JP3083515B1 - Impact strength modifier, production method, and vinyl chloride resin composition using the same - Google Patents

Abstract

An object of the present invention is to provide a resin composition having excellent weather resistance, particularly fading resistance and impact resistance. SOLUTION: With respect to 80 to 99.9% by weight of polyalkyl (meth) acrylate-based composite rubber (A) having a specific particle size distribution and glass transition temperature, 0.1 to 20 of vinyl-based monomer (B) is used. An impact strength modifier comprising an acrylic rubber-based graft copolymer in which the weight% is graft-polymerized is used. In particular, it is suitable for blending with hard vinyl chloride resin.

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 capable of imparting excellent weather resistance, particularly fading resistance and impact resistance, and a resin composition using the same.

[0002]

2. Description of the Related Art Vinyl chloride resin is a highly versatile resin, but has a drawback of poor impact resistance. In order to improve the impact resistance, many methods have been proposed.For example, a vinyl chloride resin is mixed with an MBS resin obtained by graft polymerization of methyl methacrylate, styrene or acrylonitrile on a butadiene rubber-like polymer. There is a way to use it. However, when the MBS resin is used in combination with a vinyl chloride resin, the impact resistance is improved, but the weather resistance is reduced, and the impact resistance is significantly reduced when the molded product is used outdoors. It is considered that the main cause of the decrease in weather resistance is due to ultraviolet degradation of the butadiene unit constituting the MBS resin.

[0003] Therefore, methyl methacrylate, styrene, acrylonitrile, or the like is graft-polymerized to a crosslinked alkyl (meth) acrylate rubber polymer comprising 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.

[0004]

However, when such an acrylic graft copolymer is used, the molded article produced is excellent in weather resistance and little in impact resistance, but exerts impact strength. For this purpose, it is necessary to add a large amount thereof, and there is a problem that the impact strength, particularly the impact strength at low temperature, is inferior to that of the MBS resin.

The present invention has been made in view of the above circumstances, and improves the impact resistance of a resin by adding a small amount thereof, especially the low-temperature impact resistance, and also provides the molded article obtained with a fade resistance, an impact resistance and the like. It is an object of the present invention to obtain an impact strength modifier which maintains the weather resistance of the steel.

[0006]

The object of the present invention is to provide a polyalkyl (meth) acrylate-based composite rubber (A) 80-9.
An acrylic rubber-based graft copolymer in which 20 to 0.1% by weight of a vinyl monomer (B) is graft-polymerized to 9.9% by weight, and a polyalkyl (meth) acrylate-based composite rubber (A) is used. And two or more types of acrylic rubber components having different glass transition temperatures, each acrylic rubber component containing a monomer having two or more unsaturated bonds in a molecule in a range of 20% by weight or less, and a polyalkyl The number distribution of the particle diameter of the (meth) acrylate-based composite rubber (A) is 0.05
a polydisperse distribution having at least two peaks in the range from μm to 0.4 μm, and 70% by weight or more of the polyalkyl (meth) acrylate-based composite rubber (A) is 0.05% or more.
The problem can be solved by an impact strength modifier characterized by particles having a particle size of from μm to 0.4 μm and a resin composition containing the impact strength modifier, particularly a vinyl chloride resin composition.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The polyalkyl (meth) acrylate-based composite rubber (A) used in the present invention is a composite rubber containing two or more types of acrylic rubber components having different glass transition temperatures. Each acrylic rubber component is obtained by polymerizing a monomer containing one or more alkyl (meth) acrylates, and has at least two unsaturated bonds in the molecule in the monomer. The monomer may be contained in a range of 20% by weight or less. Further, the monomers include styrene, α-methylstyrene, aromatic alkenyl compounds such as vinyl toluene, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, methacrylic acid-modified silicone, and various vinyl compounds such as fluorine-containing vinyl compounds. The system monomer may be contained as a copolymer component in a range of 30% by weight or less. The alkyl (meth) acrylate used is not particularly limited, and examples thereof include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, ethoxyethoxyethyl acrylate, methoxytripropylene glycol acrylate, -Hydroxybutyl acrylate, lauryl methacrylate, stearyl methacrylate and the like. These alkyl (meth) acrylates are used alone or in combination of two or more.

The monomer having two or more unsaturated bonds in the molecule has a role as a crosslinking agent or a graft-crosslinking agent. Examples of the crosslinking agent include ethylene glycol dimethacrylate and propylene glycol dimethacrylate. 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate,
Silicones such as divinylbenzene and polyfunctional methacrylic group-modified silicones are exemplified. 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. These cross-linking agents and graft crossing agents are used alone or in combination of two or more.

The polyalkyl (meth) acrylate-based composite rubber (A) contains two or more of the above-mentioned acrylic rubber components, and those acrylic rubber components having different glass transition temperatures are used. The obtained polyalkyl (meth) acrylate-based composite rubber (A)
It preferably has two or more glass transition temperatures at 10 ° C. or lower, and at least one glass transition temperature is n−
It is preferably lower than the glass transition temperature of the butyl acrylate homopolymer. When the glass transition temperature of the polyalkyl (meth) acrylate-based composite rubber (A) is in such a case, the resulting impact strength modifier can impart more impact resistance, and is thus preferable. Here, the glass transition temperature of the polymer is measured as a transition point of Tan δ measured by a dynamic mechanical property analyzer (hereinafter, DMA). Generally, a polymer obtained from a monomer has a unique glass transition temperature, and a single transition point is observed for a single component (a random copolymer of a single component or a plurality of components), but a mixture of a plurality of components, Alternatively, a unique transition point is observed in each of the composited polymers. For example, if it consists of two components,
Two transition points are observed. Ta measured by DMA
In the nδ curve, two peaks are observed, but when there is a bias in the composition ratio or when the transition temperature is close, the respective peaks may approach each other, and may be observed as a peak having a shoulder portion. However, it can be distinguished from a simple one-peak curve seen in the case of a single component.
The glass transition temperature of an n-butyl acrylate homopolymer varies depending on the presence or absence and degree of crosslinking. The expression “below the glass transition temperature of the n-butyl acrylate homopolymer” used herein means that, when there is a component in which n-butyl acrylate is used, the glass transition temperature of this component alone and the other component are used. Comparing the glass transition temperature of the component alone, the glass transition temperature of the other component is n-
Preferably, the glass transition temperature is lower than that of the component in which butyl acrylate is used. If n-butyl acrylate is not used, the monomer of each component is replaced with n-butyl acrylate, and a crosslinking agent or a grafting agent is used. When a cross-linking agent is used, these and the mole fraction of the monomer to be cross-linked are set to be equal, and when the glass transition temperatures of the respective polymers obtained by polymerization are compared, It is preferable that the above condition is satisfied.

The polyalkyl (meth) acrylate-based composite rubber (A) is not particularly limited as long as it contains two or more acrylic rubber components having different glass transition temperatures.
-An acrylic rubber (A1) component containing at least one of ethylhexyl acrylate, ethoxyethoxyethyl acrylate, methoxytripropylene glycol acrylate, 4-hydroxybutyl acrylate, lauryl methacrylate, and stearyl methacrylate as components, and n-butyl acrylate. What consists of an acrylic rubber (A2) component contained as a constituent component
It is preferable because it has excellent impact resistance. Further, when the acrylic rubber (A1) contains at least one of 2-ethylhexyl acrylate, lauryl methacrylate, and stearyl methacrylate as a component, impact resistance, particularly at low temperatures, is improved. It is more preferable because it has excellent impact resistance. When using stearyl methacrylate or the like which has crystallinity at around room temperature, it is used by mixing with a monomer which dissolves it. Further, 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 changed by the glass transition temperature (Tg) derived from the acrylic rubber (A2) component.
It is preferable that the temperature is lower than 2) because the impact resistance at low temperatures is excellent.

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 simple rubber containing one or more alkyl (meth) acrylates is used. Polymerize the monomer
A method in which a first acrylic rubber component latex is obtained, and then a monomer constituting a second acrylic rubber component is added to the acrylic rubber component latex, impregnated, and then polymerized in the presence of a radical polymerization initiator. And the like. Polyalkyl (meth) acrylate-based composite rubber (A) in which two types of acrylic rubber components are composited with the progress of polymerization
Latex is obtained. In addition, it can be produced by a method such as drop polymerization of the second rubber in the presence of the first rubber, or a method of enlarging the composite rubber with an acid or a salt.

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 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, but may be usually emulsion polymerization, and if necessary, forced emulsion polymerization. In particular, for the polymerization of the acrylic rubber (A1) component preferably used in the present invention, forced emulsion polymerization is preferably used. Can be Further, since 2-ethyl acrylate, lauryl methacrylate, and stearyl methacrylate are poorly water-soluble as monomers constituting the acrylic rubber (A1) component, it is preferable to produce the acrylic rubber (A1) component by forced emulsion polymerization. . Here, a known arbitrary surfactant such as anionic, nonionic or cationic can be used as the emulsifier and the dispersion stabilizer. The mixture can be used if necessary, but it is preferable to use an emulsifier having a large micelle-forming ability and a small emulsifier in combination.

The obtained polyalkyl (meth) acrylate-based composite rubber (A) has a number distribution of particle diameters of 0.1 to 0.1.
A polydisperse distribution having at least two peaks in a range of from 0.05 μm to 0.4 μm, and 70% by weight or more of the polyalkyl (meth) acrylate-based composite rubber (A) has a particle size of from 0.05 μm to 0.4 μm It is necessary that the particles have the following. Here, the number distribution means a certain particle diameter d.
₅ is a distribution in which the number ratio of particles within a minute interval between _p and d _p + Δd _p 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 such a particle size distribution is used as an impact strength modifier, even when a small amount is blended with the resin, the resin has an excellent resistance. Impact resistance can be imparted, which is preferable. Furthermore, 0.05-0.15 μm and 0.15-
An impact strength modifier using a polyalkyl (meth) acrylate-based composite rubber (A) showing a particle size distribution having at least one or more peaks at 0.4 μm each is preferable because higher impact resistance can be imparted. .

A vinyl monomer (B) to be graft-polymerized to the 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 having two or more unsaturated bonds in the molecule, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate,
A crosslinking agent such as 1,4-butylene glycol dimethacrylate, divinylbenzene, a silicone such as a polyfunctional methacryl group-modified silicone, or a graft crossing agent such as allyl methacrylate, triallyl cyanurate, triallyl isocyanurate is used in an amount of 20% by weight or less. You may use it adding in a range.

The ratio of the polyalkyl (meth) acrylate rubber (A) to the vinyl monomer (B) in the acrylic rubber graft copolymer is such that the polyalkyl (meth) acrylate rubber is 80 to 99. 9% by weight, 20 to 0.1% by weight of the vinyl monomer (B), preferably 85 to 95% by weight of the polyalkyl (meth) acrylate composite rubber (A), B) is 1
5 to 5% by weight. If the amount of the vinyl monomer (B) is less than 0.1% by weight, the dispersibility of the obtained acrylic rubber-based graft copolymer in the resin is reduced, and the processability of the resin composition obtained by blending the same is reduced. May decrease. Meanwhile, 2
If the content exceeds 0% by weight, the impact strength of the acrylic rubber-based graft copolymer may be reduced.

The acrylic rubber-based graft copolymer is obtained by adding a vinyl-based monomer (B) to a latex of a polyalkyl (meth) acrylate-based composite rubber (A) and polymerizing it in one or more stages by radical polymerization. . Acrylic rubber-based graft copolymer, this graft copolymer latex, sulfuric acid, acid such as hydrochloric acid, calcium chloride, calcium acetate, or poured into hot water dissolved metal salts such as magnesium sulfate, salting out, It is obtained as particles by coagulation, separation and recovery. 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. The acrylic rubber-based graft copolymer thus obtained is
Hard vinyl chloride resin (PVC)
(Based resin).

The resin to which the impact strength modifier is blended is not limited to hard vinyl chloride resin (PVC resin), but also semi-hard, soft vinyl chloride resin (PVC resin), polypropylene (PP), polyethylene (PE). ), Polystyrene (PS), high impact polystyrene (HIPS), (meth) acrylate
Styrene resin (St resin) such as styrene copolymer (MS), styrene / acrylonitrile copolymer (SAN), styrene / maleic anhydride copolymer (SMA), ABS, ASA, AES, polymethacrylic acid Acrylic resin (Ac resin) such as methyl (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 /
PC-based resin such as PBT / PEs-based resin alloy, polyolefin-based resin / TPE, alloy of olefin-based resins such as PP / PE, PPE / HIPS, PPE / P
BT, PPE resin alloys such as PPE / PA, PVC
And polymer alloys such as PVC resin / Ac resin alloy such as / PMMA.

The resin composition obtained by blending the impact strength modifier may contain a conventional stabilizer at the time of compounding, kneading, molding, etc., depending on the purpose, as long as the physical properties are not impaired. , Fillers and the like can be added. Examples of the stabilizer include lead-based stabilizers such as tribasic lead sulfate, dibasic lead phosphite, basic lead sulfite, and lead silicate; and metals such as potassium, magnesium, barium, zinc, cadmium, and lead. And metal soaps derived from fatty acids such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, oleic acid, ricinoleic acid, linoleic acid, and behenic acid, and alkyl groups , An organic tin-based stabilizer derived from an ester group and a fatty acid salt, a maleate, or a sulfide-containing compound, Ba-Zn-based, Ca-Zn-based, Ba-Ca-S
n-based, Ca-Mg-Sn-based, Ca-Zn-Sn-based, Pb
-Sn-based, Pb-Ba-Ca-based composite metal soap-based stabilizers, barium, metal groups such as zinc and 2-ethylhexanoic acid, isodecanoic acid, branched fatty acids such as trialkylacetic acid, oleic acid, ricinoleic acid, Metal salt stabilizers usually derived from two or more organic acids such as unsaturated fatty acids such as linoleic acid, alicyclic acids such as naphthenic acid, and aromatic acids such as phenolic acid, benzoic acid, salicylic acid, and substituted derivatives thereof. , These stabilizers as petroleum hydrocarbons, alcohols,
Dissolves in organic solvents such as glycerin derivatives, and furthermore, phosphites, epoxy compounds, color development inhibitors, transparency improvers, light stabilizers, antioxidants, plate-out inhibitors,
In addition to metal-based stabilizers such as metal salt liquid stabilizers and the like, which contain stabilizing aids such as lubricants, epoxy compounds such as epoxy resins, epoxidized soybean oil, epoxidized vegetable oils, epoxidized fatty acid alkyl esters, and phosphorus Alkyl group,
Organic phosphites substituted with an aryl group, a cycloalkyl group, an alkoxyl group or the like and having an aromatic compound such as a dihydric alcohol such as propylene glycol, hydroquinone or bisphenol A; BHT, sulfur or a methylene group; UV absorbers such as hindered phenols such as bisphenols, salicylic acid esters, benzophenone and benzotriazole, light stabilizers of hindered amines or nickel complex salts, carbon blacks, UV shielding agents such as rutile type titanium oxide, trimerol propane, Polyhydric alcohols such as pentaerythritol, sorbitol and mannitol, β-aminocrotonates, 2-phenylindoles, nitrogen-containing compounds such as diphenylthiourea and dicyandiamide, dialkylthiodipro Non-metallic stabilizers such as sulfur-containing compounds such as onion esters, keto compounds such as acetoacetate, dehydroacetic acid, and β-diketone; organosilicon compounds; borate esters; and the like, alone or in combination of two or more Used as

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.

In addition, 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 ester-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 polyhydric carboxylic 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 polycondensates of about 600 to 8,000 whose ends are sealed with monohydric alcohol or monocarboxylic acid, 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 of blending the impact strength modifier of the present invention with a resin to produce a resin composition is not particularly limited, and a usual method can be used, but it is usually preferable to produce by a melt mixing method. Moreover, you may use a small amount of solvent as needed. Examples of an apparatus to be used include an extruder, a Banbury mixer, a roller, a kneader, and the like, which are operated batchwise or continuously. The order of mixing the components is not particularly limited. The use of the obtained vinyl chloride resin composition is not limited. For example, building materials, automobiles, toys, stationery, and other miscellaneous goods, as well as OA equipment, home electric appliances, and other molded products requiring impact resistance. Widely used for.

[0022]

The present invention will be described in more detail with reference to the following examples and comparative examples. "Parts" in the description is "parts by weight"
And “%” indicates “% by weight”. (Production Example 1) Production of acrylic rubber-based graft copolymer (1) 99.5 parts of 2-ethylhexyl acrylate and 0.5 part of allyl methacrylate were mixed to obtain 100 parts of a (meth) acrylate monomer mixture. 100 parts of the above (meth) acrylate monomer mixture was added to 195 parts of distilled water in which 1 part of dipotassium alkenyl succinate was dissolved, and the mixture was preliminarily stirred with a homomixer at 10,000 rpm, and then pressured to 300 kg / cm ^{2 with} a homogenizer. To obtain a (meth) acrylate emulsion. This mixed solution was transferred to a separable flask equipped with a condenser and a stirring blade, and heated while being replaced with nitrogen and mixed with stirring. When the temperature reached 50 ° C., 0.5 parts of tert-butyl hydroperoxide was added, and then the temperature was raised to 50 ° C. Then, ferrous sulfate 0.002 part, ethylenediaminetetraacetic acid disodium salt 0.006 part, Rongalite 0.26 part and distilled water 5
Parts of the mixed solution, the mixture was left for 5 hours to complete the polymerization, and an acrylic rubber (A1) component latex was obtained. The polymerization rate of the obtained acrylic rubber (A1) component latex is 99.9%.
Met. This latex was coagulated and dried with ethanol to obtain a solid, and extracted with toluene at 90 ° C. for 12 hours.
The gel content was determined to be 92.4%.

The acrylic rubber (A1) component latex was sampled so that the solid content of poly-2-ethylhexyl acrylate containing allyl methacrylate was 10 parts, put into a separable flask equipped with a stirrer, and distilled water in the system. Was added to be 195 parts, and then a mixture of 78 parts of n-butyl acrylate containing 2.0% of allyl methacrylate constituting the acrylic rubber (A2) component and 0.32 parts of tert-butyl hydroperoxide was added. The mixture was stirred for 10 minutes, and the mixed solution was permeated into the acrylic rubber (A1) component particles. Further, 0.5 part of polyoxyethylene ether sulfate was added, and the mixture was further stirred for 10 minutes.
A radical polymerization was started by charging 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, and then kept at an internal temperature of 70 ° C. for 2 hours. After completion of the polymerization, a latex of a polyalkyl (meth) acrylate-based composite rubber comprising an acrylic rubber (A1) component and an acrylic rubber (A2) component was obtained. Take a part of this latex,
This was used for the 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. 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 was added dropwise to the polyalkyl (meth) acrylate-based composite rubber latex at 70 ° C. for 15 minutes, and then maintained at 70 ° C. for 4 hours. Thus, the graft polymerization to the polyalkyl (meth) acrylate-based composite rubber was completed. The polymerization rate of methyl methacrylate was 99.4%. The obtained acrylic rubber-based graft copolymer latex was dropped into 200 parts of hot water containing 1.5% of calcium chloride, coagulated, separated, washed, and dried at 75 ° C. for 16 hours.
A powdery acrylic rubber-based graft copolymer (1) was produced and used as an impact strength modifier. Further, the glass transition temperature of the acrylic rubber-based graft copolymer (1) was measured. The measured glass transition temperature is a value derived from a polyalkyl (meth) acrylate-based composite rubber. Table 2 shows the results. Table 1 summarizes the above charged compositions. The particle size distribution measurement and the glass transition temperature measurement were performed as follows.

Measurement of Particle Size Distribution of Polyalkyl (meth) acrylate Composite Rubber The obtained latex was diluted with distilled water as a sample and measured using a CHDF2000 type particle size distribution meter manufactured by MATEC, USA. 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 almost neutral, the flow rate is 1.4 ml / min, and the pressure is about 4000 ps.
i. While maintaining the temperature at 35 ° C., 0.1 ml of a diluted latex sample having a concentration of about 3% was used for 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.・ Measurement of glass transition temperature of acrylic rubber-based graft copolymer 70 parts of the obtained acrylic rubber-based graft copolymer (1) and 30 parts of polymethyl methacrylate (PMMA) were both subjected to 250 ° C. 25φ single-screw extruder. Pellets, 20
Using a press machine set at 0 ° C., a plate prepared to a thickness of 3 mm was cut out to a width of about 10 mm and a length of 12 mm,
Instruments DMA 983,
Measured under the condition of a temperature rising rate of 2 ° C./min, the obtained Tan
The temperature corresponding to the transition point of the δ curve was determined as the glass transition temperature.

(Production Examples 2 to 3) Production of Acrylic Rubber Graft Copolymers (2) to (3) The same as Production Example 1 except that the weight ratio between the A1 component and the A2 component was set to the ratio shown in Table 1. Acrylic rubber-based graft copolymers (2) to (3) comprising an acrylic rubber (A1) component and an acrylic rubber (A2) component were produced by a method and used as an impact strength modifier. Further, in the same manner as in Production Example 1, the particle size distribution of the polyalkyl (meth) acrylate-based composite rubber was measured, and the acrylic rubber-based graft copolymer (2) to
The glass transition temperature of (3) was measured. Table 2 shows the results. 1 and 2 show the particle size distribution of the polyalkyl (meth) acrylate-based composite rubber produced in Production Example 2. FIG. 1 shows the number distribution, and FIG. 2 shows the weight distribution.

(Production Example 4) Production of acrylic rubber-based graft copolymer (4) 295 parts of distilled water and 0.1 part of sodium dodecylbenzenesulfonate were added to a separable flask equipped with a stirrer, followed by purging with nitrogen. To 50 ° C., 83.3 parts of n-butyl acrylate, 1.7 allyl methacrylate
And a mixture of 0.4 parts of tert-butyl hydroperoxide was charged and stirred for 30 minutes, and the mixture was permeated into the polyorganosiloxane particles. Then, sulfuric acid 1
A mixture of 0.002 part of iron, 0.006 part of disodium ethylenediaminetetraacetate, 0.26 part of Rongalit and 5 parts of distilled water was charged to start radical polymerization, and then kept at 710 ° C. for 2 hours to carry out polymerization. Upon completion, a polyalkyl (meth) acrylate rubber latex consisting only of the acrylic rubber (A2) component was obtained. A part of this latex was collected, and the average particle size of the polyalkyl (meth) acrylate rubber was measured in the same manner as in Production Example 1.
It was monodisperse with a peak at 2 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%. To this polyalkyl (meth) acrylate rubber latex, tert-butyl hydroperoxide 0.0
A mixture of 6 parts and 15 parts of methyl methacrylate was heated to 70 ° C.
For 15 minutes, and then maintained at 70 ° C. for 4 hours to complete the graft polymerization to the polyalkyl (meth) acrylate rubber. The polymerization rate of methyl methacrylate was 97.2%. The obtained graft copolymer latex was dropped into 200 parts of hot water containing 1.5% calcium chloride, coagulated, separated, washed, and dried at 75 ° C. for 16 hours to obtain a powdery acrylic rubber-based graft copolymer. (4) was manufactured and used as an impact strength modifier. Further, in the same manner as in Production Example 1, the glass transition temperature of the acrylic rubber-based graft copolymer (4) was measured. Table 2 shows the results. Table 1 summarizes the charge composition.

(Examples 1 to 3) In Examples 1 to 3, acrylic rubber-based graft copolymers (1) to (3) were used as impact modifiers, respectively, and were blended into a hard vinyl chloride resin. A vinyl chloride resin composition was manufactured. The impact resistance and weather resistance of the obtained vinyl chloride resin composition were evaluated by the following methods. Table 2 shows the results.

Impact resistance: Evaluated by Izod impact resistance. The following two kinds of vinyl chloride resin compositions (formulations A and B) were prepared and the temperature was adjusted to 190 ° C.
Using a 5 mmφ single screw extruder, a ”″ × １ ／ ″ square bar was extruded and evaluated according to the method of ASTM D256. Incidentally, the vinyl chloride resin composition of Formulation A was mixed at 23 ° C.
Of the vinyl chloride resin composition was measured at 0 ° C., and described in the table as measurement A and measurement B, respectively. Formulation A: vinyl chloride resin (degree of polymerization: 700) 100 parts Dibutyltin malate 3.5 parts Stearyl alcohol 0.8 parts Processing aid Metablen P-700 0.4 parts Carbon black 0.5 parts Modifier 7.5 parts Formulation B: vinyl chloride resin (degree of polymerization 1100) 100 parts dibasic lead phosphite 2.5 parts dibasic lead stearate 0.7 parts lead stearate 0.5 parts calcium stearate 0.9 parts polyethylene wax ( (Molecular weight 2200) 0.1 part Calcium carbonate 5.0 parts Processing aid (METABLEN P-501) 1.0 part Carbon black 0.5 part Modifier 7.5 parts And then kneading at 200 ° C., 15 rpm for 5 minutes using a 6 inch test roll machine of Kansai Roll Co., Ltd.
Sandwiched in a mold at 200 ° C for 6 minutes, then 50kg / cm
^Two The sheet test piece obtained by cooling while applying pressure was applied to an eye super UV tester manufactured by Dainippon Plastics Co., Ltd., which was adjusted to 60 ° C., for 8 hours.
The operation of placing the sample in a thermo-hygrostat adjusted to 5% and humidity for 16 hours was repeated 5 times, and the appearance of the sheet test piece was visually evaluated. In the table, ○ indicates good fading resistance and X indicates bad.

Comparative Examples 1 and 2 In Comparative Example 1, an acrylic rubber-based graft copolymer (4) was used. In Comparative Example 2, a commercially available MBS-based modifier “METABLEN C- 223 "was used as an impact strength modifier, and mixed with a vinyl chloride resin in the same manner as in Example 1 to produce a vinyl chloride resin composition. The impact resistance and weather resistance of the obtained vinyl chloride resin composition were evaluated in the same manner as in Example 1. Table 2 shows the results.

[0030]

[Table 1]

[0031]

[Table 2]

As shown in Tables 1 and 2, the vinyl chloride resin compositions containing the acrylic rubber-based graft copolymers (1) to (3) of Production Examples 1 to 3 as impact modifiers were weather resistant and impact resistant. The properties were both excellent and the low-temperature impact properties were also good. In addition, as shown in FIG. 1, the particle diameter of the polyacryl (meth) acrylate-based composite rubber of Production Example 2 has peaks at 0.11 μm and 0.19 μm in the number distribution. From the weight distribution shown in FIG. 2, 90% of the total weight of the polyalkyl (meth) acrylate rubber
It can be seen that the above exists in the range of the particle diameter of 0.05 to 0.4 μm. Although the graph is omitted here, the particle diameter distributions of the polyalkyl (meth) acrylate-based composite rubbers produced in Production Examples 1 and 3 also showed almost the same bidispersion. Further, the acrylic rubber-based graft copolymers (1) to (3) of Production Examples 1 to 3 each have a glass transition temperature Tg1 derived from the A1 component and a Tg2 derived from the A2 component, and Tg1 is higher than Tg2. And both were below 10 ° C.
On the other hand, the acrylic rubber-based graft copolymer (4) of Production Example 4 is the same as the acrylic rubber-based graft copolymer (1).
Unlike (3), a polyacryl (meth) acrylate rubber containing one type of acrylic rubber (A2) component is used, and the vinyl chloride of Comparative Example 1 blended with an acrylic rubber graft copolymer (4) The resin composition was inferior in impact resistance, and the vinyl chloride resin composition of Comparative Example 2 in which the MBS-based modifier “METABLEN C-223” was blended, the test piece after the weather resistance test faded, and the weather resistance was poor. Was not enough.

[0033]

As described above, the impact strength modifier of the present invention can be added in a small amount to improve the impact resistance of a resin, especially the low-temperature impact resistance, and to improve the fading resistance of the obtained molded article. And good weather resistance such as impact resistance. Particularly, the compounding with a vinyl chloride resin is suitable. Further, the resin composition containing such an impact strength modifier is excellent in both impact resistance and weather resistance.

[Brief description of the drawings]

FIG. 1 is a graph showing a particle size distribution (number distribution) of a polyalkyl (meth) acrylate rubber according to an example of the present invention.

FIG. 2 is a graph showing a particle size distribution (weight distribution) of a polyalkyl (meth) acrylate rubber according to an example of the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08L 51/06 C08L 27/06 C08F 265/06

Claims (8)

(57) [Claims] 1. An acrylic rubber-based graft obtained by graft-polymerizing 20 to 0.1% by weight of a vinyl monomer (B) with 80 to 99.9% by weight of a polyalkyl (meth) acrylate-based composite rubber (A). Polyalkyl (meth) acrylate-based composite rubber (A) consisting of a copolymer
Contains two or more types of acrylic rubber components having different glass transition temperatures, each acrylic rubber component contains a monomer having two or more unsaturated bonds in a molecule in a range of 20% by weight or less, and The particle size distribution of the alkyl (meth) acrylate-based composite rubber (A) is 0.05 μm to 0.4 μm.
a bidisperse distribution having at least two peaks at μm, and 70% by weight or more of the polyalkyl (meth) acrylate-based composite rubber (A) is 0.05 μm to 0.4 μm.
An impact strength modifier comprising particles having a particle size of μm. 2. The impact strength modifier according to claim 1, wherein the polyalkyl (meth) acrylate-based composite rubber (A) has two or more glass transition temperatures at 10 ° C. or lower. 3. The polyalkyl (meth) acrylate-based composite rubber (A) has two or more glass transition temperatures, and at least one glass transition temperature is lower than the glass transition temperature of an n-butyl acrylate homopolymer. The impact strength modifier according to claim 1, characterized in that: 4. The polyalkyl (meth) acrylate-based composite rubber (A) comprises at least one of 2-ethylhexyl acrylate, ethoxyethoxyethyl acrylate, methoxytripropylene glycol acrylate, 4-hydroxybutyl acrylate, lauryl methacrylate, and stearyl methacrylate. It is composed of an acrylic rubber (A1) component containing one type as a component and an acrylic rubber (A2) component containing n-butyl acrylate as a component, and has a glass transition temperature (Tg) derived from the acrylic rubber (A1) component.
The impact strength modifier according to claim 1, wherein 1) is lower than the glass transition temperature (Tg2) derived from the acrylic rubber (A2) component. 5. The polyalkyl (meth) acrylate-based composite rubber (A) has a number distribution of particle diameters of 0.05 to 0.1.
5 μm and at least 0.15 to 0.45 μm respectively
The impact strength modifier according to claim 1, wherein the impact strength modifier has a particle size distribution having two or more peaks. 6. The polyalkyl (meth) acrylate-based composite rubber (A) comprises at least one of 2-ethylhexyl acrylate, ethoxyethoxyethyl acrylate, methoxytripropylene glycol acrylate, 4-hydroxybutyl acrylate, lauryl methacrylate, and stearyl methacrylate. It is obtained by emulsion polymerization of a monomer containing n-butyl acrylate constituting an acrylic rubber (A2) component in the presence of an acrylic rubber (A1) component containing one kind as a component. 5. The method for producing an impact strength modifier according to any one of 1 to 4. 7. An acrylic rubber (A1) component containing at least one of 2-ethylhexyl acrylate, ethoxyethoxyethyl acrylate, methoxytripropylene glycol acrylate, 4-hydroxybutyl acrylate, lauryl methacrylate and stearyl methacrylate as a component. 5. The method for producing an impact strength modifier according to claim 1, wherein the impact strength modifier is obtained by forced emulsion polymerization. 8. A vinyl chloride resin composition comprising the impact strength modifier according to claim 1 and a hard vinyl chloride resin.