JPH11130826A - Rubber-modified thermoplastic resin and its composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject weather resistant resin having excellent colorability, chemical resistance an impact strength, by subjecting an aromatic vinyl compound to graft polymerization in the presence of a specific ethylene-α- olefin-based copolymer and a hydrogenated rubber. SOLUTION: An aromatic vinyl compound is subjected to graft polymerization in the presence of (A) 10-100 wt.% of (i) 90-10 wt.% of a rubber-like polymer comprising 60-95 wt.% of ethylene, 40-5 wt.% of a 3-18C α-olefin and 0-20 wt.% of a nonconjugated diene and having the ratio of a weight-average molecular weight to a number-average molecular weight of 1.2-5 and (ii) 10-90 wt.% of a rubber-like polymer of the formula, (A-B)nAm (A is an aromatic vinyl compound polymer block; B is a hydrogenated polymer block of a conjugated diene- based compound; (n) is >=2; (m) is 0 or 1) obtained by hydrogenating >=95 mol.% of the unsaturated bond part of a block copolymer composed of an aromatic vinyl compound and a conjugated diene and (B) 90-0 wt.% of a rubber-like polymer of the formula, A-B-Am to give the objective resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a specific EP (D)
M and an aromatic vinyl-conjugated diene block copolymer obtained by graft polymerization of a monomer component mainly composed of an aromatic vinyl compound in the presence of a rubbery polymer obtained by hydrogenating an unsaturated bond portion, The present invention relates to a rubber-modified thermoplastic resin having excellent coloring properties, remarkably improved defect phenomena such as flow marks, and excellent weatherability, impact resistance, chemical resistance and moldability, and a composition thereof.

[0002]

2. Description of the Related Art An E which does not substantially contain an unsaturated bond in its main chain.
Graft copolymer (AES resin) obtained by graft polymerization of styrene, acrylonitrile, etc. using PM or EPDM as a rubber component is more resistant to ultraviolet rays, oxygen and ozone than ABS resin using conjugated diene rubber. It is known that the weather resistance is remarkably good. However, since the AES resin is inferior in chemical resistance, it is necessary to take measures such as reducing the amount of rubber, and as a result, the strength is reduced, and there are cases where the use site and the use method are restricted. Therefore, in order to improve the chemical resistance, blending of a polyolefin resin such as polypropylene or polyethylene has been performed.
Resin is not said to have good compatibility with these polyolefin resins, and by blending with these resins,
Problems such as a decrease in impact resistance and a decrease in the appearance of the molded article have occurred. A method of blending a graft copolymer containing a triblock type hydrogenated rubbery polymer such as SEBS as a rubber component with a polyolefin resin is also known.
When a block copolymer having a hard block such as BS at both ends is used, rubber is likely to be restricted, and the compatibility with the polyolefin resin is not sufficient. For this reason,
These blended resin compositions do not exhibit impact resistance and are restricted in the method of use and the like. Further, when a hydrogenated rubber such as SEBS is used as a rubber component, there is a problem that the styrene block lowers chemical resistance.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and has problems in coloring, chemical resistance, and the like.
It is an object of the present invention to provide a weather-resistant rubber-modified thermoplastic resin having remarkably excellent impact strength, and a composition thereof.

[0004]

SUMMARY OF THE INVENTION The present invention provides an ethylene 60
Α-olefin having 3 to 18 carbon atoms
5% by weight and 0 to 20% by weight of a non-conjugated diene (provided that
Ethylene + α-olefin + non-conjugated diene = 100% by weight), and the ratio of weight average molecular weight to number average molecular weight (M
w / Mn) is from 1.2 to 5, a rubbery polymer (A) 90
10 to 10% by weight of the block copolymer composed of an aromatic vinyl compound and a conjugated diene compound,
The following rubbery polymer (b) 10 hydrogenated at least 5 mol%
10 to 100% by weight of the block copolymer comprising the aromatic vinyl compound and the conjugated diene compound, and 95% by weight of the unsaturated bond portion of the block copolymer comprising the aromatic vinyl compound and the conjugated diene compound. % Of the following rubbery polymer (c) 90 to 0% by weight [provided that (a) +
(B) + (c) = 100% by weight], and graft-polymerize a monomer component comprising an aromatic vinyl compound and, if necessary, another vinyl monomer copolymerizable therewith. The graft ratio is less than 45%, intrinsic viscosity [η] of acetone-soluble component (measured in methyl ethyl ketone at 30 ° C)
Is 0.2 to 0.7 dl / g. (AB) nAm (where A is an aromatic vinyl compound polymer block, B is a hydrogenated polymer block of a conjugated diene compound, and n ≧
2, m is 0 or 1. AB-Am (where A, B, and m are the same as described above) Here, the monomer component is an aromatic vinyl compound in an amount of from 8 to 85% by weight and copolymerized. It is preferable to use 92 to 15% by weight of another possible vinyl monomer [however, aromatic vinyl compound + another copolymerizable vinyl monomer = 100% by weight]. Further, the other copolymerizable vinyl monomer,
Those which are alkyl (meth) acrylates and / or vinyl cyanide compounds are preferred. Next, the present invention provides (I) 2 to 70 parts by weight of the rubber-modified thermoplastic resin, (II) 1 to 50 parts by weight of the polyolefin-based resin, and (III) a rubber-modified resin other than the component (I). ) 0 to 50 parts by weight of thermoplastic resin [however, (I) + (II) + (II)
I) = 100 parts by weight].

[0005]

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a specific ethylene-α-
Olefin- (non-conjugated diene) copolymer [EP (D)
M] (hereinafter also referred to as an “ethylene-α-olefin-based copolymer”) and a hydrogenated rubber (hydrogenated block copolymer) in the presence of a graft polymerization of a monomer component mainly composed of an aromatic vinyl compound By doing so, a weather-resistant rubber-modified thermoplastic resin having remarkably excellent coloring properties, chemical resistance and impact strength is obtained. The rubber-modified thermoplastic resin of the present invention contains the above-mentioned specific rubbery polymer (a) to (b), and optionally, a rubbery polymer (c) in the presence of an aromatic vinyl compound, or It is obtained by graft polymerization of a monomer component comprising an aromatic vinyl compound and another vinyl monomer copolymerizable therewith.

The rubbery polymer used in the present invention (a)
Is an ethylene-α-olefin- (non-conjugated diene) copolymer. Here, the α-olefin has 3 to 1 carbon atoms.
8, preferably 3 to 10, particularly preferably 3 to 8. Preferred α-olefins include propylene, butene-1, hexene-1, 3-methylpentene-1, and octene-1. Particularly preferred are butene-1 and octene-1. Examples of the non-conjugated diene used as needed include dicyclopentadiene and ethylidene norbornene. Particularly preferred rubbery polymers (a) are ethylene-butene rubber and ethylene-octene rubber, which are copolymers of butene-1, octene-1 and ethylene. The rubbery polymer (a) may be a block copolymer, a random copolymer, or a combination thereof, as long as the rubber structure exhibits a rubber-like property at room temperature.

The rubbery polymer (a) is ethylene / α
The proportion of olefins is 60 to 95% by weight of ethylene, preferably 70 to 90% by weight, 40 to 5% by weight of α-olefin, preferably 30 to 10% by weight, non-conjugated diene 0 to 0%;
20% by weight, preferably 0 to 15% by weight, and the ratio (Mw / Mn) of the weight average molecular weight to the number average molecular weight is 1.2 to
5, preferably 1.4 to 3.5, particularly preferably 1.5
~ 3. If the ethylene content is less than 60% by weight or the α-olefin content exceeds 40% by weight, the moldability deteriorates, while the ethylene content exceeds 95% by weight,
Alternatively, if the α-olefin content is less than 5% by weight, rubber-like properties are reduced and impact resistance is deteriorated, which is not preferable. When the non-conjugated diene content exceeds 20% by weight,
It is not preferable because a gel is generated during the graft polymerization, and as a result, the appearance of the resin is deteriorated. On the other hand, if the molecular weight distribution Mw / Mn is less than 1.2, the balance between impact resistance and fluidity deteriorates, which is not preferable. On the other hand, if it exceeds 5, gels are generated during polymerization, resulting in molding. The appearance of the product deteriorates, which is not preferable.

Next, the rubbery polymers (b) and (c) used in the present invention comprise an aromatic vinyl compound polymer block A and 95 moles of an unsaturated bond portion of a conjugated diene compound polymer block. % Obtained by adding more than 1% hydrogen
Is a hydrogenated block copolymer consisting of N in the rubbery polymer (b) is 2 or more. When n is 1, it has the same block structure as the rubbery polymer (c),
Warm kerosene resistance and compatibility with olefin resins are undesirably reduced.

The proportion of the aromatic vinyl compound polymer block A in the rubbery polymers (b) to (c) is preferably from 10 to 50% by weight, more preferably from 13 to 40% by weight, in the block copolymer. It is. If it is less than 10% by weight,
If the surface appearance of the resin is unfavorably reduced, on the other hand, if it exceeds 50% by weight, impact resistance is not exhibited, which is not preferred.
In addition, the block B in the rubbery polymers (b) to (c)
Is composed of a hydrogenated portion of a conjugated diene compound polymer block, and its hydrogenation rate is 95 mol% or more, preferably 97% or more. If the hydrogenation rate is less than 95 mol%,
Gel is generated during graft polymerization, and stable polymerization cannot be performed. In addition, the 1,2-vinyl bond content of the block B is preferably from 10 to 90 mol%,
80 mol% is more preferred. If the 1,2-vinyl bond content is less than 10 mol%, rubber-like properties are lost and impact resistance is lowered, which is not preferable. On the other hand, if it exceeds 90 mol%, chemical resistance is not exhibited, which is not preferable.

The aromatic vinyl compound used in the rubbery polymers (b) to (c) includes styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene , N, N
-Diethyl-p-aminoethylstyrene, N, N-diethyl-p-aminomethylstyrene, vinylpyridine, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, ethylstyrene, vinylnaphthalene, etc. Styrene and α-methylstyrene are particularly preferred. These aromatic vinyl compounds can be used alone or
Used as a mixture of more than one species.

The conjugated diene compounds used for the rubbery polymers (b) to (c) include 1,3-butadiene, isoprene, 1,3-pentadiene, chloroprene and the like. In order to obtain a hydrogenated diene rubber polymer which can be used and has excellent physical properties, 1,3-butadiene and isoprene are preferred.

The weight average molecular weight (Mw) (hereinafter also referred to as "molecular weight") of the rubbery polymers (b) to (c) in terms of polystyrene is preferably from 60,000 to 300,000, more preferably 70,000. ~ 250,000. If it is less than 60,000, impact resistance will not be exhibited, while if it has a high molecular weight exceeding 300,000, molding appearance such as flow mark will be deteriorated during molding, which is not preferable. In addition, rubbery polymers (b) to (c)
Has a molecular weight distribution (Mw / Mn) of preferably 1.1 to
3, more preferably 1.15 to 2.5. Mw /
When Mn is less than 1.1, the balance between impact resistance and fluidity is poor, which is not preferable. On the other hand, when Mn is more than 3, the appearance of the flow mark is deteriorated due to the occurrence of flow marks, which is not preferable.

In order to obtain a pre-hydrogenated block copolymer constituting the rubbery polymer (b), an organic lithium compound such as n-butyllithium or another organic lithium compound such as n-butyllithium is used as a polymerization catalyst in an inert solvent such as cyclohexane. Using an alkali metal compound, if necessary, to adjust the vinyl bond content, using a polar organic compound such as tetrahydrofuran, hexamethylphosphoryltriamide, thioether, and other tertiary amines, for example, an aromatic vinyl compound, Block copolymerization is performed in the order of a conjugated diene compound, an aromatic vinyl compound, and a conjugated diene compound. Alternatively, a branched polymer may be obtained by coupling the polymer chain having an active terminal obtained by the above method with a polyfunctional compound such as silicon tetrachloride or tin tetrachloride. Further, these branched polymers may be mixed with the block copolymer. The block copolymer before hydrogenation constituting the rubbery polymer (c) is basically produced in the same manner as the above block copolymer. In addition, rubbery polymer (b)
In order to obtain (c), the block copolymer is converted to di-p-
It is obtained by adding and hydrogenating a hydrogenation catalyst such as a solution of tolylbis (1-cyclopentadiene) titanium / cyclohexane.

The proportion of the rubbery polymer (a) to (b) is such that the component (a) is 90 to 1 in the components (a) to (b).
0% by weight, preferably 70 to 30% by weight, more preferably 65 to 40% by weight, and the component (ii) has a content of 10 to 90% by weight, preferably 30 to 70% by weight, and more preferably 3 to 70% by weight.
5 to 60% by weight. When the proportion of the component (a) exceeds 90% by weight, the chemical resistance typified by gasoline resistance decreases, while when the proportion is less than 10% by weight, the balance between impact resistance and appearance is not good, which is not preferable. . Also, (a) ~
In the component (c), the use ratio of the components (a) to (b) and the component (c) is as follows.
100% by weight, preferably 50 to 100% by weight, more preferably 60 to 90% by weight, and component (c) is 90 to 0% by weight, preferably 80 to 0% by weight, more preferably 5 to 5% by weight.
It is 0 to 0% by weight, particularly preferably 40 to 10% by weight. If the component (c) exceeds 90% by weight, chemical resistance such as hot kerosene resistance deteriorates, and when the composition is used, the compatibility with the polyolefin resin described later deteriorates, which is not preferable.

The rubber-modified thermoplastic resin of the present invention can be prepared by preparing an aromatic vinyl resin in the presence of the rubbery polymers (a) to (b) and, if necessary, the rubbery polymer (c). It can be obtained by graft-polymerizing a compound and, if necessary, a monomer component composed of another vinyl monomer copolymerizable therewith. Here, the aromatic vinyl compound constituting the monomer component is the same as the aromatic vinyl compound constituting the rubbery polymers (b) to (c), but is preferably styrene or an aromatic vinyl compound. Of styrene of 50% by weight or more.

Other vinyl monomers copolymerizable with the aromatic vinyl compound include methyl methacrylate,
Examples thereof include vinyl cyanide compounds such as alkyl (meth) acrylates such as butyl acrylate, acrylonitrile, and methacrylonitrile. As the alkyl (meth) acrylate, methyl methacrylate is preferable, and as the vinyl cyanide compound, acrylonitrile is preferable. These other vinyl monomers can be used alone or in combination of two or more.

The proportion of the monomer component used is such that the aromatic vinyl compound is preferably 8 to 85% by weight, more preferably 10 to 80% by weight, particularly preferably 11 to 75% by weight.
Another vinyl monomer is preferably 92 to 15% by weight,
More preferably 90 to 20% by weight, particularly preferably 8% by weight.
9 to 25% by weight. If the amount of the aromatic vinyl compound is less than 8% by weight, the thermal stability of the resin decreases, which is not preferable. On the other hand, if the amount exceeds 85% by weight, the toughness of the resin decreases, which is not preferable.

The amount of rubber in the rubber-modified thermoplastic resin of the present invention, that is, the total amount of the rubbery polymers (a) to (c) used is preferably 12 to 40% by weight, more preferably 15 to 40% by weight. To 35% by weight, particularly preferably 18 to 32%
% By weight. If the amount is less than 12% by weight, the balance between impact resistance and appearance is poor. On the other hand, if it exceeds 40% by weight, deterioration in appearance is extremely undesirable.

The graft ratio of the rubber-modified thermoplastic resin of the present invention is less than 45%, preferably 20 to 43%, more preferably 22 to 40%. If the graft ratio is 45% or more, the balance between appearance and impact resistance is deteriorated, which is not preferable. The graft ratio can be adjusted by the amount of a polymerization initiator, a chain transfer agent, a solvent, and the like. For example, to increase the graft ratio, increase the amount of the polymerization initiator used,
It is effective to reduce the amount of solvent used. vice versa,
In order to reduce the graft ratio, in addition to reducing the amount of the polymerization initiator, increasing the amount of the chain transfer agent or increasing the amount of the solvent may be mentioned. Here, graft ratio (%)
Represents the weight of the rubber component in 1 g of the rubber-modified thermoplastic resin as x,
Assuming that the weight of the acetone-insoluble matter is y, the value is obtained by the following equation. Graft ratio (%) = [(y−x) / x] × 100

The intrinsic viscosity [η] of the acetone-soluble component which is a matrix component of the rubber-modified thermoplastic resin of the present invention.
(Measured in methyl ethyl ketone at 30 ° C.)
0.7 dl / g, preferably 0.22 to 0.65 dl / g
g, more preferably 0.25 to 0.6 dl / g. If the intrinsic viscosity [η] is less than 0.2 dl / g, the impact resistance is undesirably reduced, and if it exceeds 0.7 dl / g, the molding processability is undesirably reduced. The intrinsic viscosity [η] can be easily controlled by changing the types and amounts of the polymerization initiator, the chain transfer agent, the emulsifier, the solvent, and the like, and further, the polymerization time, the polymerization temperature, and the like.

The rubber-modified thermoplastic resin of the present invention comprises:
Its total light transmittance is preferably 20% or more, more preferably 25% or more. If it is less than 20%, the coloring property is reduced, and the appearance is unfavorably deteriorated. Here, the total light transmittance can be adjusted by increasing or decreasing the styrene content of the rubbery polymers (a) and (b) used. That is, when the styrene content is increased, the refractive index of the rubbery polymer is increased and can be made closer to the refractive index of the matrix component, so that the total light transmittance can be increased.

The rubber-modified thermoplastic resin of the present invention may be obtained by adding the above monomer containing an aromatic vinyl compound as a main component in the presence of the rubbery polymer (a) to (b) or (a) to (c). It can be produced by subjecting the body component to radical graft polymerization by emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or the like. Preferred are solution polymerization, bulk polymerization and suspension polymerization. In addition,
For the radical graft polymerization, a polymerization initiator, a chain transfer agent, and the like are used. Further, the rubbery polymer and the monomer component used to produce the rubber-modified thermoplastic resin may be polymerized by adding the monomer component at a time in the presence of the entire amount of the rubbery polymer, Alternatively, polymerization may be performed by continuous addition. Moreover, you may superpose | polymerize by the method which combined these. Further, the whole or a part of the rubbery polymer may be added during the polymerization to carry out the polymerization.

Examples of the polymerization initiator include organic hydroperoxides represented by cumene hydroxyperoxide, diisopropylbenzene hydroperoxide, paramenthane hydroperoxide and the like, sugar-containing pyrophosphate formulations, sulfoxylate formulations and the like. A redox system in combination with a reducing agent, or a peroxide such as persulfate, azobisisobutyronitrile, benzoyl peroxide or the like is used. Preferably, it is an oil-soluble initiator, and is a redox system obtained by combining a cumene hydroperoxide, a diisopropylbenzene hydroperoxide, a paramenthane hydroperoxide with a reducing agent represented by a sugar-containing pyrophosphate formulation, a sulfoxylate formulation, and the like. Is good. Moreover, you may combine the said oil-soluble initiator and a water-soluble initiator. When combined, the addition ratio of the water-soluble initiator is preferably 50% by weight or less, more preferably 25% by weight or less of the total amount. Further, the polymerization initiator can be added to the polymerization system all at once or continuously. The amount of the polymerization initiator to be used is generally 0.1 to 1.5% by weight, preferably 0.2 to 0.7% by weight, based on the monomer component.

Examples of the chain transfer agent include mercaptans such as octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, t-tetradecyl mercaptan, tetraethylthiuram sulfide, and the like. Examples include hydrocarbons such as carbon tetrachloride, ethylene bromide and pentaphenylethane, or dimers of acrolein, methacrolein, allyl alcohol, 2-ethylhexylthioglycolate, and α-methylstyrene. These chain transfer agents can be used alone or in combination of two or more. The method of using the chain transfer agent may be any of batch addition, divisional addition, and continuous addition. The amount of the chain transfer agent is usually about 0.05 to 2.0% by weight based on the monomer component. The rubber-modified thermoplastic resin has a polymerization temperature of 10 to 10.
It is desirable to carry out solution polymerization or suspension polymerization at 140 ° C, preferably 30 to 130 ° C.

Next, the thermoplastic resin composition of the present invention comprises (I) a rubber-modified thermoplastic resin, (II) a polyolefin-based resin, and, if necessary, (III) a component other than the component (I). (Rubber modified) A composition mainly composed of a thermoplastic resin. Here, (II) polyolefin resins include ethylene, propylene, butene-1,3-methylbutene-
1,3-methylpentene-1,4-methylpentene-1
And α-olefin homopolymers and copolymers thereof. Representative examples include high-density, medium-density, low-density polyethylene, linear low-density polyethylene, ultra-high-molecular-weight polyethylene, ethylene-vinyl acetate copolymer, polyethylene such as ethylene-ethyl acrylate copolymer, and propylene alone. Polymers, polypropylenes such as propylene-ethylene-diene copolymers, polybutene-
1, poly-4-methylpentene-1 and the like.
Of these, crystalline polyethylene and crystalline polypropylene are preferred.

Here, the crystalline polypropylene includes, for example, an isotactic polypropylene homopolymer having crystallinity, and a copolymer part composed of an ethylene-propylene copolymer having a small ethylene unit content. Is commercially available as a so-called propylene block copolymer. In fact, a block copolymer of crystalline propylene and ethylene, or each homopolymer or copolymer in this block copolymer further comprises butene-1 Consisting of copolymerized α-olefin such as
Practically, a crystalline propylene-ethylene-α-olefin copolymer is preferably exemplified.

(III) Other (rubber-modified) thermoplastic resins other than the above (I) component which may be used in the thermoplastic resin composition of the present invention include high impact polystyrene (HIPS) and ABS resin. , AES resin, ACS
Resin, acrylic rubber reinforced AS resin, AS resin and the like. Further, a modified rubber-modified thermoplastic resin obtained by modifying these resins with a small amount of functional groups may be used. Among them, ABS resin, AES resin, acrylic rubber reinforced A
S resin and AS resin are preferred.

In the thermoplastic resin composition of the present invention, the compounding amount of the rubber-modified thermoplastic resin (I) of the present invention is (I)
2 to 70 parts by weight, preferably 5 to 60 parts by weight, more preferably 10 to 100 parts by weight based on 100 parts by weight of the total amount of the component (III).
５５55 parts by weight. If the amount is less than 2 parts by weight, the effect of improving the impact resistance is not exhibited, while if it exceeds 60 parts by weight, the chemical resistance is undesirably reduced. The amount of the polyolefin resin (II) in the thermoplastic resin composition of the present invention is 1 to 100 parts by weight in the total amount of the components (I) to (III).
50 parts by weight, preferably 5 to 45 parts by weight, more preferably 10 to 40 parts by weight. If the amount is less than 1 part by weight, physical properties such as chemical resistance characteristic of the polyolefin resin are not exhibited, which is not preferable. On the other hand, when it exceeds 50 parts by weight, the impact resistance is lowered, which is not preferable. Further, in the thermoplastic resin composition of the present invention, the compounding amount of the (III) other (rubber-modified) thermoplastic resin is 1% in total of the components (I) to (III).
The amount is 0 to 50 parts by weight, preferably 2 to 40 parts by weight, more preferably 3 to 35 parts by weight in 00 parts by weight. If it exceeds 50 parts by weight, the appearance is unpreferably deteriorated.

The rubber-modified thermoplastic resin and the thermoplastic resin composition of the present invention may be blended with other polymers depending on the purpose. As other polymers, for example, polyvinyl chloride, polyphenylene ether, polycarbonate, polyethylene terephthalate,
Examples thereof include polybutylene terephthalate, polyacetal, polyamide, polyvinylidene fluoride, polystyrene, styrene-methyl methacrylate copolymer, styrene-maleic anhydride copolymer, and chlorinated polyethylene.
These other polymers can be used alone or in combination of two or more.

The rubber-modified thermoplastic resin and the thermoplastic resin composition of the present invention may contain an antioxidant such as a hindered phenol-based, phosphorus-based or sulfur-based compound, a light stabilizer, an ultraviolet absorber, a lubricant, and a coloring agent. Commonly used additives such as agents and enhancers can be blended.

To mix the above additives with the rubber-modified thermoplastic resin of the present invention, obtain the thermoplastic resin composition of the present invention, or further mix the above additives with the composition, various extrusion methods are used. It is obtained by kneading each component using a machine, a Banbury mixer, a kneader, a roll, a feeder ruder, or the like. A preferred production method is a method using an extruder and a Banbury mixer. The kneading temperature is preferably 150 to 270 ° C, more preferably 170 to 250 ° C, and particularly preferably 200 to 270 ° C.
２３０230 ° C. If it exceeds 270 ° C., decomposition of the resin occurs, which is not preferable. When kneading each component, each component may be kneaded at once, or may be added and kneaded in several times. For kneading, kneading may be carried out in an extruder in a multi-stage addition system, or a Banbury mixer,
It can also be kneaded with a kneader or the like, and then pelletized with an extruder.

The thus obtained rubber-modified thermoplastic resin or thermoplastic resin composition of the present invention can be obtained by injection molding, sheet extrusion, vacuum molding, heteromorphic molding, foam molding, injection press, press molding, blow molding, or the like. And can be molded into various molded products. The rubber-modified thermoplastic resin or the thermoplastic resin composition of the present invention has a molded appearance,
It has excellent weather resistance, impact resistance, molding processability, and chemical resistance.
It can be used for various parts, housings, chassis, trays, etc. in the fields of electronics, miscellaneous goods, sanitary, and automobile.

[0033]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. In the examples, parts and% are by weight unless otherwise specified. The various evaluations in the examples were measured as follows.

The degree of hydrogenation was calculated from the decrease in the unsaturated bond portion of the 100 MHz ¹ H-NMR spectrum measured at a concentration of 15% using ethylene tetrachloride as a solvent. The weight average molecular weight (molecular weight) was measured as follows according to Mw / Mn Takeuchi, Gel Permeation Chromatograph, published by Maruzen Co., Ltd. [1] Using standard polystyrene of known molecular weight (monodisperse polystyrene, manufactured by Toyo Soda Co., Ltd.)
And its GPC (Gel Permeation Chr)
Omatograph) count is measured, and a correlation curve calibration curve of molecular weight M and EV (Elution Volume) is drawn. The concentration at this time is 0.02
%. The calibration curve based on standard polystyrene was obtained by the universal method using EBM [EB Synthetic Rubber Co., Ltd., EB
M2041P]. [2] The GPC pattern of the sample is obtained by the GPC measurement method, and M is obtained by the above [1]. The sample adjustment conditions and GPC measurement conditions at that time are as follows.

Sample preparation; (a) To a solvent of o-dichlorobenzene, 0.08% of 2,6-di-t-butyl-cresol as an antioxidant is added and dissolved. (B) Aliquot the sample into an Erlenmeyer flask together with the o-dichlorobenzene solvent so as to have a concentration of 0.1%. (C) Heat the Erlenmeyer flask to 120 ° C. and stir for about 60 minutes to dissolve the sample. (D) GPC the solution. In addition, in a GPC apparatus, it filters automatically with a 0.5-micron sintered filter.

GPC measurement conditions; (a) Apparatus; 150C type, manufactured by Waters (b) Column: H type, manufactured by Toyo Soda Co., Ltd. (c) Sample amount: 500 μl (d) Temperature: 120 ° C. (e) Flow rate 1 ml / min (f) Total number of theoretical plates 1 * 10 2 * 1 (measured value with acetone)

Styrene Block Content Using ¹³ C-NMR, the composition ratio of the styrene polymer block to the hydrogenated polymer block of the conjugated diene compound was determined. The ethylene content ethylene -α- olefin copolymer, ¹ H-NM
Using R and ¹³ C-NMR, the composition ratio of ethylene / α-olefin was determined, and a calibration curve showing the relationship between the composition ratio and the result of infrared analysis previously determined was prepared. Based on this calibration curve, the composition of the copolymer obtained in each example was determined.

The infrared absorption value of a standard sample whose iodine value was determined in advance by the iodine value titration method was measured, and based on this, an infrared spectral calibration curve showing the relationship between the iodine value and the infrared absorption value was obtained. The copolymer was prepared, and the iodine value of the copolymer obtained in the example was determined from the infrared absorption value using the calibration curve.

Graft ratio A fixed amount (z) of the graft copolymer (rubber-modified thermoplastic resin) is put into acetone, and shaken for 2 hours with a shaker to dissolve the free copolymer. Using a centrifuge, this solution is centrifuged at 15,000 rpm for 30 minutes to obtain an insoluble content. Next, by vacuum drying, 120 ° C.
For 1 hour to obtain acetone-insoluble matter (y). The graft ratio was calculated from the following equation. Graft ratio (%) = {[(y)-(z) × Rubber fraction of graft copolymer] / [(z) × Rubber fraction of graft copolymer]} × 100 Intrinsic viscosity Obtained above. The acetone-soluble matter was dried and then dissolved in methyl ethyl ketone to obtain a solution having a concentration of 0.5%. The solution was determined by measuring the flow time at 30 ° C. using an Ubbelohde type viscosity tube.

Total light transmittance ( haze value) Measured according to the method of ASTM D1003 (3.2 mm thick). Izod impact strength Measured according to ASTM D256 (1/4 cross section)
1/2 inch, notched). Using a falling weight impact strength DuPont impact tester, hitting rod tip R = 1
/ 2 ″, the falling weight impact strength of a 1.6 mm thick molded product was measured.

The sample was exposed to a sunshine weatherometer (WEL-6XS-DC, manufactured by Suga Test Instruments Co., Ltd.) using a weather-resistant carbon arc as a light source for 1,000 hours, and the Izod impact strength was measured.
The retention was calculated. Test conditions; Black panel temperature 63 ± 3 ° C Humidity in the chamber 60 ± 5% RH Rain cycle 18 minutes every 2 hours Carbon exchange cycle 60 hours Izod impact strength ASTM D256

The coloring thermoplastic resin was blended according to the following formulation and colored pellets were obtained through an extruder. This was further molded to obtain a color tone evaluation plate. In addition, about the coloring property of the black compound, the lightness was measured with a color difference meter, and it was represented by the Munsell color value (the larger the value, the worse the coloring property). For other coloring formulations, the saturation was visually determined. Black composition; resin 100 parts Carbon black 0.5 part Calcium stearate 0.3 part Red composition: Resin 100 parts Bengala 1.0 part Calcium stearate 0.3 part Judgment criteria; ◎: Very clear. ；: Clear. Δ: between ○ and × ×; lack of sharpness XX; lack of sharpness.

Using an injection molding machine with a flow mark mold clamping pressure of 120 tons,
A flat plate having a length of 150 mm and a width of 150 mm was formed (molding temperature: 210 ° C.), and the occurrence of flow marks was visually determined. ；: There is no uneven gloss on the surface. X: There is uneven gloss on the surface. The surface gloss was measured according to the method of ASTM D523 (450).

A molded article made of warm kerosene-resistant black pellets (formulation: resin 100 parts, carbon black 0.5 part, calcium stearate 0.3 part) is immersed in JIS No. 6 kerosene (kerosene temperature 80 ° C.) After leaving at 50 ° C for 1 hour, wipe the surface,
After drying, the presence or absence of abnormality was determined. A: No discoloration is observed. ；: Discoloration is slightly observed. X: Changes such as whitening and gloss reduction are observed.

Surface appearance Using an injection molding machine with a mold clamping pressure of 30 tons, a wall thickness of 2.4 was used.
A molded product having a size of 80 mm × 50 mm in length and width was formed, and the surface appearance of the molded product was visually observed. ；: No gloss unevenness, rough skin, or surface peeling. Δ: Partly uneven gloss and rough skin. X: Uneven gloss, rough skin, and peeling of the surface.

Reference Example 1 (Production of hydrogenated block copolymer b-1) In an autoclave, 400 parts of cyclohexane, 1,3
-Butadiene 15 parts, tetrahydrofuran 0.05 parts,
After adding 0.04 part of n-butyllithium and polymerizing at 60 ° C. for 4 hours, adding 10 parts of styrene, polymerizing at 60 ° C. for 4 hours, further adding 65 parts of 1,3-butadiene,
C. for 4 hours, and finally 10 parts of styrene were added.
Polymerization was performed at 4 ° C. for 4 hours. The obtained active polymer was deactivated with methanol, the polymer solution was transferred to a reactor equipped with a jacket, and a di-p-tolylbis (1-cyclopentadienyl) titanium / cyclohexane solution (concentration) was used as a hydrogenation catalyst. (1 mmol / l) 250 ml and n-butyllithium solution (concentration 5 mmol / l) 50 ml at 0 ° C.
A mixture mixed under a hydrogen pressure of 2.0 kg / cm ² was added, and 0.2 parts of toluene was added per polymer at a hydrogen partial pressure of 3.0 kg / cm ^{2 for} 30 minutes to remove the solvent.
The hydrogenated block copolymer (hereinafter also referred to as “hydrogenated rubber”) obtained by this method is referred to as b-1.

Reference Example 2 (Production of hydrogenated block copolymer b-2) According to the method used in Reference Example 1, 1,3-butadiene was changed to isoprene, hydrogenated, and hydrogenated block copolymer Polymer b-2 was obtained.

Reference Example 3 (Production of hydrogenated block copolymer b-3) In an autoclave, 400 parts of cyclohexane, 15 parts of styrene, 0.05 parts of tetrahydrofuran, and 0.04 parts of n-butyllithium were added, and the mixture was heated at 60 ° C. For 4 hours,
70 parts of 1,3-butadiene was added and polymerized at 60 ° C. for 4 hours. Finally, 15 parts of styrene was added and polymerized at 60 ° C. for 4 hours. This polymer solution was hydrogenated in the same manner as in Reference Example 1 to obtain a hydrogenated block copolymer b-3.

Reference Examples 4 to 6 (hydrogenated block copolymer b-
4 to 6) The styrene content, the hydrogenation rate, the molecular weight, and the block structure differ according to the same method as in Reference Example 1.
Hydrogenated block copolymers b-4 to 6 were obtained. Table 1 shows details of these hydrogenated block copolymers.

[0050]

[Table 1]

*) S is a styrene polymer block, B is a butadiene polymer block, and I is an isoprene polymer block.

Reference Example 7 (Production of ethylene-α-olefin copolymer c-1) Copolymerization was carried out using a continuous polymerization apparatus having an internal volume of 10 liters. In a polymerization vessel sufficiently purged with nitrogen gas, a flow rate of 6.5 g / hour of ethyl sesqui-aluminum chloride, 0.15 g / hour of oxyvanadium trichloride, 7.2 liter / hour of n-hexane, and 615 g / hour of butene-1 At a temperature of 20 ° C., hydrogen at a flow rate of 3 Nl / hour, and a pressure of 3.0 kg / cm ^2.
-Ethylene was continuously supplied so as to reach G, and polymerization was performed under the condition of a residence time of 1 hour. A small amount of water was added as a reaction terminator to the polymerization liquid extracted from the reactor, the solvent was driven out of the system by steam distillation, and dried in the finishing step to obtain a copolymer c-1.

Reference Example 8 (Preparation of ethylene-α-olefin copolymer c-2) Commercially available ethylene-octene rubber [Dupont Dow KK]
Manufactured by ENGAGE 8200, octene content 24%, Mw
/Mn=1.8]. Reference Examples 9 to 12 (Production of ethylene-α-olefin-based copolymers c-3 to 6) In the same manner as for copolymer c-1, the amount of catalyst and the amount of 5-ethylidene-2-norbornene (ENB) supplied , Hydrogen supply,
The polymerization temperature was changed, and the pressure was further increased to 1.5 to 8 kg / cm ^2.
-The polymerization was carried out by continuously supplying ethylene while changing the range of G. Table 2 shows the details of these ethylene-α-olefin copolymers.

[0054]

[Table 2]

Example 1 (Production of Rubber-Modified Thermoplastic Resin) A hydrogenated block copolymer b-1 and a copolymer c-1 were added to a 10-liter stainless steel autoclave equipped with a ribbon-type stirring blade. 26 parts, styrene 52 parts, acrylonitrile 22 parts, toluene 120 parts and t-
0.1 part of dodecyl mercaptan is charged and stirred,
After making sure that the solid content of the hydrogenated block copolymer and the like was dissolved, a t-butyl peroxyisopropyl carbonate was added, and the temperature was further increased.
Stirring rotation speed 200 rpm while keeping constant at 95 ° C
The polymerization reaction was carried out. From the 6th hour after the start of the reaction, the temperature was raised to 120 ° C. over 1 hour, and the reaction was further performed for 2 hours to complete the reaction. The polymerization conversion was 97%. 100 ℃
After cooling to 2,2-methylenebis-4-methyl-6-
After addition of 0.2 parts of butylphenol, the reaction mixture was extracted from the autoclave, unreacted substances and the solvent were distilled off by steam distillation, and finely pulverized.
Extruder with φ vent (220 ° C, 700mmHg
(Vacuum), the volatile components were substantially distilled off, and the polymer was pelletized. This is called resin A1. Table 3 shows the results.

Examples 2 to 8, Comparative Examples 1 to 10 (Production of Rubber-Modified Thermoplastic Resin) Types of rubbery polymer (hydrogenated rubber, copolymer) used,
Resins A2 to A8 of Examples and Resins A9 to A18 of Comparative Examples were obtained by changing the amounts and the composition ratios of the monomer components used.
The results are shown in Tables 3 and 4.

From Table 3, it is found that the rubber-modified thermoplastic resins A1 to A8 of Examples 1 to 8 are required to be weather-resistant resins on the assumption that they are not subjected to surface treatment such as coating, that is, impact resistance and total light rays. A product that satisfies all of transmittance, molded appearance (colorability, flow mark, etc.), and weather resistance is obtained. In contrast, as apparent from Table 4, Comparative Example 1 (resin A
In 9), the hydrogenation rate of the hydrogenated rubber is low, so that the weather resistance is poor. Comparative Examples 2-3 (Resins A10-11) are cases where the butene-1 content falls outside the range of the present invention. In Comparative Example 2 (Resin A10), the resistance to hot kerosene was reduced, and in Comparative Example 3 (Resin A11), the molded appearance was reduced. In Comparative Example 4 (Resin A12), only the ethylene-α-olefin copolymer was used as the rubbery polymer, and the appearance was significantly reduced. Comparative Example 5 (Resin A13)
Is the one using only the rubbery polymer (c) as the rubbery polymer, and the hot kerosene resistance deteriorated. Comparative Example 6 (resin A14) is a case where the graft ratio is out of the range of the present invention, and the balance between the appearance and the impact strength is low. Comparative Example 7
(Resin A15) had a too wide molecular weight distribution of the ethylene-α-olefin-based copolymer, so that the hot kerosene resistance was reduced. Comparative Example 8 (Resin A16) is an example in which the rubbery polymer (b) of the present invention was not used, and the balance between the appearance and the impact strength was poor, and as described later, the compatibility with the polyolefin resin was poor. And the impact resistance of the resulting composition is reduced. Comparative Examples 9 to 10 (Resins A17 to 18) are examples in which the monomer component to be grafted deviates from the present invention, and have poor balance in transparency, impact resistance, warm kerosene resistance and the like.

[0058]

[Table 3]

[0059]

[Table 4]

Reference Example 13 (Production of ABS resin) A polybutadiene latex produced by a conventional method, having a toluene gel content of 80% and a particle size (measured by drying the latex into a film and measuring it with an electron micrograph).
40 nm of a solid having a thickness of 0 nm was charged into a separable flask having a volume of 10 liters in terms of solid content. After adding 100 parts of deionized water to this and stirring, nitrogen replacement was performed. To this, 15 parts of styrene and 5 parts of acrylonitrile were added, and the temperature was raised to 60 ° C. After the temperature was raised, 0.2 part of t-dodecyl mercaptan was added, and 0.4 part of sodium pyrophosphate, 0.01 part of iron (II) sulfate and 0.5 part of glucose previously dissolved in deionized water were added. added. Continue stirring and add 0.1% cumene hydroperoxide.
And the polymerization was started. One hour after the start of the polymerization, 45 parts of styrene, 15 parts of acrylonitrile, 0.2 parts of t-dodecylmercaptan, and 0.2 parts of cumene hydroperoxide were continuously added over 3 hours. After completion of the polymerization, the mixture was cooled to room temperature and then taken out. At this time, the polymerization conversion was 95%. 50 parts of this resin latex
In a liter coagulation bath, the mixture was coagulated at 95 ° C., washed with water and dried to obtain an ABS resin. Incidentally, 2 phr of sulfuric acid was added to the coagulation tank in advance.

Examples 9 to 16 and Comparative Examples 11 to 17 (Production of Thermoplastic Resin Composition) The rubber-modified thermoplastic resin obtained in the above Examples and Comparative Examples was replaced with polypropylene [MC0, manufactured by Mitsubishi Chemical Corporation].
1C], the ABS resin produced in Reference Example 13 (graft ratio = 55%, [η] = 0.5 dl / g, measured at 30 ° C., methyl ethyl ketone), AS resin (acrylonitrile / styrene (weight ratio) = 24/76) , [Η] = 0.7 dl /
g, methyl ethyl ketone, measured at 30 ° C.)
The mixture was kneaded at 220 ° C. with a 0 mmφ NVC extruder to obtain pellets. This was molded into a flat plate using an injection molding machine [NN30B molding machine, manufactured by Niigata Iron Works Co., Ltd.], and the appearance of the molded body was visually determined. The falling weight impact strength was measured by the same method as the above method. The results are shown in Tables 5-6.

As is clear from Table 5, Examples 9 to 16
The compositions of the present invention (compositions P1 to P8) are excellent in balance between falling weight impact strength and surface appearance. In contrast, as apparent from Table 6, Comparative Examples 11 to 17 (composition P9
To P15), the rubber-modified thermoplastic resin is out of the range of the present invention, and does not show good physical properties. Also,
Comparative Example 16 (Composition P14) does not show good physical properties because the compounding ratio of the compounded polypropylene is out of the range of the present invention.

[0063]

[Table 5]

[0064]

[Table 6]

[0065]

According to the present invention, impact resistance, molded appearance,
A rubber-modified thermoplastic resin having excellent chemical resistance and an excellent balance of physical properties required as a weatherable material that can be used outdoors, and a composition thereof are obtained.

Continued on the front page (72) Inventor Masaaki Mawatari 1-18-1, Kyobashi, Chuo-ku, Tokyo Techno Polymer Co., Ltd. (72) Inventor Fusumitsu Kitada 1-1-18 Kyobashi, Chuo-ku, Tokyo Techno Polymer Co., Ltd. Inside

Claims (4)

[Claims] 1. Ethylene 60 to 95% by weight, carbon number 3 to
No. 18 consisting of 40 to 5% by weight and a non-conjugated diene of 0 to 20% by weight (however, ethylene + α-olefin + non-conjugated diene = 100% by weight), and a ratio of a weight average molecular weight to a number average molecular weight (Mw / Mn) 1.2 to 5; 90 to 10% by weight of a rubbery polymer (a); and 95% by mole or more of hydrogenated unsaturated bond portion of a block copolymer comprising an aromatic vinyl compound and a conjugated diene compound. 10 to 90% by weight of the following rubbery polymer (b)
(A) + (b) = 100% by weight] and 10 to 100% by weight, and 95% of the unsaturated bond portion of the block copolymer comprising the aromatic vinyl compound and the conjugated diene compound.
The following rubbery polymer (C) 90% or more hydrogenated by mol% or more
In the presence of 0% by weight (provided that (a) + (b) + (c) = 100% by weight), an aromatic vinyl compound and, if necessary, another vinyl monomer copolymerizable therewith Is obtained by graft polymerization of a monomer component consisting of
%, Acetone-soluble component intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of 0.2 to 0.7 dl / g
Is a rubber-modified thermoplastic resin. (AB) nAm (where A is an aromatic vinyl compound polymer block, B is a hydrogenated polymer block of a conjugated diene compound, and n ≧
2, m is 0 or 1. AB-Am (where A, B, and m are the same as above). 2. The method according to claim 1, wherein the monomer component is an aromatic vinyl compound 8 or more.
85% by weight, other copolymerizable vinyl monomers 92-1
2. The composition according to claim 1, comprising 5% by weight (however, an aromatic vinyl compound + another copolymerizable vinyl monomer = 100% by weight).
The rubber-modified thermoplastic resin described in the above. 3. A copolymerizable other vinyl monomer,
3. The rubber-modified thermoplastic resin according to claim 1, which is an alkyl (meth) acrylate and / or a vinyl cyanide compound. 4. The rubber modified thermoplastic resin according to claim 1, wherein (I) 2 to 70 parts by weight of the rubber-modified thermoplastic resin, (II) 1 to 50 parts by weight of a polyolefin resin, and (III) the above (I).
0 to 50 parts by weight of a (rubber-modified) thermoplastic resin other than the component (provided that (I) + (II) + (III) = 100 parts by weight)
A thermoplastic resin composition containing as a main component.