JPH01236215A - Thermoplastic resin - Google Patents

Abstract

PURPOSE:To provide a thermoplastic resin excellent in an orientation strength, an elongation, an appearance of a weld, etc., by grafting an aromatic vinyl compound and a copolymerizable monomer compound in a specified weight ratio in the presence of a specified rubbery polymer. CONSTITUTION:99-1wt.% product of hydrogenation of a block copolymer comprising an aromatic vinyl compound and a conjugated diene compound (e.g., styrene/butadiene block copolymer) is mixed with 1-99wt.% acrylic rubber and/or ethylene/alpha-olefin rubber (e.g., ethylene/propylene copolymer rubber). 30-98wt.% aromatic vinyl compound (e.g., styrene) and 70-2wt.% monomer compound copolymerizable therewith (e.g., acrylonitrile) are grafted in the presence of the obtained rubbery polymer to produce a rubber-modified thermoplastic resin of an intrinsic viscosity of the methyl ethyl ketone solubles >=0.2dl/g.

Description

Detailed Description of the Invention a. Industrial Application Field The present invention relates to a rubbery polymer mixture comprising a hydrogenated block copolymer comprising an aromatic vinyl compound and a conjugated diene compound and a specific rubbery polymer. It is obtained by graft copolymerizing an aromatic vinyl compound and a monomer compound that can be copolymerized with the aromatic vinyl compound in the presence of This invention relates to thermoplastic resins with excellent weather resistance, impact resistance, and chemical resistance.

b. Conventional technology ABS resin in which styrene, acrylonitrile, etc. are graft copolymerized to diene rubber, ABS resin in which styrene, acrylonitrile, etc. are graft copolymerized to ethylene-propylene rubber, styrene, acrylonitrile, etc. in acrylic rubber. Rubber-reinforced styrenic resins such as graft copolymerized AAS resins are widely used as molding materials because of their excellent moldability, impact resistance, and chemical resistance.

However, ABS resin does not have sufficient weather resistance and thermal stability,
Furthermore, ABS resins and AAS resins have excellent weather resistance, but have insufficient orientation strength and elongation, and furthermore, ABS resins are insufficient in the appearance of weld portions, elongation, colorability, and gloss.

On the other hand, as these rubber-reinforced styrenic resins are used in various applications, alignment strength, weld appearance, colorability,
A high level of quality with excellent elongation, thermal stability, weather resistance, impact resistance, and moldability is now required, and conventional ABS resins, ABS resins, and AAS resins are no longer able to meet recent quality demands. It's here.

Problems to be Solved by the C0 Invention As a result of intensive studies regarding these points, we have developed a rubbery polymer consisting of a hydrogenated block copolymer consisting of an aromatic vinyl compound and a conjugated diene compound, and a specific rubbery polymer. By graft copolymerizing an aromatic vinylated metal material and a monomer compound copolymerizable with it in the presence of the mixture, alignment strength, weld appearance, elongation, thermal stability,
The present invention was achieved by successfully obtaining a resin with outstanding weather resistance, colorability, impact resistance, and chemical resistance.

61 Means for Solving the Problems The present invention provides 99 to 1% by weight of a hydrogenated block copolymer consisting of an aromatic vinyl compound and a conjugated diene compound;
In the presence of a rubbery polymer consisting of 1 to 99 weight percent of acrylic rubber and/or ethylene-α-olefin rubber, 30 to 98 weight percent of an aromatic vinyl compound (A) and a monomer copolymerizable therewith. 70 to 2% by weight of compound (B) is graft copolymerized, and the intrinsic viscosity (η) of the methyl ethyl ketone soluble portion (measured at 30"C) is 0.2 d17.
The present invention provides a rubber-modified thermoplastic resin having a molecular weight of at least 99-3.
aromatic vinyl compound (A) 30-9 in the presence of a rubbery polymer consisting of 0% by weight and 1-70% by weight of diene rubber.
8% by weight and a monomer compound copolymerizable therewith (B)
To provide a rubber-modified thermoplastic resin obtained by graft copolymerizing 70 to 2% by weight of methyl ethyl ketone and having an intrinsic viscosity [η] (measured at 30°C) of 0.2 a/g or more. It is.

The present invention will be explained in more detail below.

The hydrogenated product of the block copolymer consisting of an aromatic vinyl compound and a conjugated diene compound used in the present invention includes:
For example, there is one in which a block copolymer, such as a block copolymer of styrene and butadiene, is hydrogenated to saturate the aliphatic double bonds based on a conjugated diene compound, thereby converting it into an olefinic polymer. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, and vinyltoluene, with styrene being preferred. Conjugated diene compounds include butadiene, isoprene, 1,3
-pentadiene, 2,3-dimethyl-1,3-butadiene, etc., among which butadiene, isoprene and combinations thereof are preferred.

The ratio of aromatic vinyl to conjugated diene is not particularly specified, but in order to maintain the impact resistance strength when used as a resin, the ratio of aromatic vinyl to conjugated diene should be 5 to 60/95 to 60/95.
It is preferably 40%, especially 10 to 50/9
It is preferably 0 to 50% by weight.

The molecular structure of this block copolymer is linear, branched,
The block structure may be radial or a combination thereof, and the block structure may be diblock, tribronch, multiblock, or a combination thereof. In addition, it is necessary that 50% or more of the olefinic double bonds in these block copolymers are hydrogenated, preferably 65% or more, particularly preferably 80%.
That's all. If it is less than 50%, it becomes difficult to substantially maintain weather resistance.

The method for producing these hydrogenated block copolymers is as follows:
- Boat fishing methods can be used.

Typical methods include those described in Japanese Patent Publications No. 42-8704 and Japanese Patent Publication No. 43-6636.

Further, as such a hydrogenated block polymer, a commercially available polymer such as KRATON-G (trade name manufactured by Shell Chemical Company) can be used.

In the invention described in claim (1), acrylic rubber and/or ethylene-α-olefin rubber is used as another rubbery polymer to be used in combination with the hydrogenated material.

The acrylic rubber is a rubber-like polymer containing (meth)acrylic acid alkyl ester as an essential component, such as a homopolymer of methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, or other monomers. Examples include copolymers with

As the ethylene-α-olefin rubber, ethylene-
There are rubber-like polymers (EPDM) consisting of propylene or ethylene-propylene-non-conjugated diene, or rubber-like polymers (EBM) consisting of ethylene-butene or ethylene-butene-non-conjugated diene, and their structures are particularly defined. Although not necessarily, the polymerization ratio of ethylene-α-olefin is 90/10 to 20/80, preferably 85
/15 to 40/60. The amount of unsaturated groups in EPDM or EBM is preferably in the range of 4 to 40 in terms of iodine value. The types of non-conjugated dienes used are alkenylnorbornenes, cyclic dienes, and aliphatic dienes.
Preferred are 5-ethylidene-α-norbornene and dicyclopentadiene.

In the invention described in claim (2), a diene rubber is used as the other rubbery polymer.

The diene rubber is a rubber-like polymer containing a conjugated diene as an essential component, and includes, for example, natural rubber, polybutadiene, polyisoprene, styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, and the like.

Rubber-modified thermoplastic resins using acrylic rubber and/or ethylene-α-olefin rubber have superior weather resistance and heat resistance, and those using ethylene-α-olefin rubber have excellent impact resistance. Moreover, those using acrylic rubber are preferable because they have excellent chemical resistance.

A rubber-modified thermoplastic resin using a diene rubber is preferable because it provides even better low-temperature properties, colorability, orientation strength, and appearance of the welded part.

The proportion of the hydrogenated block copolymer and the rubbery polymer made of acrylic rubber and/or ethylene-α-olefin rubber is 99 to 1/1 to 99% by weight.
, preferably 95-515-95% by weight, more preferably 90-10/10-90% by weight. If the hydrogenated block copolymer content exceeds 99% by weight, a difference in color tone will appear on both sides of the weld line, resulting in a decrease in the commercial value of the molded product and poor low-temperature impact resistance. On the other hand, if it is less than 1% by weight, the elongation and orientation strength will decrease, causing a decrease in the strength of the molded product. Furthermore, the colorability and gloss are poor, and weld lines are noticeable, resulting in a significant reduction in the commercial value of the molded product.

The ratio of the hydrogenated block copolymer to the diene rubber used is 99 to 30/1 to 70% by weight, preferably 95% by weight.
~5075~50% by weight. If the hydrogenated block copolymer exceeds 99% by weight, it is unfavorable for the same reason as above, while if it is less than 30% by weight, the diene rubber will exceed 70% by weight, resulting in poor weather resistance and heat resistance. It is not preferred because of its poor stability.

Hydrogenated block copolymer, acrylic rubber and/or
Alternatively, diene rubber can be added to a rubbery polymer mixture consisting of ethylene-α-olefin rubber, but the amount of diene rubber used is limited to the total rubbery polymer mixture including diene rubber. The content of diene rubber is preferably 50% by weight or less, more preferably 40% by weight or less. If the content of diene rubber increases, weather resistance and heat resistance will decrease, which is not preferable.

The rubber-deformed thermoplastic resin of the present invention can be produced by various methods of radically polymerizing vinyl monomers in the presence of the rubbery polymer mixture of the present invention, such as emulsion polymerization, bulk polymerization, and suspension polymerization. Legal etc. can be adopted.

In the present invention, an aromatic vinyl compound (
A) and a monomer compound (B) copolymerizable therewith are used together.

Examples of the aromatic vinyl compound (A) include styrene, α-methylstyrene, methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromustyrene, dibromostyrene, fluorostyrene, p-tert-butylstyrene, and ethylstyrene. , vinylnaphthalene, etc., and these may be used alone or in combination of two or more. A preferred aromatic vinyl compound is styrene or an aromatic vinyl compound containing styrene in an amount of 50 weight percent or more.

Other monomer compounds (B) to be copolymerized include vinyl cyanide compounds such as acrylonitrile and methacrylate trile, which may be used alone or in combination of two or more. Acrylonitrile is particularly preferred.

Furthermore, acrylic acids such as methyl acrylate, ethyl acrylate, propylene acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate, benzyl acrylate, etc. Alkyl esters; methacrylic acids such as methyl methacrylate, ethyl methacrylate, propylene methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, hensyl methacrylate Alkyl ester;
Unsaturated acid anhydrides such as maleic anhydride, itaconic anhydride, and laconic anhydride; acrylic acid, methacrylic acid, etc., as well as maleimide, N-methylmaleimide, N-butylmaleimide, N-(p-methylphenyl ) maleimide, N-phenylmaleimide, N-cyclohexylmaleimide, and other α/β-unsaturated dicarboxylic acid imide compounds. Or used in two or more types.

As the monomer compound (B), vinyl cyanide and/
Alternatively, (meth)acrylic acid alkyl ester (general term for acrylic acid alkyl ester and methacrylic acid alkyl ester) is preferable, and even more excellent effects aimed at by the present invention can be obtained. Using vinyl cyanide,
It is preferable to use a (meth)acrylic acid alkyl ester because it provides a product with even better impact resistance, chemical resistance, and paintability, and it provides a product with even better weather resistance. As vinyl cyanide, acrylonitrile (meth)
Methyl methacrylate is preferred as the acrylic acid alkyl ester.

The ratio of aromatic vinyl compound (A) to other copolymerizable monomer compound III (B) is 30-98/70-2
% by weight, preferably 60-95/40-5% by weight. When (A) is less than 30% by weight, moldability is poor;
On the other hand, if it exceeds 98% by weight, the amount of (B) used will decrease, and (B) is generally used to impart performance that cannot be obtained with (A).
This is not preferable because the effect of B) cannot be expected.

When a monomer containing an aromatic vinyl compound (A) and a vinyl cyanide compound as main components is used as a monomer, the obtained rubber-modified thermoplastic resin is obtained without using a vinyl cyanide compound. It has excellent chemical resistance compared to other products, and is less likely to cause defects such as uneven coating, cracks, and adhesion when painting molded products, and has excellent properties. You can get something even better.

When using an aromatic vinyl compound (A) and a vinyl cyanide compound as monomer components, the preferable usage ratio is aromatic vinyl compound (A)/vinyl cyanide compound = 30 to 9.
8/70~2, more preferably 60~95/40~
5 (wt%).

If the vinyl cyanide compound (B) exceeds 70% by weight, moldability, thermal stability and color fastness will be poor. If it is less than 2% by weight, the chemical resistance, which is an effect of the vinyl cyanide compound, will be poor, so it is not preferable.

The content of the rubbery polymer mixture component in the rubber-modified thermoplastic resin of the present invention can be arbitrarily determined depending on the purpose, but in order not to impair the impact resistance of the resin, it is necessary to
ffi amount%, preferably in the range of 10 to 40% by weight.

Specific examples of preferred combinations of the aromatic vinyl compound (A) and the monomeric compound (B) in the present invention are illustrated below. Among these, ■ is preferable.

■ Styrene-acrylonitrile ■ Styrene-methyl methacrylate ■ Styrene-acrylonitrile-methyl methacrylate Heat resistance can be imparted by replacing part or all of the above styrene with α-methylstyrene. Furthermore, flame retardancy can be imparted by replacing part or all of styrene with halogenated styrene. Also,
When methyl methacrylate is used in combination with the above monomer combinations, the transparency of rubber-modified thermoplastic resins is improved,
-Excellent coloring properties.

The rubber-modified thermoplastic resin of the present invention has an intrinsic viscosity [η] (measured at 30°C) of methyl ethyl ketone soluble portion of 0.2 dl.
It is 7g or more, preferably 0.25 to 1.5, more preferably 0.3 to 1.2. If the intrinsic viscosity is less than 0.2, impact resistance and chemical resistance will be poor, which is not preferable.

The rubber-modified thermoplastic resin of the present invention can be blended with the following other polymers depending on the purpose.

For example, polyvinyl chloride, polyphenylene ether, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyacetal, polyamide,
Polyvinylidene fluoride, polystyrene, high impact polystyrene, styrene-acrylonitrile copolymer,
^BS resin, styrene-methyl methacrylate copolymer,
Styrene-maleic anhydride copolymer, chlorinated polyethylene, AES resin other than the present invention, EPR, EPDM, 1
．． Examples include 2-polybutadiene. These can be used alone or in combination of two or more.

e. Examples Next, the present invention will be specifically explained by examples, but the present invention is not limited thereto.

Example-1 Hydrogenated block copolymer KRATON G-165 as a base rubber was made into a homogeneous solution in advance in a stainless steel autoclave with an internal volume of 50 f equipped with a ribbon-type stirring blade.
30 parts by weight of a rubber component consisting of 80% by weight of 0 (5EBS manufactured by Shell Chemical Co., Ltd.) and 20% by weight of ethylene propylene rubber EP-22 (manufactured by Japan Synthetic Rubber Co., Ltd.), styrene 4
9 parts by weight, 120 parts by weight of toluene, and tertiary
A mixed solution of 0.1 parts by weight of dodecyl mercaptan was charged, the temperature was raised while stirring, and 2 parts of acrylonitrile was added at 50°C.
1 part by weight, 0.5 part by weight of benzoyl peroxide, and 0.1 part by weight of dicumyl peroxide, and the temperature was further raised to 80°C. After that, the stirring speed was increased while controlling the temperature to be constant. The polymerization reaction was carried out at 1100 rpm.

After the start of the reaction, the temperature was raised to 120° C. over 1 hour from 6 hours, and the reaction was continued for an additional 2 hours. The polymerization rate was 97%.

After cooling to 100°C, 0.2 parts by weight of 2,2'-methylenebis(4-methyl-6-t-butylphenol) was added, and the reaction mixture was taken out from the autoclave.
After distilling off unreacted monomers and solvent by steam distillation and finely pulverizing, the 40mmφ vented extruder (220℃1
The volatiles were substantially distilled off (700 mm Hg vacuum) and the polymer was pelletized. The evaluation results of this pellet are shown in Table-1.

Example 2 A rubber-modified thermoplastic resin was obtained in the same manner as in Example 1, except that the rubber components and monomer components shown in Table 1 were used.

Example-3 KRATON G-1 as a hydrogenated block copolymer
701 (5EP manufactured by Shell Chemical Co.) and a graft copolymer obtained in the same manner as in Example 1 except that the rubber components and monomers shown in Table 1 were used, and the AS resin LITAC
-A120pc (manufactured by Mitsui Toatsu Co., Ltd.) at the blending ratio shown in Table 1 to obtain a rubber-modified thermoplastic resin.

Example 4 This is an example in which methyl methacrylate was used in place of acrylonitrile in Example 1, and rubber was prepared in the same manner as in Example 1 except that the rubber components and monomers shown in Table 1 were used. l
, a modified thermoplastic resin was obtained.

Examples 5 and 6 This is an example in which acrylic rubber (n-butyl acrylate polymer) was used in place of the ethylene-propylene rubber in Example 1, and the rubber components and monomers shown in Table 1 were used. A rubber-modified thermoplastic resin was obtained in the same manner as in Example-1 except that the resin was used.

Examples 7 and 8 This is an example in which polybutadiene rubber BRO2LL (manufactured by Japan Synthetic Rubber Co., Ltd.) was used in place of the ethylene-propylene rubber in Example-1, and the other methods were the same as in Example-1. A rubber-modified thermoplastic resin was obtained.

Example 9 This is an example in which three components consisting of hydrogenated bronc copolymer/ethylene-propylene rubber/acrylic rubber were used as rubber components, and the rubber components and monomers shown in Table 1 were used. A rubber-modified thermoplastic resin was obtained in the same manner as in Example-1.

Comparative Examples-1 to 6 Rubber-modified thermoplastic resins were obtained in the same manner as in Example-1 except that the rubber components and monomers shown in Table-1 were used.

The evaluation results are shown in Table-1.

In addition, in Comparative Example 5, a rubber-modified thermoplastic resin having an intrinsic viscosity of 0.15 was obtained by increasing the amount of tertiary dodecyl mercaptan used.

The evaluation method for the rubber-modified thermoplastic resins of Examples and Comparative Examples is as follows.

90 rubber-modified thermoplastic resin pellets of Examples and Comparative Examples
It was molded using a TON injection molding machine (220° C.), and the physical properties of the obtained test piece were measured. Further, the rubber-modified thermoplastic resin pellets of Examples and Comparative Examples were colored by passing through an extruder in the following formulation, and the obtained colored pellets were molded to obtain a color tone evaluation plate. Regarding the colorability of the black blend, the lightness was measured using a color difference meter and expressed as a Munsell color table value (the larger the value, the worse the colorability). For other coloring formulations, saturation was determined visually.

Black blended resin 100 carbon black 0.5 Ca stearate 0.3 Red blended resin 100 red iron
1.0 Ca stearate O,5 Blue blend resin 100 Ultramarine
1.0 Ca Stearate O,5 Weather resistance: 10 on Sunshine Weather-Ometer
The Izod impact value was measured after 00 hours of irradiation.

The results are shown in Table-1.

In Table 1, each characteristic was measured as follows.

(1) Izot Imp: ASTM D-2
56 (cross section soot 14 inches, with notch) (2) Weather resistance test conditions: Sunshine Weather-Ometer (Suga Test Instruments WEL-6X5-DC) Black panel temperature 63±
3℃ Tank humidity 60±5%RH Rainfall cycle 18/120 minutes Carbon exchange cycle 60Hr Measurement method: ASTM D-256 (cross section 1/8 x % inch) (3) Kerosene resistance: Black pellets (composition resin 100 weight) 0.5 parts by weight of carbon black, 0.3 parts by weight of Ca stearate) is immersed in JIS No. 6 kerosene, left at 50°C for 1 hour, then wiped off the surface, and after drying determine whether or not it has been left in place. did.

Judgment ◎-------- Judgment o- where no discoloration is observed
−−−−−− Judgment with slight discoloration ×・−−1−−
-Changes such as whitening and decreased gloss are observed (4) Elongation at break AST row D-638 (5) Using an injection molding machine with orientation strength of 1 oz, at a constant temperature of 220°C, wall thickness of 2.4
An oriented plate of Mi'J was molded, and its bending strength in the vertical direction (±) and horizontal direction (11) with respect to the flow direction of the resin was measured.

Bending strength measurement conditions Test speed 5mm/min Chart speed 100 Full scale 40kg Span 201 (6) Conspicuousness of weld and presence or absence of color difference bordering on weld area Conspicuousness of weld: Visually check for presence or absence of weld line ◎: Dovetail Not observed at all O: Slightly observed ×: Obvious presence or absence of color difference bordering on the weld area Not confirmed by second sight: Almost no color difference: Obvious color difference (7) Thermal stability 5oz Using an injection molding machine, the retention rate of Izod Imp was measured in continuous molded products and molded products after 15 minutes of retention.As is clear from the results shown in Table 1, the results obtained in Examples 1 to 9 were The rubber-modified thermoplastic resin thus obtained exhibits excellent physical properties in all evaluation items.

On the other hand, Comparative Example 1 is an example outside the scope of the present invention in which only a hydrogenated block copolymer was used as a rubber component.
There is a large difference in low temperature impact resistance and color tone on both sides of the weld line, which is not desirable.

Comparative Examples 2 and 3 are examples that do not use a hydrogenated block copolymer and are outside the scope of the present invention, and are inferior in elongation, orientation strength, and appearance of weld lines.

Comparative Example 4 is an example in which the diene rubber as a rubber component is beyond the scope of the present invention, and is inferior in weather resistance and thermal stability.

Comparative Example 5 has an intrinsic viscosity below the range of the present invention, and is inferior in impact resistance, oil resistance, elongation, and orientation strength.

Comparative Example 6 is an example in which the ratio of the aromatic vinyl compound used is less than the range of the present invention, and is inferior in moldability, thermal stability, and color fastness.

f1 Effects of the Invention The rubber-modified thermoplastic resin of the present invention is excellent in a wide range of physical properties such as orientation strength, elongation, appearance of weld parts, colorability, thermal stability, impact resistance, weather resistance, and chemical resistance. Conventionally, ABS resin, AES resin, and AAS resin, which have been widely used as rubber-modified thermoplastic resins, have not been able to provide these wide range of physical properties, but because they have such excellent physical properties, it is possible to develop them into new applications. Therefore, the rubber-modified thermoplastic resin of the present invention has extremely high industrial value.

Patent applicant: Japan Synthetic Rubber Co., Ltd. (2 idiots)

Claims (3)

[Claims] (1) Rubber material consisting of 99 to 1% by weight of a hydrogenated block copolymer consisting of an aromatic vinyl compound and a conjugated diene compound, and 1 to 99% by weight of acrylic rubber and/or ethylene-α-olefin rubber In the presence of a polymer, 30 to 98% by weight of an aromatic vinyl compound (A) and 70 to 2% by weight of a monomer compound (B) copolymerizable therewith are graft copolymerized, and the methyl ethyl ketone soluble content is A rubber-modified thermoplastic resin having an intrinsic viscosity [η] (measured at 30°C) of 0.2 dl/g or more. (2) An aromatic vinyl compound in the presence of 99 to 30% by weight of a hydrogenated block copolymer consisting of an aromatic vinyl compound and a conjugated diene compound and a rubbery polymer consisting of 1 to 70% by weight of diene rubber. (A) 30-98% by weight and a monomer compound copolymerizable therewith (B) 70-2% by weight
The intrinsic viscosity [η] (measured at 30°C) of the methyl ethyl ketone soluble portion is 0.2 dl/g.
The above rubber-modified thermoplastic resin. (3) The monomer compound (B) is a vinyl cyanide compound,
Claim (1) is at least one selected from acrylic acid alkyl ester and methacrylic acid alkyl ester.
) or the rubber-modified thermoplastic resin described in (2).