WO2013099234A1 - ポリフェニレンスルフィド樹脂組成物、該樹脂組成物の成形品、および該樹脂組成物の製造方法 - Google Patents
ポリフェニレンスルフィド樹脂組成物、該樹脂組成物の成形品、および該樹脂組成物の製造方法 Download PDFInfo
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- WO2013099234A1 WO2013099234A1 PCT/JP2012/008306 JP2012008306W WO2013099234A1 WO 2013099234 A1 WO2013099234 A1 WO 2013099234A1 JP 2012008306 W JP2012008306 W JP 2012008306W WO 2013099234 A1 WO2013099234 A1 WO 2013099234A1
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- polyphenylene sulfide
- weight
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- sulfide resin
- resin composition
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- 0 *1C=C*C=C1 Chemical compound *1C=C*C=C1 0.000 description 6
- APDUDRFJNCIWAG-UHFFFAOYSA-N CC(C)c(cc1)ccc1S Chemical compound CC(C)c(cc1)ccc1S APDUDRFJNCIWAG-UHFFFAOYSA-N 0.000 description 1
- ICHZCMIOUZHWGE-UHFFFAOYSA-N CS(C)C(CCCC1)C1S Chemical compound CS(C)C(CCCC1)C1S ICHZCMIOUZHWGE-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/04—Polysulfides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/02—Polythioethers; Polythioether-ethers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2081/00—Use of polymers having sulfur, with or without nitrogen, oxygen or carbon only, in the main chain, as moulding material
- B29K2081/04—Polysulfides, e.g. PPS, i.e. polyphenylene sulfide or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Definitions
- the present invention relates to a polyphenylene sulfide resin composition, a molded product thereof, and a method for producing the same, which significantly improve heat resistance without impairing the inherent properties of the polyphenylene sulfide resin and which generate a small amount of gas.
- Polyphenylene sulfide resin (hereinafter abbreviated as PPS resin) has a high melting point and has suitable properties as an engineering plastic such as excellent flame retardancy, rigidity, and chemical resistance.
- PPS resin is mainly formed by injection molding, and is widely used in various electric / electronic parts, machine parts, automobile parts, home appliances, and the like.
- a PPS resin material having excellent heat resistance and good fluidity has been strongly desired in order to meet the needs for the thinning of molded products accompanying the modularization and weight reduction of large parts for automobiles.
- the PPS resin alone has a problem of insufficient high-temperature rigidity due to thinning of the molded product.
- PPS resin blended with inorganic fillers such as glass fiber improves heat resistance and rigidity but significantly increases the melt viscosity. Therefore, the amount of gas generated increases due to high shear heat generation during injection molding, and the molding processability decreases. There was a problem.
- Patent Document 1 discloses a resin composition in which polyphenylene sulfide having a weight reduction rate ⁇ Wr during heating of 0.18% or less and a fibrous and non-fibrous filler are blended.
- the resin composition described in Patent Document 1 has a problem that the fluidity is remarkably lowered although the amount of gas generation is small and the material rigidity is improved.
- the resin composition described in Patent Document 1 has not been sufficiently improved in filler adhesion, and has not reached a level at which surface smoothness and rigidity can be satisfied.
- Patent Document 2 discloses a PPS resin composition in which polyphenylene oxide, which is an amorphous resin, and glass fibers having a fiber diameter of 7 ⁇ m or less are blended.
- polyphenylene oxide which is an amorphous resin
- glass fibers having a fiber diameter of 7 ⁇ m or less are blended.
- molding shrinkage in the thickness direction was improved by blending the amorphous resin, and a certain improvement effect was observed with respect to surface smoothness.
- the adhesion with the filler has not been improved, and the surface smoothness was not satisfactory because the filler was unevenly distributed on the surface of the molded product.
- Patent Document 3 discloses a PPS resin composition containing a fibrous filler and a particulate filler having a specific shape.
- the resin composition described in Patent Document 3 both surface smoothness and rigidity are achieved by using a filler having a small particle diameter and a fibrous filler in combination.
- the adhesion between the PPS resin and the filler has not been sufficiently improved, the surface smoothness of the PPS resin composition has not been satisfactory for practical use.
- Patent Document 4 discloses a PPS resin composition in which an ethylene / ⁇ -olefin copolymer having a glass transition temperature of ⁇ 50 ° C. or lower and an inorganic filler are blended.
- the rigidity is improved by blending the inorganic filler, there is a problem of low-temperature toughness reduction, which is not a satisfactory level for actual use.
- Patent Document 5 polyphenylene sulfide having a weight reduction rate ⁇ Wr of 0.18% or less is known from Patent Document 5, and an olefin copolymer containing an epoxy group and an olefin containing no epoxy group with respect to such polyphenylene sulfide.
- Patent Document 6 describes a resin composition containing a copolymer. However, in the resin composition described in Patent Document 6, the gas generation amount is reduced and the moldability is improved, but the compatibility between the PPS resin and the epoxy group-containing olefin resin is not sufficient. Satisfactory toughness was not obtained.
- JP 2008-231141 (Claims, Examples) JP-A-7-53865 (Claims, Examples) JP-A-2005-171242 (Claims, Examples) JP 2011-195824 (Claims, Examples) International Publication No. 2007-034800 (Claims, Examples) JP 2008-222889 A (Claims, Examples)
- the present invention greatly improves heat resistance without impairing the fluidity and mechanical properties inherent in the polyphenylene sulfide resin, and the gas generation amount is small. It is an object to obtain a polyphenylene sulfide resin composition and a molded product comprising the same.
- the present invention has been made to solve at least a part of the above-described problems, and can be realized as the following forms.
- a polyphenylene sulfide resin composition comprising a component (A) and a component (B),
- ⁇ Wr is a weight reduction rate (%), and when thermogravimetric analysis was performed at a temperature rising rate of 20 ° C./min from 50 ° C. to an arbitrary temperature of 330 ° C. or higher in a normal pressure non-oxidizing atmosphere, (This is a value obtained from the sample weight (W2) when reaching 330 ° C.
- the component (B) is a polyphenylene sulfide resin having a weight average molecular weight of 10,000 or more and a weight reduction rate ⁇ Wr at the time of heating represented by the above formula (1) of 0.18% or less, When the total of the component (A) and the component (B) is 100% by weight, the component (B) 5 to 95% by weight is added to the component (A) 95 to 5% by weight.
- a polyphenylene sulfide resin composition is a polyphenylene sulfide resin having a weight average molecular weight of 10,000 or more and a weight reduction rate ⁇ Wr at the time of heating represented by the above formula (1) of 0.18% or less.
- the component (B) is a cyclic polyphenylene sulfide represented by the following general formula (I) (Here, m is an integer of 4 to 20, and the component (B) may be a mixture of plural kinds of cyclic polyphenylene sulfides having different m.)
- a polyphenylene sulfide resin obtained by heating a polyphenylene sulfide prepolymer having a weight average molecular weight of less than 10,000 and converting it to a high degree of polymerization having a weight average molecular weight of 10,000 or more. 10.
- the polyphenylene sulfide resin composition according to any one of 1 to 9.
- a molded article comprising the polyphenylene sulfide resin composition according to any one of 11.1 to 10.
- a process for producing a polyferrenin sulfide resin composition comprising:
- the present invention by blending a PPS resin having a weight reduction rate ⁇ Wr during heating of more than 0.18% and a PPS resin having a weight reduction rate ⁇ Wr during heating of 0.18% or less, fluidity and heat resistance It is possible to obtain a polyphenylene sulfide resin composition having excellent properties and a small amount of gas generation.
- the polyphenylene sulfide resin composition of the present invention since the polyphenylene sulfide resin composition of the present invention has both fluidity and heat resistance at a high level, it is also excellent in thin-wall moldability and thin-wall heat resistance. It is useful for conversion.
- PPS resin composition that is suitable and particularly suitable as a material for use in automotive lighting parts, which requires a high molded article appearance and high rigidity.
- a functional group-containing olefin copolymer by adding 1 to 70 parts by weight of a functional group-containing olefin copolymer to 100 parts by weight of the two types of PPS resins, the high toughness due to the blending of the olefin resin is greatly increased. Rigidity can be improved without loss, and a polyphenylene sulfide resin composition with less gas generation can be obtained.
- the polyphenylene sulfide resin used in the embodiment of the present invention has the following structural formula: It is a polymer which has a repeating unit shown by these.
- the (A) polyphenylene sulfide resin is preferably a polymer containing 70 mol% or more, more preferably 90 mol% or more of a polymer containing a repeating unit represented by the above structural formula.
- the polyphenylene sulfide resin (A) has less than about 30 mol% of the repeating units having the following structure: It may be composed of a repeating unit having
- a polyphenylene sulfide copolymer having a part of such a structure has a low melting point, such a resin composition is advantageous in terms of moldability.
- melt viscosity of (A) polyphenylene sulfide resin used by embodiment of this invention is 1000 Pa * s (300 degreeC, shear rate 1000 / s) or less. It is preferably 700 Pa ⁇ s or less, more preferably 500 Pa ⁇ s or less.
- the melt viscosity in the embodiment of the present invention is a value measured using a capillograph manufactured by Toyo Seiki Co., Ltd. under conditions of 300 ° C. and a shear rate of 1000 / s.
- the molecular weight of the (A) polyphenylene sulfide resin of the embodiment of the present invention is 10,000 or more, preferably 15,000 or more, more preferably 18,000 or more in terms of weight average molecular weight.
- weight average molecular weight is less than 10,000, the moldability at the time of processing is low, and the properties such as mechanical strength and heat resistance of the molded product are low.
- limiting in particular in the upper limit of a weight average molecular weight Less than 1,000,000 can be illustrated as a preferable range, More preferably, it is less than 500,000, More preferably, it is less than 200,000. By setting the upper limit of the weight average molecular weight within such a range, high moldability can be obtained.
- (A) the molecular weight distribution of the polyphenylene sulfide resin that is, the degree of dispersion represented by the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight) is preferably 2.5 or more. 2.6 or more is more preferable, 2.7 or more is more preferable, and 3.0 or more is even more preferable. Although there is no restriction
- the degree of dispersion exceeds 5.0, the amount of low-molecular components contained in (A) polyphenylene sulfide resin is extremely large, which means that (A) mechanical properties when polyphenylene sulfide resin is used for molding processing and It causes a decrease in melt residence stability.
- the weight average molecular weight and number average molecular weight can be determined using, for example, SEC (size exclusion chromatography) equipped with a differential refractive index detector.
- the weight reduction rate upon heating satisfies the following formula (1).
- ⁇ Wr (W1-W2) / W1 ⁇ 100> 0.18 (%) (1)
- ⁇ Wr is the weight reduction rate (%), and when thermogravimetric analysis was performed at a temperature rising rate of 20 ° C./min from 50 ° C. to an arbitrary temperature of 330 ° C. or higher in a non-oxidizing atmosphere at normal pressure The value obtained from the sample weight (W2) when reaching 330 ° C. with reference to the sample weight (W1) when reaching 100 ° C.
- the ⁇ Wr of the (A) polyphenylene sulfide resin used in the embodiment of the present invention is selected within a range where the lower limit exceeds 0.18%.
- the upper limit value of ⁇ Wr of the polyphenylene sulfide resin is preferably 0.40% or less, more preferably 0.30% or less, in order to reduce the amount of gas generated during molding. It is still more preferable that it is 0.25% or less.
- a polyhalogenated aromatic compound refers to a compound having two or more halogen atoms in one molecule. Specific examples include p-dichlorobenzene, m-dichlorobenzene, o-dichlorobenzene, 1,3,5-trichlorobenzene, 1,2,4-trichlorobenzene, 1,2,4,5-tetrachlorobenzene, hexa Polyhalogenation such as chlorobenzene, 2,5-dichlorotoluene, 2,5-dichloro-p-xylene, 1,4-dibromobenzene, 1,4-diiodobenzene, and 1-methoxy-2,5-dichlorobenzene An aromatic compound may be mentioned, and p-dichlorobenzene is preferably used. It is also possible to use a copolymer in which two or more different polyhalogenated aromatic compounds are combined, but it is preferable to use a
- the amount of the polyhalogenated aromatic compound used is 0.9 mol or more, preferably 0.95 mol or more, more preferably from the viewpoint of obtaining a (A) polyphenylene sulfide resin having a viscosity suitable for processing. May be 1.005 mol or more. Further, for the same reason, the polyhalogenated aromatic compound may be used in an amount of 2.0 mol or less, preferably 1.5 mol or less, more preferably 1.2 mol or less, per mol of the sulfidizing agent. .
- sulfiding agent examples include alkali metal sulfides, alkali metal hydrosulfides, and hydrogen sulfide.
- alkali metal sulfide examples include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide and a mixture of two or more of these, and sodium sulfide is preferably used.
- These alkali metal sulfides can be used as hydrates or aqueous mixtures or in the form of anhydrides.
- alkali metal hydrosulfide examples include, for example, sodium hydrosulfide, potassium hydrosulfide, lithium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide and a mixture of two or more of these. Preferably used.
- These alkali metal hydrosulfides can be used as hydrates or aqueous mixtures or in the form of anhydrides.
- alkali metal sulfides generated in the reaction system from alkali metal hydrosulfides and alkali metal hydroxides can also be used.
- alkali metal sulfide can be prepared in advance from alkali metal hydrosulfide and alkali metal hydroxide, and transferred to a polymerization tank for use.
- generated in a reaction system from alkali metal hydroxides, such as lithium hydroxide and sodium hydroxide, and hydrogen sulfide can also be used.
- an alkali metal sulfide can be prepared in advance from an alkali metal hydroxide such as lithium hydroxide or sodium hydroxide and hydrogen sulfide, and transferred to a polymerization tank for use.
- the amount of the sulfidizing agent charged means the remaining amount obtained by subtracting the loss from the actual charged amount when a partial loss of the sulfidizing agent occurs before the start of the polymerization reaction due to dehydration operation or the like.
- alkali metal hydroxide and / or an alkaline earth metal hydroxide in combination with the sulfidizing agent.
- alkali metal hydroxide include sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, and a mixture of two or more of these.
- alkaline earth metal hydroxide include calcium hydroxide, strontium hydroxide, and barium hydroxide. Sodium hydroxide is preferably used among them.
- an alkali metal hydrosulfide is used as the sulfiding agent, it is particularly preferable to use an alkali metal hydroxide at the same time.
- the amount of the alkali metal hydroxide used at the same time can be 0.95 mol or more, preferably 1.00 mol or more, more preferably 1.005 mol or more per 1 mol of the alkali metal hydrosulfide.
- the amount of alkali metal hydroxide used at the same time is 1.20 mol or less, preferably 1.15 mol or less, more preferably 1.100 mol or less, per 1 mol of alkali metal hydrosulfide. it can.
- An organic polar solvent is preferably used as the polymerization solvent.
- N-alkylpyrrolidones such as N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone
- caprolactams such as N-methyl- ⁇ -caprolactam, 1,3-dimethyl-2-imidazo
- aprotic organic solvents represented by lysinone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, dimethyl sulfone, and tetramethylene sulfoxide, and mixtures thereof. Both are preferably used because of high stability of the reaction.
- NMP N-methyl-2-pyrrolidone
- NMP is particularly preferably used.
- the amount of the organic polar solvent used is 2.0 mol or more, preferably 2.25 mol or more, more preferably 2.5 mol or more per mol of the sulfidizing agent.
- the amount of the organic polar solvent used may be 10 mol or less, preferably 6.0 mol or less, more preferably 5.5 mol or less per mol of the sulfidizing agent.
- a monohalogen compound (not necessarily an aromatic compound) is combined with the polyhalogenated aromatic compound in order to form a terminal of the (A) PPS resin to be produced or to adjust a polymerization reaction or a molecular weight. Can be used together.
- polymerization aid In order to obtain the (A) polyphenylene sulfide resin having a relatively high degree of polymerization in a shorter time, it is one of preferred embodiments to use a polymerization aid.
- the polymerization aid means a substance having an action of increasing the viscosity of the resulting (A) PPS resin.
- Specific examples of such polymerization aids include, for example, organic carboxylates, water, alkali metal chlorides, organic sulfonates, alkali metal sulfates, alkaline earth metal oxides, alkali metal phosphates and alkaline earths. Metal phosphates and the like. These may be used alone or in combination of two or more. Of these, organic carboxylates, water, and alkali metal chlorides are preferred. Further, an alkali metal carboxylate is preferable as the organic carboxylate, and lithium chloride is preferable as the alkali metal chloride.
- the alkali metal carboxylate is a general formula R (COOM) n (wherein R is an alkyl group, cycloalkyl group, aryl group, alkylaryl group or arylalkyl group having 1 to 20 carbon atoms).
- M is an alkali metal selected from lithium, sodium, potassium, rubidium and cesium, and n is an integer of 1 to 3.
- Alkali metal carboxylates can also be used as hydrates, anhydrides or aqueous solutions. Specific examples of the alkali metal carboxylate include, for example, lithium acetate, sodium acetate, potassium acetate, sodium propionate, lithium valerate, sodium benzoate, sodium phenylacetate, potassium p-toluate, and mixtures thereof. Can be mentioned.
- the alkali metal carboxylate is an organic acid and one or more compounds selected from the group consisting of alkali metal hydroxides, alkali metal carbonates, and alkali metal bicarbonates, and are allowed to react by adding approximately equal chemical equivalents. You may form by.
- the alkali metal carboxylates lithium salts are highly soluble in the reaction system and have a large auxiliary effect, but are expensive, and potassium salts, rubidium salts, and cesium salts are insufficiently soluble in the reaction system. It appears to be. Therefore, it is most preferable to use sodium acetate which is inexpensive and has an appropriate solubility in the polymerization system.
- the amount used is usually 0.01 mol or more per 1 mol of the alkali metal sulfide charged, and in the sense of obtaining a higher degree of polymerization, it is 0.00. 1 mol or more is preferable, and 0.2 mol or more is more preferable.
- the amount used is usually 2 mol or less per 1 mol of the alkali metal sulfide charged, and is preferably 0.6 mol or less, more preferably 0.5 mol or less in terms of obtaining a higher degree of polymerization. preferable.
- the addition amount is usually 0.3 mol or more per 1 mol of the alkali metal sulfide charged, and 0.6 mol or more in order to obtain a higher degree of polymerization. Is preferable, and 1 mol or more is more preferable. Further, the addition amount is usually 15 mol or less with respect to 1 mol of the alkali metal sulfide charged, and is preferably 10 mol or less and more preferably 5 mol or less in order to obtain a higher degree of polymerization.
- polymerization aids can be used in combination.
- an alkali metal carboxylate and water it is possible to increase the molecular weight in a smaller amount.
- the timing for adding these polymerization aids is not particularly specified, and they may be added at any time during the previous step, at the start of polymerization, or during the polymerization described later, or may be added in multiple portions.
- an alkali metal carboxylate used as a polymerization aid, it is more preferable that it is added at the start of the previous step or at the start of the polymerization from the viewpoint of easy addition.
- water used as a polymerization aid, it is effective to add the polyhalogenated aromatic compound during the polymerization reaction after charging.
- a polymerization stabilizer can also be used to stabilize the polymerization reaction system and prevent side reactions.
- the polymerization stabilizer contributes to stabilization of the polymerization reaction system and suppresses undesirable side reactions.
- One measure of the side reaction is the generation of thiophenol, and the addition of a polymerization stabilizer can suppress the generation of thiophenol.
- Specific examples of the polymerization stabilizer include compounds such as alkali metal hydroxides, alkali metal carbonates, alkaline earth metal hydroxides, and alkaline earth metal carbonates. Among these, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide are preferable.
- the alkali metal carboxylate described above also acts as a polymerization stabilizer, it is one of the polymerization stabilizers.
- an alkali metal hydrosulfide is used as a sulfidizing agent, it has been described above that it is particularly preferable to use an alkali metal hydroxide at the same time.
- Oxides can also be polymerization stabilizers.
- the amount of the polymerization stabilizer used is usually 0.02 mol or more, preferably 0.03 mol or more, more preferably 0.04 mol or more per 1 mol of the alkali metal sulfide charged. .
- the amount used is usually 0.2 mol or less, preferably 0.1 mol or less, more preferably 0.09 mol or less with respect to 1 mol of the alkali metal sulfide charged. If this ratio is small, the stabilizing effect is insufficient, while if it is too large, there is an economic disadvantage and the polymer yield tends to decrease.
- the addition timing of the polymerization stabilizer is not particularly specified, and it may be added at any time during the previous step, at the start of polymerization, or during the polymerization described later, or may be added in multiple times. However, it is preferable to add at the start of the previous step or at the start of the polymerization because the addition becomes easy.
- the sulfiding agent is usually used in the form of a hydrate. Before adding the polyhalogenated aromatic compound, a mixture containing an organic polar solvent and the sulfiding agent is added. It is preferable to raise the temperature and remove excess water out of the system.
- a sulfidizing agent a sulfidizing agent produced in a reaction system from an alkali metal hydrosulfide and an alkali metal hydroxide, or a sulfidation prepared in a tank separate from the polymerization tank Agents can also be used.
- an alkali metal hydrosulfide and an alkali metal hydroxide are added to the organic polar solvent in an inert gas atmosphere at a temperature ranging from room temperature to 150 ° C., preferably from room temperature to 100 ° C.
- a method of raising the temperature to at least 150 ° C. or more, preferably 180 to 260 ° C. under normal pressure or reduced pressure, to distill off the water can be mentioned.
- a polymerization aid may be added at this stage.
- moisture content you may react by adding toluene etc.
- the amount of water in the polymerization system is preferably 0.3 to 10.0 mol per mol of the sulfidizing agent charged.
- the amount of water in the polymerization system is an amount obtained by subtracting the amount of water removed from the polymerization system from the amount of water charged in the polymerization system.
- the water to be charged may be in any form such as water, an aqueous solution, and crystal water.
- the temperature of such a mixture is usually raised to a range of 200 ° C to 290 ° C.
- rate of 0.01 degree-C / min or more is selected, and the speed
- the rate of temperature increase is usually 5 ° C./min or less, more preferably 3 ° C./min or less.
- the water used is preferably distilled water or deionized water.
- the hot water treatment for example, a method of adding a predetermined amount of (A) polyphenylene sulfide resin to a predetermined amount of water, heating and stirring in a pressure vessel, and a method of performing continuous hot water washing Etc.
- the ratio of (A) polyphenylene sulfide resin to water is preferably larger, but usually a bath ratio of 200 g or less of (A) polyphenylene sulfide resin is selected per liter of water.
- the (B) polyphenylene sulfide resin has a repeating unit of the formula: — (Ar—S) — as a main structural unit.
- the homopolymer or copolymer preferably contains 80 mol% or more of the repeating unit.
- Ar includes units represented by the following formulas (a) to (k), among which the formula (a) is particularly preferable.
- Examples include nolactone, ⁇ -heptanolactone, ⁇ -octanolactone, ⁇ -nonalactone, and ⁇ -decalactone.
- polyphenylene sulfide prepolymer (B) Polyphenylene sulfide prepolymer (B)
- the polyphenylene sulfide prepolymer containing the cyclic polyphenylene sulfide as described above is heated to a high polymerization degree. It is characterized by being converted.
- the polyphenylene sulfide prepolymer used here contains at least 50% by weight of cyclic polyphenylene sulfide, preferably 70% by weight or more, more preferably 80% by weight or more, and still more preferably 90% by weight or more. That's fine.
- the polymerization degree and melt viscosity of the obtained PPS can be easily adjusted by adjusting the abundance ratio of the cyclic polyphenylene sulfide in the polyphenylene sulfide prepolymer. It is possible to adjust.
- the weight ratio of the cyclic polyphenylene sulfide in the polyphenylene sulfide prepolymer exceeds the above upper limit, the melting temperature of the polyphenylene sulfide prepolymer tends to increase, so the weight of the cyclic polyphenylene sulfide in the polyphenylene sulfide prepolymer It is preferable to set the ratio in the above range because the temperature when the polyphenylene sulfide prepolymer is converted into a high degree of polymerization can be further lowered.
- the component other than cyclic polyphenylene sulfide in the polyphenylene sulfide prepolymer is particularly preferably a linear polyphenylene sulfide oligomer.
- the linear polyphenylene sulfide oligomer is a homo-oligomer or co-oligomer having a repeating unit of the formula, — (Ar—S) —, as a main constituent unit, and preferably containing 80 mol% or more of the repeating unit.
- Ar includes units represented by the above-described formulas (a) to (k), among which the formula (a) is particularly preferable.
- the alkali metal refers to lithium, sodium, potassium, rubidium, cesium, and francium belonging to Group IA of the periodic table, but the polyarylene sulfide prepolymer of the embodiment of the present invention contains an alkali metal other than sodium. Preferably not.
- the atmosphere containing substantially no oxygen means an atmosphere of an inert gas such as nitrogen, helium, or argon. Of these, a nitrogen atmosphere is particularly preferred from the viewpoint of economy and ease of handling.
- the reduced pressure condition means that the pressure in the reaction system is lower than atmospheric pressure, and the upper limit is preferably 50 kPa or less, more preferably 20 kPa or less, and even more preferably 10 kPa or less.
- An example of the lower limit of the pressure in the system is 0.1 kPa or more.
- Fibrous and / or non-fibrous filler examples include glass fiber, glass milled fiber, carbon fiber, metal fiber, carbon nanotube, carbon nanohorn, aramid fiber, ceramic fiber, and Examples include mineral fibers.
- examples of the mineral fiber include potassium titanate whisker, zinc oxide whisker, calcium carbonate whisker, wollastonite whisker, asbestos fiber, and stone koji fiber.
- examples of the ceramic fiber include alumina fiber and silicon carbide fiber.
- preferred fibrous fillers are those generally referred to as short fibers, having a fiber length of 1 to 5 mm before blending and a fiber diameter of 1 to 25 ⁇ m. By using such a short fiber filler, it tends to be easy to obtain a resin composition having good filler dispersibility.
- silicates such as zeolite, sericite, mica, talc, kaolin, clay, pyrophyllite, bentonite, alumina silicate, and glass powder, alumina, silicon oxide, magnesium oxide, zirconium oxide, Metal compounds such as titanium oxide and iron oxide, carbonates such as calcium carbonate, magnesium carbonate, and dolomite, sulfates such as calcium sulfate and barium sulfate, hydroxides such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide Products, glass beads, ceramic beads, boron nitride, silicon carbide, graphite, carbon black, fullerene and silica.
- fibrous and / or non-fibrous fillers glass fibers, silica and calcium carbonate are preferable, and calcium carbonate and silica are particularly preferable from the viewpoint of the effect of the anticorrosive material and the lubricant.
- the fibrous and / or non-fibrous filler may be hollow, and two or more kinds of these fillers may be used in combination.
- a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, or an epoxy compound, more excellent mechanical strength is obtained. Preferred in meaning.
- alkoxysilane compound having one or more groups selected from an epoxy group, an amino group, an isocyanate group, a hydroxyl group, a mercapto group, and a ureido group
- alkoxysilane compounds having at least one functional group selected from a hydroxyl group, a mercapto group and a ureido group include ⁇ -glycidoxypropyltrimethoxysilane and ⁇ -glycidoxypropyltriethoxysilane.
- epoxy group-containing alkoxysilane compounds such as ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, mercapto group-containing alkoxysilane compounds such as ⁇ -mercaptopropyltrimethoxysilane and ⁇ -mercaptopropyltriethoxysilane, ⁇ -Ure Ureido group-containing alkoxysilane compounds such as dopropyltriethoxysilane, ⁇ -ureidopropyltrimethoxysilane, and ⁇ - (2-ureidoethyl) aminopropyltrimethoxysilane, ⁇ -isocyanatopropyltriethoxysilane, ⁇ -isocyanate Natopropyltrimethoxysilane, ⁇ -isocyanatopropylmethyldimethoxysilane, ⁇ -isocyanatopropylmethyldiethoxysilane,
- Examples of the epoxy group-containing olefin copolymer used in the embodiment of the present invention include olefin copolymers obtained by introducing a monomer component having an epoxy group into the olefin copolymer. Moreover, the copolymer which epoxidized the double bond part of the olefin polymer which has a double bond in a principal chain can also be used.
- Examples of functional group-containing components for introducing a monomer component having an epoxy group into an olefin copolymer include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, and glycidyl citraconic acid.
- Examples include monomers containing an epoxy group.
- the introduction amount of the monomer component containing an epoxy group is 0.001 mol% or more, preferably 0.01 mol% or more, based on the whole monomer as a raw material of the epoxy group-containing olefin copolymer. Is appropriate. Further, the introduction amount is suitably 40 mol% or less, preferably 35 mol% or less, based on the whole monomer as a raw material for the epoxy group-containing olefin copolymer.
- Examples of the (E) functional group-containing olefin copolymer particularly useful in the embodiment of the present invention include an olefin copolymer comprising an ⁇ -olefin and a glycidyl ester of an ⁇ , ⁇ -unsaturated carboxylic acid as a copolymerization component.
- Preferred examples of the ⁇ -olefin include ethylene.
- These copolymers further include ⁇ , ⁇ -unsaturated carboxylic acids such as acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and the like. It is also possible to copolymerize the alkyl ester, styrene, acrylonitrile and the like.
- the olefin copolymer may be any random, alternating, block, or graft copolymerization mode.
- an olefin copolymer obtained by copolymerizing an ⁇ -olefin and a glycidyl ester of ⁇ , ⁇ -unsaturated carboxylic acid and among them, the ⁇ -olefin is 60 to 99% by weight.
- An olefin copolymer obtained by copolymerizing 1 to 40% by weight of a glycidyl ester of an ⁇ , ⁇ -unsaturated carboxylic acid is particularly preferable.
- the above glycidyl ester of ⁇ , ⁇ -unsaturated carboxylic acid is (Wherein R represents a hydrogen atom or a linear or branched lower alkyl group having 1 to 6 carbon atoms).
- R represents a hydrogen atom or a linear or branched lower alkyl group having 1 to 6 carbon atoms.
- Specific examples include glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylate. Among them, glycidyl methacrylate is preferably used.
- an olefin-based copolymer comprising an ⁇ -olefin and a glycidyl ester of ⁇ , ⁇ -unsaturated carboxylic acid as an essential copolymerization component
- an ethylene / propylene-g-glycidyl methacrylate copolymer (“g" Representing a graft, the same shall apply hereinafter), ethylene / butene-1-g-glycidyl methacrylate copolymer, ethylene-glycidyl methacrylate copolymer-g-polystyrene, ethylene-glycidyl methacrylate copolymer-g-acrylonitrile-styrene copolymer Copolymer, ethylene-glycidyl methacrylate copolymer-g-PMMA, ethylene / glycidyl acrylate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene
- carboxyl group-containing olefin copolymers used in the embodiments of the present invention, carboxyl group-containing olefin copolymers, acid anhydride group-containing olefin copolymers, amino group-containing olefin copolymers, and mercapto groups
- the containing olefin copolymer is obtained by introducing a monomer component having a carboxyl group, an acid anhydride group, an amino group, or a mercapto group into the olefin copolymer.
- olefin copolymer a copolymer in which the functional group is introduced into the double bond portion of the olefin copolymer having a double bond in the main chain can also be used.
- a particularly useful olefin copolymer is an ethylene / ⁇ -olefin copolymer obtained by copolymerizing ethylene and an ⁇ -olefin having 3 to 20 carbon atoms.
- olefin copolymers examples include polyethylene, polypropylene, polystyrene, polybutene, ethylene-propylene-diene copolymer, styrene-butadiene copolymer, styrene-butadiene-styrene block copolymer (SBS), Styrene-isoprene-styrene block copolymer (SIS), polybutadiene, butadiene-acrylonitrile copolymer, polyisoprene, butene-isoprene copolymer, styrene-ethylene / butylene-styrene block copolymer (SEBS), styrene-ethylene Examples thereof include a propylene-styrene block copolymer (SEPS) and an olefin copolymer composed of the above ⁇ -olefin and the ⁇ , ⁇ -unsaturated carboxylic acid alkyl este
- such ethylene copolymers comprise at least 60 wt% ethylene, 5-15 wt% acrylic acid or methacrylic acid, 0-25 wt% methyl acrylate, iso-butyl acrylate, And a moiety selected from at least one of n-methyl acrylate, and further, 0 to 70% of acid groups by metal ions selected from lithium, potassium, sodium, zinc, magnesium, aluminum, and calcium Preferably, it is neutralized by 30 to 70%.
- Examples of functional group-containing components for introducing a monomer component having a carboxyl group or an acid anhydride into an olefin copolymer include acid anhydrides such as maleic anhydride, succinic anhydride, and fumaric anhydride. Products, carboxylic acids such as acrylic acid, methacrylic acid and vinyl acetate, and monomers having salts such as Na, Zn, K, Ca and Mg.
- Examples of functional group-containing components for introducing a monomer component having an amino group or a mercapto group into an olefin copolymer include ⁇ -mercaptopropyltrimethoxysilane, ⁇ -mercaptopropyltriethoxysilane, ⁇ And monomers having an alkoxysilane compound such as-(2-aminoethyl) aminopropylmethyldimethoxysilane, ⁇ - (2-aminoethyl) aminopropyltrimethoxysilane, and ⁇ -aminopropyltrimethoxysilane.
- a functional group-containing component having a carboxyl group, an acid anhydride group, an amino group and a mercapto group into the olefin copolymer.
- copolymerize an olefin copolymer and a functional group-containing component graft copolymerize a functional group-containing component using a radical initiator to the olefin copolymer, or surface-treat the olefin copolymer.
- the amount of the monomer component containing the functional group introduced can be 0.001 mol% or more, preferably 0.01 mol% or more, relative to the olefin copolymer. Moreover, it can be 40 mol% or less, Preferably it can be 35 mol% or less.
- MFR Melt flow rate of an olefin-based copolymer containing a carboxyl group, an acid anhydride group, an amino group, and a mercapto group used in the embodiment of the present invention. Measured by load) is preferably 0.01 g / 10 min or more, more preferably 0.03 g / 10 min or more. Moreover, it is preferable that it is 70 g / 10min or less, More preferably, it is 60 g / 10min or less. When MFR is less than 0.01 g / 10 min, the fluidity is poor, and when it exceeds 70 g / 10 min, the impact strength may be lowered depending on the shape of the molded product, so care must be taken.
- the density of the olefin copolymer containing a carboxyl group, an acid anhydride group, an amino group and a mercapto group used in the embodiment of the present invention is preferably 800 to 870 kg / m 3 .
- the density exceeds 870 kg / m 3 , low-temperature toughness is hardly exhibited, and when it is less than 800 kg / m 3 , the handling property tends to decrease.
- An olefin-based copolymer not containing a functional group that is particularly useful in the embodiment of the present invention includes ethylene and an ⁇ -olefin having 3 to 20 carbon atoms. An ethylene / ⁇ -olefin copolymer obtained by copolymerization may be mentioned.
- ⁇ -olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-decene, Undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl- 1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4- Ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene,
- olefin-based copolymer containing no functional group examples include polyethylene, polypropylene, polystyrene, polybutene, ethylene-propylene-diene copolymer, styrene-butadiene copolymer, and styrene-butadiene-styrene block.
- SBS Styrene-isoprene-styrene block copolymer
- SIS Styrene-isoprene-styrene block copolymer
- SEBS Styrene-isoprene-styrene block copolymer
- SEPS styrene-ethylene / propylene-styrene block copolymer
- olefin copolymer comprising the ⁇ -olefin and the ⁇ , ⁇ -unsaturated carboxylic acid alkyl ester described above.
- such ethylene copolymers comprise at least 60 wt% ethylene, 5-15 wt% acrylic acid or methacrylic acid, 0-25 wt% methyl acrylate, iso-butyl acrylate, And a moiety selected from at least one of n-methyl acrylate, and further, 0 to 70% of acid groups by metal ions selected from lithium, potassium, sodium, zinc, magnesium, aluminum, and calcium Preferably, it is neutralized by 30 to 70%.
- the melt flow rate (MFR) of the olefin copolymer containing no functional group (F) used in the embodiment of the present invention is preferably 0.01 g / 10 min or more, more preferably 0.03 g / 10 minutes or more.
- the MFR is preferably 70 g / 10 min or less, more preferably 60 g / 10 min or less.
- MFR is less than 0.01 g / 10 min, the fluidity is poor, and when it exceeds 70 g / 10 min, the impact strength may be lowered depending on the shape of the molded product, so care must be taken.
- the component (A) is a polyphenylene sulfide resin having a weight reduction rate ⁇ Wr of 0.18% when heated
- the component (B) is The polyphenylene sulfide resin has a weight reduction rate ⁇ Wr of 0.18% or less when heated.
- the blending amount of the component (B) exceeds 95% by weight, the resin solidifies in the mold very rapidly, and there is a possibility that a filling defect may occur particularly when injection molding a thin molded product. It is not preferable.
- the PPS resin composition of the embodiment of the present invention has extremely excellent heat resistance, and the deflection temperature under load (measured according to ASTM D648) of the resin molded product is 200 ° C. or higher. Yes, preferably 220 ° C. or higher, and more preferably 240 ° C. or higher.
- PPS resin composition comprising (C) component in addition to (A) component and (B) component
- the PPS resin composition in the embodiment of the present invention is formed by further blending the component (C) in addition to the component (A) and the component (B), the components (A) and (B)
- the blending ratio of component (A) when the total is 100% by weight is selected in the range of 95 to 5% by weight.
- the blending ratio of the component (A) is preferably in the range of 5 to 20% by weight.
- the blending ratio of the component (A) when the total of the component (A) and the component (B) is 100% by weight. is preferably selected in the range of 80 to 95% by weight. If the blending amount of the component (B) is less than 5% by weight, solidification on the surface layer of the molded product in the mold is slowed down, and flow marks and molded product sink marks (defects on the surface of the molded product that are dents) ) In the flow direction of the molten resin is greatly increased, and it becomes difficult to obtain a molded product having high surface smoothness.
- the blending amount of the component (B) exceeds 95% by weight, the adhesion with the filler is inhibited, and the uneven distribution of the filler on the surface of the molded product is observed, and the surface smoothness and mechanical strength are remarkable. Since it falls, it is not preferable.
- the blending amount when blending the (C) fibrous and / or non-fibrous filler is 500 weights as the upper limit with respect to a total of 100 parts by weight of the (A) component and the (B) component.
- a range of less than or equal to parts is selected, a range of 350 parts by weight is more preferred, and a range of 200 parts by weight is even more preferred.
- the range of 1 weight part or more is selected, 10 weight part or more is more preferable, and the range of 15 weight part or more is more preferable.
- the blending amount of component (C) exceeds 500 parts by weight, the melt fluidity is remarkably impaired, and when it is 1 part by weight or less, the filler reinforcing effect is not sufficiently exhibited, which is not preferable.
- the total of the (A) component, the (B) component, and the (C) component is 100% by volume, and the (A) component and the (B) component are 50 volumes. % Or more, preferably 55% by volume or more, and good workability is easily obtained in such a range.
- the adhesion between the PPS resin and the filler is improved, and the high rigidity is achieved. Not only can it be expressed, but it can also impart excellent surface smoothness.
- the blending amounts are the (A) component and the (B) component.
- 0.05 weight part or more is selected with respect to a total of 100 weight part of (C) component, More preferably, it is 0.1 weight part or more.
- the blending amount of the component (D) is selected to be 10 parts by weight or less, more preferably 5 parts by weight or less, with respect to 100 parts by weight of the total of the components (A), (B) and (C). .
- the PPS resin composition according to the embodiment of the present invention has a conventional filler reinforcement due to a synergistic effect such as improvement in adhesion to the filler by blending the component (A) and high crystallization of the surface layer of the molded product by blending the component (B).
- a synergistic effect such as improvement in adhesion to the filler by blending the component (A) and high crystallization of the surface layer of the molded product by blending the component (B).
- the uneven distribution of filler on the surface of the molded product of the PPS resin composition of the embodiment of the present invention has a clear correlation with the center line average roughness Ra and the temperature-falling crystallization temperature Tmc, while the flow direction of the molten resin on the surface of the molded product is undulated. Found that there was a clear correlation with the arithmetic mean waviness Wa and the cooling crystallization temperature Tmc.
- the arithmetic average waviness Wa in the embodiment of the present invention employs a numerical value measured in accordance with JISB0601 using an ASTM No. 1 dumbbell test piece obtained from the PPS resin composition.
- the arithmetic average waviness Wa is 3.0 ⁇ m or less, preferably 2 ⁇ m or less, and more preferably 1.5 ⁇ m or less.
- the PPS resin composition according to the embodiment of the present invention by setting the arithmetic average waviness Wa to 3 ⁇ m or less, the flow marks and sink marks on the surface of the molded product are greatly improved, and a high-quality molded product appearance can be obtained. Therefore, it is preferable.
- the temperature-falling crystallization temperature Tmc in the embodiment of the present invention is obtained by melt-kneading the PPS resin composition of the embodiment of the present invention and drying the pellet at 120 ° C. for 8 hours in the atmosphere and pre-drying the pellet at 130 ° C. for 3 hours. After that, about 10 mg of pellets were charged into DSC-7 manufactured by PerkinElmer, and the temperature measured under the following measurement conditions in a nitrogen atmosphere was adopted.
- the cooling crystallization temperature Tmc is 225 ° C. or higher, preferably 230 ° C. or higher, and more preferably 235 ° C. or higher.
- PPS resin composition comprising (E) component in addition to (A) component and (B) component
- the PPS resin composition in the embodiment of the present invention is formed by further blending the component (E) in addition to the component (A) and the component (B), the component (A) and the component (B)
- the blending ratio of the component (A) when the total is 100% by weight is selected from 5 to 95% by weight.
- the blending ratio of the component (A) is preferably in the range of 5 to 20% by weight.
- the blending ratio of the component (A) when the total of the component (A) and the component (B) is 100% by weight is A range of 80 to 95% by weight is preferably selected. If the blending ratio of the component (B) is less than 5% by weight, the molten resin is cooled and solidified in the mold slowly, and the flow direction of the molten resin causing flow marks and sink marks on the surface of the molded product is delayed. This is not preferable because the swell is remarkably increased.
- the blending amount of the component (E) when blending the (E) functional group-containing olefin copolymer is 1 with respect to a total of 100 parts by weight of the component (A) and the component (B).
- the amount can be not less than 3 parts by weight, more preferably not less than 3 parts by weight, and still more preferably not less than 5 parts by weight.
- the compounding quantity of (E) component can be 70 weight part or less, 50 weight part or less is more preferable, and 25 weight part or less is still more preferable.
- the total amount of the (A) component, the (B) component, and the (E) component is 100 parts by weight, and (F) an olefin copolymer having no functional group. 1 to 70 parts by weight of the coalesce can be contained.
- a compounding quantity of the olefin type copolymer which does not contain the (F) functional group of embodiment of this invention is 1 weight part with respect to a total of 100 weight part of (A) component, (B) component, and (E) component. It can be 1 or more, more preferably 3 parts by weight or more, still more preferably 10 parts by weight or more. Moreover, the compounding quantity of (F) component can be 70 weight part or less, 60 weight part or less is more preferable, and 40 weight part or less is still more preferable.
- an inorganic filler is blended by adding the (E) component to the (A) component and the (B) component, or further adding the (F) component. Even if it is not, since high rigidity can be imparted by blending PPS resins having specific gas generation amounts, the excellent toughness inherent in the olefin copolymer is not impaired, and excellent processability Can be realized.
- (A) a functional composition (E) is added to a resin composition in which (A) a polyphenylene sulfide resin having a weight reduction rate ⁇ Wr exceeding 0.18% and (B) a polyphenylene sulfide resin having a weight reduction rate ⁇ Wr of 0.18% or less.
- phase structure In order to develop such characteristics, it is preferable to form the following morphology (phase structure).
- the PPS resin forms a sea phase (continuous phase or matrix), and (E) contains functional groups It is preferable that the olefin copolymer forms a dispersed phase (island phase).
- the number average dispersed particle size of the (E) functional group-containing olefin copolymer is preferably 1 nm or more, more preferably 10 nm or more, and further preferably 50 nm or more.
- the number average dispersed particle size is preferably 500 nm or less, more preferably 400 nm or less, and further preferably 300 nm or less. If the number average dispersed particle size is within the above preferred range, the high toughness of the functional group-containing olefin resin is manifested as an effect of improving the toughness of the PPS resin composition, and mass production is also possible.
- the PPS resin forms a sea phase (continuous phase or matrix)
- the olefin copolymer comprising the component (E) and the component (F) forms a dispersed phase (island phase).
- the number average dispersed particle diameter of the olefin copolymer comprising the component (E) and the component (F) is preferably 1 nm or more, more preferably 10 nm or more, and further preferably 50 nm or more.
- the number average dispersed particle size is preferably 500 nm or less, more preferably 400 nm or less, and further preferably 300 nm or less. If the number average dispersed particle size is within the above preferred range, the high toughness of the functional group-containing olefin resin is manifested as an effect of improving the toughness of the PPS resin composition, and mass production is also possible.
- the PPS resin composition according to the embodiment of the present invention has swells in the flow direction of the molten resin in the mold that causes flow marks and sink marks on the surface of the molded product, as compared with a PPS resin composition containing a conventional olefin resin. Can be significantly suppressed, and a high-quality appearance of the molded product can be obtained.
- the flow direction waviness of the molten resin of the PPS resin composition of the embodiment of the present invention was found to have a clear correlation with the arithmetic average waviness Wa and the temperature-falling crystallization temperature Tmc.
- the arithmetic average waviness Wa in the embodiment of the present invention employs a numerical value measured in accordance with JISB0601 using an ASTM No. 1 dumbbell test piece obtained from the PPS resin composition.
- the arithmetic average waviness Wa is 3.0 ⁇ m or less, preferably 2 ⁇ m or less, and more preferably 1.5 ⁇ m or less.
- the PPS resin composition according to the embodiment of the present invention by setting the arithmetic average waviness Wa to 3 ⁇ m or less, the flow marks and sink marks on the surface of the molded product are greatly improved, and a high-quality molded product appearance can be obtained. Therefore, it is preferable.
- the temperature drop crystallization temperature Tmc in the embodiment of the present invention is obtained by melt-kneading the PPS resin composition of the embodiment of the present invention and drying the pellets at 120 ° C. for 8 hours in the atmosphere for 3 hours and pre-drying at 130 ° C. for 3 hours. After that, about 10 mg of pellets were charged into DSC-7 manufactured by PerkinElmer, and the temperature measured under the following measurement conditions in a nitrogen atmosphere was adopted.
- the cooling crystallization temperature Tmc is 225 ° C. or higher, preferably 230 ° C. or higher, and more preferably 235 ° C. or higher.
- the PPS resin composition of the embodiment of the present invention is usually obtained by melt kneading.
- the melt kneader is supplied to a generally known melt kneader such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader, or a mixing roll, and kneaded at a melting peak temperature of the PPS resin + a processing temperature of 5 to 100 ° C.
- a representative example the method of performing can be cited.
- the mixing order of the raw materials is not particularly limited, and a method in which all raw materials are blended and then melt-kneaded by the above method, a part of the raw materials are blended and then melt-kneaded by the above method, and the remaining raw materials are blended.
- Any method such as a method of melt kneading or a method of mixing a part of raw materials and mixing the remaining raw materials using a side feeder during melt kneading by a single-screw or biaxial extruder may be used.
- the small amount additive component other components can be kneaded by the above-mentioned method and pelletized, then added before molding and used for molding.
- composition of the embodiment of the present invention may be produced by a method other than melt kneading.
- a method in which the blend is compressed and solidified into a tablet form in the solid state is also possible to employ a method in which the blend is compressed and solidified into a tablet form in the solid state, and this is subjected to molding such as injection molding.
- one or more kinds of oxidation selected from phenolic compounds and phosphorus compounds with respect to a total of 100 parts by weight of resin components It is preferable to contain an inhibitor.
- the blending amount of the antioxidant is 0.01 parts by weight or more, particularly 0.02 parts by weight or more with respect to 100 parts by weight in total of the component (A) and the component (B) from the viewpoint of the heat resistance improving effect. It is preferable. From the viewpoint of the gas component generated during molding, it is preferably 5 parts by weight or less, particularly preferably 1 part by weight or less, with respect to 100 parts by weight of the total of the component (A) and the component (B).
- the combined use of phenolic and phosphorus antioxidants is particularly preferable because of their large heat resistance and heat stability retention effects.
- phenolic antioxidant a hindered phenolic compound is preferably used.
- Specific examples include triethylene glycol-bis [3-tert-butyl- (5-methyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate ] Methane, pentaerythrityltetrakis [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-t-butyl- 4-hydroxybenzyl) -s-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,1,3-tris (2-methyl- -Hydroxy-5-t-butylphenyl) butan
- ester type polymer hindered phenol type is preferable, and specifically, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, pentaerythrityl. Tetrakis [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate], and 3,9-bis [2- (3- (3-t-butyl-4-hydroxy-5) -Methylphenyl) propionyloxy) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane and the like are preferably used.
- Phosphorus antioxidants include bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol-di -Phosphite, bis (2,4-di-cumylphenyl) pentaerythritol-di-phosphite, tris (2,4-di-t-butylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) ) -4,4′-bisphenylene phosphite, di-stearyl pentaerythritol di-phosphite, triphenyl phosphite, and 3,5-dibutyl-4-hydroxybenzyl phosphonate diethyl ester.
- an antioxidant having a high melting point is preferable.
- bis (2,6-di-t-butyl-4-methyl) is preferable.
- Phenyl) pentaerythritol-di-phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol-di-phosphite, bis (2,4-di-cumylphenyl) pentaerythritol-di-phosphite, etc. Is preferably used.
- a flame retardant may be blended in order to improve the flame retardancy of the PPS resin composition.
- the flame retardant include hydrated metal flame retardants such as aluminum hydroxide and magnesium hydroxide, bromo flame retardant flames, chlorine flame retardant flames, phosphorus flame retardant flames, and inorganic flame retardants such as antimony trioxide.
- a phosphorus-based flame retardant is preferable.
- the phosphorus-based flame retardant is not particularly limited as long as it is a compound having a phosphorus atom, and examples thereof include red phosphorus and organic phosphorus compounds.
- organic phosphorus compounds include phosphoric acid esters, phosphonic acids and derivatives thereof (including salts), phosphinic acids and derivatives thereof (including salts), phosphines, phosphine oxides, biphosphines, phosphonium salts, phosphazenes, phosphaphenanthrene derivatives, And inorganic phosphates.
- the content of the flame retardant component is selected in the range of 50% by weight or less, preferably 30% by weight or less, more preferably 20% by weight or less of the entire resin composition.
- a fluorine-based resin such as polytetrafluoroethylene, ethylene-tetrafluoroethylene, or silicone oil may be added.
- the amount of such an additive is usually selected within the range of 0.1 to 10% by weight of the entire resin composition.
- the following resins can be added to the PPS resin composition according to the embodiment of the present invention as long as the effects of the present invention are not impaired.
- Specific examples thereof include polyamide resin, polybutylene terephthalate resin, polyethylene terephthalate resin, modified polyphenylene ether resin, polysulfone resin, polyallyl sulfone resin, polyketone resin, polyarylate resin, liquid crystal polymer, polyether ketone resin, polythioether ketone.
- Olefin-based polymers that do not contain epoxy groups such as resins, polyether ether ketone resins, polyimide resins, polyether imide resins, polyether sulfone resins, polyamide imide resins, tetrafluoropolyethylene resins, ethylene / 1-butene copolymers , Copolymers, and novolac type epoxy resins.
- the novolac type epoxy resin has two or more epoxy groups and is usually obtained by reacting a novolac type phenol resin with epichlorohydrin. Moreover, a novolac type phenol resin is obtained by a condensation reaction of phenols and formaldehyde.
- the raw material phenols are not particularly limited, and examples thereof include phenol, o-cresol, m-cresol, p-cresol, bisphenol A, resorcinol, p-tertiary butylphenol, bisphenol F, bisphenol S, and condensates thereof.
- Plasticizers such as polyalkylene oxide oligomer compounds, thioether compounds, ester compounds, and organophosphorus compounds, crystal nucleating agents such as organophosphorus compounds and polyetheretherketone, montanic acid waxes, lithium stearate, and stearin Metal soaps such as acid aluminum, release agents such as ethylenediamine / stearic acid / sebacic acid polycondensate and silicone compounds, anti-coloring agents such as hypophosphite, (3,9-bis [2- (3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane) Phenolic antioxidant, (bis (2,4-di-cumylphenyl) pentaerythritol-di-phosphite And other additives such as water,
- the PPS resin composition of the embodiment of the present invention is excellent in molding processability, heat resistance, low gas properties, flame retardancy, important properties, mechanical properties and electrical properties as characteristics, and is injection molding, injection compression molding. It can be used to produce various molded articles by blow molding and extrusion molding.
- Examples of uses of the molded article made of the PPS resin composition of the embodiment of the present invention include sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, optical pickups, oscillators, Various terminal boards, transformers, plugs, printed circuit boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, and computers Electrical / electronic parts such as parts, VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio / laser discs (registered trademark), compact discs Audio / video equipment parts such as digital video discs, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, and word processor parts, home appliances, office electrical product parts, office computer related parts, telephone equipment related parts, Machine-related parts such as facsimile-related parts, copier-related parts, cleaning j
- Senshu Science SSC-7100 Column name: Senshu Science GPC3506 Eluent: 1-chloronaphthalene detector: differential refractive index detector Column temperature: 210 ° C Pre-constant temperature: 250 ° C Pump bath temperature: 50 ° C Detector temperature: 210 ° C Flow rate: 1.0 mL / min Sample injection amount: 300 ⁇ L (sample concentration: about 0.2% by weight)
- the weight reduction rate when reaching 300 ° C. based on the sample weight at 100 ° C. is ⁇ Wr300
- the weight reduction rate when reaching 340 ° C. based on the sample weight at 100 ° C. is represented by ⁇ Wr340 and shown as a reference.
- thermal desorption apparatus TDU manufactured by Supelco.
- the thermally desorbed component was divided into components using gas chromatography, the amount of ⁇ -butyrolactone in the gas was measured as the amount of lactone type compound, and the amount of 4-chloro-N-methylaniline was measured as the amount of aniline type compound. .
- ⁇ Heat sag deformation> Hold the one end 30mm of the injection molded heat sag test piece and fix it in a cantilevered state so that the test piece is horizontal, and then treat it for 15 hours in a 190 ° C hot air gear oven, and then the tip opposite to the held part
- the distance from the horizontal state depending on its own weight was obtained and used as the heat sag deformation amount. It can be said that the smaller the amount of deformation, the better the thin wall heat resistance.
- ⁇ Tensile test> The tensile strength and tensile elongation of the injection-molded ASTM No. 1 dumbbell test piece were measured according to ASTM D638 using a Tensilon UTA2.5T tensile tester under the conditions of a distance between fulcrums of 114 mm and a tensile speed of 10 mm / min. It can be said that the larger these values, the better the tensile properties.
- ⁇ Number average dispersed particle size measurement> The central part of the injection-molded ASTM No. 1 dumbbell test piece was cut in a direction perpendicular to the resin flow direction, and a thin piece of 0.1 ⁇ m or less was cut from the central part of the cross section at ⁇ 20 ° C. The cut flakes were observed at a magnification of 10,000 times with a Hitachi H-7100 transmission electron microscope (resolution (particle image) 0.38 nm, magnification of 500 to 600,000 times). With respect to any 100 olefin copolymer components observed, the maximum diameter and the minimum diameter were first measured, and the average value of the maximum diameter and the minimum diameter was defined as the dispersed particle diameter. Thereafter, the number average dispersed particle size, which is the average value of the dispersed particle sizes of the 100 olefin copolymer components, was determined.
- reaction vessel was cooled to 200 ° C.
- the residual water content in the system per 1 mol of the alkali metal sulfide charged was 1.06 mol including the water consumed for the hydrolysis of NMP.
- the amount of hydrogen sulfide scattered was 0.02 mole per mole of charged alkali metal sulfide.
- the content was diluted with about 35 liters of NMP, stirred as a slurry at 85 ° C. for 30 minutes, and then filtered through an 80 mesh wire mesh (aperture 0.175 mm) to obtain a solid.
- the obtained solid was similarly washed and filtered with about 35 liters of NMP.
- the obtained solid was added to 70 liters of ion exchange water, stirred at 70 ° C. for 30 minutes, and then filtered through an 80 mesh wire net to collect the solids three times in total.
- the obtained solid and 32 g of acetic acid were added to 70 liters of ion exchange water, stirred at 70 ° C. for 30 minutes, and then filtered through an 80 mesh wire net.
- the obtained solid was further added to 70 liters of ion exchange water, stirred at 70 ° C. for 30 minutes, and then filtered through an 80 mesh wire net to collect the solid.
- the solid material thus obtained was dried at 120 ° C. under a nitrogen stream to obtain a dry PPS resin (PPS resin (A-1)).
- the obtained dry PPS resin was completely dissolved in 1-chloronaphthalene at 210 ° C., and GPC measurement was performed on the obtained dry PPS resin.
- the weight average molecular weight was 50,000 and the dispersity was 2.66. It was.
- ⁇ Wr was 0.23%.
- ⁇ Wr300 (%) 0.18
- ⁇ Wr320 (%) 0.21
- ⁇ Wr340 (%) 0.25.
- the Na content was 120 ppm by weight, and no other alkali metals were detected.
- the content was diluted with about 35 liters of NMP, stirred as a slurry at 85 ° C. for 30 minutes, and then filtered through an 80 mesh wire mesh (aperture 0.175 mm) to obtain a solid.
- the obtained solid was similarly washed and filtered with about 35 liters of NMP.
- the obtained solid was added to 70 liters of ion exchange water, stirred at 70 ° C. for 30 minutes, and then filtered through an 80 mesh wire net to collect the solids three times in total.
- the obtained solid and 32 g of acetic acid were added to 70 liters of ion exchange water, stirred at 70 ° C. for 30 minutes, and then filtered through an 80 mesh wire net.
- the obtained solid was further added to 70 liters of ion exchange water, stirred at 70 ° C. for 30 minutes, and then filtered through an 80 mesh wire net to collect the solid.
- the solid material thus obtained was dried at 120 ° C. under a nitrogen stream to obtain a dry PPS resin (PPS resin (A-2)).
- the obtained dry PPS resin was completely dissolved in 1-chloronaphthalene at 210 ° C., and GPC measurement was performed on the obtained dry PPS resin.
- the weight average molecular weight was 70000, and the dispersity was 2.60. It was.
- ⁇ Wr was 0.21%.
- the Na content was 50 ppm by weight, and no other alkali metals were detected.
- the residual water content in the system per 1 mol of the alkali metal sulfide charged was 1.06 mol including the water consumed for the hydrolysis of NMP.
- the amount of hydrogen sulfide scattered was 0.02 mole per mole of charged alkali metal sulfide.
- the obtained solid and 76 liters of ion-exchanged water were placed in an autoclave equipped with a stirrer, washed at 70 ° C. for 30 minutes, and then suction filtered through a glass filter.
- 76 liters of ion-exchanged water heated to 70 ° C. was poured into a glass filter, and suction filtered to obtain a cake.
- the obtained cake and 90 liters of ion-exchanged water were charged into an autoclave equipped with a stirrer, and acetic acid was added so that the pH was 7.
- the temperature was raised to 192 ° C. and held for 30 minutes. Thereafter, the autoclave was cooled and the contents were taken out.
- the contents were subjected to suction filtration with a glass filter, and then 76 liters of ion-exchanged water at 70 ° C. was poured into the contents, followed by suction filtration to obtain a cake.
- the obtained cake was dried at 120 ° C. under a nitrogen stream to obtain a dry PPS resin (PPS resin (A-3)).
- the obtained dry PPS resin was completely dissolved in 1-chloronaphthalene at 210 ° C., and GPC measurement was performed on the obtained dry PPS resin.
- the weight average molecular weight was 20000, and the dispersity was 3.10. It was.
- ⁇ Wr was 0.53%.
- the Na content was 976 ppm by weight, and no other alkali metal was detected.
- the temperature was raised from room temperature to 200 ° C. over 25 minutes while stirring at 400 rpm. Next, the temperature was raised to 250 ° C. over 35 minutes, and the reaction was performed at 250 ° C. for 2 hours. Next, the extraction valve was gradually opened while maintaining the internal temperature at 250 ° C., and 26.6 kg of the solvent was distilled off over 40 minutes. After completion of the solvent distillation, the autoclave was cooled to near room temperature and the contents were collected.
- the collected contents were heated and stirred under nitrogen so that the temperature of the reaction solution was 100 ° C.
- solid-liquid separation was performed using a stainless steel mesh having an average opening of 10 ⁇ m, and the obtained filtrate component was dropped into about 3 times the amount of methanol to recover the precipitated component.
- the solid component collected after precipitation was reslurried with about 2.5 L of 80 ° C. warm water, stirred for 30 minutes at 80 ° C., and then filtered three times.
- the solid content thus obtained was reduced to 8 ° C. at 80 ° C. under reduced pressure. Time drying was performed to obtain a dry solid.
- time drying was performed to obtain a dry solid.
- the obtained dried solid contained 85% by weight of cyclic polyphenylene sulfide.
- the obtained dried solid was charged into a glass test tube equipped with a distilling tube and a stirring blade, and then decompression and nitrogen substitution in the test tube were repeated three times. While maintaining the inside of the test tube at about 0.1 kPa, the temperature was adjusted to 340 ° C. and heated for 120 minutes, and then cooled to room temperature to obtain a polymer. Based on the infrared spectrum, the product obtained was found to be polyphenylene sulfide. Further, GPC measurement showed that the obtained product had a weight average molecular weight of about 50,000 and a dispersity of 2.35. As a result of measuring the weight loss rate during heating of the obtained product, ⁇ Wr was 0.055%.
- Reference Example 7 Alkoxysilane compound (D-1) having one or more groups selected from epoxy group, amino group, isocyanate group, hydroxyl group, mercapto group, and ureido group 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (KBM-303, Shin-Etsu Chemical Co., Ltd.)
- Examples 1 to 4 Comparative Examples 1 to 3
- the mixture was melt-kneaded using 5 screws rotating in the same direction and fully meshed and pelletized with a strand cutter.
- the melt kneading conditions were a screw rotation speed of 300 rpm, a discharge amount of 20 kg / hr, and the cylinder temperature was set so that the resin temperature of the die discharge part was 300 ° C.
- Pellets dried overnight at 130 ° C are subjected to injection molding, heat loss ⁇ Wh, rod flow length, tensile properties (tensile strength and tensile elongation), bending properties (bending strength and elastic modulus), impact properties, deflection temperature under load The amount of heat sag deformation was evaluated. The results were as shown in Table 1.
- Examples 1 to 4 in which (A) a polyphenylene sulfide resin having ⁇ Wr of more than 0.18% and (B) a polyphenylene sulfide resin having ⁇ Wr of 0.18% or less are comparative examples in which component (B) is not blended It can be seen that, compared with 1, the amount of gas generation is suppressed and the heat resistance is improved without impairing the original mechanical properties of the PPS resin. In particular, in Examples 1 to 3 in which the weight average molecular weight of the PPS resin was small (B-2), the heat sag deformation amount was significantly reduced.
- the PPS resins (A-2) and (A-3) having different weight average molecular weights are used instead of the component (B) with respect to the PPS resin (A-1) as the component (A).
- the deflection temperature under load was low, the heat sag deformation amount was not reduced, and the heat resistance was hardly improved.
- the melt kneading conditions were a screw rotation speed of 300 rpm, and the cylinder temperature was set so that the resin temperature of the die discharge part was 330 ° C. or lower.
- the pellets dried at 130 ° C. overnight were subjected to injection molding, and the temperature drop crystallization temperature, heating loss ⁇ Wh, rod flow length, tensile properties, bending properties, impact properties, deflection temperature under load, and surface smoothness were evaluated. The results were as shown in Table 2 and Table 3.
- Example 5 Example 7 and Example 9 in which the component (A), the component (B) and the component (C) were blended, the component (A) and the component (C) were blended without blending the component (B).
- Comparative Example 4 and Comparative Example 7 in which only the component (B) and the component (C) were blended without blending the component (A), the amount of gas generated was not impaired without deteriorating the excellent mechanical properties and heat resistance. It can be seen that the surface smoothness is remarkably improved.
- Example 6 in which the (D) component was further blended had the (A) component and (C) without blending the (B) component.
- Comparative Example 6 having the same composition as Example 8 except that the component (A-3) has the same molecular weight as the component (B-2) was changed. It was inferior result.
- the melt kneading conditions were a screw rotation speed of 300 rpm, a discharge amount of 20 kg / hr, and the cylinder temperature was set so that the resin temperature of the die discharge part was 300 ° C. Pellets dried overnight at 130 ° C.
- Example 10 which mix
- the rigidity and mold dirtiness were improved without impairing the high toughness, and the molten resin was cooled and solidified quickly in the mold, and the mold transferability was excellent. Therefore, the appearance of the molded product was extremely good.
- Examples 12 and 15 to 16 in which the molecular weight and the blending amount of the component (A) and the component (B) are appropriately changed with respect to the tenth embodiment are the same as the component (A) without blending the component (B).
- the results showed that the rigidity increased and the appearance improved without significantly impairing the toughness.
- the component (F) was further blended with the example 10, and the rigidity was improved compared to the comparative example 10 in which the component (B) was removed from the example 11, the mold contamination was small, and excellent low temperature toughness. It was a result that can be maintained.
- Example 13 had significantly less gas generation than Comparative Example 11, had improved mold contamination and rigidity, and had a good appearance of the molded product.
- PPS resin having a lower molecular weight than PPS resin (B-1) was used as the component (B), compared to Example 10 in which PPS resin (B-1) was blended as component (B).
- the resin composition is changed to (B-2).
- Comparative Example 11 was the same as Example 13 except that the PPS resin (B-2) blended in Example 13 was changed to a PPS resin (A-3) component having the same molecular weight as the PPS resin (B-2). Composition.
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Abstract
Description
前記(A)成分は、下記式(1)
ΔWr=(W1-W2)/W1×100(%)・・・(1)
(ここでΔWrは重量減少率(%)であり、常圧の非酸化性雰囲気下で50℃から330℃以上の任意温度まで昇温速度20℃/分で熱重量分析を行った際に、100℃到達時点の試料重量(W1)を基準とした330℃到達時の試料重量(W2)から求められる値である。)
で表わされる加熱時の重量減少率ΔWrが0.18%を超えるポリフェニレンスルフィド樹脂であり、
前記(B)成分は、重量平均分子量が10,000以上であって、且つ、上記(1)式で表わされる加熱時の重量減少率ΔWrが0.18%以下のポリフェニレンスルフィド樹脂であり、
前記(A)成分と前記(B)成分の合計を100重量%としたときに、前記(A)成分95~5重量%に対して、前記(B)成分5~95重量%を配合してなるポリフェニレンスルフィド樹脂組成物。
を少なくとも50重量%以上含み、且つ重量平均分子量が10,000未満のポリフェニレンスルフィドプレポリマーを加熱して重量平均分子量10,000以上の高重合度体に転化させることにより得られたポリフェニレンスルフィド樹脂である1~9のいずれか1項に記載のポリフェニレンスルフィド樹脂組成物。
(A)成分として、下記式(1)
ΔWr=(W1-W2)/W1×100(%)・・・(1)
(ここでΔWrは重量減少率(%)であり、常圧の非酸化性雰囲気下で50℃から330℃以上の任意温度まで昇温速度20℃/分で熱重量分析を行った際に、100℃到達時点の試料重量(W1)を基準とした330℃到達時の試料重量(W2)から求められる値である。)
で表わされる加熱時の重量減少率ΔWrが0.18%を超えるポリフェニレンスルフィド樹脂を用意する工程と、
(B)成分として、重量平均分子量が10,000以上であって、且つ、上記(1)式で表わされる加熱時の重量減少率ΔWrが0.18%以下のポリフェニレンスルフィド樹脂を用意する工程と、
前記(A)成分と前記(B)成分の合計を100重量%としたときに、前記(A)成分95~5重量%に対して、前記(B)成分5~95重量%を配合する工程と、
を備えるポリフェレニンスルフィド樹脂組成物の製造方法。
本発明の実施形態で用いられる(A)ポリフェニレンスルフィド樹脂は、下記構造式
△Wr=(W1-W2)/W1×100>0.18(%)・・・(1)
ポリハロゲン化芳香族化合物とは、1分子中にハロゲン原子を2個以上有する化合物をいう。具体例としては、p-ジクロロベンゼン、m-ジクロロベンゼン、o-ジクロロベンゼン、1,3,5-トリクロロベンゼン、1,2,4-トリクロロベンゼン、1,2,4,5-テトラクロロベンゼン、ヘキサクロロベンゼン、2,5-ジクロロトルエン、2,5-ジクロロ-p-キシレン、1,4-ジブロモベンゼン、1,4-ジヨードベンゼン、および1-メトキシ-2,5-ジクロロベンゼンなどのポリハロゲン化芳香族化合物が挙げられ、好ましくはp-ジクロロベンゼンが用いられる。また、異なる2種以上のポリハロゲン化芳香族化合物を組み合わせた共重合体を用いることも可能であるが、p-ジハロゲン化芳香族化合物を主要成分とすることが好ましい。
スルフィド化剤としては、アルカリ金属硫化物、アルカリ金属水硫化物、および硫化水素が挙げられる。
重合溶媒としては有機極性溶媒を用いるのが好ましい。具体例としては、N-メチル-2-ピロリドン、N-エチル-2-ピロリドンなどのN-アルキルピロリドン類、およびN-メチル-ε-カプロラクタムなどのカプロラクタム類、1,3-ジメチル-2-イミダゾリジノン、N,N-ジメチルアセトアミド、N,N-ジメチルホルムアミド、ヘキサメチルリン酸トリアミド、ジメチルスルホン、およびテトラメチレンスルホキシドなどに代表されるアプロチック有機溶媒、並びにこれらの混合物などが挙げられ、これらはいずれも反応の安定性が高いために好ましく使用される。これらのなかでも、特にN-メチル-2-ピロリドン(以下、NMPと略記することもある)が好ましく用いられる。
生成する(A)PPS樹脂の末端を形成させるため、あるいは重合反応や分子量を調節するなどのために、モノハロゲン化合物(必ずしも芳香族化合物でなくともよい)を、上記ポリハロゲン化芳香族化合物と併用することができる。
比較的高重合度の(A)ポリフェニレンスルフィド樹脂をより短時間で得るために、重合助剤を用いることも好ましい態様の一つである。ここで重合助剤とは、得られる(A)PPS樹脂の粘度を増大させる作用を有する物質を意味する。このような重合助剤の具体例としては、例えば有機カルボン酸塩、水、アルカリ金属塩化物、有機スルホン酸塩、硫酸アルカリ金属塩、アルカリ土類金属酸化物、アルカリ金属リン酸塩およびアルカリ土類金属リン酸塩などが挙げられる。これらは単独で用いてもよく、また2種以上を同時に用いることもできる。なかでも、有機カルボン酸塩、水、およびアルカリ金属塩化物が好ましい。さらに有機カルボン酸塩としてはアルカリ金属カルボン酸塩が好ましく、アルカリ金属塩化物としては塩化リチウムが好ましい。
重合反応系を安定化し、副反応を防止するために、重合安定剤を用いることもできる。重合安定剤は、重合反応系の安定化に寄与し、望ましくない副反応を抑制する。副反応の一つの目安としては、チオフェノールの生成が挙げられ、重合安定剤の添加によりチオフェノールの生成を抑えることができる。重合安定剤の具体例としては、アルカリ金属水酸化物、アルカリ金属炭酸塩、アルカリ土類金属水酸化物、およびアルカリ土類金属炭酸塩などの化合物が挙げられる。そのなかでも、水酸化ナトリウム、水酸化カリウム、および水酸化リチウムなどのアルカリ金属水酸化物が好ましい。上述のアルカリ金属カルボン酸塩も重合安定剤として作用するので、重合安定剤の一つに入る。また、スルフィド化剤としてアルカリ金属水硫化物を用いる場合には、アルカリ金属水酸化物を同時に使用することが特に好ましいことを前述したが、ここでスルフィド化剤に対して過剰となるアルカリ金属水酸化物も重合安定剤となり得る。
(A)ポリフェニレンスルフィド樹脂の製造方法において、スルフィド化剤は通常水和物の形で使用されるが、ポリハロゲン化芳香族化合物を添加する前に、有機極性溶媒とスルフィド化剤を含む混合物を昇温し、過剰量の水を系外に除去することが好ましい。
有機極性溶媒中でスルフィド化剤とポリハロゲン化芳香族化合物とを200℃以上290℃未満の温度範囲内で反応させることにより(A)ポリフェニレンスルフィド樹脂を製造する。
転化率=〔PHA仕込み量(モル)-PHA残存量(モル)〕/〔PHA仕込み量(モル)-PHA過剰量(モル)〕
(b)上記(a)以外の場合
転化率=〔PHA仕込み量(モル)-PHA残存量(モル)〕/〔PHA仕込み量(モル)〕
(A)ポリフェニレンスルフィド樹脂の製造方法においては、上記重合反応工程の終了後に、重合体、溶媒などを含む重合反応物から固形物を回収する。回収方法については、公知の如何なる方法を採用してもよい。
(A)ポリフェニレンスルフィド樹脂は、上記重合反応工程および回収工程を経て生成した後に、酸処理、熱水処理、または有機溶媒による洗浄を施されたものであってもよい。また、(A)ポリフェニレンスルフィド樹脂を製造するためのいずれかの工程において、アルカリ金属処理やアルカリ土類金属処理を施されたものであってもよい。
本発明の実施形態における(B)ポリフェニレンスルフィド樹脂とは、式、-(Ar-S)-の繰り返し単位を主要構成単位とする、好ましくは当該繰り返し単位を80モル%以上含有するホモポリマーまたはコポリマーである。Arとしては下記の式(a)~式(k)などで表される単位などがあるが、中でも式(a)が特に好ましい。
△Wr=(W1-W2)/W1×100≦0.18(%) ・・・(2)
ここで△Wrは重量減少率(%)であり、常圧の非酸化性雰囲気下で50℃から330℃以上の任意の温度まで昇温速度20℃/分で熱重量分析を行った際に、100℃到達時点の試料重量(W1)を基準とした330℃到達時の試料重量(W2)から求められる値である。
本発明の実施形態の上記(B)ポリフェニレンスルフィド樹脂の製造方法としては、環式ポリフェニレンスルフィドを少なくとも50重量%以上含み、且つ重量平均分子量が10,000未満のポリフェニレンスルフィドプレポリマーを加熱して重量平均分子量10,000以上の高重合度体に転化させることによって製造する方法が例示できる。この方法によれば、容易に、前述した特性を有する本発明の実施形態で用いる(B)ポリフェニレンスルフィド樹脂を得ることができる。
本発明の実施形態で用いる(B)ポリフェニレンスルフィド樹脂の好ましい製造方法における環式ポリフェニレンスルフィドとしては、下記一般式(I)で表される環式ポリフェニレンスルフィド(以下、環式PPSと略すこともある)を使用することができる。ここで、mは4~20の整数であり、用いる環式ポリフェニレンスルフィドは、異なるmを有する複数種類の環式ポリフェニレンスルフィドの混合物でもよい。
本発明の実施形態で用いる(B)ポリフェニレンスルフィド樹脂の好ましい製造方法では、前記したごとき環式ポリフェニレンスルフィドを含むポリフェニレンスルフィドプレポリマーを加熱して高重合度体に転化させることを特徴とする。ここで用いるポリフェニレンスルフィドプレポリマーは、環式ポリフェニレンスルフィドを少なくとも50重量%以上含むものであり、好ましくは70重量%以上、より好ましくは80重量%以上、更に好ましくは90重量%以上含むものとすればよい。また、ポリフェニレンスルフィドプレポリマーにおける環式ポリフェニレンスルフィドの含有率の上限値には特に制限は無いが、98重量%以下が好ましい範囲として例示できる。通常、ポリフェニレンスルフィドプレポリマーにおける環式ポリフェニレンスルフィドの重量比率が高いほど、加熱後に得られるPPSの重合度および溶融粘度が高くなる傾向にある。すなわち、本発明の実施形態の(B)ポリフェニレンスルフィド樹脂の製造法においては、ポリフェニレンスルフィドプレポリマーにおける環式ポリフェニレンスルフィドの存在比率を調整することで、得られるPPSの重合度および溶融粘度を容易に調整することが可能である。また、ポリフェニレンスルフィドプレポリマーにおける環式ポリフェニレンスルフィドの重量比率が前記した上限値を超えると、ポリフェニレンスルフィドプレポリマーの溶融解温度が高くなる傾向にあるため、ポリフェニレンスルフィドプレポリマーにおける環式ポリフェニレンスルフィドの重量比率を前記範囲にすることは、ポリフェニレンスルフィドプレポリマーを高重合度体へ転化する際の温度をより低くできるため好ましい。
前記ポリフェニレンスルフィドプレポリマーを得る方法としては例えば以下の方法が挙げられる。
前記した本発明の実施形態の(B)ポリフェニレンスルフィド樹脂は、前記ポリフェニレンスルフィドプレポリマーを加熱して高重合度体に転化させる方法によって製造することが好ましい。この加熱の温度は前記ポリフェニレンスルフィドプレポリマーが溶融解する温度であることが好ましく、このような温度条件であれば特に制限は無い。加熱温度がポリフェニレンスルフィドプレポリマーの溶融解温度未満ではPPSの高重合度体を得るのに長時間が必要となる傾向がある。なお、ポリフェニレンスルフィドプレポリマーが溶融解する温度は、ポリフェニレンスルフィドプレポリマーの組成や分子量、また、加熱時の環境により変化するため、一意的に示すことはできないが、例えばポリフェニレンスルフィドプレポリマーを示差走査型熱量計で分析することで溶融解温度を把握することが可能である。但し、加熱時の温度が高すぎると、ポリフェニレンスルフィドプレポリマー間、加熱により生成した高重合度体間、及び高重合度体とポリフェニレンスルフィドプレポリマー間などでの架橋反応や分解反応に代表される好ましくない副反応が生じやすくなる傾向にあり、得られるPPS樹脂の特性が低下する場合がある。そのため、このような好ましくない副反応が顕著に生じる温度は避けることが望ましい。加熱温度としては180以上が例示でき、好ましくは200℃以上、より好ましくは250℃以上である。また、加熱温度としては400℃以下が例示でき、好ましくは380℃以下、より好ましくは360℃以下である。
本発明の実施形態における繊維状フィラーとしては、ガラス繊維、ガラスミルドファイバー、炭素繊維、金属繊維、カーボンナノチューブ、カーボンナノホーン、アラミド繊維、セラミック繊維、および鉱物繊維などが挙げられる。この中で、鉱物繊維としては、例えば、チタン酸カリウムウィスカ、酸化亜鉛ウィスカ、炭酸カルシウムウィスカ、ワラストナイトウィスカ、アスベスト繊維、および石コウ繊維などが挙げられる。セラミック繊維としては、例えばアルミナ繊維および炭化珪素繊維などが挙げられる。本発明の実施形態において好ましい繊維状フィラーは、一般に短繊維と称される、配合前の繊維長1~5mm、繊維直径1~25μmのものである。このような短繊維フィラーを用いることで、フィラーの分散性の良好な樹脂組成物を得やすくなる傾向にある。
本発明の実施形態における(D)エポキシ基、アミノ基、イソシアネート基、水酸基、メルカプト基およびウレイド基の中から選ばれた少なくとも1種の官能基を有するアルコキシシラン化合物の具体例としては、γ-グリシドキシプロピルトリメトキシシラン、γ-グリシドキシプロピルトリエトキシシシラン、およびβ-(3,4-エポキシシクロヘキシル)エチルトリメトキシシランなどのエポキシ基含有アルコキシシラン化合物、γ-メルカプトプロピルトリメトキシシランおよびγ-メルカプトプロピルトリエトキシシランなどのメルカプト基含有アルコキシシラン化合物、γ-ウレイドプロピルトリエトキシシラン、γ-ウレイドプロピルトリメトキシシシラン、およびγ-(2-ウレイドエチル)アミノプロピルトリメトキシシランなどのウレイド基含有アルコキシシラン化合物、γ-イソシアナトプロピルトリエトキシシラン、γ-イソシアナトプロピルトリメトキシシラン、γ-イソシアナトプロピルメチルジメトキシシラン、γ-イソシアナトプロピルメチルジエトキシシラン、γ-イソシアナトプロピルエチルジメトキシシラン、γ-イソシアナトプロピルエチルジエトキシシラン、およびγ-イソシアナトプロピルトリクロロシランなどのイソシアナト基含有アルコキシシラン化合物、γ-(2-アミノエチル)アミノプロピルメチルジメトキシシラン、γ-(2-アミノエチル)アミノプロピルトリメトキシシラン、およびγ-アミノプロピルトリメトキシシランなどのアミノ基含有アルコキシシラン化合物、並びにγ-ヒドロキシプロピルトリメトキシシランおよびγ-ヒドロキシプロピルトリエトキシシランなどの水酸基含有アルコキシシラン化合物などが挙げられる。
本発明の実施形態で用いる(E)官能基含有オレフィン系共重合体として、エポキシ基含有オレフィン系共重合体、カルボキシル基含有オレフィン系共重合体、酸無水物基含有オレフィン系共重合体、アミノ基含有オレフィン系共重合体およびメルカプト基含有オレフィン系共重合体が挙げられる。その中でも特にエポキシ基含有オレフィン系共重合体が、PPS樹脂との相溶性が良好で高靱性が発現するために、好ましく用いられる。本発明の実施形態で用いるエポキシ基含有オレフィン系共重合体としては、オレフィン系共重合体にエポキシ基を有する単量体成分を導入して得られるオレフィン共重合体が挙げられる。また、主鎖中に二重結合を有するオレフィン系重合体の二重結合部分をエポキシ化した共重合体も使用することができる。
本発明の実施形態で特に有用な(E)官能基を含有しないオレフィン系共重合体としては、エチレンと炭素数3~20のα-オレフィンを共重合して得られるエチレン・α-オレフィン系共重合体が挙げられる。上記の炭素数3~20のα-オレフィンとしては、具体的にはプロピレン、1-ブテン、1-ペンテン、1-ヘキセン、1-ヘプテン、1-オクテン、1-ノネン、1-デセン、1-ウンデセン、1-ドデセン、1-トリデセン、1-テトラデセン、1-ペンタデセン、1-ヘキサデセン、1-ヘプタデセン、1-オクタデセン、1-ノナデセン、1-エイコセン、3-メチル-1-ブテン、3-メチル-1-ペンテン、3-エチル-1-ペンテン、4-メチル-1-ペンテン、4-メチル-1-ヘキセン、4,4-ジメチル-1-ヘキセン、 4,4-ジメチル-1-ペンテン、4-エチル-1-ヘキセン、3-エチル-1-ヘキセン、9-メチル-1-デセン、11-メチル-1-ドデセン、12-エチル-1-テトラデセン及びこれらの組み合わせが挙げられる。これらα-オレフィンの中でも炭素数6から12であるα-オレフィンを用いた共重合体が機械強度の向上、改質効果の一層の向上が見られるためより好ましい。
本発明の実施形態のPPS樹脂組成物では、既述したように、(A)成分は、加熱した際の重量減少率ΔWrが0.18%を超えるポリフェニレンスルフィド樹脂であり、(B)成分は、加熱した際の重量減少率ΔWrが0.18%以下のポリフェニレンスルフィド樹脂である。このような(A)成分と(B)成分とを配合してなるPPS樹脂組成物において、(A)成分と(B)成分の合計を100重量%としたときに、(A)成分の配合割合は、95重量%以下が選択され、90重量%以下が好ましく、85重量%以下がより好ましく、80重量%以下がさらに好ましい。また、(A)成分の配合割合は、5重量%以上が選択され、30重量%以上が好ましく、40重量%以上がより好ましく、50重量%以上がさらに好ましい。なお、(B)成分の配合量が5重量%未満であると十分な耐熱性向上効果が得られないために好ましくない。一方で(B)成分の配合量が95重量%を越えると金型内での樹脂の固化が極めて速くなり、特に薄肉成形品を射出成形する際に充填不良を発生する可能性があるために好ましくない。
本発明の実施形態におけるPPS樹脂組成物が、(A)成分と(B)成分に加えてさらに(C)成分を配合してなる場合であっても、(A)成分と(B)成分の合計を100重量%としたときの(A)成分配合割合は、95~5重量%の範囲が選択される。特に、本発明の実施形態のPPS樹脂組成物の成形加工性、耐熱性及び表面平滑性を大幅に向上させるためには、(A)成分と(B)成分の合計を100重量%としたときの(A)成分の配合割合は、5~20重量%の範囲が選択されることが好ましい。また、本発明の実施形態のPPS樹脂組成物の大幅な材料剛性向上を図るためには、(A)成分と(B)成分の合計を100重量%としたときの(A)成分の配合割合は、80~95重量%の範囲が選択されることが好ましい。尚、(B)成分の配合量が5重量%未満であると、金型内での成形品表層での固化が遅くなり、フローマークや成形品ヒケ(成形品の表面に凹みができる外観不良)の原因となる溶融樹脂の流動方向うねりが大幅に大きくなり、高度な表面平滑性を有した成形品を得ることが困難になる。一方で、(B)成分の配合量が95重量%を超えると、フィラーとの密着性が阻害され、成形品表面でのフィラー偏在が見られるようになり、表面平滑性、機械強度が顕著に低下するために好ましくない。
測定条件:
(a)50℃で1分保持
(b)50℃から340℃まで昇温(昇温速度20℃/分)
(c)340℃で1分間保持
(d)340℃から100℃まで降温(降温速度20℃/分)
(溶融・冷却による結晶化時の吸熱ピークの頂点温度を降温結晶化温度とする)。
本発明の実施形態におけるPPS樹脂組成物が、(A)成分と(B)成分に加えてさらに(E)成分を配合してなる場合であっても、(A)成分と(B)成分の合計を100重量%としたときの(A)成分の配合割合は、5~95重量%が選択される。特に本発明の実施形態のPPS樹脂組成物の金型汚れ性、耐熱性及び成形品外観を大幅に向上させるためには、(A)成分と(B)成分の合計を100重量%としたときの(A)成分の配合割合は、5~20重量%の範囲が選択されることが好ましい。また、本発明の実施形態のPPS樹脂組成物の靱性を大幅に向上させるためには、(A)成分と(B)成分の合計を100重量%としたときの(A)成分の配合割合は、80~95重量%の範囲が選択されることが好ましい。尚、(B)成分の配合割合が5重量%未満であると、金型内での溶融樹脂の冷却・固化が遅くなり、成形品表面のフローマークやヒケの原因となる溶融樹脂の流動方向うねりが顕著に大きくなるために好ましくない。一方で、(B)成分の配合割合が95重量%を超えると、本発明の実施形態の(E)官能基含有オレフィン系共重合体と十分に相溶せず、顕著な靱性低下をもたらすために好ましくない。
測定条件:
(a)50℃で1分保持
(b)50℃から340℃まで昇温(昇温速度20℃/分)
(c)340℃で1分間保持
(d)340℃から100℃まで降温(降温速度20℃/分)
(溶融・冷却による結晶化時の吸熱ピークの頂点温度を降温結晶化温度とする)。
ポリフェニレンスルフィド及びポリフェニレンスルフィドプレポリマーの分子量は、サイズ排除クロマトグラフィー(SEC)の一種であるゲルパーミエーションクロマトグラフィー(GPC)により、ポリスチレン換算で算出した。GPCの測定条件を以下に示す。
カラム名:センシュー科学 GPC3506
溶離液:1-クロロナフタレン
検出器:示差屈折率検出器
カラム温度:210℃
プレ恒温槽温度:250℃
ポンプ恒温槽温度:50℃
検出器温度:210℃
流量:1.0mL/min
試料注入量:300μL (サンプル濃度:約0.2重量%)
ポリフェニレンスルフィドの加熱時重量減少率は熱重量分析機を用いて下記条件で行った。なお、試料は2mm以下の細粒物を用いた。
測定雰囲気:窒素気流下
試料仕込み重量:約10mg
測定条件:
(a)プログラム温度50℃で1分保持
(b)プログラム温度50℃から400℃まで昇温。この際の昇温速度20℃/分
重量減少率△Wrは、(b)の昇温の際に、100℃到達時の試料重量(W1)を基準として、330℃到達時の試料重量(W2)から以下の式(3)を用いて算出した。
△Wr=(W1-W2)/W1×100 ・・・(3)
ポリフェニレンスルフィド樹脂の含有するアルカリ金属含有量の定量は下記により行った。
(a)試料を石英るつぼに計りとり、電気炉を用いて灰化した。
(b)灰化物を濃硝酸で溶解した後、希硝酸で一定の容積に希釈した。
(c)得られた溶液中のアルカリ金属含有量を、ICP重量分析法(装置;Agilent製4500)及びICP発光分光分析法(装置;PerkinElmer製Optima4300DV)により測定した。
ポリフェニレンスルフィド樹脂を加熱した際に発生する成分の定量は以下の方法により行った。なお、試料は2mm以下の細粒物を用いた。
(a)加熱時発生ガスの捕集
約10mgのポリフェニレンスルフィド樹脂を窒素気流下(50ml/分)の320℃で60分間加熱し、発生したガス成分を大気捕集用加熱脱離用チューブcarbotrap400に捕集した。
(b)ガス成分の分析
上記チューブに捕集したガス成分を熱脱着装置TDU(Supelco社製)を用いて室温から280℃まで5分間で昇温することで熱脱離させた。熱脱離した成分をガスクロマトグラフィーを用いて成分分割して、ラクトン型化合物量としてガス中のγ-ブチロラクトン量を測定し、アニリン型化合物量として4-クロロ-N-メチルアニリン量を測定した。
住友重機械社製射出成形機プロマット40/20を用い、樹脂温度320℃、金型温度130℃とする条件にて、(長さ)130mm×(幅)12.7mm×(厚み)1mmのヒートサグ試験片を成形した。
前記射出成形したヒートサグ試験片の片端30mmを保持し、試験片が水平になるように片持ち状態で固定しながら、190℃の熱風ギアオーブンで15hr処理した後、保持した部分と反対側の先端が、水平状態から自重によって垂れ下がった距離を求めヒートサグ変形量とした。この変形量が小さいほど、薄肉耐熱性に優れているといえる。
住友重機械社製射出成形機プロマット40/20を用い、樹脂温度320℃、金型温度130℃、射出速度設定99%、射出圧力設定45%(実際の射出圧力98MPa)とする条件にて、(長さ)150mm×(幅)12.6mm×(厚み)0.5mm(ゲート位置:成形片の幅側、ゲート形状:フィルムゲート)の成形片を連続的に10回射出成形した。得られた成形片それぞれの、ゲート位置側から長手方向における充填末端長さを測定し、その平均値を棒流動長とした。棒流動長の値が大きいほど、薄肉流動性に優れているといえる。
住友重機械社製射出成形機SE75-DUZを用い、樹脂温度320℃、金型温度130℃とする条件にて、ASTM1号ダンベル試験片を成形した。
前記射出成形したASTM1号ダンベル試験片を支点間距離114mm、引張速度10mm/minの条件でテンシロンUTA2.5T引張試験機を用い、ASTM D638に準じて引張強度および引張伸度を測定した。これらの値が大きいほど引張特性に優れているといえる。
住友重機械社製射出成形機SE75-DUZを用い、樹脂温度320℃、金型温度130℃とする条件にて、(幅)12.5mm×(長さ)130mm×(厚み)3.2mmの曲げ試験片を成形した。
前記射出成形した曲げ試験片をスパン間距離100mm、クロスヘッドスピード1.0mm/minの条件で、ASTM D790に準じてテンシロンRTM1T曲げ試験機を用い、曲げ強度および曲げ弾性率を測定した。これらの値が大きいほど曲げ特性に優れているといえる。
前記射出成形した曲げ試験片を用いて、ASTM D648に準じて、0.46MPa荷重下での荷重たわみ温度を測定した。この値が大きいほど耐熱性に優れているといえる。
住友重機械社製射出成形機SE75-DUZを用い、樹脂温度320℃、金型温度130℃とする条件にて、(幅)12.7mm×(長さ)60mm×(厚み)3.2mmのモールドノッチ付きアイゾット衝撃試験片を成形した。
前記射出成形したモールドノッチ付きアイゾット衝撃試験片を用いて、ASTM D256に準じてノッチ付きアイゾット衝撃強度を測定した。この値が大きいほど衝撃特性に優れているといえる。
前記射出成形したモールドノッチ付きアイゾット衝撃試験片を用いて、-20℃の超低温恒温槽にて120分冷却した後、ASTM D256に準じてノッチ付きアイゾット衝撃強度を測定した。この値が大きいほど低温靭性に優れた材料といえる。
配合物を溶融混練し、大気下120℃で8時間乾燥して得られたPPS樹脂組成物ペレットを130℃で3時間予備乾燥した後、約10gをアルミカップに精秤した。これを大気下320℃で2時間加熱処理した際の加熱減量ΔWhを測定した。加熱減量ΔWhは、加熱前の試料重量(W3)を基準として、加熱処理後の試料重量(W4)から以下の式(4)を用いて算出した。
△Wh=(W3-W4)/W3×100 ・・・(4)
上記加熱減量が少ないほどガス発生量が少ないといえる。
前記射出成形したASTM1号ダンベル試験片を用いて、未処理時と熱処理後のそれぞれについて、中心線平均粗さRa(JISB0601に準拠)を測定した。当該成形品の熱処理は、熱風ギアオーブンを用いて180℃、15時間の条件で実施した。尚、この値が小さいほど成形品表層でのフィラー偏在が少なく、表面平滑性に優れているといえる。
前記射出成形したASTM1号ダンベル試験片を用いて、未処理時と熱処理後のそれぞれについて、算術平均うねりWa(JISB0601に準拠)を測定した。当該成形品の熱処理は、熱風ギアオーブンを用いて180℃、15時間の条件で実施した。尚、この値が小さいほど成形品表面のフローマークやヒケが少なく、表面平滑性に優れているといえる。
配合物を溶融混練し、大気下120℃で8時間乾燥して得られたPPS樹脂組成物ペレットを130℃で3時間予備乾燥した。その後、ペレット約10mgをパーキンエルマー製DSC-7に仕込み、窒素雰囲気下、下記測定条件で降温結晶化温度Tmcを測定した。尚、この温度が高いほど、金型内での溶融樹脂の冷却・固化が進行しやすく、金型転写性に優れているといえる。
測定条件:
(a)50℃で1分保持
(b)50℃から340℃まで昇温(昇温速度20℃/分)
(c)340℃で1分間保持
(d)340℃から100℃まで降温(降温速度20℃/分)
(溶融後の冷却により結晶化する際の吸熱ピークの頂点温度を降温結晶化温度とした)。
前記射出成形したASTM1号ダンベル試験片の中央部を樹脂の流れ方向に対して直角方向に切断し、その断面の中心部から、-20℃で0.1μm以下の薄片を切削した。切削した薄片を、日立製作所製H-7100型透過型電子顕微鏡(分解能(粒子像)0.38nm、倍率50~60万倍)にて、1万倍に拡大して観察した。観察された任意の100個のオレフィン系共重合体成分について、まずそれぞれの最大径と最小径を測定して、最大径と最小径の平均値をその分散粒子径とした。その後、上記100個のオレフィン系共重合体成分についての分散粒子径の平均値である数平均分散粒子径を求めた。
住友重機械社製射出成形機SE75-DUZを用い、ガスベント部を有する80mm×80mm×3mm厚の角板金型を用いて、樹脂温度320℃、金型温度130℃、射出時間15s、冷却時間20s、成形サイクル40sにて、モールドデポジット(金型付着物)がガスベント部に付着するまで全自動運転による連続成形を行った。その際には、100ショット毎にモールドデポジットの付着状況を目視確認し、金型汚れの評価を行った。なお、金型汚れの評価基準として、500ショット以下でモールドデポジットが発生した場合に「×:かなり劣る」、500~1000ショットでモールドデポジットが発生した場合には「△:劣る」、1000ショットを超えるまでモールドデポジットが発生しなかった場合には「○:優れる」とした。
撹拌機および底栓弁付きの70リットルオートクレーブに、47.5%水硫化ナトリウム8.27kg(70.00モル)、96%水酸化ナトリウム2.94kg(70.63モル)、N-メチル-2-ピロリドン(NMP)11.45kg(115.50モル)、酢酸ナトリウム1.89kg(23.1モル)、及びイオン交換水5.50kgを仕込み、常圧で窒素を通じながら245℃まで約3時間かけて徐々に加熱し、水9.77kgおよびNMP0.28kgを留出した後、反応容器を200℃に冷却した。アルカリ金属硫化物の仕込み量1モル当たりの系内残存水分量は、NMPの加水分解に消費された水分を含めて1.06モルであった。また、硫化水素の飛散量は、アルカリ金属硫化物の仕込み量1モル当たり0.02モルであった。
撹拌機および底栓弁付きの70リットルオートクレーブに、47.5%水硫化ナトリウム8.27kg(70.00モル)、96%水酸化ナトリウム2.94kg(70.63モル)、N-メチル-2-ピロリドン(NMP)11.45kg(115.50モル)、酢酸ナトリウム2.24kg(27.3モル)、及びイオン交換水5.50kgを仕込み、常圧で窒素を通じながら245℃まで約3時間かけて徐々に加熱し、水9.77kgおよびNMP0.28kgを留出した後、反応容器を200℃に冷却した。アルカリ金属硫化物の仕込み量1モル当たりの系内残存水分量は、NMPの加水分解に消費された水分を含めて1.06モルであった。また、硫化水素の飛散量は、アルカリ金属硫化物の仕込み量1モル当たり0.02モルであった。
撹拌機および底栓弁付きの70リットルオートクレーブに、47.5%水硫化ナトリウム8.27kg(70.00モル)、96%水酸化ナトリウム2.91kg(69.80モル)、N-メチル-2-ピロリドン(NMP)11.45kg(115.50モル)、及びイオン交換水10.5kgを仕込み、常圧で窒素を通じながら245℃まで約3時間かけて徐々に加熱し、水14.78kgおよびNMP0.28kgを留出した後、反応容器を200℃に冷却した。アルカリ金属硫化物の仕込み量1モル当たりの系内残存水分量は、NMPの加水分解に消費された水分を含めて1.06モルであった。また、硫化水素の飛散量は、アルカリ金属硫化物の仕込み量1モル当たり0.02モルであった。
撹拌機および上部に抜き出しバルブを具備したオートクレーブに、水硫化ナトリウムの48重量%水溶液1.648kg(水硫化ナトリウム0.791kg(14.1モル))、水酸化ナトリウムの48重量%水溶液1.225kg(水酸化ナトリウム0.588kg(14.7モル))、N-メチル-2-ピロリドン(NMP)35L、およびp-ジクロロベンゼン(p-DCB)2.120kg(14.4モル)を仕込んだ。
p-ジクロロベンゼンの仕込み量を2.278kg(15.5モル)に変えた以外は参考例4と同様に行った。得られた乾燥固体の分析の結果、環式ポリフェニレンスルフィドを72%含有していることがわかり、また、重合物の重量平均分子量は約2万、分散度は1.90であることがわかった。得られた生成物の加熱時重量減少率の測定を行った結果、△Wrは0.065%であった。また、△Wr300(%)=0.045、△Wr320(%)=0.055、△Wr340(%)=0.070であった。さらに、得られた生成物のアルカリ金属含有量の定量化をした結果、Na含有量は重量比で280ppmであり、これ以外のアルカリ金属は検出されなかった。最後に、得られた生成物について加熱時の発生ガス成分の分析を行った結果、加熱前の生成物の重量に対して、γ-ブチロラクトンが24ppm、4-クロロ-N-メチルアニリンが19ppm検出された。上記得られた生成物を、PPS樹脂(B-2)と呼ぶ。
ガラス繊維(旭ファイバーグラス社製T747、平均繊維直径13μm、平均繊維長3mm)
2-(3、4-エポキシシクロヘキシル)エチルトリメトキシシラン(信越化学工業社製KBM-303)
エチレン/メタクリル酸グリシジル=88/12(重量比)の共重合体(住友化学製"ボンドファースト"BF-E)
MFR=0.5g/10分(190℃、2.16kg荷重)、密度0.861g/cm3のエチレン/1-ブテン共重合体(三井化学製"タフマー"TX-610)
表1に示す各成分を、表1に示す割合でドライブレンドした後、真空ベントを具備した日本製鋼所社製TEX30α型二軸押出機(スクリュー径30mm、L/D=45、ニーディング部は5箇所、同方向回転完全噛み合い型スクリュー)を用いて溶融混練し、ストランドカッターによりペレット化した。溶融混練の条件は、スクリュー回転数300rpm、吐出量20Kg/hrであって、ダイス吐出部の樹脂温度が300℃となるようにシリンダー温度を設定した。130℃で一晩乾燥したペレットを射出成形に供し、加熱減量ΔWh、棒流動長、引張特性(引張強度および引張伸度)、曲げ特性(曲げ強度および曲げ弾性率)、衝撃特性、荷重たわみ温度、ヒートサグ変形量を評価した。結果は表1に示す通りであった。
表2および表3に示す(A)成分、(B)成分および(D)成分を、表2および表3に示す割合でドライブレンドした後、真空ベントを具備した日本製鋼所社製TEX30α型二軸押出機(L/D=45.5、ニーディング部は5箇所)を用いて溶融混練し、ストランドカッターによりペレット化した。上記ドライブレンドした原料は、押出機の根元(ダイヘッドからL/D=45.5の箇所)から供給した。(C)成分は、ダイヘッドからL/D=15の箇所から、表1に示した割合になるようにサイドフィーダーを用いて途中から供給した。溶融混練の条件は、スクリュー回転数300rpmであって、ダイス吐出部の樹脂温度が330℃以下になるようにシリンダ温度を設定した。130℃で一晩乾燥したペレットを射出成形に供し、降温結晶化温度、加熱減量ΔWh、棒流動長、引張特性、曲げ特性、衝撃特性、荷重たわみ温度、表面平滑性を評価した。結果は表2および表3に示す通りであった。
表4および表5に示す各成分を、表4および表5に示す割合でドライブレンドした後、真空ベントを具備した日本製鋼所社製TEX30α型二軸押出機(スクリュー径30mm、L/D=45、ニーディング部5箇所、同方向回転完全噛み合い型スクリュー)を用いて溶融混練し、ストランドカッターによりペレット化した。溶融混練の条件は、スクリュー回転数300rpm、吐出量20Kg/hrであって、ダイス吐出部の樹脂温度が300℃となるようにシリンダー温度を設定した。130℃で一晩乾燥したペレットを射出成形に供し、降温結晶化温度、加熱減量ΔWh、棒流動長、引張伸度、曲げ弾性率、衝撃特性、成形品外観評価、金型汚れ評価およびオレフィン系共重合体の数平均分散粒子径を測定した。結果は表4および表5に示す通りであった。
Claims (12)
- (A)成分と(B)成分とを配合してなるポリフェニレンスルフィド樹脂組成物であって、
前記(A)成分は、下記式(1)
ΔWr=(W1-W2)/W1×100(%)・・・(1)
(ここでΔWrは重量減少率(%)であり、常圧の非酸化性雰囲気下で50℃から330℃以上の任意温度まで昇温速度20℃/分で熱重量分析を行った際に、100℃到達時点の試料重量(W1)を基準とした330℃到達時の試料重量(W2)から求められる値である。)
で表わされる加熱時の重量減少率ΔWrが0.18%を超えるポリフェニレンスルフィド樹脂であり、
前記(B)成分は、重量平均分子量が10,000以上であって、且つ、上記(1)式で表わされる加熱時の重量減少率ΔWrが0.18%以下のポリフェニレンスルフィド樹脂であり、
前記(A)成分と前記(B)成分の合計を100重量%としたときに、前記(A)成分95~5重量%に対して、前記(B)成分5~95重量%を配合してなるポリフェニレンスルフィド樹脂組成物。 - 前記(B)成分であるポリフェニレンスルフィド樹脂は、重量平均分子量を数平均分子量で除した分散度が2.5以下である請求項1に記載のポリフェニレンスルフィド樹脂組成物。
- 前記(A)成分と前記(B)成分の合計100重量部に対して、(C)繊維状および/または非繊維状フィラー1~500重量部を配合してなる請求項1または2に記載のポリフェニレンスルフィド樹脂組成物。
- 前記(A)成分、前記(B)成分および前記(C)成分の合計100重量部に対し、さらに(D)エポキシ基、アミノ基、イソシアネート基、水酸基、メルカプト基、ウレイド基から選択される一種以上の基を有するアルコキシシラン化合物0.05~10重量部を配合してなる請求項3に記載のポリフェニレンスルフィド樹脂組成物。
- 前記(A)成分と前記(B)成分の合計100重量に対して、(E)官能基含有オレフィン系共重合体1~70重量部を配合してなる請求項1~4のいずれか1項に記載のポリフェニレンスルフィド樹脂組成物。
- 前記(E)官能基含有オレフィン系共重合体の有する官能基が、エポキシ基、カルボキシル基、酸無水物基、アミノ基、メルカプト基から選択される一種以上の基を有する請求項5記載のポリフェニレンスルフィド樹脂組成物。
- 前記(B)成分のアルカリ金属含有量が、重量比で700ppm未満である請求項1~6のいずれか1項に記載のポリフェニレンスルフィド樹脂組成物。
- 前記(B)成分を加熱したときに発生するガスの成分におけるラクトン型化合物の含有割合が、ポリフェニレンスルフィド重量基準で500ppm以下である請求項1~7のいずれか1項に記載のポリフェニレンスルフィド樹脂組成物。
- 前記(B)成分を加熱したときに発生するガスの成分におけるアニリン型化合物の含有率が、ポリフェニレンスルフィド重量基準で300ppm以下である請求項1~7のいずれか1項に記載のポリフェニレンスルフィド樹脂組成物。
- 請求項1~10のいずれか1項に記載のポリフェニレンスルフィド樹脂組成物からなる成形品。
- ポリフェニレンスルフィド樹脂組成物の製造方法であって、
(A)成分として、下記式(1)
ΔWr=(W1-W2)/W1×100(%)・・・(1)
(ここでΔWrは重量減少率(%)であり、常圧の非酸化性雰囲気下で50℃から330℃以上の任意温度まで昇温速度20℃/分で熱重量分析を行った際に、100℃到達時点の試料重量(W1)を基準とした330℃到達時の試料重量(W2)から求められる値である。)
で表わされる加熱時の重量減少率ΔWrが0.18%を超えるポリフェニレンスルフィド樹脂を用意する工程と、
(B)成分として、重量平均分子量が10,000以上であって、且つ、上記(1)式で表わされる加熱時の重量減少率ΔWrが0.18%以下のポリフェニレンスルフィド樹脂を用意する工程と、
前記(A)成分と前記(B)成分の合計を100重量%としたときに、前記(A)成分95~5重量%に対して、前記(B)成分5~95重量%を配合する工程と、
を備えるポリフェレニンスルフィド樹脂組成物の製造方法。
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EP (1) | EP2789655B1 (ja) |
JP (1) | JP5582244B2 (ja) |
KR (1) | KR101475658B1 (ja) |
CN (1) | CN103987784B (ja) |
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JPWO2014157543A1 (ja) * | 2013-03-27 | 2017-02-16 | Kbセーレン株式会社 | ポリフェニレンスルフィドモノフィラメントおよびその製造方法 |
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Cited By (14)
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JPWO2014157543A1 (ja) * | 2013-03-27 | 2017-02-16 | Kbセーレン株式会社 | ポリフェニレンスルフィドモノフィラメントおよびその製造方法 |
CN105358501A (zh) * | 2013-07-10 | 2016-02-24 | 提克纳有限责任公司 | 具有耐磨性包覆层的复合杆 |
US20150017437A1 (en) * | 2013-07-10 | 2015-01-15 | Ticona Llc | Composite Rod Having an Abrasion Resistant Capping Layer |
US10294330B2 (en) | 2015-07-31 | 2019-05-21 | Toray Industries, Inc. | Polyphenylene sulfide resin composition and method of manufacturing same |
JPWO2017022524A1 (ja) * | 2015-07-31 | 2017-11-24 | 東レ株式会社 | ポリフェニレンスルフィド樹脂組成物およびその製造方法 |
WO2017022524A1 (ja) * | 2015-07-31 | 2017-02-09 | 東レ株式会社 | ポリフェニレンスルフィド樹脂組成物およびその製造方法 |
WO2019093237A1 (ja) * | 2017-11-10 | 2019-05-16 | 東レ株式会社 | ポリフェニレンスルフィド樹脂組成物、その製造方法および成形体 |
JPWO2019093237A1 (ja) * | 2017-11-10 | 2020-09-17 | 東レ株式会社 | ポリフェニレンスルフィド樹脂組成物、その製造方法および成形体 |
US11306204B2 (en) | 2017-11-10 | 2022-04-19 | Toray Industries, Inc. | Polyphenylene sulfide resin composition, method of producing same, and molded article |
JP7081500B2 (ja) | 2017-11-10 | 2022-06-07 | 東レ株式会社 | ポリフェニレンスルフィド樹脂組成物、その製造方法および成形体 |
WO2020116434A1 (ja) * | 2018-12-06 | 2020-06-11 | Dic株式会社 | 樹脂組成物およびその成形体 |
JPWO2020116434A1 (ja) * | 2018-12-06 | 2021-02-15 | Dic株式会社 | 樹脂組成物およびその成形体 |
WO2023002903A1 (ja) * | 2021-07-19 | 2023-01-26 | 東レ株式会社 | ガラス繊維強化再生ポリフェニレンスルフィド樹脂組成物の製造方法、およびガラス繊維強化再生ポリフェニレンスルフィド樹脂組成物を成形してなる成形品 |
JP7235177B1 (ja) * | 2021-07-19 | 2023-03-08 | 東レ株式会社 | ガラス繊維強化再生ポリフェニレンスルフィド樹脂組成物の製造方法、およびガラス繊維強化再生ポリフェニレンスルフィド樹脂組成物を成形してなる成形品 |
Also Published As
Publication number | Publication date |
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US20160032100A1 (en) | 2016-02-04 |
CN103987784B (zh) | 2015-11-25 |
JPWO2013099234A1 (ja) | 2015-04-30 |
KR101475658B1 (ko) | 2014-12-22 |
EP2789655A1 (en) | 2014-10-15 |
US9187641B2 (en) | 2015-11-17 |
US9416272B2 (en) | 2016-08-16 |
TW201348337A (zh) | 2013-12-01 |
CN103987784A (zh) | 2014-08-13 |
US20140343215A1 (en) | 2014-11-20 |
TWI542634B (zh) | 2016-07-21 |
JP5582244B2 (ja) | 2014-09-03 |
MY164329A (en) | 2017-12-15 |
EP2789655A4 (en) | 2014-12-17 |
KR20140102224A (ko) | 2014-08-21 |
EP2789655B1 (en) | 2017-03-08 |
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