group, and the like, and having an aromatic compound such as a dihydric alcohol such as propylene glycol, hydroquinone, and bisphenol A; UV absorbers such as hindered phenols such as bisphenol dimerized with methylene groups, salicylic acid esters, benzophenone, and benzotriazole; light stabilizers such as hindered amines or nickel complex salts; and UV shielding agents such as carbon black and rutile-type titanium oxide. And polyhydric alcohols such as trimerol propane, pentaerythritol, sorbitol and mannitol, β-aminocrotonates, nitrogen-containing compounds such as 2-phenylindole, diphenylthiourea and dicyandiamide; Sulfur-containing compounds such as Ruki thio dipropionate ester, acetoacetic ester, dehydroacetic acid, keto compounds such as β- diketones, organic silicon compounds,
Non-metallic stabilizers such as borate esters may be used, and these may be used alone or in combination of two or more.

Examples of the filler include carbonates such as heavy calcium carbonate, precipitated calcium carbonate and colloidal calcium carbonate, titanium oxide, clay, talc, mica, silica, carbon black, graphite, glass beads, and the like.
Examples include inorganic fibers such as glass fibers, carbon fibers, and metal fibers, organic fibers such as polyamide, organic materials such as silicone, and natural organic materials such as wood flour.

Others, MBS, ABS, AES, NB
R, EVA, impact strength modifiers such as chlorinated polyethylene, acrylic rubber, polyalkyl (meth) acrylate rubber-based graft copolymers, thermoplastic elastomers, and processing aids for (meth) acrylate-based copolymers Agents, dibutyl phthalate, dioctyl phthalate, diisodecyl phthalate, diisononyl phthalate, diundecyl phthalate, trioctyl trimellitate, triisooctyl trimellitate, alkyl esters of aromatic polybasic acids such as pyromet, dibutyl adipate, dioctyl adipate, disiononyl adiate Alkyl esters of fatty acid polybasic acids such as peat, dibutyl azelate, dioctyl azelate, diisononyl azelate, phosphate esters such as tricresyl phosphate, adipic acid, azelaic acid, Molecular weight of polycarboxylic acids such as basic acid and phthalic acid and polyhydric alcohols such as ethylene glycol, 1,2-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, and 1,4-butylene glycol Polyester plasticizers such as those in which the ends of about 600 to 8,000 polycondensates are sealed with monohydric alcohols or monocarboxylic acids, epoxidized soybean oil, epoxidized linseed oil, epoxidized tall oil fatty acid-2 -Epoxy plasticizers such as ethylhexyl, plasticizers such as chlorinated paraffin, liquid paraffin, pure hydrocarbons such as low molecular weight polyethylene, halogenated hydrocarbons, higher fatty acids, fatty acids such as oxy fatty acids, fatty acid amides such as fatty acid amides, Polyhydric alcohol esters of fatty acids such as glycerides, fatty alcohols of fatty acids Ester (ester wax), metal soap, fatty alcohol, polyhydric alcohol, polyglycol, polyglycerol, partial ester of fatty acid and polyhydric alcohol, ester such as fatty acid and polyglycol, partial ester of polyglycerol, (meth) acrylic acid Ester copolymers and other such lubricants, chlorinated paraffins, aluminum hydroxide, antimony trioxide, flame retardants such as halogen compounds, (meth)
Heat-resistant improvers such as acrylate-based copolymers, imide-based copolymers, styrene-acrylonitrile-based copolymers, release agents, crystal nucleating agents, fluidity improvers, coloring agents, antistatic agents, and conductivity imparting Agents, surfactants, antifogging agents, foaming agents, antibacterial agents and the like can be added.

The method for producing the thermoplastic resin composition is not particularly limited, and a usual method can be used, but it is usually preferable to produce the composition by a melt mixing method. Moreover, you may use a small amount of solvent as needed. The equipment used is
Extruders, Banbury mixers, rollers, kneaders and the like can be mentioned by way of example, which are operated batchwise or continuously. The order of mixing the components is not particularly limited. Moreover, the obtained thermoplastic resin composition is not limited in its use, for example, building materials, automobiles, toys, miscellaneous goods such as stationery,
Furthermore, it is widely used for molded products requiring impact resistance, such as OA equipment and home electric appliances.

[0068]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. Unless otherwise specified, “parts” indicates “parts by mass” and “%” indicates “% by mass”, and a commercially available good reagent was used.

(Measurement method) (a) Measurement of particle size distribution of polyalkyl (meth) acrylate-based composite rubber A latex of polyalkyl (meth) acrylate-based composite rubber diluted with distilled water was used as a sample,
The measurement was performed using a CHDF2000 type particle size distribution meter manufactured by EC Company. The measurement was performed under standard conditions recommended by MATEC. Using a dedicated capillary cartridge for particle separation and a carrier liquid, the liquidity is neutral and the flow rate is 1.
4mL / min, pressure 27.6MPa, temperature 35 ° C
While maintaining the pH of the diluted latex sample at 3%.
1 mL was used for the measurement. As the standard particle size substance, a total of 12 points of monodisperse polystyrene having a known particle diameter manufactured by DUKE in the United States were used within a range of 0.02 μm to 0.8 μm.

(A) Measurement of glass transition temperature of acrylic rubber-based graft copolymer 70 parts of acrylic rubber-based graft copolymer and 30 parts of poly (methyl methacrylate) were pelletized together at 250 ° C. using a 25 mmφ single-screw extruder. Using a press machine set at 200 ° C, a plate molded to a thickness of 3 mm is width 10 mm and length 12 m
m, cut by TA Instruments, DM
The viscoelastic properties were measured with a model A983 at a heating rate of 2 ° C./min, and the temperature corresponding to the transition point of the obtained Tan δ curve was determined as the glass transition temperature.

(C) Measurement of the amount of compound (E) in the acrylic rubber-based graft copolymer The acrylic rubber-based graft copolymer recovered in powder form by salt coagulation or the like is subjected to washing after solid-liquid phase separation. In some cases, part of the compound (E) was released outside the copolymer system, and the amount was quantified by the following method.

The weighed sample was dissolved and dispersed in chloroform, extracted with 10 times the amount of methanol, and the methanol layer was concentrated. Thereafter, the resultant was washed again with methanol and then concentrated.
100 mL of pure water was added to the thus concentrated sample, and the mixture was heated and extracted at 70 ° C. for 24 hours, cooled to room temperature, filtered, and the filtrate was dried and weighed. The obtained water extract was measured using HPLC and FT-IR to identify and quantify components.

HPLC measurement conditions are as follows: Column: ODS system (Zorbax-OD manufactured by Hewlett-Packard Company, USA)
S, 4.6 mm diameter, 150 mm length), measurement temperature: 40 ° C., eluent: acetonitrile / DIW from 10/90 to 20
After 100 min, changed to 100/0, eluent speed: 1.0 ml / min, detector: DAD (250 nm).

(D) Impact resistance of vinyl chloride resin composition An acrylic rubber-based graft copolymer was blended into a vinyl chloride resin as an impact strength modifier, and the impact resistance of the obtained vinyl chloride resin composition was measured by Izod. It was evaluated by an impact resistance test. That is, the following two kinds of blending ratios of the vinyl chloride resin compositions (formulations A and B) were produced, and the temperature was adjusted to 190 ° C.
With a 5 mmφ single screw extruder, a ”″ × １ ／ ″ square bar was extruded and evaluated according to ASTM D256. Incidentally, the vinyl chloride resin composition of Formulation A was mixed at 23 ° C. with Formulation B.
Was measured at 0 ° C. and described as measurement A and measurement B, respectively.

Formulation A: 100 parts of vinyl chloride resin (trade name: TK-700) manufactured by Shin-Etsu Chemical Co., Ltd. (number average degree of polymerization 700) 3.5 parts of dibutyltin malate manufactured by Nitto Kasei Co., Ltd. Stearyl alcohol manufactured by Kao Corporation 0.8 part Processing aid manufactured by Mitsubishi Rayon Co., Ltd. 0.4 parts of metabrene P-700 0.5 part manufactured by Mitsubishi Chemical Corporation 0.5 part of carbon black # 690B Impact strength modifier (acrylic rubber-based graft copolymer) 7.5 parts.

Formulation B: 100 parts of vinyl chloride resin (trade name: TK-1000) manufactured by Shin-Etsu Chemical Co., Ltd. (number average degree of polymerization: 1100) 2 dibasic lead phosphite manufactured by Sakai Chemical Industry Co., Ltd. .5 parts Dibasic lead stearate manufactured by Sakai Chemical Industry Co., Ltd. 0.7 parts Lead stearate manufactured by Sakai Chemical Industry Co., Ltd. 0.5 parts Calcium stearate manufactured by Shinagawa Chemical Co., Ltd. 0.9 parts Mitsui Chemicals, Inc. ) Company polyethylene wax (trade name: High Wax 220MP, number average polymerization degree: 2200) 0.1 part Calcium carbonate manufactured by Ishihara Sangyo Co., Ltd. 5.0 parts Processing aid Metablen P-501 manufactured by Mitsubishi Rayon Co., Ltd. 1.0 part Mitsubishi 0.5 parts of carbon black # 690B manufactured by Kagaku Co., Ltd. 7.5 parts of impact strength modifier (acrylic rubber-based graft copolymer).

(E) Weather Resistance of Vinyl Chloride Resin Composition A vinyl chloride resin composition was prepared in the above-mentioned mixing ratio of B, and was subjected to 200 ° C., 15 rpm using a 6-inch test roll machine manufactured by Kansai Roll Co., Ltd. After kneading for 5 minutes at 200 ° C
And then cooled while applying a pressure of 4.9 MPa to obtain a sheet test piece.
After 8 hours in a tester, the operation of adjusting the temperature and humidity to 60 ° C. and 95% for 16 hours was repeated 5 times, and the appearance of the sheet test piece was visually evaluated. The evaluation results were as follows: ○ for good fading resistance, Δ for worse
Worse ones are indicated by a cross.

(F) Thermal Stability of Vinyl Chloride Resin Composition A vinyl chloride resin composition was produced in a white composition excluding the carbon black from the above-mentioned composition A, and was heated at 200 ° C. using a 6-inch test roll machine. After kneading at 15 rpm for 5 minutes, insert it into a mold at 200 ° C. for 6 minutes and then 4.9MPa.
The sheet test piece obtained by cooling while applying the pressure of a was heated in a gear oven adjusted to 180 ° C. for 30 minutes, and the appearance was judged by coloring. Those with poor thermal stability turned into darker brown, and the evaluation results were indicated by ○, Δ, ×, XX in order of decreasing thermal stability.

(G) Gelation behavior of vinyl chloride resin composition A vinyl chloride resin composition was produced in the above-mentioned blending ratio B except that the amount of the acrylic rubber-based graft copolymer was changed to 5 parts. Brabender PL200 manufactured by Brabender
Mixer type head as plast mill for type 0: W-50
E3 zone equipped, container temperature 180 ° C, filling amount 55
g, the retention time was 4 minutes, and the gelation time was measured at a mixer rotation speed of 30 rpm. In the time-torque curve, the point at which the torque showed the maximum value was defined as the gel time, and the performance was judged based on the speed of the gel time. The faster this time, the better the workability.

(Production Example 1) Production of acrylic rubber-based graft copolymer (1) 98 parts of 2-ethylhexyl acrylate and 2.0 parts of allyl methacrylate were mixed to obtain 100 parts of a (meth) acrylate monomer mixture. . As an emulsifier (compound E), 100 parts of the above (meth) acrylate monomer mixture was added to 195 parts of distilled water obtained by dissolving 1 part of sodium alkyldiphenyl ether disulfonate (trade name: Perex SS-H) manufactured by Kao Corporation at a solid content. In addition, 1
After preliminary stirring at 000 rpm, the mixture was emulsified and dispersed with a homogenizer at a pressure of 29.4 MPa, and (meth)
An acrylate emulsion was obtained. This emulsion was transferred to a separable flask equipped with a condenser and a stirring blade, and heated while being replaced with nitrogen and mixed and stirred, and when the temperature reached 50 ° C., tert-butyl hydroperoxide was added.
After adding 5 parts, the temperature was raised to 50 ° C., and ferrous sulfate 0.00
2 parts, disodium ethylenediaminetetraacetate 0.00
A mixed solution of 6 parts, 0.26 part of Rongalit (CH ₃ NaO ₃ S) and 5 parts of distilled water was added, and the mixture was allowed to stand for 5 hours to complete polymerization, thereby obtaining an acrylic rubber (A1) component latex.

The polymerization rate of the obtained acrylic rubber (A1) component latex was 99.9%. This latex was coagulated and dried with ethanol to obtain a solid, which was then extracted with toluene at 90 ° C. for 12 hours.
3.7%. Further, 5.0 parts of Perex SS-H was added to the obtained latex as a solid content.

The acrylic rubber (A1) component latex was collected so that the solid content of poly-2-ethylhexyl acrylate containing allyl methacrylate was 20 parts, put into a separable flask equipped with a stirrer, and distilled in the system. It was added so that the amount of water became 195 parts. At this time,
Perex SS-H will be present in this latex as 1.2 parts solids. Next, a mixed liquid of 65 parts of n-butyl acrylate containing 2% of allyl methacrylate, 3 parts of methacrylic acid and 0.32 part of tert-butyl hydroperoxide was charged and stirred for 10 minutes, and the mixed liquid was subjected to acrylic rubber (A1) component particles. Infiltrated. After stirring for another 10 minutes, the atmosphere in the system was replaced with nitrogen, and
℃, ferrous sulfate 0.002 parts, ethylenediaminetetraacetic acid disodium salt 0.006 parts, mixed solution of Rongalit 0.26 parts and distilled water 5 parts was charged to start radical polymerization, then the internal temperature The polymerization was completed by maintaining the temperature at 70 ° C. for 2 hours to obtain a polyalkyl (meth) acrylate-based composite rubber latex comprising the acrylic rubber (A1) component and the acrylic rubber (A2) component.

A part of the latex was collected and used for measurement of the particle size distribution of the polyalkyl (meth) acrylate-based composite rubber. Table 2 shows the measurement results of the particle size distribution.
The chart is shown in FIG. The mass ratio of the particles having a particle diameter of 0.4 to 1.0 μm to all the particles was 5% by mass.

Further, this latex was dried to obtain a solid, and extracted with toluene at 90 ° C. for 12 hours. The gel content was measured and found to be 98.3%.

A mixture of 0.06 part of tert-butyl hydroperoxide and 12 parts of methyl methacrylate (hereinafter abbreviated as MMA) was added to 88 parts of the polyalkyl (meth) acrylate composite rubber latex at 70 ° C. for 15 minutes.
Then, the mixture was kept at 70 ° C. for 4 hours to complete the graft polymerization of MMA as a vinyl monomer (B) onto the polyalkyl (meth) acrylate composite rubber. The conversion of MMA was 99.4%. The obtained acrylic rubber-based graft copolymer latex was dropped into 200 parts of hot water containing 1.5% of aluminum sulfate, coagulated, separated, washed, and dried at 75 ° C. for 16 hours to obtain a powdery acrylic rubber-based graft. A copolymer (1) was produced and used as an impact strength modifier.

The glass transition temperature of the acrylic rubber-based graft copolymer (1) was measured, and the results are shown in Table 2. The measured glass transition temperature is a value derived from a polyalkyl (meth) acrylate rubber, and a glass transition temperature Tg1 derived from an acrylic rubber (A1) component and a glass transition temperature Tg2 derived from an acrylic rubber (A2) component were measured. .

The amount of Perex SS-H (compound (E)) in the acrylic rubber graft copolymer (1) finally obtained was 550 ppm by mass.

Further, the above charged compositions are shown in Table 1.

(Production Example 2) Production of acrylic rubber-based graft copolymer (2) 98 parts of butyl acrylate, allyl methacrylate
0 parts, and (meth) acrylate monomer mixture 10
0 parts were obtained. 100 parts of the above (meth) acrylate monomer mixture was dissolved in 195 parts of distilled water in which 10 parts of sodium alkyldiphenyl ether disulfonate (trade name: Perex SS-H) manufactured by Kao Corporation was dissolved as an emulsifier (compound E) at a solid content. In addition, the mixture was transferred to a separable flask equipped with a condenser and a stirring blade, and heated to 50 ° C. while replacing with nitrogen and mixing and stirring. When the temperature reached 50 ° C., 0.5 parts of tert-butyl hydroperoxide was added, and the temperature was raised to 50 ° C. , Ferrous sulfate 0.002 parts, ethylenediaminetetraacetic acid disodium salt 0.006 parts, Rongalit 0.26
Parts and a mixed liquid of 5 parts of distilled water, and then left for 5 hours.
The polymerization was completed to obtain an acrylic rubber (A2-1) component latex.

Next, the acrylic rubber (A) shown in Production Example 1 was used.
1) The component latex was used as a solid content of poly-2-ethylhexyl acrylate containing allyl methacrylate as 2
It was collected so as to be 0 parts, placed in a separable flask equipped with a stirrer, and added so that the amount of distilled water in the system became 195 parts. Further, the acrylic rubber (A2-1) component latex was collected so that the solid content of poly n-butyl acrylate containing allyl methacrylate was 3 parts. At this time, 1.2 parts of the emulsifier derived from the component (A1) latex and 0.1 part of the emulsifier derived from the component (A2-1).
Three parts, a total of 1.5 parts, will be present in the system.

Further, for the next polymerization, 64 parts of n-butyl acrylate containing 2% of allyl methacrylate as a monomer as the component (A2-2), 1 part of methacrylic acid and 0.3 part of tert-butyl hydroperoxide
Two parts of the mixture was charged and stirred for 10 minutes. The mixture was mixed with the acrylic rubber (A1) component and the acrylic rubber (A2-
1) Permeated the component particles. After stirring for another 10 minutes, the atmosphere in the system was replaced with nitrogen, the temperature of the system was raised to 50 ° C.,
A radical polymerization was started by charging a mixed solution of 0.002 part of iron, 0.006 part of disodium ethylenediaminetetraacetate, 0.26 part of Rongalite and 5 parts of distilled water, and then kept at an internal temperature of 70 ° C. for 2 hours to perform polymerization. Was completed to obtain a latex of a polyalkyl (meth) acrylate-based composite rubber containing an acrylic rubber (A1) component and an acrylic rubber (A2) component. In addition, the acrylic rubber (A2) component
It consists of a component (A2-1) and a component (A2-2).

A part of this latex was collected and prepared in Production Example 1.
In the same manner as in the above, the same method was used for measuring the particle size distribution of the polyalkyl (meth) acrylate-based composite rubber. Table 2 shows the measurement results of the particle size distribution. Further, this latex was dried to obtain a solid, which was extracted with toluene at 90 ° C. for 12 hours, and the gel content was measured to be 98.3%.

A mixture of 0.06 part of tert-butyl hydroperoxide and 12 parts of methyl methacrylate (hereinafter abbreviated as MMA) was added to 88 parts of the polyalkyl (meth) acrylate composite rubber latex at 70 ° C. for 15 minutes.
Then, the mixture was kept at 70 ° C. for 4 hours to complete the graft polymerization of MMA as a vinyl monomer (B) onto the polyalkyl (meth) acrylate composite rubber. The conversion of MMA was 99.4%. The obtained acrylic rubber-based graft copolymer latex was dropped into 200 parts of hot water containing 1.5% of aluminum sulfate, coagulated, separated, washed, and dried at 75 ° C. for 16 hours to obtain a powdery acrylic rubber-based graft. A copolymer (2) was produced and used as an impact strength modifier.

The glass transition temperature of the acrylic rubber-based graft copolymer (2) was measured in the same manner as in Production Example 1. Table 2 shows the results. The measured glass transition temperature is a value derived from a polyalkyl (meth) acrylate rubber.

The amount of Perex SS-H (compound (E)) in the acrylic rubber-based graft copolymer (2) finally obtained was 610 ppm by mass.

Further, Table 1 summarizes the above charged compositions.

(Production Example 3) Production of acrylic rubber-based graft copolymer (3) To a separable flask equipped with a stirrer, 295 parts of distilled water in which 0.8 part of potassium tallowate was dissolved as a solid content was added, and 10 parts were added. After stirring for 0.3 minutes, 0.3 part of boric acid and 0.03 part of sodium carbonate were added, the atmosphere was replaced with nitrogen, the temperature was raised to 50 ° C, 88 parts of n-butyl acrylate containing 2% of allyl methacrylate, and tert-butyl. A mixed solution of 0.4 part of hydroperoxide was charged and stirred for 30 minutes, and the mixed solution was permeated into the polyorganosiloxane particles. Next, a mixed solution of 0.002 part of ferrous sulfate, 0.006 part of disodium ethylenediaminetetraacetate, 0.26 part of Rongalit and 5 parts of distilled water was charged to start radical polymerization. After holding for 2 hours to complete the polymerization, a polyalkyl (meth) acrylate rubber latex was obtained. A part of this latex was collected, and the particle size of the polyalkyl (meth) acrylate rubber was measured in the same manner as in Production Example 1. As a result, the dispersion was monodisperse with a peak at 0.1 μm. Further, this latex was dried to obtain a solid, which was extracted with toluene at 90 ° C. for 12 hours, and the gel content was measured to be 97.3%.

A mixture of 0.06 part of tert-butyl hydroperoxide and 12 parts of MMA was added to this polyalkyl (meth) acrylate rubber latex at 70 ° C. for 1 hour.
Dropwise over 5 minutes, then hold at 70 ° C. for 4 hours,
The graft polymerization of MMA onto the polyalkyl (meth) acrylate rubber was completed.

The conversion of MMA was 97.2%.
The obtained graft copolymer latex was dropped into 200 parts of hot water containing 1.0% of aluminum sulfate, coagulated, separated, washed, and dried at 75 ° C. for 16 hours to obtain a powdery acrylic rubber-based graft copolymer. (3) was manufactured and used as an impact strength modifier.

The glass transition temperature of the acrylic rubber-based graft copolymer (3) was measured in the same manner as in Production Example 1. The results are shown in Table 2. Table 1 shows the charged compositions.

(Examples 1 and 2) As Examples 1 and 2, acrylic rubber-based graft copolymers (1) and (2)
Was used as an impact strength modifier, and blended with a hard vinyl chloride resin to produce a vinyl chloride resin composition. The impact resistance, weather resistance, thermal stability, and processability (gelling behavior) of the obtained vinyl chloride resin composition were evaluated. The obtained results are shown in Table 2.

Comparative Example 1 An acrylic rubber-based graft copolymer (3) was mixed with a vinyl chloride resin in the same manner as in Example 1 to produce a vinyl chloride resin composition. The properties of the obtained vinyl chloride resin composition were evaluated in the same manner as in Example 1, and the obtained results are shown in Table 2.

(Comparative Example 2) Instead of the acrylic rubber-based graft copolymer, an MBS-based modifier was used as an impact strength modifier. A composition was prepared. The MBS used
The system modifier contains 70% of a rubber component composed of butadiene / styrene = 76/24, and methyl methacrylate /
A monomer mixture consisting of styrene = 70/40 is graft-polymerized to a final average particle size of 100 nm.

The properties of the obtained vinyl chloride resin composition were evaluated in the same manner as in Example 1, and the obtained results are shown in Table 2.

[0105]

[Table 1]

[0106]

[Table 2]

As shown in Table 2, the thermoplastic resin composition obtained by blending the acrylic rubber-based graft copolymers (1) and (2) with the resin as an impact strength modifier has a low processability. Excellent, thermal stability and impact resistance, especially at low temperatures. Further, after the weather resistance test, almost no fading occurred and the weather resistance was excellent.

The particle size of the polyacryl (meth) acrylate-based composite rubber (1) is, as shown in FIG.
It had peaks at around 2 μm and 0.7 μm, and 95% by mass of the total mass constituting the polyalkyl (meth) acrylate rubber was present in the particle size range of 0.05 to 0.4 μm. Although the particle size distribution is not shown here, the particle size distribution of the polyacryl (meth) acrylate-based composite rubber (2) also showed bidispersion. The particle size distribution of the polyacryl (meth) acrylate-based composite rubber (3) was monodispersed.

The acrylic rubber-based graft copolymers (1) and (2) each have a glass transition temperature Tg1 derived from the acrylic rubber (A1) component and an acrylic rubber (A2).
And Tg2 derived from the component, wherein Tg1 is lower than Tg2,
Both were below 10 ° C.

On the other hand, the acrylic rubber-based graft copolymer (3) differs from the acrylic rubber-based graft copolymers (1) and (2) in that it contains only one type of acrylic rubber (A2) component, The vinyl chloride resin composition of Comparative Example 1 containing the graft copolymer (3) had insufficient impact resistance.

Further, in the vinyl chloride resin composition of Comparative Example 2 containing MBS, the test piece after the weather resistance test faded, the weather resistance was insufficient, and the workability was somewhat insufficient.

[0112]

As described above, by using the acrylic rubber-based graft copolymer of the present invention as an impact strength modifier, it is possible to improve the impact resistance of the resin, especially the low temperature impact resistance, in a small amount. In addition, sufficient fading resistance, weather resistance, and workability can be realized.

[Brief description of the drawings]

FIG. 1 is an example of a measurement result of a particle size distribution.

[Explanation of symbols]

 10 Mass distribution 20 Integral value

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J002 AA001 AA011 AA021 BN112 BN122 FD20 GT00 4J011 AA05 KB19 PA69 PA78 PC06 4J026 AA45 AA48 AC22 BA05 BA24 BA27 BA31 BB03 BB04 DA04 DA13 DB04 DB15 FA03

Claims (12)

[Claims] 1. A polyalkyl (meth) acrylate composite rubber comprising a vinyl monomer (B) graft-polymerized to a polyalkyl (meth) acrylate composite rubber (A) and containing an acid group. (A) shows the glass transition temperature (T
g) comprises two or more different types of acrylic rubber components different from each other. 2. The polyalkyl (meth) acrylate-based composite rubber (A) includes 2-ethylhexyl acrylate, ethoxyethoxyethyl acrylate, methoxytripropylene glycol acrylate, 4-hydroxybutyl acrylate, lauryl methacrylate, tridecyl methacrylate and stearyl methacrylate. An acrylic rubber (A1) component obtained by polymerizing at least one selected from the group consisting of as a monomer component;
2. The acrylic rubber-based graft copolymer according to claim 1, comprising an acrylic rubber (A2) component obtained by polymerizing at least n-butyl acrylate as a monomer component. 3. The glass transition temperature (Tg1) of the acrylic rubber (A1) component is lower than the glass transition temperature (Tg2) of the acrylic rubber (A2) component, and Tg2 is 10 ° C. or less. The acrylic rubber-based graft copolymer according to the above. 4. The acrylic rubber-based graft copolymer according to claim 1, wherein the polyalkyl (meth) acrylate-based composite rubber (A) has a bidisperse particle size distribution. 5. The polyalkyl (meth) acrylate-based composite rubber (A) has a particle size distribution of 0.05 μm to 0.4 μm.
m is at least two peaks, and 70% by mass or more of the polyalkyl (meth) acrylate-based composite rubber (A) is 0.05 μm to 0.4%.
The acrylic rubber-based graft copolymer according to claim 4, having a particle size of µm. 6. The acrylic rubber-based graft copolymer according to claim 1, wherein the acid group is a carboxyl group. 7. The acrylic rubber-based graft copolymer according to claim 6, wherein the carboxyl group is derived from (meth) acrylic acid. 8. The acrylic rubber according to claim 1, wherein the compound (E) having a benzene ring skeleton having a sulfonyl group or a sulfate group is contained in an amount of 0.1 to 100,000 mass ppm. Graft copolymer. 9. An impact strength modifier comprising the acrylic rubber-based graft copolymer according to any one of claims 1 to 8. 10. The impact strength modifier 0.1 according to claim 9, wherein
A resin composition comprising -30 parts by mass and 100 parts by mass of a thermoplastic resin. 11. The resin composition according to claim 10, wherein the thermoplastic resin is a hard vinyl chloride resin. 12. A process for producing a polyalkyl (meth) acrylate-based composite rubber (A) by an emulsion polymerization method and said polyalkyl (meth) acrylate-based composite rubber (A)
And a step of graft-polymerizing the vinyl monomer (B) by an emulsion polymerization method.