JP7096650B2 - Resin composition - Google Patents

Description

The present invention relates to a resin composition.

Polyphenylene sulfide resin contains a filler such as glass fiber as one of the crystalline resins having high heat resistance, and is an electric / electronic / OA resin molding material having excellent heat resistance, chemical resistance, rigidity and flame retardancy. It is used as a part and an automobile electrical component. In recent years, parts for these applications have been made smaller and finer from the viewpoint of weight reduction and performance improvement, and improvements have been made to improve the dimensional accuracy of the resin.

These techniques include cross-linking with a composition (for example, see Patent Document 1) in which an inorganic filler having a specific average fiber diameter and aspect ratio is added to a thermoplastic resin to improve warpage, or a linear polyphenylene sulfide resin. A composition in which a filler is added to a type polyphenylene sulfide resin to improve mechanical properties, reduction of burrs, and fluidity (see, for example, Patent Document 2) has been proposed.

However, in recent years, precision molded products such as optical equipment mechanism parts, printer parts, light source lamp peripheral parts, copier parts, automobile engine room parts, etc. have been made even smaller, lighter, and thinner. In addition to improving moldability such as low warpage, low burrs, and mold releasability, higher levels of water vapor barrier properties are required.

Regarding the compatibility between this precise molding processability and the water vapor barrier property, the actual situation is that no solution has been found for many polyphenylene sulfide resin compositions including the above-mentioned documents.

Japanese Patent Application Laid-Open No. 62-115060 Japanese Patent Application Laid-Open No. 09-087518

An object of the present invention is to provide a polymer alloy composed of a polyphenylene sulfide resin and a polyphenylene ether-based resin, which is excellent in various properties including water vapor barrier properties.

As a result of diligent studies on a resin composition composed of a polyphenylene sulfide resin and a polyphenylene ether-based resin in order to solve the above problems, the present invention has resulted in a polyphenylene ether-based resin having a specific viscosity range and a fibrous inorganic filler having a specific fiber length. We have found that a resin composition having excellent various properties including water vapor barrier property can be obtained by using a talc having a specific particle size, and have reached the present invention.
That is, the present invention is as follows.

[1] (a) Polyphenylene sulfide resin and
(B) A polyphenylene ether-based resin having an ultimate viscosity of 0.16 to 0.36 dL / g measured at 30 ° C. in chloroform.
(C) A fibrous inorganic filler having an average fiber length of 0.01 to 0.10 mm,
(D) Containing talc having an average particle size of 5 to 25 μm,
A resin composition, wherein the blending ratio of the component (a) and the component (b) is (a) / (b): 65 to 85/15 to 35 in terms of mass ratio .
[2] The resin composition according to [1], wherein the content of the component (c) is 25 to 150 parts by mass when the total of the component (a) and the component (b) is 100 parts by mass. thing.
[3] In [1] or [2], the content of the component (d) is 25 to 150 parts by mass when the total of the component (a) and the component (b) is 100 parts by mass. The resin composition described.
[4] Described in any one of [1] to [3], wherein the content mass ratio (c) / (d) of the component (c) to the component (d) is 1/5 to 5/1. Resin composition.
[5] The resin composition according to any one of [1] to [4], wherein the component (c) is a glass fiber having an average fiber length of 0.01 to 0.10 mm.
[6] The resin composition according to any one of [1] to [5], further containing at least one of (e) a phosphorus compound and (f) a compatibility agent.

According to the present invention, it is possible to provide a resin composition excellent in various properties including water vapor barrier property.

FIG. 1 is a schematic view (plan view) and a side view (b) showing a hinge test piece used for evaluating the amount of burr generation.

Hereinafter, embodiments for carrying out the present invention (hereinafter, also referred to as “the present embodiment”) will be described in detail. The present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist thereof.

The resin composition of the present embodiment includes (a) a polyphenylene sulfide resin, (b) a polyphenylene ether-based resin having an ultimate viscosity of 0.16 to 0.36 dL / g measured at 30 ° C. in chloroform, and (c). ) A fibrous inorganic filler having an average fiber length of 0.01 to 0.10 mm and (d) talc having an average particle size of 5 to 25 μm.

[(A) Polyphenylene sulfide resin]
The (a) polyphenylene sulfide resin used in the present embodiment may be made into a linear polyphenylene sulfide resin (hereinafter abbreviated as linear PPS) and a crosslinked polyphenylene sulfide resin (hereinafter abbreviated as crosslinked PPS) depending on the production method thereof. Divided into two.

[[Linear PPS]]
The former linear PPS is a polymer containing a repeating unit of arylene sulfide represented by the following chemical formula (1) in an amount of usually 50 mol% or more, preferably 70 mol% or more, and more preferably 90 mol% or more.
[-Ar-S-] ... (1)
(Here, Ar represents an arylene group, and examples of the arylene group include a p-phenylene group, an m-phenylene group, and a substituted phenylene group (the substituent is preferably an alkyl group having 1 to 10 carbon atoms and a phenyl group). Examples thereof include p, p'-diphenylene sulfone group, p, p'-biphenylene group, p, p'-diphenylene carbonyl group, naphthylene group and the like.)

The linear PPS may be a homopolymer having one type of arylene group as a constituent unit, and is a copolymer obtained by mixing two or more different types of arylene groups from the viewpoint of processability and heat resistance. May be good. Among them, linear PPS having a repeating unit of p-phenylene sulfide as a main component is preferable because it is excellent in processability and heat resistance and is easily available industrially.

The method for producing this linear PPS is usually a method of polymerizing a halogen-substituted aromatic compound such as p-dichlorobenzene in the presence of sulfur and sodium carbonate, sodium sulfide or sodium hydrogen sulfide and sodium hydroxide in a polar solvent. Examples thereof include a method of polymerizing in the presence or in the presence of hydrogen sulfide and sodium hydroxide or sodium aminoalkanoate, self-condensation of p-chlorthiophenol, and the like, among which amides such as N-methylpyrrolidone and dimethylacetamide are used. A method of reacting sodium sulfide with p-dichlorobenzene in a solvent or a sulfonic solvent such as sulfolane is preferable.

These manufacturing methods are known, and for example, Japanese Patent No. 251388, Japanese Patent Application Laid-Open No. 44-27671, Japanese Patent Publication No. 45-3368, Japanese Patent Application Laid-Open No. 52-12240, Japanese Patent Application Laid-Open No. 61-225217 are known. And the methods described in US Pat. No. 3,274,165, Japanese Patent Publication No. 46-27255, Belgian Patent No. 29437, Japanese Patent Application Laid-Open No. 5-222196, etc., and prior art exemplified in these documents. Linear PPS can be obtained by the method of technology.

A preferable linear PPS has an extraction amount of 0.7% by mass or less, preferably 0.5% by mass or less by methylene chloride, and a terminal-SX group (S is a sulfur atom, X is an alkali metal or a hydrogen atom). Is 20 μmol / g or more, preferably 20 to 60 μmol / g.

Here, the amount of extraction with methylene chloride can be measured by the following method.
5 g of linear PPS powder is added to 80 mL of methylene chloride, Soxhlet extraction is performed for 6 hours, the mixture is cooled to room temperature, and the extracted methylene chloride solution is transferred to a weighing bottle. Further, the container used for the above extraction is washed with a total of 60 mL of methylene chloride in three portions, and the washing liquid is collected in the weighing bottle. Next, the mixture is heated to about 80 ° C. to evaporate and remove methylene chloride in the weighing bottle, and the residue is weighed. The ratio can be calculated.
Further, the quantification of the -SX group can be performed by the following method. That is, after drying the linear PPS powder at 120 ° C. for 4 hours in advance, 20 g of the dried linear PPS powder is added to 150 g of N-methyl-2-pyrrolidone, and the mixture is vigorously stirred and mixed at room temperature for 30 minutes so that the powder agglomerates disappear, and the slurry is obtained. Put it in a state. After filtering the slurry, washing is repeated 7 times with 1 liter of warm water at about 80 ° C. each time. The filtered cake obtained here is reslurried in 200 g of pure water, and then 1N hydrochloric acid is added to adjust the pH of the slurry to 4.5.

Next, the mixture is stirred at 25 ° C. for 30 minutes, filtered, and then washed 6 times with 1 liter of warm water at about 80 ° C. each time. The obtained filtered cake can be slurried again in 200 g of pure water, then titrated with 1N sodium hydroxide, and the amount of —SX groups present in the linear PPS can be determined from the amount of sodium hydroxide consumed.

Here, as a specific example of a method for producing a linear PPS satisfying an extraction amount of 0.7% by mass or less with methylene chloride and a terminal-SX group of 20 μmol / g or more, Japanese Patent Application Laid-Open No. 8-253587 is described. The alkali metal sulfide and the dihalo aromatic compound are reacted in an organic amide-based solvent, and a part of the gas phase in the reaction can is condensed by cooling the gas phase portion of the reaction can during the reaction. , A method of reducing the oligomer component by refluxing this to the liquid layer above the reaction solution can be mentioned.

[[Crosslink PPS]]
Then, the crosslinked (including semi-crosslinked) polyphenylene sulfide resin is polymerized with the above-mentioned linear PPS and then heat-treated in the presence of oxygen at a temperature equal to or lower than the melting point of the polyphenylene sulfide resin to promote oxidative crosslinking. The polymer molecular weight and viscosity are appropriately increased.

The most preferable of the crosslinked PPS is the volatile matter collected in the molten state at 320 ° C. from the viewpoint of gas and tar generation when molding the resin composition obtained in the present invention and from the viewpoint of releasability. Cross-linked PPS of 1000 mass ppm or less. The quantification of the volatile matter collected in the molten state at 320 ° C. referred to here can be performed by the following method.

That is, 0.5 g of the crosslinked PPS powder was weighed in a test tube with a closed plug having an air flow inlet and an outlet, and while being immersed in a solder bath heated to 320 ° C. for 30 minutes, 100 cc / min of nitrogen gas was added from the air flow port inlet of the test tube. It is injected at a flow velocity, and the gas containing volatile matter derived from the crosslinked PPS generated in the test tube is purged from the air outlet of the test tube, and the purged gas is a test tube with a closed plug having an air inlet and an outlet containing acetone. Bubbling is performed in acetone in a test tube from the air inlet of the gas, and the volatile components are dissolved in acetone. The volatile content of the crosslinked PPS dissolved in acetone is assumed to have the same sensitivity as monochlorobenzene for all components detected by temperature analysis at 50 ° C to 290 ° C using a gas chromatograph mass spectrometer (GC-MS). It can be quantified and the volatile content in the crosslinked PPS can be determined.

In order to obtain a crosslinked PPS in which the volatile matter collected in the molten state at 320 ° C. is 1000 mass ppm or less, usually, the polymer concentration and solvent composition at the stage of polymerizing the linear PPS are devised, or the polymer is prepared at the stage of polymerization. The cleaning method to be recovered is devised, and the temperature and time of high-temperature treatment in the subsequent cross-linking stage are changed. In this way, a crosslinked PPS having a desired volatile content can be obtained.

[[Acid-denatured PPS]]
Further, these PPSs (linear PPS, crosslinked PPS) may be acid-modified PPS. Here, the acid-modified PPS is obtained by modifying the above PPS with an acid compound, and the acid compound includes unsaturated acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, and maleic anhydride. Examples thereof include carboxylic acid or an anhydride thereof, saturated aliphatic carboxylic acid and aromatic substituted carboxylic acid. Further, inorganic compound-based acid compounds such as acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, and carbonic acid can also be mentioned as the acid compound.

[[Melting viscosity of PPS]]
The melt viscosities of the above-mentioned linear PPS and crosslinked PPS at 300 ° C. are 1 to 10000 Pa · s, preferably 50 to 8000 Pa · s, and more preferably 100 to 5000 Pa · s.

In the specification, the melt viscosity is defined by preheating PPS at 300 ° C. for 6 minutes using a flow tester (CFT-500 type manufactured by Shimadzu Corporation) using JIS K-7210 as a reference test method, and then loading 196 N. , Die length (L) / die diameter (D) = 10 mm / 1 mm.

（ここで、Ｒ１，Ｒ２，Ｒ３およびＲ４はそれぞれ、水素原子、ハロゲン原子、炭素数１～７までの第一級または第二級低級アルキル基、フェニル基、ハロアルキル基、アミノアルキル基、炭化水素オキシ基または少なくとも２個の炭素原子がハロゲン原子と酸素原子とを隔てているハロ炭化水素オキシ基からなる群から選択されるものであり、互いに同一であっても異なっていてもよい。また、ｎは１以上の整数である。） [(B) Polyphenylene ether-based resin]
The polyphenylene ether-based resin of the component (b) used in the present embodiment has a repeating unit (structural unit) represented by the following chemical formula (2), and has an ultimate viscosity of 0.16 measured at 30 ° C. in chloroform. It is a polyphenylene ether resin of a homopolymer and / or a copolymer having an amount of about 0.36 dL / g, or a mixture of the polyphenylene ether resin and a styrene resin in an arbitrary ratio. (Hereafter, abbreviated as PPE.)

(Here, R1, R2, R3 and R4 are hydrogen atom, halogen atom, primary or secondary lower alkyl group having 1 to 7 carbon atoms, phenyl group, haloalkyl group, aminoalkyl group and hydrocarbon, respectively. The oxy group or at least two carbon atoms are selected from the group consisting of halohydrocarbon oxy groups separating the halogen atom and the oxygen atom, and may be the same or different from each other. n is an integer of 1 or more.)

By setting the ultimate viscosity of PPE to 0.16 dL / g or more, the balance between mechanical properties, fluidity and releasability is good, and by setting it to 0.36 dL / g or less, the fluidity in a particularly high share region (for example). (SFD characteristic of 0.5 mm) and flame retardancy can be improved. In the specification, "extreme viscosity" refers to the value of viscosity measured by a Ubbelohde viscous tube at 30 ° C. using a 0.5 g / dL chloroform solution. From the viewpoint of the balance between mechanical properties, fluidity, low warpage, low burr property, releasability, and flame retardancy, the content is preferably 0.20 to 0.34 dL / g. More preferably, it is 0.25 to 0.34 dL / g.

Specific examples of this PPE include, for example, poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), and poly (2-). Methyl-6-phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether) and the like, and further 2,6-dimethylphenol and other phenols (eg, 2). , 3,6-trimethylphenol and 2-methyl-6-butylphenol) and polyphenylene ether copolymers as well. The polyphenylene ether copolymer is a copolymer having a repeating unit represented by the above chemical formula (2) as a main repeating unit. Of these, poly (2,6-dimethyl-1,4-phenylene ether), a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol is preferable, and poly (2,6-dimethyl-1) is preferable. , 4-Phenylene ether) is more preferable.

The method for producing PPE is not particularly limited, and for example, a complex of ferrous salt and amine according to Hay described in US Pat. No. 3,306,874 is used as a catalyst to oxidatively polymerize 2,6-xylenol, for example. As a result, PPE can be easily produced, and in addition, US Pat. No. 3,306,875, US Pat. No. 3,257,357, US Pat. No. 3,257,358, Japanese Patent Application Laid-Open No. 52-17880, Japanese Patent Application Laid-Open No. 50-51197 PPE can be easily produced by adjusting the ultimate viscosity by the method described in Japanese Patent Application Laid-Open No. 63-152628 and the like.

It is preferable that the content is 100% by mass consisting of only the PPE component described above, but a PPE / styrene resin = 50 to 100% by mass / 0 to 50% by mass can also be used. It is preferably 65 to 100% by mass / 0 to 35% by mass. More preferably, it is 80 to 100% by mass / 0 to 20% by mass.

[[Styrene resin]]
The styrene-based resin is a polymer in which a rubber-like polymer is dispersed in a matrix composed of a homopolymer of a styrene-based compound, a copolymer of two or more kinds of styrene-based compounds, and a polymer of the styrene-based compound. Examples include rubber-modified styrene resin (high impact polystyrene). Examples of the styrene-based compound that brings about these polymers include styrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, α-methylstyrene, ethylstyrene, α-methyl-p-methylstyrene, 2,4. -Dimethylstyrene, monochlorostyrene, p-tert-butylstyrene and the like can be mentioned.

These styrene-based compounds may be copolymers obtained by using two or more kinds in combination, but polystyrene obtained by polymerizing using styrene alone is particularly preferable. For example, polystyrene having a three-dimensional ordered structure such as atactic polystyrene and syndiotactic polystyrene can be effectively used.

[[Mixing ratio of component (a) and component (b)]]
In the resin composition of the present embodiment, the blending ratio of (a) polyphenylene sulfide resin and (b) polyphenylene ether resin is (a) polyphenylene sulfide resin: 50 to 95 parts by mass, (b) polyphenylene ether resin: 50 to 5 It is preferably composed of parts by mass. By using 5 parts by mass or more of the polyphenylene ether resin as the component (b), burrs during molding of the resin composition are suppressed, and the releasability is improved. By using 50 parts by mass or less, the fluidity is increased. A resin composition having an excellent balance of flame retardancy and water vapor barrier property is provided. More preferably, the compounding ratio is (a) / (b): 65 to 85/15 to 35. More preferably, the compounding ratio is (a) / (b): 70 to 80/20 to 30.

[(C) Fibrous inorganic filler having an average fiber length of 0.01 to 0.10 mm]
The fibrous inorganic filler used in this embodiment has (c) an average fiber length in the range of 0.01 to 0.10 mm, and includes glass fibers, carbon fibers, carbon nanotubes, cellulose fibers, silicon carbide fibers, and ceramic fibers. At least one selected from the group consisting of aramid fiber, alumina fiber, gypsum fiber, metal fiber, calcium titanate whisker, calcium carbonate whisker, and wallastnite can be used. These fibrous inorganic fillers were further treated with a surface treatment agent such as a silane coupling agent, a titanate coupling agent, or an aliphatic metal salt, or a resin such as a urethane resin or an epoxy resin as a binder. It doesn't matter what. Of these, glass fiber is preferable from the viewpoint of heat resistance and adhesion to the resin.

In this embodiment, it is important that the average fiber length of (c) the fibrous inorganic filler is in the range of 0.01 to 0.10 mm. When the average fiber length is 0.01 mm or more, mechanical strength and low warpage are improved, and when it is 0.10 mm or less, the fluidity in a particularly low share region (eg, at 300 ° C. and 10.0 kg). MVR), low warpage, low burr, water vapor barrier, and excellent balance of appearance. The reason for improving the releasability, water vapor barrier property, and appearance is that by using a fibrous inorganic filler having a short fiber length, the fluidity during molding is improved and the filler protrudes to the surface of the molded product. Is suppressed. The average fiber length is preferably 0.02 to 0.10 mm from the viewpoint of the balance between mechanical strength, low warpage, fluidity, low burr property, water vapor barrier property, appearance, and releasability. More preferably, it is 0.03 to 0.06 mm.

The resin composition of the present embodiment is obtained through the melt-kneading step described later, and the average fiber length of the (c) fibrous inorganic filler after the melt-kneading step is within the above range. As a method for measuring the average fiber length after melt-kneading, 2 to 3 g of resin composition pellets are heated in an electric furnace at 650 ° C. for 2 hours, and the remaining ash is dispersed in water with a surfactant, and a particle shape image analyzer is used. A method of measuring using (PITA-3) can be mentioned. More specifically, it can be obtained according to the method described in the examples.

[[Ratio of component (c) to component (a) + component (b)]]
In the present embodiment, when the total of the component (a) and the component (b) is 100 parts by mass, the content of the component (c) is preferably 25 to 150 parts by mass. (C) A resin having a component content of 25 parts by mass or more, which has improved low warp property, low burr property, and water vapor barrier property, and a resin content of 150 parts by mass or less, which has good appearance and releasability. The composition is obtained. From the viewpoint of small and thin precision molding that requires low water vapor permeability, the content of the component (c) is more preferably 30 to 100 parts by mass. More preferably, it is 30 to 70 parts by mass.

[(D) Talc with an average particle size of 5 to 25 μm]
The talc used in the present embodiment (d) having an average particle size of 5 to 25 μm is generally hydrated magnesium silicate (SiO ₂ : 58 to 64%, MgO: 28 to 32%, Al ₂ O ₃ : It is a plate-like crystal containing 0.5 to 5%, Fe ₂ O ₃ : 0.3 to 5%) as a main component.

In this embodiment, it is important that the average particle size is 5 to 25 μm. When the average particle size is in this range, the balance between fluidity, low burr property, and low warpage property is improved. From the viewpoint of small size and thin wall precision molding, it is preferably 10 to 22 μm. More preferably, it is 15 to 22 μm.

The average particle size of talc can be measured by a laser diffraction method, for example, by a laser diffraction method using a Shimadzu particle size distribution measuring instrument SALD-2000A manufactured by Shimadzu Corporation.

Further, the talc as the component (d) may be surface-treated with a silane coupling agent, a titanate coupling agent, an aliphatic metal salt or the like, and an ammonium salt or the like may be used by an intercalation method. It may be subjected to an organic treatment, or may be subjected to a binder treatment using a resin such as a urethane resin or an epoxy resin.

[[Ratio of component (d) to component (a) + component (b)]]
In the present embodiment, when the total of the component (a) and the component (b) is 100 parts by mass, the content of the component (d) is preferably 25 to 150 parts by mass. (D) When the content of the component is 25 parts by mass or more, low warpage and releasability are improved, and when it is 150 parts by mass or less, the balance between fluidity, low burrness and low warpage is achieved. improves. From the viewpoint of compact and thin-walled precision molding that requires low water vapor permeability, it is more preferably 30 to 100 parts by mass. More preferably, it is 30 to 70 parts by mass.

[[Mixing ratio of component (c) and component (d)]]
Further, in the present embodiment, the content mass ratio of the component (c) to the component (d) is preferably (c) / (d) = 1/5 to 5/1, and 1/3 to 3/1. Is more preferable. When the content ratio of the component (c) to the component (d) is within the above range, a resin composition having excellent fluidity, low warpage, low burr property, and water vapor barrier property can be obtained.

[(E) Phosphorus compound]
The (e) phosphorus-based compound used in the present embodiment is used as a flow modifier and a flame retardant, and examples of typical compounds include organic phosphoric acid ester compounds.

Examples of the organic phosphate ester compound include triphenyl phosphate, phenyl bisdodecyl phosphate, phenyl bisneopentyl phosphate, phenyl-bis (3,5,5'-tri-methyl-hexyl phosphate), ethyldiphenyl phosphate, 2-. Ethyl-hexyldi (p-tolyl) phosphate, bis- (2-ethylhexyl) p-tolyl phosphate, tritryl phosphate, bis- (2-ethylhexyl) phenyl phosphate, tri- (nonylphenyl) phosphate, di (dodecyl) p- Trill phosphate, tricresyl phosphate, dibutylphenyl phosphate, 2-chloroethyldiphenyl phosphate, p-tolylbis (2,5,5'-trimethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate, bisphenol A. bis (diphenyl phosphate), Diphenyl- (3-hydroxyphenyl) phosphate, bisphenol A-bis (dicredyl phosphate), resorcin bis (diphenyl phosphate), resorcin bis (dixylenyl phosphate), 2-naphthyldiphenyl phosphate, 1-naphthyldiphenylphos Examples include fate and di (2-naphthyl) phenyl phosphate.

[[Ratio of component (e) to component (a) + component (b)]]
(E) One type of phosphorus compound may be used alone, or two or more types may be used in combination. In the resin composition of the present embodiment, the content of the (e) phosphorus-based compound is preferably 30 parts by mass or less when the total of the components (a) and (b) is 100 parts by mass. By containing the component (e) in an amount of 30 parts by mass or less, a composition having an excellent balance between mechanical strength, fluidity, releasability and low burr property can be obtained. 25 parts by mass or less is more preferable, and 20 parts by mass or less is further preferable.

Further, in the present embodiment, it is preferable to add (f) a compatibilizer when mixing the polyphenylene sulfide resin of the component (a) and the polyphenylene ether-based resin of the component (b).

Examples of the compatibilizer used as the component (f) include (1) an epoxy resin, (2) a silane coupling agent, (3) a compound containing an epoxy group and / or a copolymer containing an oxazolyl group. Among them, a copolymer of an unsaturated monomer containing an epoxy group and / or an oxazolyl group and a monomer containing styrene as a main component can be more preferably used.

[[Monomer whose main component is styrene]]
There is no problem with the monomer containing styrene as the main component when the styrene component is 100% by mass, but when there is another monomer copolymerizable with styrene, the copolymer chain is the component (b). In order to maintain the compatibility with the polyphenylene ether-based resin, at least 65% by mass or more, more preferably 75 to 95% by mass of the styrene monomer is contained. Specifically, as an example of these, a copolymer of an unsaturated monomer containing an epoxy group and / or an oxazolyl group and a styrene monomer, an unsaturated monomer containing an epoxy group and / or an oxazolyl group and a styrene / acrylonitrile = 90 to 75% by mass /. Examples thereof include a copolymer of 10 to 25% by mass.

[[Epoxy group-containing unsaturated monomer]]
Examples of the epoxy group-containing unsaturated monomer include glycidyl methacrylate, glycidyl acrylate, vinyl glycidyl ether, hydroxyalkyl (meth) acrylate glycidyl ether, polyalkylene glycol (meth) acrylate glycidyl ether, and glycidyl itaconate. Glycidyl methacrylate is preferred.

[[Oxazolyl group-containing unsaturated monomer]]
As the oxazolyl group-containing unsaturated monomer, for example, 2-isopropenyl-2-oxazoline is industrially available and can be preferably used.

[[Other unsaturated monomers]]
Other unsaturated monomers that copolymerize with these epoxy group and / or oxazolyl group-containing unsaturated monomers include vinyl aromatic compounds such as styrene, vinyl cyanide monomers such as acrylonitrile as copolymerization components, and vinyl acetate. , (Meta) acrylic acid ester and the like.

In the present embodiment, it is preferable that the styrene monomer is contained in an amount of at least 65% by mass or more in the component excluding the unsaturated monomer containing an epoxy group and / or the oxazolyl group. Further, the unsaturated monomer having an epoxy group and / or an oxazolyl group is contained in the copolymer of the component (f) in an amount of 0.3 to 20% by mass, preferably 1 to 15% by mass, and more preferably 3 to 10% by mass. Will be done.

The amount of the epoxy group and / or oxazolyl group-containing unsaturated monomer of the copolymer of the component (f) is preferably 0.3% by mass or more, and if it is 20% by mass or less, the polyphenylene of the component (a) is used. The miscibility between the sulfide resin and the polyphenylene ether-based resin of the component (b) becomes good, which can greatly suppress the generation of burrs in the molded product molded using the obtained resin composition, and further, the toughness. It has the effect of excellent balance between (impact strength) and rigidity.

Examples of the copolymer of the component (f) obtained by copolymerizing a copolymerizable unsaturated monomer include, for example, a styrene-glycidyl methacrylate copolymer, a styrene-glycidyl methacrylate-methyl methacrylate copolymer, and a styrene-glycidyl. Examples thereof include a methacrylate-acrylonitrile copolymer, a styrene-vinyloxazoline copolymer, and a styrene-vinyloxazoline-acrylonitrile copolymer.

[[Ratio of component (f) to component (a) + component (b)]]]
The blending amount of the admixture for the component (f) is 1 to 20 parts by mass, preferably 2 to 15 parts by mass, more preferably 2 to 15 parts by mass with respect to 100 parts by mass in total of the above-mentioned components (a) and (b). 3 to 10 parts by mass. If the blending amount of the component (f) is 1 part by mass or more, the miscibility between the polyphenylene sulfide resin of the component (a) and the polyphenylene ether-based resin of the component (b) is good, and if it is 20 parts by mass or less. It is possible to greatly suppress the generation of burrs in the molded product molded using the obtained resin composition, and further bring about an excellent effect on the balance between toughness (impact strength) and rigidity.

[Contents of (a) component and (b) component]
When the total amount of the resin composition is 100% by mass, the component (a) is preferably 20 to 75% by mass, the component (b) is preferably 2 to 40% by mass, and the component (a) is 38 to 65% by mass. b) The component is more preferably 9 to 27% by mass.

[Other additives]
In addition to the above components, if necessary, coloring of stabilizers such as heat stabilizers, antioxidants, ultraviolet absorbers, crystal nucleating agents, conductivity-imparting agents, antistatic agents, flame retardants, pigments and dyes, etc. Known demolding agents such as agents, polyethylene wax, polypropylene wax, montanate wax, stearate wax and the like can also be appropriately added.

[Manufacturing method of resin composition]
In the method for producing the resin composition of the present embodiment, various melt kneaders, kneading extruders, and the like can be used. As the melt kneader and the kneading extruder, a known kneader can be used. For example, an extruder such as a multi-screw extruder such as a single-screw extruder or a twin-screw extruder; roll, kneader, brabender plast graph. , A heating / melting kneader such as a Banbury mixer; and the like. Of these, a twin-screw extruder is preferable.

A method of melt-kneading using each of the above-mentioned components using a twin-screw extruder set at 280 ° C. or higher having at least two vent ports and at least one side supply port is preferable.

One of the specific methods for producing the resin composition of the present embodiment by a more preferable twin-screw extruder is a mixture of the polyphenylene sulfide resin of the component (a), the polyphenylene ether-based resin of the component (b), and the component (f). The agent is simultaneously supplied to the first supply port of the twin-screw extruder and melt-kneaded, and the basic resin composition composed of these components (a), (b) and (f) is melt-kneaded. The first vent port of the shaft extruder is sucked and degassed at an absolute vacuum pressure of 95 kPa or less, and then, for example, the liquid component (e) is supplied by a liquid addition pump, and the side 1 of the twin-screw extruder provided downstream thereof is supplied. The talc of the component (d) is supplied from the supply port, and the fibrous inorganic filler of the component (c) is supplied from the side 2 supply port further downstream, and the components (a) to (f) are melt-kneaded, and finally biaxial. This is a method of suctioning and degassing the second vent port of the extruder at an absolute vacuum pressure of 95 kPa or less.

A precision molded product can be manufactured using the resin composition thus obtained. As the molding method, for example, injection molding, metal in-mold molding, outsert molding, hollow molding, extrusion molding, sheet molding, film molding, hot press molding, rotary molding, laminated molding and the like can be applied.

By these molding methods, parts in the automobile engine room such as optical equipment mechanism parts, light source lamp surrounding parts, optical fiber connector ferrules, printer parts, copy machine parts, automobile radiator tank parts, automobile lamp parts, water pipes and casings are used. It can be widely used as a molded product such as.

Hereinafter, the above embodiments will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. The methods for measuring physical properties and raw materials used in Examples and Comparative Examples are shown below.

[Measurement method of physical properties]
(1) Average fiber length (mm) of fibrous inorganic filler in molded product
2-3 g of the resin composition pellets were heated in an electric furnace at 650 ° C. for 2 hours, and the remaining ash was dispersed in water with a surfactant. This solution was passed through a particle shape image analyzer (PITA-3), the major axis of the inorganic substance was scanned, and the particle size distribution was measured. The average particle size (mm) in the range of the aspect ratio of 1.5 or more of this measurement result was obtained. The same measurement was performed three times from the ash content of the same resin pellet, and the average value of the average particle diameter (mm) of the three times was defined as "the average fiber length (mm) of the fibrous inorganic filler in the molded product".

(2) High market share liquidity (0.5mm-SFD)
Using an injection molding machine (IS-80EPN, manufactured by Toshiba Machine Co., Ltd.), a 0.5 mm thick SFD (spiral flow) molded product was produced as follows.
The pellets of the resin compositions obtained in the following Examples and Comparative Examples were dried at 120 ° C. for 3 hours. The dried resin composition was molded using the above injection molding machine under the conditions of cylinder temperature 310 ° C., mold temperature 120 ° C., gauge pressure 120 MPa, injection speed 95%, molding cycle: injection time / cooling time = 10 sec / 10 sec. Molding was performed to obtain the above-mentioned molded product. The spiral length (cm) of the obtained molded piece was measured, and it was judged that the longer the spiral length, the better the fluidity at a high share, which is advantageous for reducing warp and burrs.

(3) Low share liquidity (MVR)
The resin composition pellets obtained in Examples and Comparative Examples were dried in a hot air dryer at 120 ° C. for 3 hours. After drying, MVR (melt volume rate) (cm ^3/10 min) was measured using a semi-automatic melt indexer (2A, manufactured by Toyo Seiki Co., Ltd.) at a cylinder set temperature of 300 ° C. and a load of 10 kg according to ISO1133.
As an evaluation standard, it was determined that the higher the MVR value, the better the liquidity with a low share and the more advantageous for the reduction of warpage and burrs.

(4) Low warpage evaluation (flatness)
The pellets of the obtained resin composition are supplied to a screw in-line type injection molding machine (manufactured by Toshiba Machine Co., Ltd., product name "EC75SXII injection molding machine"), and the conditions are a cylinder temperature of 300 ° C. and a mold temperature of 120 ° C. A flat plate having a thickness of 50 cm ² , 1 mm was formed. This flat plate is placed on a flat table and analyzed three-dimensionally with an atomic force microscope (VR-3000, manufactured by KEYENCE) to determine the difference (mm) between the highest point and the lowest point in the thickness direction. rice field. As an evaluation standard, if it is less than 0.10 mm, it is judged that the low warpage property is excellent.

(5) Amount of burr generation The pellets of the above resin composition are supplied to an injection molding machine (TOYOblaster TI50G2) set at 320 ° C., the resin composition is flowed from the gate 3, and the width connecting the two structural portions 4 and these. A test piece 1 (test piece shown in FIG. 1) including a hinge portion 2 having a w of 7 mm, a length of l of 18 mm, and a thickness of 0.25 mm was formed. Here, for each resin composition, SSP (short shot pressure) at an injection speed of 80% was obtained, and molding was performed at an injection pressure of SSP + 10%.
At that time, among the burrs generated in the gap between the hinge portion 2 and the mold, the length from the end of the hinge portion at the maximum point was measured and defined as the amount of burrs generated (mm). As an evaluation standard, if it is 0.25 mm or less, it is judged that the low burr property is excellent.

(6) Releasability When molding a 50 cm ² , 1 mm thick flat plate shown in (4), if the phenomenon that the resin remains in the sprue and does not release the mold in 10 shots is once or more, ×, it should not occur at all. It was marked as ○.

(7) Moisture vapor transmission rate Using the flat plate formed in (4), use the steam permeability tester PERMATRAN W3 / 31 (manufactured by Mocon) under an atmosphere of temperature 40 ° C. and humidity 90% RH, JIS K7129 B method. The water vapor transmission rate (g / (m ² · day)) was measured according to the above. As an evaluation standard, if it was 0.30 g / (m ² · day) or less, it was judged that the water vapor barrier property was good.

The raw materials used are as follows.
(A) Polyphenylene sulfide resin (a-1): melt viscosity (value measured using a flow tester at 300 ° C., a load of 196 N, and L / D = 10/1 for 6 minutes) is 30 Pa · s. A linear PPS having a repeating unit of p-phenylene sulfide having an extraction amount of 0.7% by mass with methylene chloride and a -SX group amount of 32 μmol / g.
(A-2): In a molten state with a melt viscosity (measured using a flow tester at 300 ° C., a load of 196 N, and held at L / D = 10/1 for 6 minutes) at 60 Pa · s and 320 ° C. A cross-linked PPS with a collected volatile content of 160 mass ppm.

(B) A polyphenylene ether obtained by oxidatively polymerizing a polyphenylene ether resin (b-1) 2,6-xylenol and measuring in chloroform at 30 ° C. with an ultimate viscosity of 0.21 dL / g.
(B-2) A polyphenylene ether obtained by oxidatively polymerizing 2,6-xylenol and measuring in chloroform at 30 ° C. with an ultimate viscosity of 0.33 dL / g.
(B-x1) A polyphenylene ether obtained by oxidatively polymerizing 2,6-xylenol and measuring in chloroform at 30 ° C. with an ultimate viscosity of 0.10 dL / g.
(B-x2) A polyphenylene ether obtained by oxidatively polymerizing 2,6-xylenol and measuring in chloroform at 30 ° C. with an ultimate viscosity of 0.46 dL / g.

(C) Fibrous inorganic filler (c-1) Glass fiber having an average fiber diameter of 6 μm and an average fiber length of 0.05 mm (manufactured by Central Glass Fiber Co., Ltd.)
(C-2) Glass fiber with an average fiber diameter of 13 μm and an average fiber length of 0.08 mm (manufactured by Nippon Electric Glass Co., Ltd.)
(C-3) Carbon fiber with an average fiber diameter of 6 μm and an average fiber length of 0.05 mm (manufactured by Nippon Graphite Fiber Corporation)
(C-x1) Glass fiber with an average fiber diameter of 13 μm and an average fiber length of 3 mm (manufactured by Nippon Electric Glass Co., Ltd.)

(D) Talc (d-1) Talc with an average particle size of 8 μm (manufactured by Fuji Tarc)
(D-2) Talc with an average particle size of 19 μm (manufactured by Fuji Tarc)
(Dx1) Talc with an average particle size of 2.3 μm (manufactured by Takehara Chemical Industry Co., Ltd.)
(Dx2) Talc with an average particle size of 30 μm (manufactured by Fuji Tarc)

(E) Phosphorus compound (e-1) Triphenylphosphine (manufactured by Daihachi Chemical Co., Ltd.)
(E-2) Bisphenol A / Bis (diphenyl phosphate) (manufactured by ADEKA)

(F) Aspectating agent (f-1): Styrene-glycidyl methacrylate copolymer containing 5% by mass of glycidyl methacrylate (weight average molecular weight 110,000)

In Examples and Comparative Examples, each raw material was melt-kneaded as follows to prepare a resin composition.
Specifically, the polyphenylene sulfide resin of the component (a), the polyphenylene ether-based resin of the component (b), and the admixture of the component (f) are simultaneously supplied to the first supply port of the twin-screw extruder and melt-kneaded. In a state where the basic resin composition composed of these components (a), (b) and (f) is melt-kneaded, the first vent port of the twin-screw extruder is suction-degassed at an absolute vacuum pressure of 95 kPa or less. Subsequently, the talc of the component (d) is supplied from the side 1 supply port of the twin-screw extruder provided downstream thereof, and the fibrous inorganic filler of the component (c) is supplied from the side 2 supply port further downstream. The components were melt-kneaded, and finally the second vent port of the twin-screw extruder was sucked and degassed at an absolute vacuum pressure of 95 kPa or less. As a twin-screw extruder, ZSK-70 (manufactured by Werner & Freiderer (Germany)) was used. When the component (e) was used, the liquid component (e) was supplied by a liquid addition pump provided between the first supply port and the side 1 supply port.

These results are shown in Table 1.
From these results, the resin composition was (a) a polyphenylene sulfide resin, (b) a polyphenylene ether-based resin having an ultimate viscosity of 0.16 to 0.36 dL / g measured at 30 ° C. in chloroform, and (c). ) By containing a fibrous inorganic filler having an average fiber length of 0.01 to 0.10 mm and (d) talc having an average particle size of 5 to 25 μm, fluidity, low warpage, and low variability can be achieved. It was clarified that a material having an excellent balance of releasability and water vapor barrier property can be obtained.

According to the present invention, a resin composition having excellent various properties including a water vapor barrier property can be realized, and a compact disc read-only memory (CDROM) and a digital versatile disc, which require precise dimensional accuracy, can be realized. -Read-only memory (DVDROM), compact disc recordable (CDR), digital versatile disc recordable-R standard (DVD-R), digital versatile disc recordable + R standard (DVD + R) , Compact Disc Rewritable (CDRW), Digital Versatile Disc Rewritable-R Standard (DVD-RW), Digital Versatile Disc Rewritable + R Standard (DVD + RW), Digital Versatile Disc Random Access Memory Chassis and cabinet such as (DVDRAM), optical equipment mechanism parts such as optical pickup slide base, light source lamp peripheral parts, optical fiber connector ferrule, laser beam printer internal parts, inkjet printer internal parts, copy machine internal parts, automobile radiator tank It can be used as at least one part of an automobile engine room part such as a part, an automobile lamp part, and a molded product such as a water pipe and a casing.

1 Test piece 2 Hinge part 3 Gate 4 Structural part l Length of hinge part w Width of hinge part t Thickness of hinge part

Claims (6)

(A) Polyphenylene sulfide resin and
(B) A polyphenylene ether-based resin having an ultimate viscosity of 0.16 to 0.36 dL / g measured at 30 ° C. in chloroform.
(C) A fibrous inorganic filler having an average fiber length of 0.01 to 0.10 mm,
(D) Containing talc having an average particle size of 5 to 25 μm,
A resin composition, wherein the blending ratio of the component (a) and the component (b) is (a) / (b): 65 to 85/15 to 35 in terms of mass ratio . The resin composition according to claim 1, wherein the content of the component (c) is 25 to 150 parts by mass when the total of the component (a) and the component (b) is 100 parts by mass. The resin composition according to claim 1 or 2, wherein the content of the component (d) is 25 to 150 parts by mass when the total of the component (a) and the component (b) is 100 parts by mass. .. The resin composition according to any one of claims 1 to 3, wherein the content mass ratio (c) / (d) of the component (c) to the component (d) is 1/5 to 5/1. The resin composition according to any one of claims 1 to 4, wherein the component (c) is a glass fiber having an average fiber length of 0.01 to 0.10 mm. The resin composition according to any one of claims 1 to 5, further comprising (e) a phosphorus-based compound and (f) at least one of a compatibilizer.

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