JP3286682B2 - Polyphenylene sulfide resin composition and molded article for light reflection - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyphenylene sulfide resin composition, and more particularly, the present invention relates to a polyphenylene sulfide resin composition having a reduced specific gravity and excellent surface smoothness. The present invention relates to a molded article for light reflection.

[0002]

2. Description of the Related Art Polyphenylene sulfide resin has attracted attention as a component material for electric / electronic devices and a component for automobile devices, taking advantage of its excellent heat resistance, chemical resistance, dimensional stability and mechanical strength. For example, it is expected to be applied to fields requiring particularly heat resistance and surface smoothness, such as lamp reflectors for automobiles.

[0003] Polyphenylene sulfide resin is known as a resin having excellent heat resistance and mechanical strength, but the resin alone is not sufficient in both heat resistance and mechanical strength.
Therefore, polyphenylene sulfide resin, by adding a fibrous reinforcing material and / or inorganic filler,
Used with increased heat resistance and mechanical strength.

Further, polyphenylene sulfide resin is
In order to reduce cost and warp, a large amount of inorganic filler is added. However, in this formulation, a large amount of the inorganic filler causes a decrease in surface smoothness, a decrease in fluidity and an increase in specific gravity of the molded article.

[0005]

SUMMARY OF THE INVENTION The present invention provides a polyphenylene sulfide resin composition having a reduced specific gravity of a molded article and excellent surface smoothness of the molded article, and a specific gravity obtained by molding the same. Another object of the present invention is to provide a light reflection molded article having excellent surface smoothness.

[0006]

That is, the present invention provides (A) a polyphenylene sulfide resin having a content of more than 65% by weight and not more than 95% by weight, and (B) an ethylene component and the following general formula (I) or (II):
Consisting of a cyclic olefin component represented by
Intrinsic viscosity [η] measured in Karin is 0.01 to 10 d
l / g, heat-resistant cyclic olefin random copolymer having a softening temperature (TMA) of 70 ° C. or higher

Embedded image

Embedded image (Where n and m are each 0 or a positive integer
L is an integer of 3 or more; ^Three Or R
¹² Represents a hydrogen atom, a halogen atom or an alkyl group, respectively.
Show. ) Resin content 1 contained at a ratio of 5% by weight or more and less than 35% by weight
(C) 0 to 10 parts by weight of the modified thermoplastic copolymer, (D) 0 to 50 parts by weight of the fibrous reinforcing material, and (E) 30 to 150 parts by weight of the inorganic filler with respect to 00 parts by weight. Polyphenylenesul characterized by containing
Fid resin composition and light reflecting composition obtained by molding the same
It is related to shapes.

The polyphenylene sulfide resin used in the present invention has a melt viscosity of 300 (measured at a measuring temperature of 300 ° C. under a load of 10 kg using a die having a diameter of 1 mm and a length of 2 mm with a Koka type flow tester). ~ 500
The polyphenylene sulfide resin is preferably 0 poise, particularly preferably in the range of 400 to 4000 poise. Also,
Amino group per phenylene sulfide unit is 0.05 to
A polyphenylene sulfide resin containing 5 mol% and having a melt viscosity in the range of 300 to 5000 poise, particularly preferably in the range of 400 to 4000 poise, is more preferable because it is excellent in an undercoat agent for vapor deposition and aluminum vapor deposition.

The polyphenylene sulfide resin used in the present invention, even if it is linear, is cured by heat treatment in an oxygen atmosphere or heat treatment with the addition of a peroxide or the like, and the degree of polymerization is reduced. The heat treatment may be carried out in a non-oxidizing inert gas, or a mixture of these structures may be used. If the melt viscosity of the polyphenylene sulfide resin is less than 300 poise, the strength is reduced, and if the amount of gas generated is large, and if it exceeds 5000 poise, the fluidity is significantly reduced, which may make the handling difficult.

[0009] The polyphenylene sulfide resin may be one in which ions are reduced by performing a deionization treatment (acid washing, hot water washing, or the like).

Further, the polyphenylene sulfide resin used in the present invention has

[0011]

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[0012] It is preferable that the composition contains 70 mol% or more, more preferably 90 mol% or more.

The structural unit is less than 30 mol%, preferably 1
If it is less than 0 mol%, m-phenylene sulfide unit,

[0014]

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O-phenylene sulfide unit,

[0016]

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A phenylene sulfide sulfone unit,

[0018]

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A phenylene sulfide ketone unit,

[0020]

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A phenylene sulfide ether unit,

[0022]

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A diphenylene sulfide unit,

[0024]

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A substituted phenylene sulfide unit,

[0026]

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(Wherein R ¹ and R ² each represent an alkyl group, a phenyl group, an alkoxyl group, a nitro group, a halogen atom, an alkylene glycol group, a hydroxyl group, a nitrile group, a sulfone group, a carboxyl group, a carboxylic acid, Represents a metal salt or an amino group.) Trifunctional binding unit,

[0028]

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Such a copolymer unit may be contained.

The heat-resistant cyclic olefin random copolymer used in the present invention comprises an ethylene component and a cyclic olefin component represented by the following general formula (I) or (II), and is measured in decalin at 135 ° C. Intrinsic viscosity [η] is 0.01 to 10 dl / g, softening temperature (TMA)
Is 70 ° C. or higher.

[0031]

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[0032]

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(Where n and m are each 0
Or a positive integer, l is an integer of 3 or more;^Three
Or R¹²Represents a hydrogen atom, a halogen atom or
Represents a kill group. ) The heat-resistant cyclic olefin random copolymer used in the present invention
Cyclic olefins represented by the general formula (I) constituting a polymer
As a specific example of the component, bicyclo [2.2.1] hept
-2-ene, 6-methylbicyclo [2.2.1] hept
-2-ene, 5,6-dimethylbicyclo [2.2.1]
Hept-2-ene, 1-methylbicyclo [2.2.1]
Hept-2-ene, 6-ethylbicyclo [2.2.1]
Hept-2-ene, 6-n-butylbicyclo [2.2.
1] Hept-2-ene, 6-isobutylbicyclo [2.
2.1] Hept-2-ene, 7-methylbicyclo [2.
2.1] Hept-2-ene, 1,4,5,8-dimethano
-1,2,3,4,4a, 5,8,8a-octahydro
Naphthalene, 2-methyl-1,4,5,8-dimethano-
1,2,3,4,4a, 5,8,8a-octahydrona
Phthalene, 2-ethyl-1,4,5,8-dimethano-
1,2,3,4,4a, 5,8,8a-octahydrona
Phthalene, 2-propyl-1,4,5,8-dimethano-
1,2,3,4,4a, 5,8,8a-octahydrona
Phthalene, 2-hexyl-1,4,5,8-dimethano-
1,2,3,4,4a, 5,8,8a-octahydrona
Phthalene, 2,3-dimethyl-1,4,5,8-dimeta
No-1,2,3,4,4a, 5,8,8a-octahydride
Lonaphthalene, 2-methyl-3-ethyl-1,4,5
8-Dimethano-1,2,3,4,4a, 5,8,8a-
Octahydronaphthalene, 2-chloro-1,4,5,8
-Dimethano-1,2,3,4,4a, 5,8,8a-e
Kutahydronaphthalene, 2-bromo-1,4,5,8-
Dimethano-1,2,3,4,4a, 5,8,8a-octane
Tahydronaphthalene, 2-fluoro-1,4,5,8-
Dimethano-1,2,3,4,4a, 5,8,8a-octane
Tahydronaphthalene, 2,3-dichloro-1,4,5
8-Dimethano-1,2,3,4,4a, 5,8,8a-
Octahydronaphthalene, 2-cyclohexyl-1,
4,5,8-Dimethano-1,2,3,4,4a, 5
8,8a-octahydronaphthalene, 2-n-butyl-
1,4,5,8-dimethano-1,2,3,4,4a,
5,8,8a-octahydronaphthalene, 2-isobutyi
1,4,5,8-Dimethano-1,2,3,4,4
octane, such as a, 5,8,8a-octahydronaphthalene
Tahydronaphthalenes, 5,10-dimethyltetracycline
B [4.4.0.1^2,5. 1^7,10-3-dodecene,
2,10-dimethyltetracyclo [4.4.0.
1^2,5. 1^7,10-3-Dodecene, 11,12-dimethyl
Letetracyclo [4.4.0.1^2,5. 1^7,10-3-
Dodecene, 2,7,9-trimethyltetracyclo [4.
4.0.1.^2,5. 1^7,10] -3-dodecene, 9-ethyl
-2,7-dimethyltetracyclo [4.4.0.
1^2,5. 1^7,103-dodecene, 9-isobutyl-
2,7-dimethyltetracyclo [4.4.0.1^2,5.
1^7,10-3-Dodecene, 9,11,12-trimethyl
Tetracyclo [4.4.0.1^2,5. 1^7,10] -3-do
Decene, 9-ethyl-11,12-dimethyltetracyclic
B [4.4.0.1^2,5. 1^7,10-3-Dodecene, 9
-Isobutyl-11,12-dimethyltetracyclo
[4.4.0.1^2,5. 1^7,10-3-dodecene, 5,
8,9,10-tetramethyltetracyclo [4.4.
0.1^2,5. 1^7,10-3-Dodecene, hexacyclo
[6.6.1.1^3,6. 1^10,13. 0^2,7. 0^9,14] -4
-Heptadecene, 12-methylhexacyclo [6.6.
1.1^3,6. 1^10,13. 0^2,7. 0^9,14] -4-Heptade
Sen, 12-ethylhexacyclo [6.6.1.
1^3,6. 1^10,13. 0^2,7. 0^9,14-4-heptadece
, 12-isobutylhexacyclo [6.6.1.1
^3,6. 1^10,13. 0^2,7. 0^9,14-4-heptadecene,
1,6,10-trimethyl-12-isobutylhexyl
Black [6.6.1.1^3,6. 1^10,13. 0^2,7. 0^9,14]
-4-heptadecene, octacyclo [8.8.0.1
^2,9. 1 ^4,7. 1^11,18. 1^13,16. 0^3,8. 0^12,17-5
-Docosene, 15-methyloctacyclo [8.8.0.
1^2,9. 1^4,7. 1^11,18. 1^13,16. 0^3,8. 0^12,17]-
5-docosene, 15-ethyloctacyclo [8.8.
0.1^2,9. 1^4,7. 1^11,18. 1^13,16. 0^3,8.
0^12,17-5-docosene, etc., and a compound represented by the general formula (I
Specific examples of the cyclic olefin component represented by I) include
Nantacyclo [6.6.1.1^3,6. 0^2,7. 0^9,14] -4
-Hexadecene, 1,3-dimethylpentacyclo [6.
6.1.1^3,6. 0^2,7. 0^9,14-4-hexadecene,
1,6-dimethylpentacyclo [6.6.1.1^3,6.
0^2,7. 0^9,14-4-hexadecene, 15,16-di
Methyl pentacyclo [6.6.1.1^3,6. 0^2,7. 0
^9,14-4-hexadecene, pentacyclo [6.5.
1.1^3,6. 0^2,7. 0^9,13-4-pentadecene, 1,
3-dimethylpentacyclo [6.5.1.1^3,6.
0^2,7. 0^9,13-4-pentadecene, 1,6-dimethyl
Lupentacyclo [6.5.1.1^3,6. 0^2,7. 0^9,13]
-4-pentadecene, 14,15-dimethylpentacyclo
B [6.5.1.1^3,6. 0^2,7. 0^9,13] -4-penta
Decene, heptacyclo [8.7.0.1^2,9. 1^4,7. 1
^11,17. 0^3,8. 0^12,16-5-eicosene, heptasi
Black [8.7.0.1^2,9, 1^4,7. 1^11,17. 0^3,8. 0
^12,17] -5-heneicosene, tricyclo [4.3.
0.1^2,5] -3-decene, 2-methyltricyclo
[4.3.0.1^2,5] -3-decene, 5-methyltri
Cyclo [4.3.0.1^2,5] -3-decene, trisic
B [4.4.0.1^2,5-3-undecene, 10-method
Tilt tricyclo [4.4.0.1^2,5-3-Undesse
And others.

The heat-resistant random cyclic olefin copolymer used in the present invention may be partially or entirely modified with an unsaturated carboxylic acid or a derivative thereof.

The modified heat-resistant cyclic olefin-based random copolymer which can be used here is a graft monomer partially or wholly selected from unsaturated carboxylic acids or derivatives thereof, and is preferably 0.01 to 10% by weight, and more preferably 0.01 to 10% by weight. 0.1
Is a heat-resistant cyclic olefin random copolymer graft-modified in the range of 5 to 5% by weight, and has an intrinsic viscosity [η] measured in decalin at 135 ° C of 0.05 to 10 dl /.
g, preferably in the range of 0.08 to 5 dl / g. The modified heat-resistant cyclic olefin-based random copolymer having the characteristic values in the above range is preferable because of its excellent compatibility with polyphenylene sulfide, heat resistance, mechanical strength, and water resistance.

Specific examples of the unsaturated carboxylic acid or its derivative grafted onto the above-mentioned heat-resistant cyclic olefin-based random copolymer include acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid and croton. Acids, isocrotonic acid, unsaturated carboxylic acids such as nadic acid or derivatives thereof, for example, acid halides, amides, imides, acid anhydrides, esters and the like, specifically, maleenyl chloride, maleimide, maleic anhydride, Citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate and the like.

The heat-resistant cyclic olefin-based random copolymer used in the present invention contains an ethylene component and the aforementioned cyclic olefin component as essential components. In addition to these essential components, the object of the present invention is as follows. Within the range not deviating from the above, other copolymerizable unsaturated monomer components may be contained.

Specific examples of the above copolymerizable unsaturated monomer component include, for example, propylene, 1-butene, and 4-methyl-1 in an amount less than equimolar to the ethylene component in the random copolymer to be produced. An α-olefin having 3 to 20 carbon atoms such as pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, norbornene, and ethylidene norbornene And cyclic olefins such as dicyclopentadiene, and cyclic dienes.

In the heat-resistant cyclic olefin-based random copolymer used in the present invention, the structural unit derived from the ethylene component is in the range of 40 to 85 mol%, preferably 50 to 75 mol%, derived from the cyclic olefin component. The structural unit is suitably in the range of 15 to 60 mol%, preferably 25 to 50 mol%.

The modified thermoplastic copolymer used in the present invention is a thermoplastic copolymer having a functional group selected from an amino group, an epoxy group, a carboxyl group, and an acid anhydride group. This copolymer is a copolymer that can be synthesized by radical polymerization of a polymerizable monomer having the above functional group and a vinyl monomer other than this monomer.

Specific examples of the monomer having an amino group as the polymerizable monomer having a functional group include:
Acrylamide, methacrylamide, N-methylacrylamide, N-ethylacrylamide, N, N-diethylacrylamide, N-methylmethacrylamide, N,
Examples of the monomer having an epoxy group include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, allyl glycidyl ether, and vinyl glycidyl ether. Specific examples of the monomer having a carboxyl group include acrylic acid and methacrylic acid. Specific examples of the monomer having an acid anhydride group include maleic anhydride, fumaric anhydride, and itaconic anhydride. ,
And halogenated maleic anhydride.

Specific examples of the vinyl monomer copolymerized with the monomer having a functional group include ethylene, propylene, 1-butene, isobutylene, butadiene, isoprene, vinyl acetate, 1,3-pentadiene, 1,4-hexadiene, Norbornene, styrene, vinyl styrene, bromostyrene, vinyl naphthalene and the like can be mentioned. These vinyl monomers may be used alone or in combination of two or more.

The copolymerization reaction between the above-mentioned monomer having a functional group and a vinyl monomer can be carried out by bulk polymerization, solution polymerization, suspension polymerization or emulsion polymerization using a known radical polymerization method.

In this reaction, both may be reacted directly, or after the vinyl monomer is polymerized in advance,
You may make it react with the monomer which has a functional group.

The modified thermoplastic copolymer used in the present invention is a copolymer of a monomer having a functional group and a vinyl monomer as described above. This copolymer is a random copolymer or a block copolymer. It may be a union, a graft copolymer or a mixture thereof. This modified thermoplastic copolymer has a number average molecular weight of 5,000 or more, preferably 100
The range is from 00 to 500,000.

The additive amount of the modified thermoplastic copolymer used in the present invention is as follows: (A) polyphenylene sulfide resin 65
More than 95% by weight and more than 5% by weight and (B) 5% by weight or more and 35% by weight of a heat-resistant cyclic olefin-based random copolymer
0 to 100 parts by weight of the resin component contained at a ratio of less than
It is 10 parts by weight, preferably 1 to 8 parts by weight. When the addition amount exceeds 10 parts by weight, the amount of gas generated by the decomposition of the modified thermoplastic copolymer during molding increases, and voids may be generated which may cause a decrease in the mechanical strength of the molded product. Absent.

The fibrous reinforcing material used in the present invention includes glass fiber, carbon fiber, metal fiber, alumina fiber,
Silica fiber, silica / alumina fiber, zirconia fiber,
Examples include boron fibers, boron nitride fibers, silicon nitride fibers, potassium titanate whiskers, aramid fibers, and wholly aromatic polyester fibers.

The amount of the fibrous reinforcing material used in the present invention is (A) more than 65% by weight and not more than 95% by weight of a polyphenylene sulfide resin, and (B) 5% by weight of a heat-resistant cyclic olefin-based random copolymer. The amount is from 0 to 50 parts by weight, preferably from 20 to 40 parts by weight, based on 100 parts by weight of the resin component contained in a proportion of at least 35% by weight. If the addition amount exceeds 50 parts by weight, the surface smoothness of the molded article is lowered, which is not preferable.

The fiber diameter of the fibrous reinforcing material used in the present invention is less than 9 μm, preferably 3 to 7 μm. When the fiber diameter is 9 μm or more, it is not preferable because the surface smoothness is reduced.

The inorganic filler used in the present invention includes:
For example, calcium carbonate, silica, glass beads, glass powder, glass balloon, phenol resin and the like can be mentioned, and those having an average particle diameter of less than 10 μm are preferable.

The amount of the inorganic filler used in the present invention is (A) more than 65% by weight of the polyphenylene sulfide resin and 95% by weight or less, and (B) 5% by weight or more of the heat-resistant cyclic olefin-based random copolymer. 30 to 150 parts by weight per 100 parts by weight of the resin component contained in a proportion of less than 35% by weight.
Parts by weight. If the amount is less than 30 parts by weight, the warpage of the molded article is significantly deteriorated, which is not preferable. On the other hand, when the amount exceeds 150 parts by weight, the surface smoothness of the molded article is decreased, the fluidity is decreased, and the specific gravity is increased.

Further, other fillers and resins may be added without departing from the object of the present invention.

Other fillers and organic and inorganic pigments that can be used in the present invention include, for example, talc, mica, barium sulfate, calcium sulfate, kaolin, clay, pyroferrite, bentonite, sericite, zeolite, nepheline sinite, Attapulgite, wollastonite,
Ferrite, calcium silicate, magnesium carbonate, dolomite, antimony trioxide, zinc oxide, titanium oxide,
Magnesium oxide, iron oxide, molybdenum disulfide, graphite,
Gypsum, quartz, quartz glass and the like can be mentioned. These are 2
It is also possible to use more than one kind in combination, and if necessary, to use them after preliminary treatment with a coupling agent such as a silane-based or titanium-based coupling agent.

Further, the resin composition of the present invention may contain a conventionally known mold release agent, lubricant, heat stabilizer, antioxidant, ultraviolet absorber, crystal nucleating agent, foaming agent as long as the object of the present invention is not impaired. One or more kinds of rust preventives, ion trapping agents, flame retardants, flame retardant aids, coloring agents such as dyes and pigments, additives such as antistatic agents, waxes and small amounts of other polymers may be used in combination.
Other polymers include, for example, olefin, styrene, urethane, ester, fluorine, amide,
Acrylic thermoplastic elastomer, polybutadiene, polyisoprene, polychloroprene, polybutene,
Styrene butadiene rubber and its hydrogenated product, acrylonitrile butadiene rubber, ethylene propylene copolymer,
Rubber components such as ethylene propylene ethylidene norbornene copolymer, nylon 6, nylon 66, nylon 4
6, polyamide resins such as 6, nylon 610, nylon 11, nylon 12, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyarylate, polystyrene, poly α-methylstyrene, polyvinyl acetate, polyvinyl chloride, polyacrylic acid Ester, polymethacrylate, polyacrylonitrile, polyurethane, polyacetal, polyphenylene oxide, polycarbonate, polysulfone, polyether sulfone, polyallylsulfone, polyphenylene sulfide sulfone, polyphenylene sulfide ketone, polyether ketone, polyether ether ketone, polyamide imide, polyimide ,Silicone resin,
Examples include homopolymers such as phenoxy resins, fluororesins, and melt-processable resins that form an anisotropic molten phase, random or block, graft copolymers, and mixtures or modified products thereof.

As a method for producing the polyphenylene sulfide resin composition of the present invention, a conventionally used heating and melting method can be used. For example, V-blender,
After mixing with various blenders such as Henschel mixer,
A method in which the mixture is heated and melted by a kneader, a mill, or a single-screw or twin-screw extruder can be used. Further, the resulting composition comprises
Molding can be performed using an injection molding machine, an extrusion molding machine, a transfer molding machine, or a compression molding machine.

[0056]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to only these Examples.

Examples 1 to 3 Polyphenylene sulfide resin (PPS, GRADE # 160 manufactured by Tosoh Sastile Co., Ltd.), heat-resistant cyclic olefin random copolymer (Apel 150R manufactured by Mitsui Petrochemical Industries, Ltd.), glass Fiber (GF, fiber diameter 6,5 μm, fiber length 3 mm), modified thermoplastic copolymer (Example 2: epoxy-modified polyethylene, Example 3: acid anhydride-modified polyethylene), and inorganic filler as shown in Table 1 And melt-kneaded at 300 ° C. using a twin-screw extruder to form pellets. Next, a test piece was molded by an injection molding machine. The characteristics described in Examples and Comparative Examples were evaluated by the following methods. Table 1 shows the results.

(1) Specific gravity: ASTM D792 (2) Izod impact strength: ASTM D256 (3) Deflection temperature under load: ASTM D648 (4) Surface roughness: JIS B0601 Comparative Example 1 Polyphenylene sulfide resin (PPS, Tosoh Sustir) After mixing GRADE # 160 (manufactured by Corporation), glass fiber (GF, fiber diameter 6,5 μm, fiber length 3 mm) and inorganic filler at the ratio shown in Table 1, the same operation and evaluation as in the example were performed. . Table 1 shows the results.

[0059]

[Table 1]

[0060]

As is apparent from the above description, according to the present invention, a polyphenylene sulfide resin composition obtained by blending a specific heat-resistant cyclic olefin-based random copolymer with a polyphenylene sulfide resin is molded. Thereby, it is possible to reduce the specific gravity and to produce a molded product for light reflection excellent in strength, heat resistance and surface smoothness with high productivity.

Claims (2)

(57) [Claims] (A) Polyphenylene sulfide resin 65
More than 95% by weight, and (B)Ethylene component and the following general formula (I) or (II)
Consisting of a cyclic olefin component represented by
Intrinsic viscosity [η] measured in Karin is 0.01 to 10 d
l / g, softening temperature (TMA) is 70 ° C or moreHeat-resistant
Cyclic olefin random copolymerEmbedded image  Embedded image  (Where n and m are each 0 or a positive integer
L is an integer of 3 or more; ^Three Or R
¹² Represents a hydrogen atom, a halogen atom or an alkyl group, respectively.
Show. ) Resin content 1 contained at a ratio of 5% by weight or more and less than 35% by weight
(C) 0 to 10 parts by weight of the modified thermoplastic copolymer, (D) 0 to 50 parts by weight of the fibrous reinforcing material, and (E) 30 to 150 parts by weight of the inorganic filler with respect to 00 parts by weight. Polyphenylenesul characterized by containing
Fid resin composition. 2. A molded article for light reflection obtained by molding the polyphenylene sulfide resin composition according to claim 1.