JPH0711078A - Aromatic vinyl-based resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition exhibiting excellent moldability by improvement of fluidity, excellent in toughness, heat resistance, transparency and weather resistance and useful for household utensils, etc., by including an aromatic vinyl-based resin and a specific copolymer resin. CONSTITUTION:This resin composition contains (A) an aromatic vinyl-based resin (B) a copolymer resin consisting essentially of (i) an aromatic vinyl-based monomer and (ii) a petroleum fraction containing a 5C hydrocarbon as a main component and/or a copolymer resin consisting essentially of the component (i) and (iii) an aliphatic polycyclic hydrocarbon monomer. Furthermore, the component A is preferably a styrenic resin having transparency and the component B is preferably a copolymer consisting of a styrenic monomer and the component (i).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aromatic vinyl resin composition, more specifically, an aromatic vinyl resin containing petroleum containing an aromatic vinyl monomer and a hydrocarbon having 5 carbon atoms as main components. Moldability, toughness, and heat resistance obtained by containing a copolymer resin containing a distillate as an essential component and / or a copolymer resin containing an aromatic vinyl monomer and an aliphatic polycyclic hydrocarbon monomer as essential components. , An aromatic vinyl-based resin composition having excellent transparency and weather resistance, which is an injection-molded product in the fields of weak electric current, electronics, toys, sundries, and extruded products such as sheets and films for packaging materials. Etc. can be widely used.

[0002]

2. Description of the Related Art Aromatic vinyl resins represented by polystyrene have been used in various fields such as household appliances, audio / visual fields, and weak electrical fields since they have been excellent in transparency and moldability. It has been used. Among them, in the field where high strength is required, it has been dealt with by increasing the molecular weight of the aromatic vinyl resin, but there is a problem that the fluidity is deteriorated and the moldability is deteriorated.

Therefore, as a technique for improving fluidity without deteriorating various physical properties, JP-A-4-370131 discloses mixing a terpene-based hydrogenated resin. Clearon P and Clearon M from Yasuhara Chemical Co., Ltd., which are hydrogenated resins using terpenes whose main component is limonene, are mentioned.

[0004]

However, the CLEARON P used in Japanese Patent Laid-Open No. 4-370131 is used.
The aromatic vinyl-based resin composition mixed with C has a problem of poor transparency and toughness, and the aromatic vinyl-based resin composition mixed with CLEARON M has a problem of poor weather resistance and toughness. .

The problem to be solved by the present invention is that an aromatic vinyl-based resin composition having excellent toughness, heat resistance, transparency and weather resistance, as well as showing excellent moldability by further improving fluidity. To provide.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that an aromatic vinyl-based resin contains an aromatic vinyl-based monomer and a hydrocarbon having 5 carbon atoms. If the copolymer resin containing the petroleum fraction as the main component as the essential component and / or the copolymer resin containing the aromatic vinyl monomer and the aliphatic polycyclic hydrocarbon monomer as the essential components is contained, the fluidity is further improved. It has been found that an aromatic vinyl resin composition having improved toughness, heat resistance, transparency and weather resistance, as well as showing extremely excellent moldability, can be obtained, thereby completing the present invention.

That is, the present invention is based on the aromatic vinyl resin (A).
And a copolymer resin and / or an aromatic vinyl monomer and an aliphatic polycyclic hydrocarbon monomer, which are essentially composed of an aromatic vinyl-based monomer and a petroleum fraction containing a hydrocarbon having 5 carbon atoms as main components. The present invention relates to an aromatic vinyl resin composition containing a copolymer resin (B) as an essential component.

Examples of the aromatic vinyl resin (A) used in the present invention include homopolymers of aromatic vinyl monomers, copolymers of aromatic vinyl monomers and other polymerizable monomers, suspension polymerization, emulsion polymerization. Examples thereof include rubber-modified aromatic vinyl-based resins obtained by graft-copolymerizing a rubbery polymer and an aromatic vinyl-based monomer by solution polymerization, bulk polymerization and the like. Among them, the weight average molecular weight thereof is 21.
When it is at least 10,000, it is preferable because the effect of the present invention becomes remarkable.

Examples of the aromatic vinyl monomer used here include styrene, alpha methyl styrene, alkylated alpha methyl styrene, ethyl styrene, isobutyl styrene, tertiary butyl styrene, bromo styrene, chloro styrene, vinyl toluene and other styrene based monomers. Examples thereof include monomers. Among them, styrene is preferable from the viewpoint of obtaining a resin having extremely excellent fluidity.

Other polymerizable monomers that can be copolymerized with the aromatic vinyl monomer include, for example, (meth) acrylic acid; methyl (meth) acrylate, (meth)
Ethyl acrylate, n-butyl (meth) acrylate,
(Meth) acrylic acid alkyl esters such as iso-butyl (meth) acrylate; vinyl cyan compounds such as (meth) acrylonitrile; itaconic acid, maleic acid,
Polymerizable unsaturated fatty acids such as fumaric acid, crotonic acid, cinnamic acid; N-methylmaleimide, N-ethylmaleimide, N
-Butyl maleimide, N-octyl maleimide, N-isopropyl maleimide, N-phenyl maleimide, N-
Maleimides such as p-bromophenylmaleimide, N-o-chlorophenylmaleimide and N-cyclohexylmaleimide; unsaturated carboxylic acid anhydrides represented by maleic anhydride, itaconic anhydride, citraconic anhydride and the like; allyl glycidyl ether Epoxy group-containing unsaturated compounds such as glycidyl (meth) acrylate; allylamine, aminoethyl (meth) acrylate, aminopropyl (meth) acrylate, aminostyrene-containing unsaturated compounds such as aminostyrene; acrylamide, N -Acrylamido compounds such as methyl acrylamide; hydroxyl group-containing unsaturated compounds such as 2-hydroxyethyl acrylate, 3-hydroxypropyl methacrylate, and 4-hydroxy-2-butene. Among them, (meth) acrylic acid is preferable from the viewpoint of improving heat resistance.

Further, examples of the rubbery polymer used for the rubber-modified aromatic vinyl resin include natural rubber (NR),
Acrylonitrile-butadiene rubber (NBR), styrene-butadiene rubber (SBR), polybutadiene rubber (BR), isoprene rubber (IR), chloroprene rubber (CR), butyl rubber (IIR), ethylene-propylene-non-conjugated diene rubber (EPDM), Acrylic rubber (A
CM, ANM), chlorinated polyethylene rubber (CSR),
Fluorine rubber (FKM), silicone rubber (Q), urethane rubber (AU, EU), polysulfide rubber (T), epichlorohydrin rubber (CO, ECO), chlorosulfonated polyethylene (CSM), norbornene rubber and / or these Examples include vulcanized polymeric materials.

Among these aromatic vinyl resins (A), a styrene resin having transparency is preferable from the viewpoint that a resin composition having excellent transparency can be obtained. Specific examples thereof include polystyrene, styrene-methacrylic acid copolymer,
Styrene-methyl methacrylate copolymer, styrene-methacrylic acid-methyl methacrylate copolymer, styrene-
Examples thereof include styrene-based resins that have not been rubber-modified such as acrylonitrile copolymerization resistance, and polystyrene is most preferable.

Next, a copolymer resin containing an aromatic vinyl monomer used in the present invention and a petroleum fraction containing a hydrocarbon having 5 carbon atoms as a main component as essential components and / or an aromatic vinyl monomer and a fat. The copolymer resin (B) containing a group polycyclic hydrocarbon monomer as an essential component will be described.

Examples of the aromatic vinyl-based monomer used here include those similar to the aromatic vinyl-based monomer used in the aromatic vinyl-based resin (A). The petroleum fraction containing a hydrocarbon having 5 carbon atoms as a main component is, for example, a carbon atom in a cracked oil fraction produced as a by-product from an ethylene plant for producing ethylene, propylene, etc. by steam cracking of petroleum. Examples include petroleum fractions containing olefins and diolefins of the number 5 as main components, and may contain other hydrocarbons.

Further, examples of the aliphatic polycyclic hydrocarbon monomer include various aliphatic polycyclic hydrocarbon monomers contained in petroleum fractions, and a typical example thereof is dicyclopentadiene.

Examples of the copolymer resin containing the above aromatic vinyl monomer and a petroleum fraction containing a hydrocarbon having 5 carbon atoms as a main component as essential components include styrene, alpha methyl styrene, and alkylated alpha methyl styrene. A copolymer of a styrene-based monomer and a petroleum fraction containing a hydrocarbon having 5 carbon atoms as a main component is preferable. Among them, those having a styrene-based monomer content of 50% by weight or more, particularly 70 to 95% by weight are most preferable in that they have particularly excellent weather resistance. As a specific example, FTR- manufactured by Mitsui Petrochemical Co., Ltd.
6125, FTR-7125 and the like.

As the copolymer resin containing an aromatic vinyl monomer and an aliphatic polycyclic hydrocarbon monomer as essential components, a copolymer of an aromatic vinyl monomer and dicyclopentadiene is preferable, and a typical example is vinyl. A copolymer containing toluene and dicyclopentadiene as main components can be mentioned. Specific examples thereof include Neopolymer S manufactured by Nippon Oil Co., Ltd.

As these copolymer resins (B), those not normally hydrogenated are used, but hydrogenated ones can also be used if necessary. However, in order to maintain the compatibility with the aromatic vinyl-based resin (A) and obtain an aromatic vinyl-based resin composition having excellent transparency, the proportion of hydrogenation is preferably 20% by weight or less.

The fluidity of the aromatic vinyl resin composition of the present invention is greatly influenced by the content ratio of the copolymer resin (B). In order to improve the fluidity, the copolymer resin (B) is added in an amount of 2 to 100 parts by weight of the aromatic vinyl resin (A).
It is preferable to contain 30 parts by weight, and especially 3 to 15 parts by weight.

In the aromatic vinyl resin composition of the present invention, the aromatic vinyl resin (A) and the copolymer resin (B) are used.
In addition, if necessary, mineral oil, terpene-based hydrogenated resin, rubbery polymer, and other thermoplastic resins; stearic acid, behenic acid, palmitic acid, calcium with them,
A salt with a metal such as magnesium, an additive such as ethylene bis stearyl amide, a silicone oil, a colorant such as a dye or a pigment, a flame retardant, or the like may be mixed. Above all, SBR
As described above, it is preferable to add a rubber-like polymer which is transparent and has excellent compatibility with an aromatic vinyl resin because the impact resistance can be improved while maintaining the transparency.

The method for producing the aromatic vinyl resin composition of the present invention is not particularly limited. For example, the aromatic vinyl resin (A), the copolymer resin (B) and, if necessary, other components are added. May be mixed by a tumbler or the like, but a method in which these components are melt-kneaded by an extruder and then pelletized, or a copolymer resin (B) is added at the time of producing the aromatic vinyl resin (A) The method of mixing is preferable.

As a method for adding and mixing the copolymer resin (B) during the production of the aromatic vinyl resin (A), a method of dissolving the copolymer resin (B) in a polymerization component or a solvent and polymerizing it, A method of adding the copolymer resin (B) during the polymerization of the aromatic vinyl resin (A), a method of adding the copolymer resin (B) after the polymerization of the aromatic vinyl resin (A) and before isolation, The method of mixing, etc. are mentioned.

[0023]

EXAMPLES Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. All parts and% in the following are on a weight basis unless otherwise specified. is there.

Various physical properties of each resin composition were tested in the following manner based on JIS K-6871 (polystyrene test method). (1) Melt flow rate: According to JIS K-7210. (2) Vicat softening point: According to JIS K-7206. (3) Bending strength: According to JIS K-7203. (4) Bending fracture energy: Based on JIS K-7203, the energy (integral value in the stress-strain curve) applied until fracture was obtained. (5) Transparency: Wall thickness 5 × 10 × 100 mm
The rectangular parallelepiped molded article was molded by injection molding, and the transparency was visually evaluated in the following four grades.

◎: Particularly good ○: Good Δ: Slightly good ×: Poor (6) Weather resistance: A test piece was molded by injection molding, and tested using a sunshine weather meter at a black panel temperature of 63 ° C. and no rain. The piece was irradiated with light for 100 hours, and the color difference ΔE was determined.

Example 1 95 parts of polystyrene (weight average molecular weight: 480,000) and petroleum resin (copolymer of styrene-based monomer and petroleum fraction mainly containing hydrocarbon having 5 carbon atoms) [Mitsui Petrochemical Industry] 5 parts of FTR-6125 manufactured by Co., Ltd. were mixed with a tumbler, and this was then kneaded with a twin-screw extruder and pelletized to obtain a polystyrene composition pellet.

Thereafter, using the pellets as raw materials, test pieces for measuring physical properties were prepared by an injection molding machine, and various physical properties were measured. The results are shown in Table 1. Example 2 A pellet of a polystyrene composition was obtained in the same manner as in Example 1 except that a petroleum resin [FTR-7125 manufactured by Mitsui Petrochemical Industry Co., Ltd.] was used in place of the petroleum resin (FTR-6125), and a test piece was obtained. Was prepared and various physical properties were measured. The results are shown in Table 1.

Example 3 95 parts of polystyrene (weight average molecular weight: 480,000) and petroleum resin (copolymer of vinyltoluene, dicyclopentadiene and other petroleum fractions) [Neopolymer S manufactured by Nippon Petrochemical Co., Ltd.] 5 parts were mixed with a tumbler, and this was then kneaded with a twin-screw extruder and pelletized to obtain polystyrene composition pellets.

Then, using the pellets as raw materials, test pieces for measuring physical properties were prepared by an injection molding machine, and various physical properties were measured. The results are shown in Table 1. Example 4 When synthesizing polystyrene from styrene monomer using a tubular continuous polymerization apparatus, the polymerization rate of styrene monomer was 4
When it reached 0%, petroleum resin dissolved in toluene (FT
R-6125) was mixed at a ratio of 5 parts with respect to 100 parts of the raw material styrene monomer, and after further polymerization,
Pelletization was performed to obtain polystyrene composition pellets composed of polystyrene having a weight average molecular weight of 390,000 and petroleum resin.

Then, using the pellet as a raw material, a test piece for measuring physical properties was prepared by an injection molding machine, and various physical properties were measured. The results are shown in Table 1. Comparative Example 1 95 parts of polystyrene (weight average molecular weight: 480,000) and 5 parts of a terpene-based hydrogenated resin [Clearon P manufactured by Yasuhara Chemical Co., Ltd.] were mixed by a tumbler and then kneaded with a twin-screw extruder to form pellets. The pellets of the polystyrene composition were obtained by liquefying.

Thereafter, using the pellets as raw materials, test pieces for measuring physical properties were prepared by an injection molding machine, and various physical properties were measured. The results are shown in Table 1. Comparative Example 2 95 parts of polystyrene (weight average molecular weight: 480,000) and 5 parts of a terpene-based hydrogenated resin [CLEARON M manufactured by Yasuhara Chemical Co., Ltd.] were mixed by a tumbler, and then this was kneaded with a twin-screw extruder to form pellets The pellets of the polystyrene composition were obtained by liquefying.

Then, using the pellets as raw materials, test pieces for measuring physical properties were prepared by an injection molding machine, and various physical properties were measured. The results are shown in Table 1.

[0033]

[Table 1]

[0034]

[Table 2]

Example 5 90 parts of polystyrene (weight average molecular weight: 480,000) and 10 parts of petroleum resin (FTR-6125) were mixed by a tumbler, and then this was kneaded by a twin-screw extruder and pelletized to form polystyrene. A pellet of the composition was obtained.

Then, using the pellets as raw materials, test pieces for measuring physical properties were prepared by an injection molding machine, and various physical properties were measured. The results are shown in Table 3. Example 6 90 parts of polystyrene (weight average molecular weight 480,000) and 10 parts of petroleum resin (Neopolymer S) were mixed by a tumbler, and then this was kneaded by a twin-screw extruder and pelletized to obtain a polystyrene composition. Pellets were obtained.

Thereafter, using the pellets as raw materials, test pieces for measuring physical properties were prepared by an injection molding machine, and various physical properties were measured. The results are shown in Table 3. Comparative Example 3 90 parts of polystyrene (weight average molecular weight 480,000) and 10 parts of a terpene resin (Clearon P) were mixed by a tumbler, and then this was kneaded by a twin-screw extruder and pelletized to form a polystyrene composition pellet. Got

Then, using the pellets as raw materials, test pieces for measuring physical properties were prepared by an injection molding machine, and various physical properties were measured. The results are shown in Table 3. Example 7 85 parts of polystyrene (weight average molecular weight 380,000), 5 parts of petroleum resin (FTR-6125) and 10 parts of SBR were mixed with a tumbler, and then this was kneaded with a twin-screw extruder,
Pelletization was carried out to obtain polystyrene composition pellets.

Then, using the pellets as raw materials, test pieces for measuring physical properties were prepared by an injection molding machine, and various physical properties were measured. The results are shown in Table 3.

[0040]

[Table 3]

[0041]

The aromatic vinyl resin composition of the present invention comprises
It exhibits excellent moldability due to improved fluidity, as well as excellent toughness, heat resistance, transparency, and weather resistance.

That is, since the resin composition of the present invention can reduce the injection pressure and the mold clamping pressure in the injection molding, it can be molded by a smaller injection molding machine, and the injection pressure and the mold clamping pressure are also possible. If it is equal, it becomes possible to reduce the wall thickness of the molded product, which has the advantages of improving the molding cycle, reducing the amount of resin, and toughness similar to conventional aromatic vinyl resins, Excellent heat resistance, transparency, and weather resistance.

Furthermore, since it has the same heat resistance and high fluidity,
It causes shear heat generation and reduction of shear stress during molding,
It also has the advantage of reducing distortion during molding and improving the molding cycle.

Claims (7)

[Claims] 1. A copolymer resin comprising an aromatic vinyl resin (A), an aromatic vinyl monomer, and a petroleum fraction containing a hydrocarbon having 5 carbon atoms as a main component as essential components, and / or
Alternatively, an aromatic vinyl-based resin composition comprising a copolymer resin (B) containing an aromatic vinyl-based monomer and an aliphatic polycyclic hydrocarbon monomer as essential components. 2. The composition according to claim 1, wherein the aromatic vinyl resin (A) is a styrene resin having transparency. 3. A petroleum fraction in which the aromatic vinyl-based resin (A) is a transparent styrene-based resin, and the copolymer (B) is mainly composed of a styrene-based monomer and a hydrocarbon having 5 carbon atoms. The composition according to claim 1, which is a copolymer consisting of: 4. The aromatic vinyl resin (A) is a transparent styrene resin, and the copolymer (B) is a copolymer composed of an aromatic vinyl monomer and dicyclopentadiene. The composition according to 1. 5. The composition according to claim 4, wherein the aromatic vinyl-based monomer is vinyltoluene. 6. The composition according to claim 2, wherein the transparent styrene resin is polystyrene. 7. The composition according to claim 1, wherein the copolymer resin (B) is contained in an amount of 2 to 30 parts by weight based on 100 parts by weight of the aromatic vinyl resin (A).