JP3465056B2 - Crosslinked rubber latex composition and use thereof - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a crosslinked rubber latex composition and its use, and more specifically, a crosslinked rubber mainly composed of an ethylene / α-olefin / non-conjugated polyene copolymer rubber containing a specific polyene component. Latex composition and uses thereof.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION A latex composition containing ethylene / α-olefin / polyene amorphous copolymer as a main component and a method for producing the same are known from Japanese Patent Publication No. 5-82415 and are A method of crosslinking an aqueous dispersion with ionizing radiation is known from JP-A-52-121054. Further, the use of crosslinked rubber latex as a resin modifier is disclosed in JP-A-62-205.
32, JP-A-62-89716, and the like. Furthermore, Japanese Laid-Open Patent Publication No.
JP-A No. 1-238842 contains an ethylene / α-olefin / polyene amorphous copolymer and a low molecular weight α-olefin copolymer and / or a modified low molecular weight α-olefin copolymer. A latex composition is disclosed in which crosslinks are formed in the amorphous copolymer component. As a preferred polyene component constituting the ethylene / α-olefin / polyene amorphous copolymer,
1,4-hexadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinylnorbornene are listed.

However, when the inventors of the present application retested the latex compositions described in the above-mentioned respective publications, it was confirmed that these latex compositions were
For example, acrylonitrile-styrene copolymer resin (AS
Although the performance of resin as a resin modifier is recognized,
The effect of modifying impact resistance and surface gloss is still insufficient.

The above-mentioned ethylene / α-olefin / polyene amorphous copolymer (hereinafter referred to as ethylene / α-olefin / non-conjugated polyene copolymer rubber) itself has excellent weather resistance and solvent resistance. Therefore, it is indispensable as a component of latex used as a resin modifier.

Therefore, the resin which could not be formed into a resin molding excellent in impact resistance and surface gloss,
A resin molded product with excellent impact resistance and surface gloss can be formed without impairing the excellent weather resistance and solvent resistance originally possessed by ethylene / α-olefin / non-conjugated polyene copolymer rubber. The advent of latex compositions that can be modified into resins is desired. Here, "excellent in surface gloss" means that the surface glossiness is high.

The inventors of the present invention have prepared an ethylene / α-olefin / non-conjugated polyene copolymer rubber containing a specific non-conjugated polyene component and a low molecular weight polyethylene or a low molecular weight ethylene / α-olefin copolymer. A crosslinked rubber latex composition was prepared by subjecting a latex composition compounded in a specific ratio to a crosslinking treatment to form crosslinks in the rubber component, and then the composition was used as a resin modifier for an AS resin. By the way, ethylene / α-olefin /
Acrylonitrile / ethylene copolymer / styrene resin (AES resin) moldings excellent in impact resistance and surface gloss without impairing the excellent weather resistance and solvent resistance originally possessed by the non-conjugated polyene copolymer rubber The present invention has been completed and the present invention has been completed.

[0007]

An object of the present invention is to solve the problems associated with the prior art as described above, and to provide a resin for which a resin molded article excellent in impact resistance and surface gloss could not be formed. , Ethylene / α-olefin / non-conjugated polyene copolymer rubber can be formed into a resin molded product with excellent impact resistance and surface gloss without impairing the excellent weather resistance and solvent resistance originally possessed by the rubber. It is an object of the present invention to provide a crosslinked rubber latex composition that can be modified into a resin that can be obtained.

Further, the present invention, compared with the conventional AES resin, does not impair the excellent weather resistance and solvent resistance originally possessed by the ethylene / α-olefin / non-conjugated polyene copolymer rubber, and has impact resistance. Another object of the present invention is to provide an AES resin capable of forming a molded article having excellent surface gloss.

[0009]

SUMMARY OF THE INVENTION A crosslinked rubber latex composition according to the present invention comprises [I] ethylene, an α-olefin having 3 to 20 carbon atoms and at least one branched chain polyene compound represented by the following general formula [I]. 100 parts by weight of ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) and [II] low molecular weight polyethylene, low molecular weight ethylene / α-olefin copolymer, unsaturated carboxylic acid compound-modified low molecular weight polyethylene And 2 to 30 parts by weight of at least one low molecular weight (co) polymer (B) selected from the group consisting of unsaturated carboxylic acid compound-modified low molecular weight ethylene / α-olefin copolymers. A latex composition comprising the ethylene / α-olefin /
The non-conjugated polyene copolymer rubber (A) component is characterized in that cross-links are formed.

[0010]

[Chemical 2]

[In the formula [I], n is an integer of 1 to 5,
R ¹ is an alkyl group having 1 to 5 carbon atoms, and R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The first AES resin according to the present invention is obtained by subjecting the crosslinked rubber latex composition according to the present invention as described above to emulsion graft polymerization of acrylonitrile and styrene, and acrylonitrile and the above-mentioned ethylene / α-olefin / non-olefin. It is characterized by comprising a copolymer of a conjugated polyene copolymer rubber (A) and styrene.

The second AES resin according to the present invention is
Acrylonitrile obtained by blending a dry product obtained by emulsion-grafting acrylonitrile and styrene with the crosslinked rubber latex composition according to the present invention as described above and acrylonitrile-styrene resin (AS resin) And a copolymer of ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) and styrene.

[0013]

DETAILED DESCRIPTION OF THE INVENTION The crosslinked rubber latex composition according to the present invention and its use will be specifically described below.

The crosslinked rubber latex composition according to the present invention comprises: [I] ethylene / α-olefin / non-conjugated polyene copolymer rubber (A); [II] low molecular weight polyethylene;
At least one selected from the group consisting of a low molecular weight ethylene / α-olefin copolymer, an unsaturated carboxylic acid compound-modified low molecular weight polyethylene, and an unsaturated carboxylic acid compound-modified low molecular weight ethylene / α-olefin copolymer
It contains a low molecular weight (co) polymer (B) of a seed in a specific proportion.

Ethylene / α-olefin / non-conjugated polyene
Copolymer rubber (A) The ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) used as the base polymer in the crosslinked rubber latex composition of the present invention is a random copolymer rubber, It consists of ethylene, an α-olefin having 3 to 20 carbon atoms, and a branched polyene compound.

Specific examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene,
1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-
Pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene,
1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like can be mentioned. Among them, propylene, 1-butene, 1-hexene and 1-octene are preferably used.

These α-olefins can be used alone or in combination of two or more. The branched polyene compound is represented by the following general formula [I].

[0018]

[Chemical 3]

In the formula [I], n is an integer of 1 to 5 and R
¹ is an alkyl group having 1 to 5 carbon atoms, and R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

As the alkyl group having 1 to 5 carbon atoms,
Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, i-pentyl group, etc. Is mentioned.

Examples of such a branched polyene compound (hereinafter also referred to as a branched polyene compound [I]) include the compounds specifically exemplified in the following (1) to (24). Among them, (5), (6), (9),
Branched chain polyene compounds (11), (14), (19) and (20) are preferably used. (1) 4-ethylidene-1,6-octadiene (2) 7-methyl-4-ethylidene-1,6-octadiene (3) 7-methyl-4-ethylidene-1,6-nonadiene (4) 7-ethyl -4-Ethylidene-1,6-nonadiene (5) 6,7-dimethyl-4-Ethylidene-1,6-octadiene (6) 6,7-Dimethyl-4-ethylidene-1,6-nonadiene (7) 4 -Ethylidene-1,6-decadiene (8) 7-methyl-4-ethylidene-1,6-decadiene (9) 7-methyl-6-propyl-4-ethylidene-1,6-octadiene (10) 4-ethylidene -1,7- Nonadiene (11) 8-methyl-4-ethylidene-1,7-nonadiene (EM
N) (12) 4-ethylidene-1,7-undecadiene (13) 8-methyl-4-ethylidene-1,7-undecadiene (14) 7,8-dimethyl-4-ethylidene-1,7-nonadiene (15 ) 7,8-Dimethyl-4-ethylidene-1,7-decadiene (16) 7,8-Dimethyl-4-ethylidene-1,7-undecadiene (17) 8-Methyl-7-ethyl-4-ethylidene-1 , 7- Undecadiene (18) 7,8-Diethyl-4-ethylidene-1,7-decadiene (19) 9-Methyl-4-ethylidene-1,8-decadiene (20) 8,9-Dimethyl-4-ethylidene -1,8-decadiene (21) 10-methyl-4-ethylidene-1,9-undecadiene (22) 9,10-dimethyl-4-ethylidene-1,9-undecadiene (23) 11-methyl-4-ethylidene -1,10-Dodecadiene (24) 10,11-Dimethyl-4-ethylidene-1,10-dodecadiene These can be used alone or in combination of two or more kinds.

The above branched polyene compound [I] is
It may be a mixture of trans isomer and cis isomer, and may be trans isomer alone or cis isomer alone. Such a branched chain polyene compound can be prepared by the method described in the specification of Japanese Patent Application No. 6-154952 filed by the applicant of the present application.

That is, it can be produced by reacting a compound having a conjugated diene represented by the following [Ia] with ethylene in the presence of a catalyst composed of a transition metal compound and an organoaluminum compound.

[0024]

[Chemical 4]

(In the formula [Ia], n, R ¹ , R ² and R
³ is n in the general formula [I] described above,
Same as R ¹ , R ² and R ³ . ) The ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) used in the present invention is a structural unit derived from the above-mentioned monomers of ethylene, α-olefin and a branched polyene compound. Has a branched structure derived from the branched chain polyene compound by randomly arranging and bonding, and the main chain has a substantially linear structure.

The fact that this copolymer rubber has a substantially linear structure and does not substantially contain a gelled crosslinked polymer means that this copolymer rubber dissolves in an organic solvent and substantially contains insoluble components. It can be confirmed by not including it. For example, when measuring the intrinsic viscosity [η], it can be confirmed by completely dissolving the copolymer rubber in decalin at 135 ° C.

In the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A), the structural unit derived from the branched polyene compound is substantially represented by the following formula [II]. It has a structure.

[0028]

[Chemical 5]

[In the formula [II], n, R ¹ , R ² and R ³
Are n, R ¹ in the above general formula [I],
Same as R ² and R ³ . The constitutional unit derived from the branched polyene compound has the above structure, which means that ¹³ C-
This can be confirmed by measuring the NMR spectrum.

Incidentally, 1,4-hexadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinylnorbornene and the like, which have been conventionally generally used as a polyene component, are within a range not impairing the object of the present invention. If it is included, it may be included.

The ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) used in the present invention has the following composition and properties. (I) This ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) comprises ethylene and 3 to 20 carbon atoms.
Of the α-olefin (ethylene / α-olefin) is 40/60 to 95/5, preferably 60/40 to
92/8, and more preferably 65/35 to 90/10.

The ethylene / α-olefin / non-conjugated polyene copolymer rubber having such an ethylene component / α-olefin component ratio is excellent in low temperature flexibility, impact resistance at low temperature and heat resistance. There is. In addition, ethylene / α-
When the ethylene / α-olefin component ratio exceeds 95/5, the olefin / non-conjugated polyene copolymer rubber exhibits resin properties and low temperature flexibility, while
If it is less than 40/60, the heat resistance tends to decrease.

(Ii) The ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) has an iodine value of 5 to 4
0, preferably 10-30, more preferably 10-2
It is in the range of 0.

The ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) having an iodine value in the above range is excellent in impact resistance and surface gloss modification effect. (Iii) This ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) has an intrinsic viscosity [η] measured in decalin of 135 ° C. of 0.5 to 2.0 dl / g, preferably 0.7. Is in the range of ~ 1.5 dl / g.

The intrinsic viscosity of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) has an important influence on the particle size control at the time of forming a latex and the properties of the obtained latex composition. In the present invention, for example, the above-mentioned intrinsic viscosity [η] of less than 0.5 dl / g ethylene · α-
A crosslinked rubber latex composition obtained by using an olefin / non-conjugated polyene copolymer rubber is not suitable for use as a resin modifier because the effect of modifying impact resistance and the like is significantly reduced. A crosslinked rubber latex composition using an ethylene / α-olefin / non-conjugated polyene copolymer rubber having an intrinsic viscosity [η] of more than 2.0 dl / g has an average particle size of solid components in the latex composition. It exceeds 3.0 μm, and as a result, the storage stability decreases, which is a disadvantage.

The above-mentioned ethylene / α-olefin /
The non-conjugated polyene copolymer rubber (A) is obtained by copolymerizing ethylene, an α-olefin having 3 to 20 carbon atoms, and a branched chain polyene compound represented by the above general formula [I] in the presence of a catalyst. It can be obtained by polymerization.

As such a catalyst, a Ziegler type catalyst composed of a transition metal compound such as vanadium (V), zirconium (Zr) and titanium (Ti) and an organic aluminum compound (organic aluminum oxy compound) can be used.

In the present invention, [a] a catalyst comprising a soluble vanadium compound and an organoaluminum compound, or [b] a metallocene compound of a transition metal selected from Group IVB of the periodic table, an organoaluminum oxy compound or an ionized ionic compound. A catalyst composed of a compound is particularly preferably used.

In the present invention, the above catalyst [a] (catalyst comprising a soluble vanadium compound and an organoaluminum compound) or catalyst [b] (a metallocene compound of a transition metal selected from Group IV of the periodic table and an organic compound) is used. In the presence of a catalyst consisting of an aluminum oxy compound or an ionized ionic compound), ethylene and α having 3 to 20 carbon atoms are present.
-The olefin and the branched polyene compound are usually copolymerized in the liquid phase.

At this time, a hydrocarbon solvent is generally used, but an α-olefin such as propylene may be used as a solvent. As such a hydrocarbon solvent, specifically, pentane, hexane, heptane, octane, decane, dodecane, aliphatic hydrocarbons such as kerosene and halogen derivatives thereof, cyclohexane, methylcyclopentane,
Alicyclic hydrocarbons such as methylcyclohexane and halogen derivatives thereof, aromatic hydrocarbons such as benzene, toluene and xylene, and halogen derivatives such as chlorobenzene are used.

These solvents may be used in combination.
The copolymerization of ethylene, an α-olefin having 3 to 20 carbon atoms and a branched polyene compound may be carried out by either a batch method or a continuous method. When carrying out the copolymerization by a continuous method, the above catalyst is used in the following concentrations.

In the present invention, when the above catalyst [a], that is, a catalyst comprising a soluble vanadium compound and an organic aluminum compound is used, the concentration of the soluble vanadium compound in the polymerization system is usually 0.01 to 5 Mmol / liter (polymerization volume), preferably 0.05 to 3 mmol / liter. It is desirable that the soluble vanadium compound is supplied at a concentration of 10 times or less, preferably 1 to 7 times, and more preferably 1 to 5 times the concentration of the soluble vanadium compound present in the polymerization system.

The organoaluminum compound has a ratio of aluminum atom to vanadium atom in the polymerization system (A
1 / V), and is supplied in an amount of 2 or more, preferably 2 to 50, more preferably 3 to 20.

The catalyst [a] consisting of a soluble vanadium compound and an organoaluminum compound is usually diluted with the above-mentioned hydrocarbon solvent and / or liquid α-olefin having 3 to 20 carbon atoms and a branched polyene compound. Supplied. At this time, the soluble vanadium compound is desirably diluted to the above-mentioned concentration, and the organoaluminum compound is diluted to a concentration of, for example, 50 in the polymerization system.
It is desirable that the concentration be adjusted to an arbitrary concentration equal to or less than twice the amount and be supplied into the polymerization system.

When a catalyst [b] comprising a metallocene compound and an organoaluminum oxy compound or an ionized ionic compound (also referred to as an ionic ionized compound or an ionic compound) is used in the present invention, a polymerization system is used. The concentration of the metallocene compound within the range of 0.
0.0005 to 0.1 mmol / liter (polymerization volume),
It is preferably 0.0001 to 0.05 mmol / liter.

Further, the organoaluminum oxy compound is
The ratio of aluminum atom to metallocene compound in the polymerization system (Al / transition metal) is supplied in an amount of 1 to 10,000, preferably 10 to 5,000.

In the case of the ionized ionic compound, the molar ratio of the ionized ionic compound to the metallocene compound in the polymerization system (ionized ionic compound / metallocene compound) is 0.5 to 20, preferably 1 to 10. Supplied.

When the organoaluminum compound is used, it is usually used in an amount of about 0 to 5 mmol / liter (polymerization product), preferably about 0 to 2 mmol / liter.

In the present invention, when ethylene, an α-olefin having 3 to 20 carbon atoms and a branched polyene compound are copolymerized in the presence of a catalyst [a] consisting of a soluble vanadium compound and an organoaluminum compound. Has
In the copolymerization reaction, the temperature is usually -50 ° C to 100 ° C, preferably -30 ° C to 80 ° C, more preferably -20 ° C to
At 60 ° C, the pressure is 50 kg / cm ² or less, preferably 2
It is carried out under the conditions of 0 kg / cm ² or less. However, the pressure is not zero.

In the present invention, ethylene, an α-olefin having 3 to 20 carbon atoms and a branched chain polyene compound are present in the presence of a catalyst [b] comprising a metallocene compound and an organoaluminum oxy compound or an ionizable ionic compound. In the case of copolymerizing and, the temperature of the copolymerization reaction is usually -20 ° C to 150 ° C, preferably 0 ° C to 12 ° C.
0 ° C., more preferably 0 ° C. to 100 ° C., pressure 80
It is carried out under the conditions of not more than kg / cm ² , preferably not more than 50 kg / cm ² . However, the pressure is not zero.

The reaction time (average residence time when the copolymerization is carried out by a continuous method) varies depending on conditions such as catalyst concentration and polymerization temperature, but is usually 5 minutes to 5 hours, preferably 10 minutes. ~ 3 hours.

In the present invention, ethylene and 3 to 2 carbon atoms are used.
Α-olefins and branched polyene compounds of 0 are
The ethylene / α-olefin / non-conjugated polyene copolymer rubber having the above-mentioned specific composition is supplied to the polymerization system in such an amount as to obtain the rubber. Further, in the copolymerization, a molecular weight modifier such as hydrogen can be used.

Ethylene and carbon atoms of 3 as described above
When an .alpha.-olefin of .about.20 and a branched chain polyene compound are copolymerized, an ethylene / .alpha.-olefin / non-conjugated polyene copolymer rubber is usually obtained as a polymerization liquid containing the same. This polymerization liquid is treated by a conventional method to obtain an ethylene / α-olefin / non-conjugated polyene copolymer rubber.

Ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) [unsaturated ethylene copolymer]
The above-mentioned preparation method is described in detail in Japanese Patent Application No. 7-69986 filed by the applicant of the present application.

Low molecular weight (co) polymer (B) The low molecular weight (co) polymer (B) used in the present invention is a low molecular weight polyethylene (ethylene homopolymer) or a low molecular weight ethylene / α-olefin copolymer. , An unsaturated carboxylic acid compound-modified low molecular weight polyethylene, or an unsaturated carboxylic acid compound-modified low molecular weight ethylene / α-olefin copolymer.

Such a low molecular weight (co) polymer (B)
Has a function of easily miniaturizing the above-mentioned ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) at the time of forming a latex.

These low molecular weight (co) polymers (B) are
It may be waxy at room temperature or liquid at room temperature. In the present invention, the waxy low molecular weight (co) polymer at room temperature and the liquid low molecular weight (co) polymer at room temperature can be used separately, or both can be used together.

Examples of the low molecular weight polyethylene include polyethylene wax, and examples of the low molecular weight ethylene / α-olefin copolymer include ethylene / propylene copolymer and ethylene / 1-butene copolymer. Examples thereof include ethylene / α-olefin copolymers and the like.

135 ° C. of the above low molecular weight polyethylene and low molecular weight ethylene / α-olefin copolymer
The intrinsic viscosity [η] measured in decalin is 0.01 to
It is preferably in the range of 0.3 dl / g.

Further, modified low molecular weight polyethylene or modified low molecular weight α obtained by copolymerizing or graft copolymerizing the below-mentioned unsaturated carboxylic acid compound with the above low molecular weight polyethylene or low molecular weight ethylene / α-olefin copolymer. -The olefin copolymer can also be used as a low molecular weight (co) polymer (B).

As the above unsaturated carboxylic acid compound,
Examples thereof include unsaturated carboxylic acids having 3 to 20 carbon atoms in the molecule, acid anhydrides thereof, amides thereof, imides thereof and esters thereof.

Specifically, acrylic acid, (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, norbornene dicarboxylic acid, tetrahydrophthalic acid, bicyclo [2,2,1] hept-2-ene Unsaturated carboxylic acids such as -5,6-dicarboxylic acid; maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic acid Acid anhydrides of unsaturated carboxylic acids such as acid anhydrides; unsaturated carboxylic acid amides such as maleic acid monoamide and maleic acid diamide; unsaturated carboxylic acid imides such as maleimide; methyl acrylate, methyl methacrylate, dimethyl maleate, Monomethyl maleate, diethyl maleate, diethyl fumarate, dimethyl itaconate, diethyl citracone, tetrahydrophthale Dimethyl bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic acid dimethyl, and unsaturated carboxylic acid esters such as glycidyl (meth) acrylate.

Of these, unsaturated carboxylic acid compounds such as maleic acid, maleic anhydride, maleic acid monoamide, maleic acid diamide, maleimide, monomethyl maleate, diethyl maleate and glycidyl (meth) acrylate are preferable.

These unsaturated carboxylic acid compounds can be used alone or in combination. The copolymerization amount or grafting amount of the unsaturated carboxylic acid compound copolymerized or graft-polymerized with the low molecular weight polyethylene and the low molecular weight ethylene / α-olefin copolymer is usually 0. It is in the range of 2 to 50% by weight, preferably 0.2 to 20% by weight, more preferably 0.2 to 10% by weight.

13 of the modified low molecular weight copolymer as described above
The intrinsic viscosity [η] measured in decalin at 5 ° C is 0.01
It is preferably in the range of 0.3 dl / g. The low molecular weight (co) polymer (B) as described above can be used alone or in combination.

In the present invention, the low molecular weight (co) polymer (B) is 2 parts by weight based on 100 parts by weight of the above-mentioned ethylene / α-olefin / non-conjugated polyene copolymer rubber (A).
-30 parts by weight, preferably 5-25 parts by weight, more preferably 5-20 parts by weight.

When the low molecular weight (co) polymer (B) is used in a proportion smaller than the above proportion, it becomes difficult to make the latex fine, and the storage stability of the resulting crosslinked rubber latex composition is reduced. Problems such as deterioration occur. When the low molecular weight (co) polymer (B) is used in a proportion higher than the above proportion, the resulting crosslinked rubber latex composition has a markedly reduced effect of modifying impact resistance and the like, and is used as a resin modifier. Not suitable for

Preparation of Crosslinked Rubber Latex Composition The crosslinked rubber latex composition according to the present invention comprises the above-mentioned ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) and a low molecular weight (co) polymer (B). Can be obtained by uniformly dispersing in an aqueous medium in the presence of a surfactant in the above-described mixing ratio to form a latex, and then subjecting the obtained latex composition to a crosslinking treatment.

As the surface active agent, conventionally known anionic surface active agents, cationic surface active agents and nonionic surface active agents can be used, and in particular, anionic surface active agents such as fatty acid sodium and fatty acid potassium. Is preferably used.

Surfactants are used (A) and (B).
Generally, the amount is preferably 0.2 to 20 with respect to 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A), although it varies depending on the kind of the polymer component of the above.
Used in proportions by weight.

In latexing, for example, the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) and the low molecular weight (co) polymer (B) are uniformly dispersed in a hydrocarbon solvent such as n-hexane. To obtain a solution,
The above solution may be mixed and dispersed in an aqueous medium in which a predetermined amount of a surfactant is dispersed with stirring, and then heated at an appropriate temperature to volatilize and remove the solvent component.

The amount of the aqueous medium used is usually selected so that the solid content concentration in the latex is in the range of 5 to 65% by weight, preferably 10 to 60% by weight, based on the product latex. It is suitable from the viewpoint of sex.

The latex composition obtained as described above is subjected to a cross-linking treatment to obtain ethylene / α-olefin /
Crosslinking bonds are formed in the molecular chain of the non-conjugated polyene copolymer rubber (A).

The cross-linking treatment of this latex composition is carried out by a known cross-linking treatment such as a cross-linking treatment method in which a polyfunctional monomer is blended in the latex composition and ionizing radiation is used, a cross-linking treatment method in which an organic peroxide is used. Can be done by law.

As the polyfunctional monomer, for example, 2
A monomer having one or more ethylenically unsaturated groups, particularly a vinyl group, is preferably used. Specifically, divinylbenzene, tetramethylene diacrylate, glyceryl triacrylate, ethylene glycol dimethacrylate,
Examples include 1,2,4-trivinylcyclohexane and tetraallyloxyethane.

These polyfunctional monomers are ethylene
α-Olefin / non-conjugated polyene copolymer rubber (A) 1
With respect to 00 parts by weight, preferably 0.1 to 20 parts by weight,
It is particularly preferably used in a proportion of 0.3 to 5 parts by weight.

As the ionizing radiation, α rays, β rays,
Any of γ-ray, electron beam and X-ray may be used. The irradiation dose of these ionizing radiations is preferably in the range of 1 to 50 Mrad.

The cross-linking treatment with the organic peroxide is carried out by uniformly dispersing the organic peroxide in the latex composition and then heating the latex composition at a temperature above the decomposition temperature of the organic peroxide.

As the organic peroxide, an organic peroxide having a 10-hour half-life temperature of 0 ° C. or more and 100 ° C. or less is preferable from the viewpoints of stability of latex particles, safety of crosslinking reaction operation, and economy. Specifically, 1,1-bis (t-butylperoxy) cyclohexane, t-butylperoxy vivarate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisopropyl carbonate, 2,
5-Dimethyl-2,5-di (benzoylperoxy) hexane, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, isobutyl peroxide Examples thereof include oxide, diisopropyl peroxydicarbonate, di (2-ethylhexyl) peroxy carbonate and the like.

The organic peroxide is usually 0.3 to 20 parts by weight, preferably 1 to 100 parts by weight with respect to 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) in the latex composition. It is used in a proportion of 10 parts by weight.

The crosslinking conditions such as heating time in the crosslinking treatment may be either normal pressure or pressure, but the content of ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) component insoluble in hot toluene. Is 30% by weight or more, preferably 5
It is set to be 0% by weight or more, and more preferably 60% by weight or more. Specifically, it is appropriate that the heating time is usually 5 to 7 times the half-life.

The above-mentioned hot toluene insoluble content (gel fraction) is expressed as the ratio of the amount of all solids in the latex composition insoluble in 120 ° C. toluene, and is used as a measure of the degree of crosslinking. can do. A detailed method for measuring the hot toluene insoluble content will be described in Examples below. When the gel fraction is smaller than the above range, the effect of improving impact resistance is insufficient.

In the crosslinked rubber latex composition according to the present invention, pigments, thickeners, plasticizers, preservatives,
A conventionally known compounding agent such as an antifoaming agent, a pH adjuster, an antioxidant, an antiaging agent or the like can be compounded within a range not impairing the object of the present invention. These compounding agents can be compounded in the latex composition before the crosslinking treatment, and can be compounded in the latex composition after the crosslinking treatment.

Crosslinked Rubber Latex Composition A crosslinked rubber latex composition containing ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) as a main component prepared as described above has an average particle diameter of solid content. Is 0.2
Since it is in the range of up to 3.0 μm, it has excellent storage stability. In addition, this crosslinked rubber latex composition is an ethylene / α-olefin / non-conjugated polyene copolymer rubber (A).
Since the content of the hot toluene insoluble component (gel fraction) of the component is 30% by weight or more, the resin which could not be formed into a molded article excellent in impact resistance and surface gloss was treated with impact resistance and surface treatment. It is extremely useful for modifying a resin capable of forming a molded article having excellent gloss.

The reason why the crosslinked rubber latex composition according to the present invention improves the effect of modifying impact resistance and surface gloss is not clear, but ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) is used. Since it contains a specific non-conjugated polyene component, the graft reactivity is high, and as a result, the dispersibility of the ethylene / α-olefin / non-conjugated polyene copolymer is improved in the resin component of the modifying component. It is presumed that.

AES Resin The AES resin according to the present invention is a copolymer of acrylonitrile, ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) and styrene, and ethylene / α-
Acrylonitrile and styrene are grafted onto the olefin / non-conjugated polyene copolymer rubber (A). This A
The ES resin also contains a low molecular weight (co) polymer (B) which is a component of the above-mentioned crosslinked rubber latex composition.

The AES resin according to the present invention can be prepared from the above-described crosslinked rubber latex composition according to the present invention by a conventionally known method. For example, the AES resin according to the present invention can be obtained by subjecting the crosslinked rubber latex composition according to the present invention to emulsion graft polymerization of acrylonitrile and styrene. Further, there are the following AES resin production methods for the purpose of dealing with various kinds, easiness of quality improvement, improvement of productivity, reduction of wastewater treatment, and the like. In this method, first, a crosslinked rubber latex composition according to the present invention is subjected to emulsion graft polymerization of acrylonitrile and styrene to prepare a dry product having a high rubber content. Next, this dry product is blended with acrylonitrile-styrene resin (AS resin), which is a resin component prepared in advance, to obtain an AES resin, and the ethylene / α-olefin / non-conjugated polyene is mixed depending on the blending ratio. The desired AES resin is obtained by adjusting the amount of the copolymer rubber (A) component. Such a blend has 15
It is carried out at a temperature of 0 to 300 ° C, preferably 180 to 250 ° C using an extruder or the like.

The AES resin prepared by using the crosslinked rubber latex composition according to the present invention has an excellent weather resistance inherent to ethylene / α-olefin / non-conjugated polyene copolymer rubber as compared with the conventional AES resin. Further, it is possible to form a molded article having excellent impact resistance and surface gloss without impairing the solvent resistance.

[0089]

The crosslinked rubber latex composition according to the present invention comprises an ethylene / α-olefin / non-conjugated polyene composed of [I] ethylene, an α-olefin having 3 to 20 carbon atoms and the above-mentioned branched polyene compound. 100 parts by weight of the copolymer rubber (A) and [II] low molecular weight polyethylene,
At least one selected from the group consisting of a low molecular weight ethylene / α-olefin copolymer, an unsaturated carboxylic acid compound-modified low molecular weight polyethylene, and an unsaturated carboxylic acid compound-modified low molecular weight ethylene / α-olefin copolymer
2 to 30 parts by weight of a low molecular weight (co) polymer (B) of a kind, and a cross-linkage bond is formed in the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) component. Therefore, the resin that could not form a molded article with excellent impact resistance and surface gloss will impair the excellent weather resistance and solvent resistance that ethylene / α-olefin / non-conjugated polyene copolymer rubber originally has. Without being modified, it can be modified into a resin capable of forming a molded article having excellent impact resistance and surface gloss.

Further, since the AES resin according to the present invention is prepared by using the crosslinked rubber latex composition according to the present invention as described above, compared with the conventional AES resin, ethylene / α-olefin / A molded article having excellent impact resistance and surface gloss can be formed without impairing the excellent weather resistance and solvent resistance originally possessed by the non-conjugated polyene copolymer rubber.

Therefore, the AES resin according to the present invention is
As such, it can be used for applications such as housings for home electric appliances, automobile interior parts such as instrument panels, and automobile exterior parts such as front grilles. Further, the AES resin according to the present invention can be blended with PVC or the like and used for modification of impact resistance and the like.

The present invention will be described below with reference to examples.
The present invention is not limited to these examples.

[0093]

[Reference Example 1] [Preparation of catalyst] Anhydrous cobalt (II) chloride 4 was placed in a 50 ml flask containing a stirrer stirrer under an argon atmosphere.
3 mg (0.33 mmol), 1,2-bis (diphenylphosphino) ethane 263 mg (0.66 mmol) and anhydrous decane 23 ml were added, and the mixture was stirred at 25 ° C. for 2 hours.

Then, at 25 ° C., 17 ml of a triethylaluminum / toluene solution (17 mmol of triethylaluminum) having a concentration of 1 mol / liter was added and the mixture was stirred for 2 hours to prepare a catalyst.

[Synthesis of 4-ethylidene-8-methyl-1,7-nonadiene (EMN)]

[0096]

[Chemical 6]

In a 300 ml stainless steel (SUS316) autoclave, under an argon atmosphere, 7-methyl-3-
Methylene-1,6-octadiene (β-myrcene) 100g
(734 mmol) and the whole amount of the catalyst prepared as above were added and the mixture was sealed.

Then, an ethylene cylinder was directly connected to the autoclave, ethylene was introduced, and the inside of the autoclave was cooled to 3
The pressure was increased to 5 kg / cm ² . Then heat to 95 ° C,
Add ethylene consumed intermittently 5 times, total 1
Reaction was carried out for 5 hours.

After completion of the reaction, the autoclave was cooled and then opened, and the obtained reaction mixture was poured into 100 ml of water to separate an organic layer and an aqueous layer. The separated organic layer,
After removing low-boiling substances with an evaporator, 20-stage precision vacuum distillation was performed.

83 g of the target product, EMN, was obtained (yield 69%, β-myrcene conversion 90%). As a reaction byproduct, 16 g of 5,9-dimethyl-1,4,8-decatriene was used.
Produced (yield 13%).

4-Ethylidene-8-methyl-obtained above
The analysis results of 1,7-nonadiene (EMN) are shown below. (1) Boiling point: 103 to 105 ° C./30 mmHg (2) GC-MS (gas chromatography mass spectrometry):
m / z 164 (M ⁺ molecular ion peak), 149, 1
23, 93, 79, 41, 27 (Gas chromatography measurement condition: column: J & W Scientific Co., capillary column DB-1701 0.25 mm × 30
m Vaporization temperature: 250 ° C. Column temperature: After holding at 60 ° C. for 5 minutes, up to 200 ° C. 10
(3) Infrared absorption spectrum (neat) Absorption peaks: 3080 cm ^-1 , 2975 cm ^-1 , 292
^{5cm -1, 2825cm -1, 1670cm -1} , 1640
^{cm -1, 1440cm -1, 1380cm -1} , 1235c
^{m -1, 1110cm -1, 910cm -1} , 830cm -1 (4) 1 H-NMR spectrum (solvent: CDCl ₃₎ shows an absorption peak below.

[0102]

[Table 1]

[Preparation of ethylene / α-olefin / non-conjugated polyene copolymer rubber] Using a polymerization vessel having a capacity of 15 liters equipped with a stirring blade, ethylene, propylene and the above
The copolymerization reaction with 4-ethylidene-8-methyl-1,7-nonadiene (EMN) was continuously carried out.

That is, first, 3.0 liters of dehydrated and purified hexane per hour was introduced into the polymerization vessel from the upper portion of the polymerization vessel, and a hexane solution of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride (concentration: 0.05 mmol / 0.1 liter / hour, hexane solution of triisobutylaluminium (concentration 20 mmol / liter)
0.2 liters / hr, hexane slurry solution of methylalumoxane (3 mg atom / liter in terms of aluminum atoms) /0.5 liter / hr, hexane solution of EMN (concentration 0.20 liter / liter) / hr 1 .2 liters were continuously fed.

Further, 340 liters / hour of ethylene, 460 liters / hour of propylene and hydrogen were continuously fed into the polymerization vessel from the upper portion of the polymerization vessel so that the concentration of the gas phase portion was 0.003 mol%. This copolymerization reaction is
Performed at 0 ° C.

Then, a small amount of methanol was added to the polymerization solution extracted from the lower part of the polymerization vessel to stop the polymerization reaction,
After separating the copolymer from the solvent by steam strip treatment, under conditions of 100 ° C. and reduced pressure (100 mmHg),
It was dried for 24 hours.

With the above operation, ethylene / propylene / E
An MN copolymer rubber was obtained. The ethylene / propylene / EMN copolymer rubber (A-1) obtained had a molar ratio of ethylene and propylene (ethylene / propylene) of 70.
/ 30, the iodine value was 20, and the intrinsic viscosity [η] measured in 135 ° C decalin was 1.0 dl / g.

[0108]

[Reference Example 2] The same operation as in Reference Example 1 was carried out, and the ethylene / 1-octene / EMN copolymer rubber (A
-2) was obtained.

[0109]

[Table 2]

[0110]

[Example 1] [Preparation of cross-linked rubber latex composition] The ethylene / propylene / EMN copolymer rubber (A-
1) 100 g and modified polyethylene wax as a low molecular weight (co) polymer (B) [maleic anhydride content: 3% by weight, intrinsic viscosity [η] measured in decalin at 135 ° C .:
0.05 dl / g] 10 g was dissolved in 900 g of n-hexane and stirred until a uniform solution was obtained.

Then, a dispersion obtained by dispersing 5 g of potassium oleate as a surfactant in 900 g of water was prepared.
Using a homomixer (rotation speed of stirring blade: 1,200 rpm), the above homogeneous solution was mixed for 30 minutes.

Next, the emulsion obtained by this mixing was volatilized to remove n-hexane at a temperature of 60 to 80 ° C. with slow stirring to obtain a latex composition. Then
This latex composition was transferred to an electron beam irradiation container so as to have a thickness of 1.5 mm, the upper part of the container was sealed with a polyethylene film of 30 μm, and an accelerating voltage of 750 kV and 10 Mrad.
And irradiated with an electron beam to prepare a crosslinked rubber latex composition.

With respect to the crosslinked rubber latex composition prepared as described above, the rubber coagulation precipitate content, average particle diameter and hot toluene insoluble content (gel fraction) were determined according to the following methods.

The results are shown in Table 3. (1) Rubber Coagulation Deposition Content A crosslinked rubber latex composition sample was poured onto a 100-mesh stainless net, and the amount of rubber coagulation deposition remaining on the net is shown in% by weight based on the total solid content in the crosslinked rubber latex composition. (2) Average particle size Coulter Using a Coulter counter manufactured by Elactronix Co., all particles in the crosslinked rubber latex composition sample are counted, and a histogram by particle size and a cumulative amount histogram are created. Here, the cumulative weight histogram is 5
The point where 0% is reached is defined as the average particle size. (3) Hot toluene insoluble content (gel fraction) The total solid content in the crosslinked rubber latex composition sample was coagulated and dried, and about 1.5 g was put in a 100 mesh stainless mesh bag.
Is collected and immersed in 100 cc of 120 ° C. toluene for 6 hours.

Then, after the net bag was taken out and dried, the weight of the solid content remaining in the net bag was measured, and the hot toluene insoluble content (gel fraction) was calculated and used as a measure of the degree of crosslinking. Regarding the above (1) to (3), the measurement was completed within 48 hours after the crosslinking treatment. (4) Put a storage-stable crosslinked rubber latex composition sample in a closed container,
It was left at room temperature for 2 months.

Then, the rubber coagulation deposit was measured by the same method as in the above (1), and this rubber coagulation deposit was used as a standard for evaluating the storage stability of the crosslinked rubber latex composition. [Preparation of AES Resin] An AES resin was produced by a known method using the crosslinked rubber latex composition obtained as described above.

That is, 100 g of the above crosslinked rubber latex composition was placed in a glass autoclave having a volume of 2 liters, 2 g of potassium oleate was additionally added, and the mixture was kept at 60 ° C., and then potassium persulfate was stirred at 0 rpm to 0%. 0.01 g / min, styrene 0.25 g / min, and acrylonitrile 0.25 g / min were added for 1 hour. After these additions were stopped, the reaction was terminated by leaving it for another 30 minutes.

Next, a small amount of dilute hydrochloric acid was added dropwise to the product obtained as described above under stirring to coagulate the product, which was washed, dehydrated and dried. The yield of the obtained product is 125 g.
Met.

Next, 125 g of this product and commercially available A
S resin [trade name AS-S, manufactured by Denki Kagaku Kogyo] 3
75 g was mixed with an extruder at 200 ° C., and then, by an injection molding machine [product number 1S22P, manufactured by Toshiba Machine Co., Ltd.]
A square plate having a thickness of 100 mm × 70 mm × 2 mm was obtained at an injection temperature of 200 ° C.

Further, the Izod impact strength and the surface glossiness of the square plate were measured according to the following methods. The results are shown in Table 3.

(1) Izod impact strength (IZ) The Izod impact strength (IZ) is based on JIS K7110, and the Izod impact tester (manufactured by Toyo Seiki Co., Ltd.))
Was measured using. -Temperature 25 ° C, -10 ° C-Test piece No. 1A (2) Measurement of surface glossiness (GLOSS) According to JIS K7105, using a gloss meter (manufactured by Nippon Denshoku Co., Ltd.), a specular gloss of 60 degrees The degree was measured.

[0122]

Comparative Example 1 In Example 1, instead of the ethylene / propylene / EMN copolymer rubber (A-1), ethylene /
Propylene copolymer rubber [Ethylene / Propylene (molar ratio): 70/30, Intrinsic viscosity [η] measured in 135 ° C. decalin: 1.0 dl / g] was used in the same manner as in Example 1. It was

The results are shown in Table 3.

[0124]

[Comparative Example 2] In Example 1, instead of the ethylene / propylene / EMN copolymer rubber (A-1), ethylene /
Propylene-5-ethylidene-2-norbornene copolymer rubber [ethylene / propylene (molar ratio): 70/30, iodine value: 20, intrinsic viscosity [η] measured in decalin at 135 ° C: 1.0 dl / g] The same procedure as in Example 1 was performed except that was used.

The results are shown in Table 3.

[0126]

Example 2 Instead of the ethylene / propylene / EMN copolymer rubber (A-1) in Example 1, the ethylene / 1-octene / EMN copolymer rubber (A-2) obtained in Reference Example 2 was used. The same procedure as in Example 1 was performed except that was used.

[0127]

Example 3 [Preparation of Crosslinked Rubber Latex Composition] Crosslinking was carried out in the same manner as in Example 1 except that an organic peroxide was used instead of electron beam irradiation as the crosslinking treatment operation. A rubber latex composition was prepared.

Crosslinking with an organic peroxide is as follows. 2 parts by weight of p-divinylbenzene was added to 100 parts by weight of the solid content of the latex composition before the crosslinking treatment and sufficiently dispersed. Then, the latex composition was transferred to a 2 liter autoclave to obtain an organic peroxide.
1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane [Brand name Perhexa 3M, NOF Corporation]
[Production] After adding 3.0 parts by weight, 120 with stirring
A crosslinking reaction was carried out at a temperature of ° C for 2 hours to prepare a crosslinked rubber latex composition.

Thereafter, in the same manner as in Example 1, the rubber coagulation precipitate content, the average particle size, and the hot toluene insoluble content (gel fraction) of this crosslinked rubber latex composition were determined according to the following methods.

The results are shown in Table 3. [Preparation of AES Resin] Same as Example 1 except that the crosslinked rubber latex composition obtained in Example 2 was used in place of the crosslinked rubber latex composition obtained in Example 1. I went to.

The results are shown in Table 3.

[0132]

[Comparative Example 3] The same procedure as in Example 1 was carried out except that the amount of electron beam irradiation during the crosslinking treatment was changed to 30 Mrad.

The results are shown in Table 3.

[0134]

[Table 3]

[0135]

Example 4 The modification effect of polyvinyl chloride by the AES dry product prepared in Example 1 was tested according to the following procedure.

That is, 10 parts by weight of this AES dry product and powdered polyvinyl chloride [trade name: ZEON 103
EP, manufactured by Nippon Zeon Co., Ltd.] 100 parts by weight and organic Cd
-Ba-Zn-based polyvinyl chloride stabilizer [trade name LK
BZ-80, Sakai Chemical Co., Ltd.] 1.5 parts by weight, and calcium stearate [Wako Pure Chemical Industries, Ltd.] 1.0 parts by weight were mixed at 50 ° C. using a Henschel mixer, and further, This mixture was kneaded with an 8-inch roll having a surface temperature of 130 to 140 ° C. for 5 minutes.

The polyvinyl chloride kneaded material obtained as described above was preheated at 170 ° C. for 30 minutes, and then hot pressed at 170 ° C. for 2 minutes under a pressure of 100 kg / cm ² , and then at 20 ° C. Cooling press under a pressure of 100 kg / cm ² for 5 minutes at 150 mm × 120 mm ×
A 2 mm thick pressed sheet was obtained.

About the obtained press sheet,
Izod impact test (JIS K71
10) was performed to measure the Izod impact strength (IZ). The results are shown in Table 4.

[0139]

Comparative Example 4 The procedure of Example 4 was repeated except that the AES dry product was not used.

The results are shown in Table 4.

[0141]

[Comparative Example 5] In the same manner as in Example 4 except that 10 parts by weight of commercially available chlorinated polyethylene [trade name Eraslen 301A, Showa Denko KK] was used in place of the AES dry product. I did.

The results are shown in Table 4.

[0143]

[Table 4]

Front page continuation (72) Inventor Toshiyuki Tsutsui 6-1-2 Waki, Waki-cho, Kuga-gun, Yamaguchi Mitsui Petrochemical Industries, Ltd. (72) Toshihiro Ane 3-chome, Kasumigaseki, Chiyoda-ku, Tokyo No. 2-5 Mitsui Petrochemical Industry Co., Ltd. (56) Reference JP-A-8-311263 (JP, A) JP-A-61-238842 (JP, A) (58) Fields investigated (Int. Cl. ⁷⁾ , DB name) C08L 23/00-23/36 C08F 255/00-255/10

Claims (6)

(57) [Claims] 1. [I] Ethylene, α having 3 to 20 carbon atoms
-Ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) comprising an olefin and at least one branched polyene compound represented by the following general formula [I]
100 parts by weight of [II] low molecular weight polyethylene, low molecular weight ethylene / α-olefin copolymer, unsaturated carboxylic acid compound-modified low molecular weight polyethylene, and unsaturated carboxylic acid compound-modified low molecular weight ethylene / α-olefin copolymer A latex composition containing 2 to 30 parts by weight of a low molecular weight (co) polymer (B) selected from the group consisting of polymers, wherein the ethylene / α-olefin / non-conjugated polyene A crosslinked rubber latex composition characterized in that a crosslink bond is formed in the copolymer rubber (A) component; [In the formula [I], n is an integer of 1 to 5, R ¹ is an alkyl group having 1 to 5 carbon atoms, and R ² and R ³ are each independently a hydrogen atom or the number of carbon atoms. 1 to 5 alkyl groups]. 2. The hot toluene insoluble content of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) component is 30% by weight or more.
The crosslinked rubber latex composition described in 1. 3. The crosslinked rubber latex composition according to claim 1, wherein the average particle diameter of the solid content is 0.2 to 3.0 μm. 4. The ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) has a molar ratio of (i) ethylene and an α-olefin having 3 to 20 carbon atoms (ethylene /
α-olefin) is in the range of 40/60 to 95/5, (ii) the iodine value is in the range of 5 to 40, and (iii)
Intrinsic viscosity [η] measured in decalin at 135 ° C is 0.5
The cross-linked rubber latex composition according to any one of claims 1 to 3, wherein the cross-linked rubber latex composition is in the range of ~ 2.0 dl / g. 5. The crosslinked rubber latex composition according to any one of claims 1 to 4, which is obtained by emulsion graft polymerization of acrylonitrile and styrene, and acrylonitrile and the ethylene / α-olefin / non-conjugated polyene copolymer rubber ( A)
AE comprising a copolymer of styrene and styrene
S resin. 6. A dry product obtained by emulsion-polymerizing acrylonitrile and styrene in the crosslinked rubber latex composition according to claim 1, and acrylonitrile.
Obtained by blending with a styrene resin (AS resin),
An AES resin comprising an acrylonitrile, a copolymer of ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) and styrene.