JPH0959325A - Rubber-reinforced vinyl-based resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a rubber-reinforced vinyl-based resin excellent in impact resistance, weather resistance, coloring property and appearance after forming. SOLUTION: This rubber-reinforced vinyl-based resin is obtained by polymerizing 95-20wt.% vinyl-based monomer in the presence of (A) 5-80wt.% rubbery copolymer obtained by polymerizing monomers having a mixing ratio of ethylene/a 3-20C α-olefin/a non-conjugated diene =(5-95)/(95-5)/(0-30) (in wt.%) by using a metallocene catalyst. The rubber-reinforced vinyl-based resin having 5-200% grafting ratio and 0.1-1.0dl/g specific viscosity [η] of a methyl elhyl ketone-soluble fraction, is obtained.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a rubber-reinforced vinyl resin excellent in impact resistance, weather resistance, colorability and molding appearance.

[0002]

2. Description of the Related Art E having substantially no unsaturated bond in its main chain
A graft copolymer (AES resin) obtained by copolymerizing PM and EPDM with rubber components such as styrene and acrylonitrile is an ABS using a conjugated diene rubber.
It is known that it has greater resistance to ultraviolet rays, oxygen, and ozone than resins and has significantly better weather resistance. However, the conventional AES resin has a poor molding appearance and is unsatisfactory in low temperature characteristics. Therefore, various improvements have been made, but since propylene is used as the α-olefin in the rubber component, it has been difficult to improve the molding appearance and low temperature characteristics more than ever.

On the other hand, AES, which has better impact resistance than before
Resins are desired. In order to increase the impact resistance, a method of increasing the rubber component amount or increasing the molecular weight of the hard resin component (matrix component) can be considered. However, when the amount of the rubber component is increased, the rigidity and the coloring property are deteriorated, and when the molecular weight of the hard resin component is increased, the workability and the molding appearance are deteriorated. As described above, conventionally, it has been difficult to improve impact resistance and other physical properties in a well-balanced manner.

[0004]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention As a result of intensive studies in view of such problems, the present inventors have found that a specific amount of a vinyl-based monomer is added in the presence of a rubber-like copolymer polymerized by using a specific catalyst. It has been found that the polymerized rubber-reinforced vinyl resin having specific physical properties is excellent in impact resistance, weather resistance, colorability and molding appearance.

[0005]

[Means for Solving the Problems] The rubber strength according to claim 1.
The vinyl chloride resin is ethylene / α-o having 3 to 20 carbon atoms.
Refin / non-conjugated diene = 5-95 / 95-5 / 0-3
A monomer consisting of a mixing ratio of 0 (% by weight) is used as a metallocene-based catalyst.
Rubber-like copolymer (A) obtained by polymerization using a medium 5 to
95 to 20% by weight of vinyl monomer in the presence of 80% by weight
Is obtained by polymerizing, and the graft ratio is 5 to 200%.
And the intrinsic viscosity [η] of the methyl ethyl ketone soluble component is
It is characterized by being 0.1 to 1.0 dl / g. Claim
The rubber-reinforced vinyl resin according to item 2 is according to claim 1.
A rubber-reinforced vinyl resin of
(A) has a molecular weight distribution of 1.2 to 20 (M _W/ M_n)
And a glass transition temperature (T_g)When,
Melting point of 50 to 100 ° C (T_m) Is included.
You.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The α-olefin having 3 to 20 carbon atoms (hereinafter referred to as "α-olefin") is specifically propylene, 1-butene, 1-pentene, 1-
Hexene, 4-methyl-1-pentene, 1-heptene,
1-octene, 1-decene, 1-dodecene, 1-hexadecene, 1-eicosene and the like can be mentioned. These α-
The olefins can be used alone or as a mixture of two or more. The α-olefin has 3 to 20 carbon atoms, preferably 3 to 16 and more preferably 6 to 1
2. When the carbon number exceeds 20, the copolymerizability is extremely lowered, so that the surface appearance of the resin is significantly deteriorated.

The ethylene / α-olefin weight ratio is 5
~ 95 / 95-5, preferably 50-90 / 50
-10, more preferably 60-88 / 40-12, particularly preferably 70-85 / 30-15. If the weight ratio value of α-olefin exceeds 95, the weather resistance is deteriorated, which is not preferable. If it is less than 5, the rubber-like copolymer does not have sufficient rubber elasticity, so that impact resistance is not exhibited. The unsaturated group amount is preferably in the range of 4 to 40 in terms of iodine value.

The non-conjugated dienes used include alkenyl norbornenes, cyclic dienes and aliphatic dienes, preferably 5-ethylidene-2-norbornene and dicyclopentadiene. These non-conjugated dienes can be used alone or in admixture of two or more. The content of the non-conjugated diene in the rubber-like copolymer (A) is 0 to 30% by weight, preferably 0 to 15
% By weight. When the content of the non-conjugated diene exceeds 30% by weight, gelation progresses and impact resistance and gloss are lowered.

The polymerization reaction for producing the rubbery copolymer (A) used in the present invention is usually carried out in an inert hydrocarbon solvent. Specific examples of such an inert hydrocarbon solvent include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane and dodecane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; benzene, toluene, Examples thereof include aromatic hydrocarbons such as xylene. These hydrocarbon solvents can be used alone or in combination of two or more. Also,
Raw material monomers can also be used as the hydrocarbon solvent.

The metallocene catalyst used in the production of the rubbery copolymer (A) used in the present invention will be specifically described below with reference to examples, but the catalysts are not limited to these examples. is not. Examples of the metallocene catalyst used in the present invention include a catalyst comprising the following component (a) and component (b), or a catalyst comprising the following component (c) and component (d).

The component (a) is a transition metal compound represented by the following general formula [I]. R ″ _S (C ₅ R _m ) _p (R ′ _n E) _q MQ _4-pq …… [I] In the formula, M is a Group IVB metal of the periodic table, and (C ₅ R _m ).
Is a cyclopentadienyl group or a substituted cyclopentadienyl group, and each R may be the same or different,
Hydrogen atom, alkyl group having 1 to 20 carbon atoms, 6 to 4 carbon atoms
It is an aryl group having 0, an alkaryl group having 7 to 40 carbon atoms, or an aralkyl group having 7 to 40 carbon atoms, or two adjacent carbon atoms are bonded to each other to form a 4- to 8-membered carbon ring. It is a thing. E is an atom having a non-bonded electron pair, R'is an alkyl group having 1 to 20 carbon atoms, and 6 carbon atoms.
To C 40 aryl group, C 7 to C 40 alkaryl group or C 7 to C 40 aralkyl group, and R ″ is C 1 to C 20 alkylene group, dialkyl silicon, or dialkyl germanium. Is a group that binds two ligands, s is 1 or 0, and when s is 1, m
Is 4, n is 2 less than the valence of E, m is 5 when s is 0, n is 1 less than the valence of E, n
When ≧ 2, each R ′ may be the same or different, and each R ′ may combine with each other to form a ring. Q is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkaryl group having 7 to 40 carbon atoms or an aralkyl group having 7 to 40 carbon atoms, and p and q Is an integer of 0 to 4 and satisfies the relationship of 0 <p + q ≦ 4.

Specific examples of the component (a) include bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl) zirconium dimethyl and bis (cyclopentadienyl). ) Zirconium diphenyl, dimethylsilylbis (cyclopentadienyl) zirconium dichloride, dimethylsilylbis (cyclopentadienyl) zirconium dimethyl, methylenebis (cyclopentadienyl) zirconium dichloride, ethylenebis (cyclopentadienyl) zirconium dichloride, bis (Indenyl) zirconium dichloride, bis (indenyl) zirconium dimethyl, dimethylsilylbis (indenyl) zirconium dichloride, methylenebis (indenyl) zirco Umujikurorido, bis (4,
5,6,7-tetrahydroindenyl) zirconium dichloride, bis (4,5,6,7-tetrahydroindenyl) zirconium dimethyl, dimethylsilylbis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride , Dimethylsilylbis (4,5
6,7-tetrahydro-1-indenyl) zirconium dimethyl, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (methylcyclopentadiene) Enyl) zirconium dimethyl, dimethylsilyl bis (3-methyl-1-cyclopentadienyl) zirconium dichloride, methylene bis (3-methyl-1-cyclopentadienyl) zirconium dichloride, bis (tertiary butylcyclopentadienyl) Zirconium dichloride, dimethylsilylbis (3-tert-butyl-1-cyclopentadienyl) zirconium dichloride, bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylbis (2,4-di Chill-1-cyclopentadienyl) zirconium dichloride, bis (1,2,4-trimethyl cyclopentadienyl) zirconium dichloride, dimethyl silyl bis (2,3,5-trimethyl -1
-Cyclopentadienyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride, dimethylsilylbis (fluorenyl) zirconium dichloride,
(Fluorenyl) (cyclopentadienyl) zirconium dichloride, dimethylsilyl (fluorenyl) (cyclopentadienyl) zirconium dichloride, (tertiary butylamide) (1,2,3,4,5-pentamethylcyclopentadienyl) Zirconium dichloride, dimethylsilyl (tertiary butylamide) (2,3,4,5-tetramethyl-1-cyclopentadienyl) zirconium dichloride, methylene (tertiary butylamide) (2
3,4,5-tetramethyl-1-cyclopentadienyl) zirconium dichloride, (phenoxy) (1,
2,3,4,5-pentamethylcyclopentadienyl)
Zirconium dichloride, dimethylsilyl (o-phenoxy) (2,3,4,5-tetramethyl-1-cyclopentadienyl) zirconium dichloride, methylene (o
-Phenoxy) (2,3,4,5-tetramethyl-1-
Cyclopentadienyl) zirconium dichloride, ethylene (o-phenoxy) (2,3,4,5-tetramethyl-1-cyclopentadienyl) zirconium dichloride, bis (dimethylamido) zirconium dichloride,
Bis (diethylamido) zirconium chloride, bis (ditertiary butylamido) zirconium dichloride, dimethylsilylbis (methylamido) zirconium dichloride, dimethylsilylbis (tertiary butylamido) zirconium dichloride, and the like. Examples thereof include compounds substituted with hafnium, but are not limited to these. These transition metal compounds can be used alone or in combination of two or more kinds.

The component (b) is a linear aluminoxane compound represented by the following general formula [II] and / or a cyclic aluminoxane compound represented by the following general formula [III]. During R ₂ -Al-O-[Al (R) -O] _n -Al-R ₂ ...... (II) [Al (R) O-] _{n + 2} ...... (III) wherein each R is either the same May be different, having 1 to 1 carbon atoms
A 20 alkyl group, a C6-40 aryl group, a C7-40 alkaryl group, or a C7-40 aralkyl group, preferably a methyl group, an ethyl group,
Particularly preferred is a methyl group, and n is an integer of 2 to 50, preferably 4 to 30. These aluminoxane compounds can be used alone or in combination of two or more. The ratio of the component (a) and the component (b) used is a molar ratio of a transition metal and an aluminum atom, and is usually
1: 1 to 1: 100,000, preferably 1: 5 to 1: 5
The range is 0000.

Further, the component (C) is represented by the following general formula [IV]
It is a transition metal alkyl compound represented by. R ″ _s (C ₅ R _m ) _p (R ′ _n E) _q MR ″ ′ ″ _4-pq (IV) In the formula, M is a Group 4 metal of the periodic table, and (C ₅ R _m ) is It is a cyclopentadienyl group or a substituted cyclopentadienyl group, and each R may be the same or different and is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, or 7 carbon atoms. Is an alkaryl group having 40 to 40 carbon atoms or an aralkyl group having 7 to 40 carbon atoms, or two adjacent carbon atoms are bonded to each other to form a 4- to 8-membered carbon ring, and E has a non-bonded electron pair. And R'is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkaryl group having 7 to 40 carbon atoms, or a carbon number of 7
To 40 aralkyl groups, R ″ is an alkylene group having 1 to 20 carbon atoms, dialkylsilicon or dialkylgermanium, which is a group that bonds two ligands, and s is 1 or 0. , When s is 1, m is 4 and n is 2 less than the valence of E, when s is 0, m is 5 and n is 1 less than the valence of E, and when n ≧ 2 Each R'may be the same or different, and each R'may combine with each other to form a ring.
An alkyl group having 20 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkaryl group having 7 to 40 carbon atoms, or an aralkyl group having 7 to 40 carbon atoms, p and q are integers of 0 to 3, and 0 The relationship of <p + q <4 is satisfied.

Specific examples of the component (c) include bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) zirconium diethyl, bis (cyclopentadienyl) zirconium diisobutyl, bis (cyclopentadienyl). Zirconium diphenyl, bis (cyclopentadienyl) zirconium di {bis (trimethylsilyl) methyl}, dimethylsilylbis (cyclopentadienyl) zirconium dimethyl, dimethylsilylbis (cyclopentadienyl) zirconium diisobutyl, methylenebis (cyclopentadienyl) ) Zirconium dimethyl, ethylene bis (cyclopentadienyl) zirconium dimethyl, bis (indenyl) zirconium dimethyl, bis (indenyl) zirconium diisobutyl, dimethyl Rubis (indenyl) zirconium dimethyl, methylenebis (indenyl) zirconium dimethyl, ethylenebis (indenyl) zirconium dimethyl, bis (4,5,6,7-tetrahydroindenyl) zirconium dimethyl, dimethylsilylbis (4,5,6,7 -Tetrahydro-1-indenyl) zirconium dimethyl, ethylenebis (4,5,6,7-
Tetrahydro-1-indenyl) zirconium dimethyl, bis (methylcyclopentadienyl) zirconium dimethyl, dimethylsilylbis (3-methyl-1-cyclopentadienyl) zirconium dimethyl, bis (third
Tert-butylcyclopentadienyl) zirconium dimethyl, dimethylsilylbis (3-tert-butyl-1-cyclopentadienyl) zirconium dimethyl, bis (1,
3-dimethylcyclopentadienyl) zirconium dimethyl, bis (1,3-dimethylcyclopentadienyl)
Zirconium diisobutyl, dimethylsilylbis (2,
4-dimethyl-1-cyclopentadienyl) zirconium dimethyl, methylenebis (2,4-dimethyl-1-cyclopentadienyl) zirconium dimethyl, ethylenebis (2,4-dimethyl-1-cyclopentadienyl)
Zirconium dimethyl, bis (1,2,4-trimethylcyclopentadienyl) zirconium dimethyl, dimethylsilylbis (2,3,5-trimethyl-1-cyclopentadienyl) zirconium dimethyl, bis (fluorenyl) zirconium dimethyl, dimethyl Silylbis (fluorenyl) zirconium dimethyl, (fluorenyl)
(Cyclopentadienyl) zirconium dimethyl, dimethylsilyl (fluorenyl) (cyclopentadienyl)
Zirconium dimethyl, (tertiary butyl amide) (1,
2,3,4,5-pentamethylcyclopentadienyl)
Zirconium dimethyl, dimethylsilyl (tertiary butylamide) (2,3,4,5-tetramethyl-1-cyclopentadienyl) zirconium dimethyl, methylene (tertiary butylamide) (2,3,4,5-tetra Methyl-
1-cyclopentadienyl) zirconium dimethyl,
(Phenoxy) (1,2,3,4,5-pentamethylcyclopentadienyl) zirconium dimethyl, dimethylsilyl (o-phenoxy) (2,3,4,5-tetramethyl-1-cyclopentadienyl) Zirconium dimethyl, methylene (o-phenoxy) (2,3,4,5-tetramethyl-1-cyclopentadienyl) zirconium dimethyl, bis (dimethylamido) zirconium dimethyl, bis (diethylamido) zirconium dimethyl, bis (di Examples include tertiary butylamido) zirconium dimethyl, dimethylsilylbis (methylamido) zirconium dimethyl, dimethylsilylbis (tertiary butylamido) zirconium dimethyl, and compounds in which zirconium in these compounds is replaced with titanium or hafnium. This The present invention is not limited to, et al. These transition metal alkyl compounds can be used alone or in combination of two or more kinds. The transition metal alkyl compound may be used after being synthesized in advance, or may be a transition metal halide in which R ″ in the general formula [IV] is substituted with a halogen atom, trimethylaluminum, triethylaluminum, diethylaluminum monochloride, It may be formed by contacting with an organometallic compound such as triisobutylaluminum, methyllithium or butyllithium in the reaction system.

The component (d) is an ionic compound represented by the following general formula [V]. ([L] ^{k +} ) _p ([M 'A ¹ A ² ...... A ⁿ ] ^- ) _q ...... [V] In the formula, [L] ^{k +} is a Bronsted acid or a Lewis acid, and M'is a periodic law. Table 13-Group 15 elements, A ¹ ~
^An is a hydrogen atom, a halogen atom, and a carbon number of 1 to 2, respectively.
0 alkyl group, C1-30 dialkylamino group, C1-20 alkoxy group, C6-40 aryl group, C6-40 aryloxy group, C7-40 alka A reel group, an aralkyl group having 7 to 40 carbon atoms, a halogen-substituted hydrocarbon group having 1 to 40 carbon atoms, an acyloxy group having 1 to 20 carbon atoms, or an organic metalloid group, and k is an ionic value of L of 1 to Is an integer of 3,
p is an integer of 1 or more, and q = (k × p).

Specific examples of the component (d) include trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, methyl (di-n-butyl) ammonium tetraphenylborate, and tetraphenyl. Dimethylanilinium borate, methylpyridinium tetraphenylborate, methyl tetraphenylborate (2-
Cyanopyridinium), methyl tetraphenylborate (4-cyanopyridinium), trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tri-n-butylammonium tetrakis (pentafluorophenyl) borate, tetrakis Methyl (di-n-butyl) ammonium (pentafluorophenyl) borate, dimethylanilinium tetrakis (pentafluorophenyl) borate, methylpyridinium tetrakis (pentafluorophenyl) borate, methyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium) ), Methyl tetrakis (pentafluorophenylphenyl) borate (4-cyanopyridinium),
Examples include dimethylanilinium tetrakis [bis (3,5-ditrifluoromethyl) phenyl] borate, ferrocenium tetraphenylborate, silver tetraphenylborate, and ferrocenium tetrakis (pentafluorophenyl) borate, but are not limited thereto. Not a thing. These ionic compounds may be used alone or in combination of two or more. (C)
The molar ratio of the component and the component (d) is usually 1:
It is in the range of 0.5 to 1:20, preferably 1: 0.8 to 1:10.

At the time of producing the rubbery copolymer (A) of the present invention, at least one of the catalyst components can be supported on a suitable carrier and used. The type of carrier is not particularly limited, and any of inorganic oxide carriers, other inorganic carriers, and organic carriers can be used. Also, the supporting method is not particularly limited, and a known method may be appropriately used.

The molecular weight distribution (M _{W of the} rubber-like copolymer (A) used in the present invention depends on the use of the rubber-reinforced vinyl resin.
/ M _n ) can be selected within the scope of the invention. That is, when the molecular weight distribution of the rubbery copolymer is 1.2 or more and less than 3, the graft reaction of the vinyl-based monomer is likely to occur uniformly, and as a result, a resin having high gloss can be obtained. The preferred range in this case is 1.7 to 2.2. On the other hand, when the molecular weight distribution is 3 or more and 20 or less, a resin having excellent impact resistance can be obtained. The preferable range in this case is 3.5 to 10. The rubbery copolymer whose molecular weight distribution is controlled as described above can be arbitrarily produced by using a metallocene catalyst.

The glass transition temperature (T _g ) of the rubbery copolymer (A) is -10 to -40 ° C, preferably -70 to.
When the rubber-like copolymer (A) has a melting point ( _Tm ) of 30 to 100 ° C, preferably 40 to 70 ° C at -50 ° C, a rubber excellent in balance between impact resistance and processability. A reinforced vinyl resin is obtained.

As the method for producing the rubber-reinforced vinyl resin of the present invention, a known method of radically polymerizing a vinyl monomer in the presence of the rubbery copolymer (A), for example, a solution polymerization method or a bulk polymerization method is used. Re-emulsification of the rubber component using a legal method and various emulsification / dispersion equipment such as homomixers and homogenizers.
An emulsion polymerization method or a suspension polymerization method in which the rubber component is used after redispersion is used. A solution polymerization method or a bulk polymerization method is preferable in order to obtain a resin excellent in transparency and colorability.
The solution polymerization method is particularly preferable.

The solution polymerization method will be described in detail below as an example. A solvent is used in the solution polymerization. The solvent is
An inert polymerization solvent used in ordinary radical polymerization, for example, ethylbenzene, aromatic hydrocarbons such as toluene, methyl ethyl ketone, ketones such as acetone,
Dichloromethylene, halogenated hydrocarbons such as carbon tetrachloride, acetonitrile, dimethylformamide, N-methylpyrrolidone and the like can be mentioned. The amount of the solvent used is 100 parts by weight of (rubber-like copolymer (A) + total monomer),
Preferably 20 to 200 parts by weight, more preferably 50
It is about 150 parts by weight.

The polymerization temperature is 80 to 140 ° C., preferably 8
The temperature is 5 to 130 ° C, more preferably 90 to 120 ° C. If the polymerization temperature is lower than 80 ° C., the viscosity of the polymer increases in the latter half of the polymerization, and stable operation is difficult. Also,
When the polymerization temperature exceeds 140 ° C., the amount of low molecular weight components due to the thermal initiation reaction increases.

In the polymerization of the present invention, an organic peroxide such as a ketone peroxide, a dialkyl peroxide, a diacyl peroxide, a peroxy ester or a hydroperoxide is used as a polymerization initiator.

As the chain transfer agent, for example, mercaptans, α-methylstyrene dimer and the like can be used. Further, other additives such as a phenol-based or phosphorus-based oxidation stabilizer, a benzotriazole-based or hindered amino-based light stabilizer, and a lubricant such as stearyl alcohol or ethylenebisstearamide can be mixed.

When the present invention is carried out by solution polymerization, either batch polymerization or continuous polymerization may be used. Further, the embodiment for maintaining the mixed state such that the reaction system is substantially uniform, but is not particularly limited, usually ribbon type stirring blade, turbine type stirring blade, screw type stirring blade, anchor type stirring blade Stirring and mixing by means such as, or circulation mixing by means of a pump or the like provided outside the reaction system is used, and a combination thereof is also suitable. Further, in the case of continuous polymerization, a tube-type polymerization machine, an extruder-type polymerization machine, a kneader-type polymerization machine or the like can be used as the second and subsequent polymerization machines.

Next, as a method for dissolving the solvent, unreacted monomers and the like from the reaction product obtained by the polymerization reaction and recovering the copolymer, a method in which the copolymer is suspended and dispersed in water and steam stripping is performed. A general method such as a method of preheating the copolymer solution and flushing it under reduced pressure, or a method of directly removing the solution with an extruder with a vent can be selected. On the other hand, other polymerization methods can also be carried out according to ordinary methods.

The vinyl monomer used in the present invention includes
Aromatic vinyl, vinyl cyanide, (meth) acrylic acid ester, unsaturated carboxylic acid, imide compound of α, β-unsaturated dicarboxylic acid and the like can be used. Among these, usable aromatic vinyl monomers are styrene and α.
-Methyl styrene, methyl styrene, vinyl xylene,
Monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, pt
There are ert-butylstyrene, ethylstyrene, vinylnaphthalene and the like, preferably styrene or α-methylstyrene, and particularly preferably styrene.

Examples of vinyl cyanide include acrylonitrile and methacrylonitrile, with acrylonitrile being particularly preferred.

As the (meth) acrylic acid ester, methyl acrylate, ethyl acrylate, propylene acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2
-Acrylic acid alkyl esters such as ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate and benzyl acrylate; methyl methacrylate, ethyl methacrylate, propylene methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-
Examples include alkyl methacrylates such as ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, and benzyl methacrylate. Particularly, methyl methacrylate is preferred.

As the unsaturated carboxylic acid, acrylic acid,
Unsaturated acids such as methacrylic acid and unsaturated acid anhydrides such as maleic anhydride, itaconic anhydride and citraconic anhydride can be used.

Examples of the imide compound of α, β-unsaturated dicarboxylic acid include maleimide, N-alkylmaleimides such as N-methylmaleimide, N-butylmaleimide and N-cyclohexylmaleimide, and N- (p-methylphenyl) maleimide. , N-aromatic maleimides such as N-phenylmaleimide. All of the above maleimides may be used after the corresponding α, β-unsaturated dicarboxylic acid is used as an imide compound, or a method may be adopted in which the corresponding α, β-unsaturated dicarboxylic acid is copolymerized and then imidized. Among these, N-cyclohexylmaleimide and N-phenylmaleimide are preferable.

It is preferable to use two or more of these vinyl-based monomers in combination. Particularly preferred specific examples of the combination of monomers are given below. Styrene-acrylonitrile, styrene-methyl methacrylate, styrene. -Acrylonitrile-methyl methacrylate. By replacing a part or all of the above styrene with α-methylstyrene, heat resistance can be imparted. Further, flame retardancy can be imparted by replacing a part or all of styrene with halogenated styrene. When methyl methacrylate is used in combination with the above-mentioned monomers, the transparency of the rubber-reinforced vinyl resin is improved and the coloring property is excellent.

The ratio of the rubbery copolymer (A) / vinyl monomer used in the present invention is 5-80 / 95-20% by weight, preferably 5-60 / 95-40% by weight, more preferably 10%. -40/90 to 60% by weight. When the use ratio of the rubbery copolymer (A) is less than 5% by weight, the impact resistance is poor, and when it exceeds 80% by weight, the surface hardness of the resin decreases, which is not preferable.

The graft ratio of the rubber-reinforced vinyl resin of the present invention is in the range of 5 to 200%, preferably 20 to 1
It is 40%, more preferably 30 to 80%. If the graft ratio is less than 5%, the impact resistance is not exhibited due to the decrease in the interfacial adhesion between the rubber phase and the matrix phase because the grafting is not performed, and if it exceeds 200%, the moldability deteriorates.

The rubber-reinforced vinyl resin described above has an intrinsic viscosity [η] (measured at 30 ° C.) of the methyl ethyl ketone soluble component of 0.1 to 1.0 dl / g, preferably 0.2 to
0.7 dl / g, more preferably 0.24 to 0.6 d
1 / g. When the intrinsic viscosity [η] is less than 0.1 dl / g, the impact resistance becomes insufficient, and when it exceeds 1.0 dl / g, the moldability is deteriorated due to the decrease in fluidity.

The rubber-reinforced vinyl-based resin of the present invention can be blended with the following other thermoplastic resins according to the purpose to form a rubber-reinforced vinyl-based resin composition. For example, polyethylene, polypropylene, polyvinyl chloride, chlorinated polyethylene, BR, NBR, SBR, SBS block copolymer, hydrogenated SBS, polystyrene, HIP.
S, styrene-acrylonitrile copolymer, ABS resin, AES resin, ASA resin, polysulfone, polyether sulfone, N-cyclohexylmaleimide copolymer styrene resin, N-phenylmaleimide copolymer styrene resin, MBS resin, methacryl Acid methyl-styrene copolymer, S-I-S block copolymer, polyimide, PPS, polyetheretherketone, vinylidene fluoride polymer, polycarbonate, polyacetal, polyamide, polyamide elastomer, polyester elastomer, PPE resin, etc. It can be illustrated. The blending ratio of these is rubber-reinforced vinyl resin / other thermoplastic resin of the present invention = 1 to 99/99 to 1 (% by weight).

The content of the rubber-like copolymer (A) in the rubber-reinforced vinyl resin composition (hereinafter referred to as rubber content) is
It can be arbitrarily selected according to the purpose, but in order to satisfy the impact resistance, moldability and transparency of the resin, the range is 5
It is 70% by weight, preferably 10 to 65% by weight. If the rubber content is less than 5% by weight, only a resin having insufficient impact resistance can be obtained, and if it exceeds 70% by weight, the surface hardness is unfavorably reduced.

The total light transmittance of the rubber-reinforced vinyl resin and composition of the present invention is preferably 30% or more, more preferably 40% or more. When the total light transmittance is 30% or more, the coloring property is improved, and a molded product having an excellent molded appearance can be obtained.

The method for obtaining the rubber-reinforced vinyl resin composition will be described in detail. After the two are mixed in the state of solution-solution or solution-latex, which is the reaction mixture after completion of the polymerization, the resin composition is prepared. May be carried out, or the both may be mixed in the form of powder-powder, powder-pellet, pellet-pellet, etc. after the resin recovery operation to produce a rubber-reinforced vinyl resin composition. May be. As a kneading method of the rubber-reinforced vinyl resin and another thermoplastic resin, various extruders, Banbury mixers, kneaders, rolls and the like are used. A preferable kneading method is a method using an extruder.

The rubber-reinforced vinyl resin of the present invention and the composition using the same are added to antioxidants such as hindered phenol, phosphorus and sulfur, light stabilizers, ultraviolet absorbers, lubricants, Additives that are commonly used, such as colorants, flame retardants, and enhancers can be added.

The molding method of the rubber-reinforced vinyl resin of the present invention and the composition using the same include injection molding type compression molding, extrusion molding and the like, but usually molding is carried out by the injection molding method. In the case of the injection molding method, the cylinder temperature of the injection molding machine is usually 180 to 280 ° C., preferably 200 to
The mold temperature is 40 to 100 ° C, preferably 5 to 240 ° C.
It is molded under the temperature condition of 0 to 80 ° C. As is clear from the above description, the present invention includes the following rubber-reinforced vinyl resin. (1) Ethylene / α-olefin having 6 to 20 carbon atoms / non-conjugated diene = 5 to 95/95 to 5/0 to 30 (% by weight)
95 to 20% by weight of a vinyl monomer is polymerized in the presence of 5 to 80% by weight of a rubbery copolymer (A) obtained by polymerizing a monomer having a mixing ratio of And a graft ratio of 5 to 200%, and an intrinsic viscosity [η] of the methyl ethyl ketone soluble component is 0.1 to 1.0.
A rubber-reinforced vinyl-based resin characterized by being dl / g. (2) the rubber-like copolymer (A), the molecular weight distribution of 1.2 or more and less than _{3 (M W / M n)} , -110~-40 ℃
The rubber-reinforced vinyl-based resin according to (1), which has a glass transition temperature (T _g ) and a melting point (T _m ) of 50 to 100 ° C. (3) the rubber-like copolymer (A), a 3 to 20 of the molecular weight distribution (M _W / M _n), the glass transition temperature of -110~-40 ℃ and (T _g), 50 to 100 ° C. Melting point (T
The rubber-reinforced vinyl resin according to (1) above, which has _{m 2} ). The rubber-reinforced vinyl-based resin thus obtained and the composition using the same are excellent in impact resistance, weather resistance, colorability, and molding appearance, and therefore should be widely used in various applications utilizing these characteristics. You can

[0043]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In addition, all "parts" and "%" in the following sentences represent "parts by weight" and "% by weight", and various physical property tests were measured according to the following procedures.

(1) Ethylene content The ethylene-α-olefin copolymer was analyzed by ¹ H-NMR,
^{Using 13} C-NMR, the ethylene / α-olefin composition ratio was obtained, and a calibration curve showing the relationship between this and the previously obtained infrared analysis result was prepared. The composition of the copolymer obtained in each example was determined based on this calibration curve. (2) Glass transition temperature (T _g ) and melting point (T _m ) Measured by a DSC (differential scanning calorimeter) measuring method. (3) using a molecular weight distribution (M _W / M _n) WATERS Corporation 150C Gel permeation chromatography (GPC) apparatus was measured at 120 ° C. The o- dichlorobenzene as a solvent.

(4) Measurement of Graft Ratio and Intrinsic Viscosity [η] A certain amount (x) of the graft polymer was put into acetone,
Shake for 2 hours on a shaker to dissolve the free copolymer. Using a centrifuge, spin this solution at 23000 rpm
Centrifuge for 30 minutes to obtain insoluble matter. Then, by vacuum drying, the insoluble matter (y) is obtained by drying at 120 ° C. for 1 hour. The graft ratio was calculated by the following formula. Graft ratio (%) = [(y) − (x) × rubber fraction in graft polymer] / [(x) × rubber fraction in graft polymer] × 100 Intrinsic viscosity [η] is methyl ethyl ketone (MEK ) Soluble content was measured in MEK at 30 ° C. (5) Izod impact strength: ASTM D-256 (1/4 × 1/2 inch cross section, with notch) (6) Weather resistance: Sunshine weatherometer with carbon arc light source (Suga Test Instruments Co., Ltd. WEL-6X)
(S-DC) after exposure for 1000 hours, the Izod impact strength was measured and the retention rate was calculated. Test conditions Black panel temperature 63 ± 3 ° C Chamber temperature 60 ± 5% RH Rain cycle 18 minutes every 2 hours Carbon exchange cycle 60Hr Izod impact strength ASTM D-256 (cross section 1/8 x 1/2 inch) (7) Rockwell hardness (R scale): ASTM D
-785 (8) Total light transmittance: ASTM D-1003 (3.2
mm thickness)

(9) Colorability: The thermoplastic resin composition was blended in the following blending amounts, and colored pellets were obtained through an extruder. It was further molded to obtain a color tone evaluation plate. Regarding the coloring property of the black compound, the lightness was measured with a formula difference meter and expressed by the Munsell color value (the larger the value, the worse the coloring property). For the other coloring formulations, the saturation was visually determined. Black blended resin 100 Carbon black 0.5 Ca stearate 0.3 Red blended resin 100 Bengal 1.0 Ca stearate Ca 0.5 Blue blended resin 100 Ultramarine blue 1.0 Stearate Ca 0.5 Criteria ◎: Very clear Is. ○: It is clear. Δ: Between ○ and × X: The sharpness is insufficient. XX: There is no sharpness. (10) Flow mark Using an injection molding machine with a mold clamping pressure of 120 tons, a wall thickness of 2.
A flat plate having a length of 5 mm and a length of 150 mm and a length of 150 mm was molded (molding temperature 220 ° C.), and the flow mark generation state was visually determined. ◯: No occurrence at all Δ: Partial occurrence ×: Occurrence on the entire surface (11) Surface gloss: ASTM D-523 (θ = 45 °)

[Rubber Copolymer No. 1] To an autoclave made of stainless steel having an internal capacity of 20 liters, which had been sufficiently replaced with nitrogen, 8 liters of purified toluene and 60 mmol of methylaluminoxane in terms of aluminum atoms dissolved in 40 ml of purified toluene were added, and the temperature was raised to 40 ° C., and then ethylene was added. 1.5 liter / hr, propylene 3.5
L / hr was continuously fed. Then, 12 μmol of dicyclopentadienyl zirconium dichloride dissolved in 12 ml of purified toluene was added to initiate polymerization. During the reaction, the temperature was kept at 40 ° C., and the reaction was carried out for 20 minutes while continuously supplying ethylene and propylene. Then, methanol was added to stop the reaction, and 926 g of a polymer was recovered from the reaction solution by steam distillation.

[Rubber-like copolymer No. 2-4 and N
o. 6-8] Rubbery copolymer No. 6 except that the types and amounts of α-olefin and non-conjugated diene were changed. Synthesis was carried out in the same manner as in 1.

[Rubber-like copolymer No. 5] ethylene / 1
-Octene copolymer rubber ENGAGE # 8200 (DOW
(Manufactured by KK)

[Rubber-like copolymer No. 9] Copolymerization was carried out using a continuous polymerization device having an internal volume of 10 liters. In a polymerization vessel sufficiently replaced with nitrogen gas, ethyl aluminum sesquichloride 6.5 g / Hr, oxyvanadium trichloride 0.15 g / Hr, n-hexane 7.2 L / Hr,
Butene-1 Continuously supplied at a flow rate of 615 g / Hr and temperature 2
While maintaining at 0 ° C., hydrogen was continuously supplied at a flow rate of 3 NL / Hr and a pressure of 3.0 kgG / cm ² , and polymerization was carried out under the condition of a residence time of 1 Hr. To the polymerization liquid withdrawn from the reactor, a small amount of water was added to stop the reaction, and the solvent was removed by steam distillation from the system,
After drying in the finishing step, the rubbery copolymer No. 9 was obtained.
The above rubbery copolymer No. 1 to No. Table 1 shows the composition and physical properties of No. 9.

[0051]

[Table 1]

Example 1 A rubber-like polymer No. 1 was placed in a stainless steel autoclave with an internal volume of 10 liter equipped with a ribbon-type stirring blade. 1 part (20 parts), styrene (4 parts), methyl methacrylate (76 parts), toluene (100 parts) and tertiary reed decyl mercaptan (0.1 part) were charged, stirred to form a uniform solution, and heated to 50 ° C. to give t-butylperoxyisopropyl carbonate. 0.5 part was added, the temperature was further raised, and after reaching 95 ° C, the polymerization reaction was carried out at a stirring rotation speed of 200 rpm while constantly controlling at 95 ° C. It took 1 hour from the 6th hour after the start of the reaction to raise the temperature to 120 ° C,
The reaction was continued for another 2 hours and the reaction was completed. After cooling to 100 ° C., 0.2 part of 2,2-methylenebis-4-methyl-6-t-butylphenol was added, the reaction mixture was extracted from the autoclave, and unreacted substances and the solvent were distilled off by steam distillation. After crushing, the volatile component was substantially distilled off with a 40 mmφ vented extruder (220 ° C., 700 mmHg vacuum), and the rubber-reinforced vinyl resin was pelletized.

[Examples 2 to 5] The base rubber was No. Two
A rubber-reinforced vinyl-based resin was obtained in the same manner as in Example 1 except that the number was changed to 5, and the types and ratios of the monomers to be copolymerized were changed.

Example 6 Rubbery copolymer No. One to one
After dissolving it in 00 parts and 1000 parts of cyclohexane, 7.0 parts of oleic acid was added to prepare a solution (a) kept at 70 ° C. 1.0 part of potassium hydroxide was dissolved in 300 parts of water, and the solution (a) was gradually added to the aqueous solution (b) kept at 70 ° C. with a homomixer at 3000 rpm to obtain an emulsified solution. . A mixture of 20 parts of latex obtained by removing cyclohexane from this emulsified solution, 180 parts of water, and 10 parts of potassium oleate was added with 0.2 parts of sodium pyrophosphate.
Part, dextrose 0.2 part, ferrous sulfate 0.004
Part, cumene hydroperoxide 0.4 part. Add 11 parts of styrene, 60 parts of methyl methacrylate, 9 parts of acrylonitrile and 0.3 parts of t-dodecyl mercaptan.
Part of the mixture was added dropwise to the reactor with stirring under a nitrogen stream. The dropping time was 2 hours, and the polymerization temperature was 60 ° C.
The obtained resin latex was coagulated, dried and pelletized.

[Examples 7 to 9] Rubbery copolymer No. 1
A rubber-reinforced vinyl resin was obtained in the same manner as in Example 1 except that the amount used, the type of monomer to be copolymerized, and the ratio were changed. Further, this rubber-reinforced resin was blended with another thermoplastic resin and kneaded with a 40 mmφ vent extruder to obtain a rubber-reinforced vinyl resin composition.

[Comparative Examples 1 to 4] 6 ~
A rubber-reinforced vinyl resin was obtained in the same manner as in Example 1 except that the number was changed to 9.

[Comparative Example 5.6] Rubbery copolymer No. 1
A rubber-reinforced vinyl resin was obtained in the same manner as in Example 1 except that the amount used, the type of monomer to be copolymerized, and the ratio were changed.

Comparative Example 7 A rubber-like polymer No. 1 was placed in a stainless steel autoclave having an internal volume of 10 liter equipped with a ribbon-type stirring blade. 1 part of 20 parts, styrene of 56 parts, acrylonitrile of 24 parts, toluene of 300 parts and tertiary reed decyl mercaptan of 2.0 parts were charged, stirred to form a uniform solution, heated to 50 ° C. and t-butylperoxyisopropyl carbonate 1 .2 parts was added and the temperature was further raised,
After the temperature reached 105 ° C., the polymerization reaction was carried out at a stirring rotation speed of 200 rpm while constantly controlling at 105 ° C. It takes 1 hour from the 3rd hour after starting the reaction to raise the temperature to 120 ° C,
The reaction was continued for another 3 hours to complete the process. After that, the same treatment as in Example 1 was performed.

[Comparative Example 8] 5 parts of potassium oleate,
Cumene hydroperoxide was 0.2 part, t-dodecyl mercaptan was 0 part, and the polymerization temperature was 50 ° C.
A rubber-reinforced vinyl resin was obtained in the same manner as in Example 6 except that the dropping time was 5 hours. Tables 2 and 3 show the results of measuring the physical properties of the above Examples and Comparative Examples.

[0060]

[Table 2]

[0061]

[Table 3]

[0062]

As is clear from the examples and comparative examples relating to the rubber-reinforced vinyl-based resin of the present invention shown in Tables 2 and 3, the rubber-reinforced vinyl-based resin of the present invention and the composition using the same are Due to its excellent impact resistance, weather resistance, colorability, and molding appearance, it can be expected to be widely used in a wide range of industrial fields.

Claims (2)

[Claims] 1. Ethylene / α-olefin having 3 to 20 carbon atoms / non-conjugated diene = 5 to 95/95 to 5/0 to 30
Rubber-like copolymer (A) 5-8 obtained by polymerizing a monomer having a mixing ratio of (% by weight) using a metallocene catalyst
It is obtained by polymerizing 95 to 20% by weight of a vinyl monomer in the presence of 0% by weight, has a graft ratio of 5 to 200%, and has an intrinsic viscosity [η] of a methyl ethyl ketone soluble component of 0.
A rubber-reinforced vinyl-based resin, which is 1 to 1.0 dl / g. 2. The rubber-like copolymer (A) is 1.2 to
The molecular weight distribution of 20 _{(M W / M n),} -110~-40
The rubber-reinforced vinyl-based resin according to claim 1, which has a glass transition temperature (T _g ) of ° C and a melting point (T _m ) of 30 to 100 ° C.