CN110283457A - Polyarylene sulfide resin composition and its formed products and surface mounted electronic parts - Google Patents
Polyarylene sulfide resin composition and its formed products and surface mounted electronic parts Download PDFInfo
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- CN110283457A CN110283457A CN201910508931.5A CN201910508931A CN110283457A CN 110283457 A CN110283457 A CN 110283457A CN 201910508931 A CN201910508931 A CN 201910508931A CN 110283457 A CN110283457 A CN 110283457A
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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
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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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
- C08L81/02—Polythioethers; Polythioether-ethers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Abstract
The present invention relates to polyarylene sulfide resin composition and its formed products and surface mounted electronic parts.Specifically, provide surface mounted electronic parts polyarylene sulfide resin composition, using the resin combination formed products and have the electronic components of the formed products, the surface mounted electronic parts polyarylene sulfide resin composition contains: polyarylene sulfide resin；With at least one kind of other ingredients in the group being made of inorganic filler, the thermoplastic resin in addition to polyarylene sulfide resin, elastomer and crosslinkable resin with 2 or more cross-linking functional groups, polyarylene sulfide resin can be obtained using including the method that reacts diiodo- aromatic compound, elemental sulfur and polymerization inhibitor in the molten mixture containing diiodo- aromatic compound, elemental sulfur and polymerization inhibitor.
Description
The application be the applying date be August in 2014 28, application No. is 201480053300.4, entitled " poly- virtues
The divisional application of the application of sulfide resin composition and its formed products and surface mounted electronic parts ".
Technical field
The present invention relates to polyarylene sulfide resin composition and its formed products and surface mounted electronic parts.
Background technique
In recent years, in electrical/electronic industrial circle, with the miniaturization of product, the raising of productivity, resin series electron
Mode is (hereinafter sometimes referred to simply as to referred to as surface mount (surface mount) for mounting means of the component on printed base plate
" SMT mode ") surface mount manner transition.The technology that electronic component is installed on substrate is led at present in the way of the SMT
It is often used tin-lead eutectic soft solder (184 DEG C of fusing point), but in recent years, the problem of due to environmental pollution, utilized using tin as base
Plinth and lead-free solder alternatively material added with various metals.
Such lead-free solder fusing point compared with tin-lead eutectic soft solder is high, for example, in Xi-silver eutectic soft solder
In the case of, fusing point reaches 220 DEG C, therefore, when surface is installed, it is necessary to further increase the temperature of heating furnace (reflow soldering).
Therefore, when by the resin systems electronic component solder such as connector, there are the electronic components in heating furnace (reflow soldering) to occur
Fusing or deformation such problems.Therefore, for resin material used in surface mounted electronic parts, it is strongly required heat resistance
High material.
On the other hand, it proposes and uses with polyphenylene sulfide (hereinafter sometimes referred to simply as " PPS resin ") as the poly- of representative
Scheme of the arylene sulfide resin (hereinafter sometimes referred to simply as " pas resin ") as the resin material of high-fire resistance, proposes and has packet
Even if the formed products of the resin combination containing the polyarylene sulfide resin and the surface mounted electronic parts of metal terminal are in heating furnace
Also it can inhibit the fusing or deformation of the electronic component in (reflow soldering) (referring for example to patent document 1).
Existing technical literature
Patent document
Patent document 1: International Publication No. 2009/096401
Summary of the invention
Problems to be solved by the invention
However, being generated for the previous composition comprising polyarylene sulfide resin due to heating when forming etc.
Gas flow it is relatively more, worry etching electronic component metal terminal.In addition, previous polyarylene sulfide resin composition or its at
In shape product, there is still room for improvement for the characteristics such as mechanical strength, metal adaptation, die cavity balance.
Therefore, the problem to be solved in the present invention is, providing can prevent from installing in heating furnace (reflow soldering) inner surface
Electronic component fusing deforms and the gas generated and then resin combination caused by heating or its formed products is inhibited to have
Have excellent mechanical strength, metal adaptation, the polyarylene sulfide resin composition of die cavity equilibrium response, using the resin combination
Formed products and have the surface mounted electronic parts of the formed products.
The solution to the problem
The inventors of the present invention have carried out various researchs, as a result, it has been found that: by using the poly- virtue in end with particular functional group
Sulfide resin is able to solve the above problem, so as to complete the present invention.
That is, containing: poly arylidene thio-ester the present invention relates to a kind of surface mounted electronic parts polyarylene sulfide resin composition
Resin；With selected from by inorganic filler, the thermoplastic resin in addition to polyarylene sulfide resin, elastomer and have 2 to submit
At least one kind of other ingredients in the group of the crosslinkable resin composition of Lian Xing functional group, polyarylene sulfide resin can be using including making
Diiodo- aromatic compound, elemental sulfur and polymerization inhibitor are mixed in the melting comprising diiodo- aromatic compound, elemental sulfur and polymerization inhibitor
The method reacted is closed in object to obtain.
The effect of invention
According to the present invention, providing can prevent from installing electronic component fusing in heating furnace (reflow soldering) inner surface or become
Shape and inhibit gas generated and then resin combination or its formed products caused by heating have excellent mechanical strength,
Metal adaptation, die cavity equilibrium response polyarylene sulfide resin composition, using the resin combination formed products and have this
The surface mounted electronic parts of formed products.
It should be noted that die cavity equilibrium relation to the injection moulding by using the mold with multiple die cavitys simultaneously at
The uniformity of the compactedness of each die cavity when the multiple formed products of shape.If the die cavity balance of moulding material is insufficient, exists and be easy
Generate the tendency that a part of die cavity is not fully filled such cob webbing.
Specific embodiment
Hereinafter, being described in detail for the preferred embodiment of the present invention.But the present invention is not limited to below
Embodiment.
Polyarylene sulfide resin used in present embodiment can using include make diiodo- aromatic compound, elemental sulfur and
Method that polymerization inhibitor reacts in the molten mixture containing diiodo- aromatic compound, elemental sulfur and polymerization inhibitor obtains.Root
According to such method, with using Phillips method as the existing method of representative compared with, can be with the shape of the higher polymer of molecular weight
Formula obtains polyarylene sulfide resin.
Diiodo- aromatic compound has aromatic ring and 2 iodine atoms with aromatic ring Direct Bonding.As diiodo-
Aromatic compound, can enumerate diiodo-benzene, two iodotoluenes, diiodo- dimethylbenzene, diiodonaphthalene, diiodide, diiodobenzophenone,
Diiodo- diphenyl ether and diiodo- diphenyl sulphone (DPS) etc., but it is not limited to these.The position of substitution of 2 iodine atoms is not particularly limited, excellent
The position for selecting 2 the position of substitution to be located in the molecule as far as possible is ideal.Preferred the position of substitution is contraposition and 4,4 '-
Position.
The aromatic ring of diiodo- aromatic compound can by selected from phenyl, the halogen atom in addition to iodine atom, hydroxyl,
At least one kind of substituent group in nitro, amino, the alkoxy of carbon atom number 1~6, carboxyl, carboxylate, aryl sulfone and aryl ketones takes
Generation.But from the viewpoints such as the crystallinity of polyarylene sulfide resin and heat resistance, the diiodo- aromatic compound being substituted is opposite
In the range that the ratio of unsubstituted diiodo- aromatic compound is preferably 0.0001~5 mass %, more preferably 0.001~1
The range of quality %.
Elemental sulfur refers to the substance (S being only made of sulphur atom8、S6、S4、S2Deng), form is not particularly limited.Specifically
For, it can be used as Pharmacopeia of Japan drug and commercially available elemental sulfur, or that can generally obtain includes S8And S6Deng
Mixture.The purity of elemental sulfur is also not particularly limited.It can be grain as long as elemental sulfur is solid under room temperature (23 DEG C)
Shape is powdered.The partial size of elemental sulfur is not particularly limited, preferably the range of 0.001~10mm, more preferably 0.01~5mm
Range, the further preferably range of 0.01~3mm.
As long as polymerization inhibitor prevents in the polymerization reaction of polyarylene sulfide resin or stops the compound of the polymerization reaction, then
It can use without particular limitation.Polymerization inhibitor preferably comprise can the end of the main chain of polyarylene sulfide resin import selected from by
The compound of at least one of the group of salt composition of hydroxyl, amino, carboxyl and carboxyl group.That is, preferably having as polymerization inhibitor
By the compound of at least one of 1 or 2 or more the group for selecting the salt of free hydroxyl, amino, carboxyl and carboxyl to form group.
In addition, polymerization inhibitor can have above-mentioned functional group, above-mentioned functional group can also be generated by the stopping of polymerization reaction etc..
As the polymerization inhibitor with hydroxyl or amino, following formula (1) or (2) compound represented conduct can be used for example
Polymerization inhibitor.
According to general formula (1) compound represented, terminal groups of the univalent perssad as main chain shown in following formula (1-1) are imported
Group.Y in formula (1-1) is hydroxyl, amino etc. from polymerization inhibitor.
According to general formula (2) compound represented, terminal groups of the univalent perssad as main chain shown in following formula (2-1) are imported
Group.Hydroxyl from general formula (1) compound represented can for example pass through the carbon atom and Thiyl Radical key of the carbonyl in formula (2)
It closes and is directed in polyarylene sulfide resin.
Think: be originated from the main chain of polyarylene sulfide resin raw material (elemental sulfur) and existing disulfide bond under melting temperature from
The Thiyl Radical that is generated by basic capsule solution is bonded with general formula (1) compound represented or general formula (2) compound represented, thus
Group shown in formula (1-1) or (2-1) is directed in polyarylene sulfide resin.The presence of the structural unit of these specific structures
It is the feature by using polyarylene sulfide resin obtained from general formula (1) or the melt polymerization of (2) compound represented.
As general formula (1) compound represented, for example, 2- iodophenol, 2- amino aniline etc..As general formula (2)
Compound represented can enumerate 2- iodine benzophenone.
As the polymerization inhibitor with carboxyl, can be used for example selected from the following general formula (3), (4) or (5) compound represented
One or more of compound.
In general formula (3), R1And R2Each independently represent hydrogen atom or the following general formula (a), (b) or (c) shown in monovalence
Group, R1Or R2At least either be general formula (a), (b) or (c) shown in univalent perssad.In general formula (4), Z indicates iodine atom
Or sulfydryl, R3Indicate the following general formula (a), (b) or (c) shown in univalent perssad.In general formula (5), R4Indicate general formula (a), (b) or
(c) univalent perssad shown in.
X in general formula (a)~(c) is hydrogen atom or alkali metal atom, becomes good aspect from reactivity, preferably
Hydrogen atom.As alkali metal atom, sodium, lithium, potassium, rubidium and caesium etc., preferably sodium can be enumerated.In general formula (b), R10Indicate carbon atom
The alkyl of number 1~6.In general formula (c), R11Indicate the alkyl of hydrogen atom or carbon atom number 1~3, R12Indicate carbon atom number 1~5
Alkyl.
According to general formula (3), (4) or (5) compound represented, univalent perssad conduct shown in following formula (6) or (7) is imported
The end group of main chain.The presence of the structural unit of the end of these specific structures is by using general formula (3), (4) or (5)
The feature of polyarylene sulfide resin obtained from the melt polymerization of compound represented.
(in formula, R5Indicate general formula (a), (b) or (c) shown in univalent perssad.)
(in formula, R6Indicate general formula (a), (b) or (c) shown in univalent perssad.)
As polymerization inhibitor, the compound etc. without functional groups such as carboxyls can be used.As such compound, such as
It can be used selected from diphenyl disulfide, single iodobenzene, benzenethiol, 2,2 '-dibenzothiazyl disulfides, 2-mercaptobenzothiazole, N-
Cyclohexyl -2-[4-morpholinodithio sulfenamide, 2- (morpholinothio) benzothiazole and N, N '-dicyclohexyl -1,3- benzothiazole -
At least one kind of compound in 2- sulfenamide.
The polyarylene sulfide resin of present embodiment generates as follows: will include diiodo- aromatic compound, elemental sulfur, polymerization inhibitor
Melt polymerization is carried out in molten mixture obtained from the heating of the mixture of agent and the catalyst being added as needed, thus raw
At.For the ratio of the diiodo- aromatic compound in molten mixture, relative to 1 mole of elemental sulfur, preferably 0.5~2 rubs
Your range, more preferably 0.8~1.2 mole of range.In addition, for the ratio of the polymerization inhibitor in mixture, relative to solid
1 mole of body sulphur, preferably 0.0001~0.1 mole of range, more preferably 0.0005~0.05 mole of range.
The period of addition polymerization inhibitor is not particularly limited, and can will include diiodo- aromatic compound, elemental sulfur and root
It is the range that makes the temperature of mixture reach preferably 200 DEG C~320 DEG C according to the mixture heating for needing catalyst to be added, more excellent
Polymerization inhibitor is added at the time of selecting 250~320 DEG C of range.
Nitro compound can be added in molten mixture as the catalyst to adjusting polymerization speed.As the nitration
Object is closed, various nitrobenzene derivatives usually can be used.As nitrobenzene derivative, for example, 1,3- bis- iodo- 4- nitre
The iodo- 4- nitrobenzene of base benzene, 1-, the iodo- 4- nitrophenol of 2,6- bis- and the iodo- 4- nitra-amine of 2,6- bis-.The amount of catalyst is usually to make
For the amount of catalyst addition, such as relative to 100 mass parts of elemental sulfur, the preferably range of 0.01~20 mass parts.
The condition of melt polymerization is carried out to be suitable for adjusting, so that polymerization reaction suitably carries out.The temperature of melt polymerization is preferred
For 175 DEG C or more and generate polyarylene sulfide resin+100 DEG C of fusing point ranges below, more preferably 180~350 DEG C of model
It encloses.Melt polymerization is in the range that absolute pressure is preferably 1 [cPa]~100 [kPa], more preferably 13 [cPa]~60 [kPa]
It is carried out in range.The condition of melt polymerization does not need constant.For example, polymerization initial stage can make preferably 175~270 DEG C of temperature
Range, more preferable 180~250 DEG C of range, and make the range of absolute pressure 6.7~100 [kPa], then, side is continuously
Or periodically heat up and depressurize side and polymerize, the poly arylidene thio-ester that the polymerization later period makes preferably 270 DEG C or more of temperature and generates
The range below of+100 DEG C of fusing point of resin, more preferable 300~350 DEG C of range, also, make absolute pressure 1 [cPa]~6
The range of [kPa] and polymerize.In this specification, the fusing point of resin refers to using differential scanning calorimetry (DSC) (PerkinElmer
Co., Ltd. manufacture DSC device Pyris Diamond), according to JIS K7121 measure value.
For melt polymerization, from the viewpoint of preventing oxidation cross-linked reaction and obtaining high polymerization degree, preferably non-oxygen
It is carried out under the property changed atmosphere.In non-oxidizing atmosphere, the oxygen concentration of gas phase is preferably less than the range of 5 volume %, is more preferably
Range, further preferred gas phase less than 2 volume % are substantially free of oxygen.Non-oxidizing atmosphere be preferably nitrogen, helium and
The non-active gas atmospheres such as argon gas.
Melt polymerization can be used for example have heating device, decompressor and agitating device melting mixing machine come into
Row.As melting mixing machine, for example, Banbury mixer, kneader, continuous mixer, single screw extrusion machine and double
Screw extruder.
Molten mixture for melt polymerization is preferably substantially free of solvent.More specifically, contain in molten mixture
Total of the amount of some solvents relative to diiodo- aromatic compound, elemental sulfur, polymerization inhibitor and the catalyst being added as needed
100 mass parts, preferably 10 range, more preferably 5 range, further preferably 1 matter below the mass below the mass
Measure part range below.The amount of solvent can be for more than 0 mass parts, more than more than 0.01 mass parts range or 0.1 mass parts
Range.
Molten mixture (reaction product) cooling after melt polymerization can also obtained into the mixture of solid state
Afterwards, mixture is heated under reduced pressure or under the atmospheric pressure of non-oxidizing atmosphere, to make polymerization reaction further progress.As a result,
Molecular weight can not only be further increased, and makes the iodine molecule generated distillation and is removed, it therefore, can be by poly arylidene thio-ester tree
Iodine atom concentration in rouge inhibits in reduced levels.By be cooled to preferably 100~260 DEG C range, more preferable 130~250
DEG C range, the temperature of further preferred 150~230 DEG C of range, the mixture of solid state can be obtained.It is cooled to solid
Heating after state can carry out at temperature same as melt polymerization and pressure condition.
The reaction product of polyarylene sulfide resin comprising being obtained by melt polymerization process can be used for by keeping former
Sample direct plunges into the methods of melting mixing machine to manufacture resin combination, but addition can dissolve reaction production in the reaction product
The solvent of object prepares dissolved matter, and when taking out reaction product from reaction unit with the state of the dissolved matter, not only productivity is excellent
It is different, and then reactivity is also good, therefore preferably.The addition that the solvent of the reaction product can be dissolved is preferably laggard in melt polymerization
Row, but can also be carried out in the reaction later period of melt polymerization, alternatively, it is also possible to as described above by molten mixture (reaction production
Object) it is cooling obtain the mixture of solid state after, under elevated pressure, under decompression or under the atmospheric pressure of non-oxidizing atmosphere, heating
Mixture adds after making polymerization reaction further progress.The process for preparing the dissolved matter can carry out under non-oxidizing atmosphere.
In addition, the temperature as heating for dissolving, as long as the range more than the fusing point of solvent that can dissolve previous reaction product, excellent
It is selected as 200~350 DEG C of range, more preferably 210~250 DEG C of range, is preferably carried out under elevated pressure.
For the compounding ratio of the solvent of previous reaction product, phase are used, can dissolved to prepare aforementioned dissolved matter
For 100 mass parts of reaction product comprising polyarylene sulfide resin, the preferably range of 90~1000 mass parts, more preferably
The range of 200~400 mass parts.
As the solvent that can dissolve reaction product, can be used for example in the polymerisation in solutions such as Phillips method as polymerization
The solvent that reaction dissolvent uses.As the example of preferred solvent, can enumerate: n-methyl-2-pyrrolidone is (hereinafter abbreviated as
NMP), n-cyclohexyl-2-pyrrolidone, 2-Pyrrolidone, 1,3- dimethyl -2- imidazolidinone, epsilon-caprolactams, N- methyl -
The aliphatic cyclics such as epsilon-caprolactams amide compound, hexamethylphosphoric triamide (HMPA), tetramethylurea (TMU), dimethyl
The amide compounds such as formamide (DMF) and dimethyl acetamide (DMA), dialkylethers (degree of polymerization be 2000 with
Under, the alkyl with carbon atom number 1~20) etc. etherificate polyethylene glycol compound and tetramethylene sulfoxide and dimethyl sulfoxide
(DMSO) sulfoxide compounds such as.As the example of solvent workable for other, can enumerate selected from the group by following material composition
One or more of solvent: benzophenone, diphenyl ether, diphenyl sulfide, 4,4 '-'-dibromobiphenyls, 1- phenylnaphthalene, diphenyl -1 2,5-,
3,4- oxadiazoles, 2,5- diphenyloxazole, triphenylcarbinol, N, N- diphenylformamide, benzil, anthracene, 4- benzoyl biphenyl,
Dibenzoyl methane, 2- biphenyl carboxylic acids, dibenzothiophenes, pentachlorophenol, 1- benzyl -2-Pyrrolidone, 9-Fluorenone, 2- benzoyl
Naphthalene, 1- bromonaphthalene, bis- phenoxy group benzene of 1,3-, fluorenes, 1- phenyl -2-Pyrrolidone, 1- methoxynaphthalene, 1- ethyoxyl naphthalene, 1,3- hexichol
Benzylacetone, 1,4- dibenzoyl butane, phenanthrene, 4- benzoyl biphenyl, 1,1- diphenyl acetone, neighbour, adjacent '-xenol, 2,6- hexichol
Base phenol, benzophenanthrene, 2- phenylphenol, thianthrene, 3- phenoxy benzenemethanol, 4- phenylphenol, bis- chrloroanthracene of 9,10-, triphenyl first
Alkane, 4,4 '-dimethoxy-benzophenones, 9,10- diphenylanthrancene, fluoranthene, diphenyl phthalate, diphenyl carbonate, 2,6-
Dimethoxy-naphthalene, endipalene, 4- dibromodiphenyl ether, pyrene, 9,9 '-two fluorenes, 4,4 '-isopropylidenes-xenol, ε-are in oneself
Amide, n-cyclohexyl-2-pyrrolidone, diphenyl iso-phthalate, diphenyl phthalate and 1- chloronaphthalene.
The dissolved matter taken out from reaction unit is kneaded after being post-processed, with aforementioned other components fuses and preparation tree
When oil/fat composition, reactivity becomes more preferably, therefore preferably.The method of post-processing as dissolved matter, is not particularly limited, such as
Following methods can be enumerated.
(1) after keeping intact or being added acid or alkali for the dissolved matter, removal solvent is distilled under reduced pressure or under atmospheric pressure, is connect
, the solid matter after distillation removal solvent is used selected from water, solvent used in the dissolved matter is (or for low polymer
Organic solvent with same solubility), acetone, the solvent in methyl ethyl ketone and alcohols etc. clean 1 time or 2 times or more, Jin Erjin
Row is neutralized, washed, filtering and dry method.
(2) it is molten that water, acetone, methyl ethyl ketone, alcohol, ether, halogenated hydrocarbons, aromatic hydrocarbon and aliphatic hydrocarbon etc. are added in the dissolved matter
Agent (dissolve in the solvent of the dissolved matter and be at least the solvent of poor solvent for polyarylene sulfide resin) makes as sedimentation agent
Solid product sedimentation comprising polyarylene sulfide resin and inorganic salts etc., is filtered solid product, cleans and dries
Method.
(3) solvent used in the dissolved matter is added in the dissolved matter (or to be had low polymer same molten
The organic solvent of Xie Du) be stirred after, filter and remove low-molecular weight polymer, then with selected from water, acetone, methyl ethyl ketone and
Solvent cleaning 1 time or 2 times or more in alcohol etc., the method for then being neutralized, washed, filtering and being dried.
It should be noted that polyarylene sulfide resin is done in such post-processing approach illustrated in above-mentioned (1)~(3)
It is dry to carry out in a vacuum, it can also be carried out in air or in the non-active gas atmosphere of nitrogen etc.It can also be in oxygen
Gas concentration makes polyarylene sulfide resin to be heat-treated in the oxidizing atmosphere of the range of 5~30 volume % or under reduced pressure
It carries out oxidation cross-linked.
It is illustrated below to go out to generate the reaction of polyarylene sulfide resin by melt polymerization.
Reaction equation (1)
Reaction equation (2)
Reaction equation (3)
Reaction equation (4)
Reaction equation (5)
2l*→l2
Reaction equation (1)~(5) be using for example with comprising general formula (a), (b) or (c) shown in group substituent R
The example of reaction when diphenyl disulfide is as polymerization inhibitor, generating polyphenylene sulfide.Reaction equation (1) is-S-S- in polymerization inhibitor
Key is issued in melting temperature is born from by the reaction of basic capsule solution.Reaction equation (2) is the Thiyl Radical attack life generated in reaction equation (1)
The adjacent carbon atom of the end iodine atom of main chain in length and be detached from iodine atom, thus make polymerization stop and at the same time in main chain
End import substituent R reaction.Reaction equation (3) is to be originated from raw material (elemental sulfur) in the main chain of polyarylene sulfide resin and exist
Disulfide bond issue and be born from by the reaction of basic capsule solution in melting temperature.Reaction equation (4) be sulphur by generating in reaction equation (3) from
Stop polymerization and at the same time substituent R is imported into master
The reaction of the end of chain.The iodine atom of disengaging is in free state (iodine free radical) or the iodine free radical as reaction equation (5)
It is bonded again each other and generates iodine molecule.
Reaction product comprising the polyarylene sulfide resin as obtained from melt polymerization contains the iodine atom from raw material.Cause
This, polyarylene sulfide resin is used for the preparation etc. of spinning resin combination usually with the state of the mixture containing iodine atom.
The concentration of iodine atom in the mixture is for example relative to the range that polyarylene sulfide resin is 0.01~10000ppm, preferably 10
The range of~5000ppm.Using the sublimability of iodine molecule, iodine atom concentration can also be inhibited in reduced levels, such case
Under, it also can be set to 900ppm range below, preferably 100ppm range below, further preferred 10ppm range below.
In turn, although can also remove iodine atom to detection limit hereinafter, it is contemplated that when productivity it is impracticable.Detection limits
0.01ppm or so.For the polyarylene sulfide resin of present embodiment that is obtained by melt polymerization or comprising its reaction product,
Include iodine atom on this point can with for example using the dichloros such as Phillips method aromatic compound it is molten in polar organic
Poly arylidene thio-ester obtained from solution polymerization process in agent clearly distinguishes.
By above-mentioned reaction equation it is also to be understood that including by the polyarylene sulfide resin that melt polymerization obtains: mainly by fragrant sulphur
The main chain and the defined substituent R being bonded with the end of the main chain that ether unit is constituted, the aromatic sulfide unit include to be originated from two
The aromatic ring of iodine aromatic compound and the sulphur atom being directly bonded.Defined substituent R is bonded directly to main chain end
The aromatic ring at end is bonded on the aromatic ring of the end of main chain via the part-structure for being originated from polymerization inhibitor.
The polyphenylene sulfide of polyarylene sulfide resin as an embodiment, such as with including the following general formula (10)
Shown in repetitive unit (aromatic sulfide unit) main chain.
Repetitive unit shown in formula (10) be more preferably repetitive unit shown in following formula (10a) with para-linkage and
With repetitive unit shown in the following formula (10b) of ortho position bonding.
Wherein, excellent in the heat resistance of resin and crystalline aspect with the repetitive unit of para-linkage shown in formula (10a)
Choosing.
The polyphenylene sulfide of one embodiment may include shown in the following general formula (11), have as with aromatic series
The repetitive unit of the substituent group of the side chain of ring bonding:
(in formula, R20And R21Each independently represent hydrogen atom, the alkyl of carbon atom number 1~4, nitro, amino, phenyl,
Methoxy or ethoxy.).But from the viewpoint of reducing crystallinity and heat resistance, polyphenylene sulfide is preferably substantially not
Repetitive unit containing general formula (11).More specifically, the ratio of the repetitive unit shown in formula (11), relative to formula (10) institute
The summation of repetitive unit shown in the repetitive unit and formula (11) shown, preferably 2 mass % or less, more preferably 0.2 mass %
Below.
The polyarylene sulfide resin of present embodiment is mainly made of above-mentioned aromatic sulfide unit, also includes source usually in main chain
The structural unit of the disulfide bond shown in the elemental sulfur of raw material, following formula (20).
From heat resistance, mechanical strength aspect, for the ratio of structural unit shown in formula (20), relative to fragrant sulphur
The summation of structure position shown in ether unit and formula (20), preferably 2.9 mass % range below, more preferably 1.2 matter
Measure % range below.By making polyarylene sulfide resin include structural unit shown in formula (20), polyarylene sulfide resin is being improved
The aspect of the adaptation of composition and metal is preferred.
The Mw/Mtop of the polyarylene sulfide resin of present embodiment be preferably 0.80~1.70 range, more preferably 0.90
~1.30 range.By making the such range of Mw/Mtop, it can be improved the processability of polyarylene sulfide resin, can assign
Good die cavity balance.In this specification, Mw indicates the weight average molecular weight measured by gel permeation chromatography, and Mtop indicates logical
The detection intensity for crossing the chromatogram that the measurement obtains reaches the average molecular weight (peak molecular weight) of maximum point.Mw/Mtop table
Show the distribution of the molecular weight of measure object, in general, indicating the narrowly distributing of molecular weight when the value is close to 1, as the value becomes larger, indicates
The distribution of molecular weight broadens.It should be noted that the determination condition of gel permeation chromatography is using the embodiment with this specification
Identical determination condition.However, it is possible to change determination condition in the range of not influencing the value of Mw, Mw/Mtop substantially.
As long as the weight average molecular weight of the polyarylene sulfide resin of present embodiment does not damage effect of the invention, without special
Limit, for its lower limit, from mechanical strength aspect, preferably 28000 or more and then more preferably 30000 with
On range.On the other hand, for the upper limit, from the aspect that can be assigned more good die cavity and balance, preferably 100000
Range below, and then more preferably 60000 ranges below, and then most preferably 55000 ranges below.In turn, slave
Tool excellent strength and from the perspective of capable of assigning good die cavity balance, can be poly- with 28000~60000 range
Arylene sulfide resin, more preferable 30000~55000 range polyarylene sulfide resin be used together weight average molecular weight be in be more than
60000 and be 100000 ranges below polyarylene sulfide resin.
The non-newtonian index of polyarylene sulfide resin is preferably 0.95~1.75 range, more preferably 1.0~1.70 model
It encloses.By making the such range of non-newtonian index, it can be improved the processability of polyarylene sulfide resin, good mould can be assigned
Chamber balance.In this specification, non-newtonian index refers under shear velocity and shear stress under conditions of meeting 300 DEG C of temperature
State the index of relational expression.Non-newtonian index can become the molecular weight or straight chain, branch, molecule as crosslinking of measure object
The relevant index of structure, in general, indicating that the molecular structure of resin is straight-chain when the value is close to 1, as the value becomes larger, indicating
Include more branch, cross-linked structure.
D=α × Sn
(in above-mentioned formula, D indicates shear velocity, and S indicates that shear stress, α indicate that constant, n indicate non-newtonian index.)
The polyarylene sulfide resin of Mw/Mtop and non-newtonian index with above-mentioned particular range can for example obtain as follows:
Make diiodo- aromatic compound, elemental sulfur and polymerization inhibitor in the melting containing diiodo- aromatic compound, elemental sulfur and polymerization inhibitor
In the method for reacting (polymerisation in solution) in mixture, make the polyarylene sulfide resin somewhat molecular weight, thus
It arrives.
The fusing point of the polyarylene sulfide resin of present embodiment is preferably 250~300 DEG C of range, is more preferably 265~300
DEG C range.Melt viscosity (V6) at 300 DEG C of polyarylene sulfide resin be preferably 1~2000 [Pas] range, more preferably
For the range of 5~1700 [Pas].Herein, melt viscosity (V6) refers to using flow tester in 300 DEG C of temperature, load
After being kept for 6 minutes under 1.96MPa using the aperture that the ratio between orifice length and orifice diameter (orifice length/orifice diameter) is 10/1
Melt viscosity.
The polyarylene sulfide resin composition of present embodiment can contain one kind or two or more inorganic filler.By matching
Mixed inorganic filler, the composition of available high rigidity, high heat resistance stability.As inorganic filler, for example: charcoal
The plate-like fillers such as the pulverulent fillers such as black, calcium carbonate, silica and titanium oxide, talcum and mica, glass microballoon, silica
Bat wools and the glass squama such as microballon and glass hollow ball equigranular filler, glass fibre, carbon fiber and calcium silica fiber
Piece.Polyarylene sulfide resin composition particularly preferably contains in the group being made of glass fibre, carbon fiber, carbon black and calcium carbonate
At least one kind of inorganic filler.
The content of inorganic filler is relative to 100 mass parts of polyarylene sulfide resin, the preferably range of 1~300 mass parts, more
The preferably range of 5~200 mass parts, the range of further preferably 15~150 mass parts.By making containing for inorganic filler
Amount can obtain superior effect in terms of the mechanical strength holding of formed products in the range.
The polyarylene sulfide resin composition of present embodiment can be containing selected from thermoplastic resin, elastomer and bridging property
Resin, resin in addition to polyarylene sulfide resin.These resins can also be compounded in resin combination together with inorganic filler
In object.
As the thermoplastic resin being compounded in polyarylene sulfide resin composition, for example, polyester, polyamide, polyamides
Imines, polycarbonate, polyphenylene oxide, polysulfones, polyether sulfone, polyether-ether-ketone, polyether-ketone, polyethylene, polypropylene, gathers at polyetherimide
Tetrafluoroethene, polyvinyldifluoride, polystyrene, ABS resin, organic siliconresin and liquid crystal polymer (liquid crystal polyester etc.).
Polyamide is the polymer with amido bond (- NHCO-).As polyamide, for example: (i) by
The polymer and (iii) that polymer that the polycondensation of diamines and dicarboxylic acids obtains, (ii) are obtained by the polycondensation of amino carboxylic acid are by interior acyl
The polymer etc. that the ring-opening polymerisation of amine obtains.Polyamide can be used alone or two or more is applied in combination.
As the example of the diamines for obtaining polyamide, fatty family diamines, aromatic system diamines and rouge can be enumerated
Ring family Diamines.As fatty family diamines, the preferably diamines of straight-chain or the carbon number 3~18 with side chain.As suitable
Fatty family diamines example, 1,3- propane diamine, Putriscine, 1,5- pentanediamine, 1,6- hexamethylene diamine, 1,7- can be enumerated
Heptamethylene diamine, 1,8- octamethylenediamine, 2- methyl-1,8- octamethylenediamine, 1,9-nonamethylene diamine, 1,10- decamethylene diamine, 1,11- hendecane diamines, 1,
12- dodecamethylene diamine, 1,13- tridecane diamine, 1,14- tetradecane diamines, 1,15- pentadecane diamines, 1,16- hexadecane two
Amine, 1,17- heptadecane diamines, 1,18- octadecamethylene diamine, 2,2,4- trimethylhexane diamine and 2,4,4- trimethylhexane diamine.It
Can be used alone or two or more is applied in combination.
As aromatic system diamines, preferably there is the diamines of the carbon number 6~27 of phenylene.As suitable aromatic system two
The example of amine can be enumerated: o-phenylenediamine, m-phenylene diamine (MPD), p-phenylenediamine, m-xylene diamine, p dimethylamine, 3,4- diamino
Diphenyl ether, 4,4 '-diaminodiphenyl ethers, 4,4 '-diaminodiphenyl-methanes, 3,3 '-diaminodiphenylsulfones, 4,4 '-diamino
Diphenyl sulphone (DPS), 4,4 '-diaminodiphenyl sulfides, 4,4 '-two (m-aminophenyl oxygroup) diphenyl sulphone (DPS)s, 4,4 '-two (p-aminophenyl oxygroups)
Bis- (4- aminophenyl) propane of diphenyl sulphone (DPS), benzidine, 3,3 '-diaminobenzophenones, 4,4 '-diaminobenzophenones, 2,2-,
1,5- diaminonaphthalene, 1,8- diaminonaphthalene, 4,4 '-bis- (4- amino-benzene oxygen) biphenyl, bis- [4- (4- amino-benzene oxygen) benzene of 2,2-
Base] hexafluoropropane, bis- (4- amino-benzene oxygen) benzene of 1,4-, bis- (4- amino-benzene oxygen) benzene of 1,3-, bis- (the 3- aminobenzene oxygen of 1,3-
Base) benzene, bis- (3- amino-benzene oxygen) benzene of 1,3-, 4,4 '-diamino -3,3 '-diethyl -5,5 '-dimethyl diphenylmethane, 4,
4 '-diamino -3,3 ', 5,5 '-tetramethyl diphenyl methanes, 2,4 di amino toluene and 2,2 '-dimethylbenzidines.
They can be used alone or two or more is applied in combination.
As alicyclic ring family diamines, preferably there is the diamines of the carbon number 4~15 of cyclohexylidene.As suitable alicyclic ring family
The example of diamines can enumerate-two cyclohexylidene methane of 4,4 '-diamino ,-two cyclohexylidene propane of 4,4 '-diamino, 4,
- two cyclohexylidene methane of 4 '-diamino -3,3 '-dimethyl, 1,4- diaminocyclohexane and piperazine.They can be used alone
Or two or more is applied in combination.
As the dicarboxylic acids for obtaining polyamide, fatty family dicarboxylic acids, aromatic system dicarboxylic acids and rouge can be enumerated
Ring family dicarboxylic acids.
As fatty family dicarboxylic acids, the preferably saturated or unsaturated dicarboxylic acids of carbon atom number 2~18.As suitable
The example of fatty family dicarboxylic acids can be enumerated: oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid,
Azelaic acid, decanedioic acid, heneicosanedioic acid, dodecanedioic acid, tridecandioic acid, tetracosandioic acid, pentacosandioic acid, octadecane two
Acid, maleic acid and fumaric acid.They can be used alone or two or more is applied in combination.
As aromatic system dicarboxylic acids, preferably there is the dicarboxylic acids of the carbon number 8~15 of phenylene.As suitable aromatic series
It is the example of dicarboxylic acids, M-phthalic acid, terephthalic acid (TPA), methylterephthalic acid, 2,2 '-dioctyl phthalate of biphenyl -, biphenyl -4,
4 '-dioctyl phthalate, diphenyl methane -4,4 '-dioctyl phthalate, diphenyl ether -4,4 '-dioctyl phthalate, diphenyl sulphone (DPS) -4,4 '-dioctyl phthalate, 2,6- naphthalene
Dioctyl phthalate, 2,7- naphthalenedicarboxylic acid and 1,4- naphthalenedicarboxylic acid.They can be used alone or two or more is applied in combination.In turn,
It can be the polybasic carboxylic acids such as trimellitic acid, trimesic acid and Pyromellitic Acid can be used in the range of melt-shaping.
As amino carboxylic acid, the preferably amino carboxylic acid of carbon number 4~18.As the example of suitable amino carboxylic acid, Ke Yiju
Out: 4-Aminobutanoicacid, 6-aminocaprolc acid, 7- aminoheptylic acid, 8- aminocaprylic acid, 9 aminononanoic acid, 10- aminocapric acid, 11- amino
Hendecanoic acid, 12 amino dodecanoic acid, 14- amino tetradecanoic acid, 16- aminohexadecanoic acid and 18- amino octadecanoid acid.It
Can be used alone or two or more is applied in combination.
As the lactams for obtaining polyamide, for example, epsilon-caprolactams, omega-lauric lactam, ζ-heptan
Lactams and η-spicy inner formyl amine.They can be used alone or two or more is applied in combination.
The combination of raw material as preferred polyamide can enumerate: epsilon-caprolactams (nylon 6), 1,6- hexamethylene diamine/oneself
Diacid (nylon 6,6), 1,4- butanediamine/adipic acid (nylon 4,6), 1,6- hexamethylene diamine/terephthalic acid (TPA), 1,6- hexamethylene diamine/right
Phthalic acid/epsilon-caprolactams, 1,6- hexamethylene diamine/terephthalic acid (TPA)/adipic acid, 1,9-nonamethylene diamine/terephthalic acid (TPA), 1,9- nonyl
Diamines/terephthalic acid (TPA)/epsilon-caprolactams, 1,9-nonamethylene diamine/1,6- hexamethylene diamine/terephthalic acid (TPA)/adipic acid and isophthalic diformazan
Amine/adipic acid.Wherein, further preferably by Putriscine/adipic acid (nylon 4,6), 1,6- hexamethylene diamine/terephthalic acid (TPA)/
Epsilon-caprolactams, 1,6- hexamethylene diamine/terephthalic acid (TPA)/adipic acid, 1,9-nonamethylene diamine/terephthalic acid (TPA), 1,9-nonamethylene diamine/to benzene
The polyamide that dioctyl phthalate/epsilon-caprolactams or 1,9-nonamethylene diamine/1,6- hexamethylene diamine/terephthalic acid (TPA)/adipic acid obtain.
The content of thermoplastic resin relative to the range that 100 mass parts of polyarylene sulfide resin are preferably 1~300 mass parts,
The more preferably range of 3~100 mass parts, the range of further preferably 5~45 mass parts.By making except polyarylene sulfide resin
The content of thermoplastic resin in addition within the above range, can obtain heat resistance, chemical resistance and mechanical properties into one
Step improves such effect.
As the elastomer being compounded in polyarylene sulfide resin composition, thermoplastic elastomer (TPE) is usually used.As thermoplasticity
Elastomer, for example, polyolefin elastomer, Fuoroelastomer and organic silicon-type elastomer.It should be noted that this
In specification, thermoplastic elastomer (TPE) is classified as elastomer, without being classified as aforementioned thermoplastic resin.
Elastomer (especially thermoplastic elastomer (TPE)) preferably have can with select free hydroxyl, amino, carboxyl and carboxyl
The functional group of at least one of group of salt composition group reaction.Thus, it is possible to obtain cementability and in terms of
It is especially excellent and be able to suppress the gas generated resin combination caused by heating.It, can be with as the functional group
It enumerates: epoxy group, amino, hydroxyl, carboxyl, sulfydryl, isocyanate group, oxazoline group and formula: R (CO) O (CO)-or R (CO) O-
Group shown in (in formula, R indicates the alkyl of carbon atom number 1~8).Thermoplastic elastomer with the functional group such as can be with
It is obtained by the copolymerization of alpha-olefin and the vinyl polymerized compound with aforementioned functional groups.Alpha-olefin for example,
The alpha-olefines of the carbon numbers 2~8 such as ethylene, propylene and 1- butylene.As the vinyl polymerized compound with aforementioned functional groups,
For example: the alpha, beta-unsaturated carboxylic acids such as (methyl) acrylic acid and (methyl) acrylate and its Arrcostab, maleic acid, richness
The α of horse acid, itaconic acid and other carbon numbers 4~10, β-unsaturated dicarboxylic and its derivative (monoesters or diester and its acid anhydrides
Deng) and (methyl) glycidyl acrylate etc..Wherein, from toughness and the raising aspect of impact resistance, preferably have
Have selected from by epoxy group, carboxyl and formula: R (CO) O (CO)-or R (CO) O- (in formula, R indicates the alkyl of carbon atom number 1~8) institute
The ethylene-propylene copolymer and ethylene-butene copolymer of at least one kind of functional group in the group of the group composition shown.
The content of elastomer is different according to its type, purposes, therefore cannot entirely provide, for example, relative to polyarylphosphorus
100 mass parts of ether resin, the preferably range of 1~300 mass parts, more preferably 3~100 mass parts range, further it is excellent
It is selected as the range of 5~45 mass parts.Content by making elastomer within the above range, can obtain ensuring the resistance to of formed products
Hot, toughness the superior effect of aspect.
The crosslinkable resin being compounded in polyarylene sulfide resin composition has 2 or more cross-linking functional groups.As crosslinking
Property functional group, can enumerate epoxy group, phenolic hydroxyl group, amino, amide groups, carboxyl, anhydride group and isocyanate group etc..As friendship
Connection property resin, for example, epoxy resin, phenolic resin and polyurethane resin.
As epoxy resin, preferred fragrance family epoxy resin.Aromatic system epoxy resin can have halogen group or
Hydroxyl etc..It as the example of suitable aromatic system epoxy resin, can enumerate: bisphenol A type epoxy resin, bisphenol F type epoxy
Resin, bisphenol-s epoxy resin, biphenyl type epoxy resin, tetramethyl biphenyl type epoxy resin, phenol novolak-type epoxy tree
Rouge, cresol novolak type epoxy resin, phenol novolak type epoxy resin, bisphenol A novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenyl
Ethane type epoxy resin, Dicyclopentadiene-phenol addition reaction-type epoxy resin, phenol aralkyl type epoxy resin, naphthols phenol
Novolac type epoxy resin, naphthols aralkyl-type epoxy resin, naphthols-phenol cocondensation phenolic resin varnish type epoxy resin, naphthols-first
Phenol cocondensation phenolic resin varnish type epoxy resin, aromatic hydrocarbon formaldehyde resin phenol-formaldehyde resin modified type epoxy resin and biphenyl phenolic aldehyde are clear
Paint shaped epoxy resin.These aromatic system epoxy resin can be used alone or two or more is applied in combination.These aromatic system rings
In oxygen resin, from the aspect excellent in compatibility with other resin components, particularly preferred phenolic resin varnish type epoxy resin, more
It is preferred that cresol novolak type epoxy resin.
The content of crosslinkable resin relative to 100 mass parts of polyarylene sulfide resin, the preferably range of 1~300 mass parts,
The more preferably range of 3~100 mass parts, the further preferably range of 5~30 mass parts.By making containing for crosslinkable resin
Within the above range, the rigidity and heat resistance that can obtain formed products especially significantly improve such effect to amount.
Polyarylene sulfide resin composition can contain silane compound, the silane compound have can with selected from by hydroxyl
The functional group of at least one of the group of salt composition of base, amino, carboxyl and carboxyl group reaction.Polyarylene sulfide resin as a result,
It is improved with the compatibility of other ingredients, furthermore it is possible to obtain being able to suppress gas generated resin combination caused by heating
Object.As the silane compound, for example: γ-glycidoxypropyltrime,hoxysilane, the third oxygen of γ-epoxy
Base propyl-triethoxysilicane, β-(3,4- epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyl two
The silane coupling agents such as Ethoxysilane and γ-epoxy propoxy propyl methyl dimethoxysilane.
The content of silane compound is for example relative to 100 mass parts of polyarylene sulfide resin, preferably 0.01~10 mass parts
Range, the even more preferably range for 0.1~5 mass parts.By making the content of silane compound within the above range, energy
The compatibility for enough obtaining polyarylene sulfide resin and aforementioned other ingredients improves such effect.
The polyarylene sulfide resin composition of present embodiment can contain release agent, colorant, heat-resisting stabilizing agent, ultraviolet light
Other additives such as stabilizer, foaming agent, antirust agent, fire retardant and lubricant.The content of drug is added for example relative to polyarylphosphorus
100 mass parts of ether resin, the preferably range of 1~10 mass parts.
Polyarylene sulfide resin composition can by will utilize polyarylene sulfide resin obtained by the above method with it is aforementioned other
Components fuse be kneaded method, such as the compound by partical in the form of obtain.The temperature of melting mixing is for example preferably 250
~350 DEG C of range is even more preferably 290~330 DEG C of range.Melting mixing can be used double screw extruder etc. into
Row.
The polyarylene sulfide resin composition of present embodiment can lead to individually or with the combinations of materials such as aforementioned other ingredients
It crosses the various melt-processed methods of injection moulding, extrusion molding, compression molding and blow molding etc and is processed into heat resistance, forming
The excellent formed products such as processability, dimensional stability.When the polyarylene sulfide resin composition of present embodiment is due to being heated
It is gas generated few, so the formed products of high-quality can be easily manufactured.
The obtained formed products are suitable for surface mounted electronic parts.Surface mounted electronic parts are for example with polyarylphosphorus
The formed products and metal terminal of ether resin composition are fixed in the cloth through printing as constituent element, by surface mount manner
On line substrate, circuit substrate.In order to make the electronic component be fixed on substrate with surface mount manner, following method can be enumerated:
The metal terminal of the electronic component is placed in substrate surface in a manner of contacting with the conducting parts on substrate by soft solder ball, leads to
It crosses above-mentioned heating method to heat in reflow soldering, thus by the electronic component solder on substrate.Pacify as the surface
Electronic parts can specifically be enumerated: for coping with connector, switch, sensor, the resistor, relay of surface mount manner
Device, capacitor, socket, socket, fuse holder (fuse holder), bobbin, shell of IC or LED etc..
When the polyarylene sulfide resin composition of present embodiment is used for surface mounted electronic parts, it can reduce by heating
Corrosion that is caused gas generated, therefore being able to suppress metal terminal etc..In addition, poly arylidene thio-ester tree according to the present embodiment
Oil/fat composition, such as in the case where being configured to the formed products with snap-fit, also show excellent mechanical strength.
Embodiment
The present invention is further elaborated with hereinafter, enumerating embodiment.But the present invention is not limited to these implementations
Example.
1. evaluation assessment
[flexural property]
Standard test method ... ASTMD-790
Test film ... 3.2mm (thickness) × 12.7mm (width) × 127mm (length)
The average value of test result ... test number n=10
[hot water resistance]
Test film is immersed in 95 DEG C of hot water, investigates the ongoing change of bending strength.
Test film ... 3.2mm (thickness) × 12.7mm (width) × 127mm (length)
Test method ... the ASTM D-790 of bending strength
Conservation rate of the bending strength relative to initial strength after assessment item ... 1000 hours, 3000 hours
The average value of test result ... test number n=5
[metal dhering strength]
The polyarylene sulfide resin with size quantity is injected on the sheet metal (SUS304) for 4 × 10 × 49mm for being placed in mold
Composition, and make its forming, which is implemented to stretch examination under conditions of 20mm, tensile speed 1mm/ minutes chuck
It tests, measures metal dhering strength.
[die cavity balance]
Using the gasket mould with 40 die cavitys, the die cavity (C1) in the position near a sprue gate has been understood
With minimum molding condition by PPS compound injection moulding under conditions of full packing.Molding condition is 75 tons of forming machines, barrel temperature
Degree 320 DEG C, 140 DEG C of mold temperature, without pressure maintaining.
By the filling of die cavity after molding (C1) and the die cavity (C10) farthest away from a sprue gate in identical runner
Degree is compared.Compactedness (quality %) is asked by the formed products of die cavity (C10) relative to the mass ratio of the formed products of die cavity (C1)
Out.It may be said that the compactedness of die cavity (C10) is higher, die cavity balance is more excellent.According to compactedness, determined using benchmark below each
The die cavity of composition balances.
The range of the mass of AA:100~90 %
The range of the mass of A:89~80 %
The range of the mass of B:79~70 %
The range of the mass of C:69~60 %
D:59% mass range below
[gas generated]
Using gas chromatography-mass spectrum device, by the sample of polyarylene sulfide resin or the specified amount of resin combination at 325 DEG C
Lower heating 15 minutes, at this time gas generated is quantified in the form of quality %.
[reflux-resisting welded heating property]
The pellet of resin combination is shaped using injection machine, production shape be long 70mm × wide 10mm × high 8mm,
The box-shaped connector of 0.8mm thickness.Then, which is positioned on printed base plate, is added under the conditions of following Reflow Solderings
Heat.Box-shaped connector is visually observed after the heating, and the benchmark of following 2 grades is utilized to carry out ocular estimate.
〇: appearance does not change.
×: observe blistering or fusing.
(Reflow Soldering condition)
Reflow Soldering heating utilizes infrared ray the reflow soldering apparatus (" TPF- of Asahi Engineering Co., Ltd. manufacture
2 ") it carries out.As heating condition at this time, preheats 100 seconds, then heated maintained until matrix at 180 DEG C respectively
Surface reaches 280 DEG C.That is, to reach 100 seconds in 200 DEG C or more of range, 90 seconds are reached in 220 DEG C or more of range,
Reach in 240 DEG C or more of range 80 seconds, reach in 260 DEG C or more of range 60 seconds modes, utilizes reflow soldering apparatus
Temperature Distribution (temperature curve) is set, heating holding is carried out.
2. the synthesis of polyphenylene sulfide (PPS resin)
(synthesis of synthesis example 1:PPS-1)
By paradiiodobenzene (Tokyo is melted into Co., Ltd., 98.0% or more paradiiodobenzene purity) 300.0g, the solid sulfur (Northeast
Chemical Co., Ltd. manufacture, sulphur (powder)) 27.00g, 4,4 '-two thiobis benzoic acid (Wako Pure Chemical Industries, Ltd.'s systems
Making, 4,4 '-two thiobis benzoic acid, Technical Grade) 2.0g heats at 180 DEG C, they are dissolved under a nitrogen,
Mixing.Then, 220 DEG C are warming up to, absolute pressure 26.6kPa is decompressed to.For obtained molten mixture, at 320 DEG C
The mode that absolute pressure reaches 133Pa periodically changes temperature and pressure, carries out 8 hours melt polymerizations.After reaction, add
Enter NMP200g, the heating stirring at 220 DEG C is filtered gained dissolved matter.It is added in dissolved matter after filtration
NMP320g carries out filter cake cleaning filtering.Ion exchange water 1L is added in the obtained filter cake containing NMP, in autoclave,
It is stirred 10 minutes in 200 DEG C.Then, filter cake is filtered, 70 DEG C of ion exchange water 1L is added in filter cake after filtration, is filtered
Cake cleaning.Ion exchange water 1L is added in the aqueous filter cake of gained, stirs 10 minutes.Then, filter cake, filter after filtration are filtered
70 DEG C of ion exchange water 1L is added in cake, carries out filter cake cleaning.After repeating the operation again, filter cake is done at 120 DEG C
Dry 4 hours, obtain PPS resin (PPS-1) 91g.
(synthesis of synthesis example 2:PPS-2)
" 2- Iodoaniline (Tokyo be melted into Co., Ltd. manufacture) " replacements " 4,4 '-two thiobis benzoic acid " is used, removes this it
Outside, it is operated in the same way with synthesis example 1, obtains PPS resin (PPS-2) 91g.
(synthesis of synthesis example 3:PPS-3)
" diphenyl disulfide (Sumitomo Seika Co., Ltd, DPDS) " replacement " 4,4 '-two thiobis benzoic acid " is used, this is removed
Except, it is operated in the same way with synthesis example 1, obtains PPS resin (PPS-3) 91g.
(synthesis of synthesis example 4:PPS-4)
N-Methyl pyrrolidone 600g and five hydrated sodium sulfide 336.3g (2.0mol) is put into the autoclave of 2L, in nitrogen
200 DEG C are warming up under gas atmosphere, thus water removal-NMP mixture is removed in distillation.Then, it adds into the system by o-dichlorobenzene
292.53g (1.99mol) and 2,5- dichloroaniline 1.62g (0.01mol) is dissolved in solution obtained in NMP230g, in nitrogen
It under atmosphere, reacts 5 hours in 220 DEG C, and then is reacted 2 hours in 240 DEG C.From content, sampling after reaction vessel taking-up cooling
A part, with gas chromatograph to unreacted 2,5- dichloroaniline is quantified.In addition, remaining slurry is cleaned with hot water several
It is secondary, leaching polymer cake.The filter cake is dried under reduced pressure at 80 DEG C, obtains the polyphenylene sulfide containing amino (PPS-4) of powder.
The character of PPS-1~PPS-4 obtained in synthesis example 1~4 is shown in table 1.
[table 1]
3. polyphenyl thioether resin composition (PPS compound)
[raw material]
In order to prepare PPS resin composition, prepare following material.
(thermoplastic resin)
PA6T: necessary to be used as 10 moles of 65 moles of % of terephthalic acid (TPA), 25 moles of % of M-phthalic acid, adipic acid %
Aromatic polyamide obtained from monomer component is reacted (310 DEG C, Tg120 DEG C of fusing point)
PA9T: polyamide obtained from reacting nonamethylene diamine and terephthalic acid (TPA) (KURARAY CO., LTD manufacture,
“Genestar N1000A”)
PA46: polyamide 46 (DSM Japan Engineering Plastics KK manufacture, " Stanyl TS300 ")
(inorganic filler)
GF: fiberglas chopped strand (10 μm of fibre diameter, length 3mm)
[production and evaluation of compound]
Machine is mixed according to formula composition shown in table 1, using bucket uniformly to mix each raw material, is then squeezed using twin-screw mixer
Machine (TEM-35B, toshiba machine) carries out melting mixing at 300 DEG C out, obtains granular compound.The compound that will be obtained
Carry out injection moulding under conditions of 300 DEG C of barrel temperature, 140 DEG C of mold temperature, production flexural property, metal dhering strength,
Test film used in die cavity balance and hot water resistance test, carries out various evaluations.In addition, for individual PPS resin and again
It is gas generated to close object measurement.Show the results of the evaluation table 2.
[table 2]
As shown in Table 2 the result shows that, PPS-1, PPS-2 and PPS-3 are compared with PPS-4, and in mechanical property, (bending is strong
Degree, bend fracture elongation), metal dhering strength, die cavity balance, hot water resistance, gas generated aspect it is excellent.
Claims (11)
1. a kind of surface mounted electronic parts have surface mounted electronic parts formed products and metal terminal, the surface
Installing electronic component-use formed products is the polyarylene sulfide resin composition obtained from shaping polyarylene sulfide resin composition
Contain:
Polyarylene sulfide resin；With
Selected from by inorganic filler, the thermoplastic resin in addition to the polyarylene sulfide resin, elastomer and have 2 to submit
At least one kind of other ingredients in the group of the crosslinkable resin composition of Lian Xing functional group,
It includes making diiodo- aromatic compound, elemental sulfur and polymerization inhibitor comprising the diiodo- virtue that the polyarylene sulfide resin, which utilizes,
The method reacted in the molten mixture of fragrant compounds of group, the elemental sulfur and the polymerization inhibitor obtains,
The polyarylene sulfide resin has disulfide bond shown in the following general formula (20) in main chain:
The polyarylene sulfide resin has in the group for selecting the salt of free carboxyl group and carboxyl to form from the polymerization inhibitor at least
A kind of group.
2. surface mounted electronic parts according to claim 1, wherein the polyarylene sulfide resin is with poly- relative to this
Arylene sulfide resin is that the ratio of the range of 0.01~10000ppm includes the mixture of iodine atom.
3. surface mounted electronic parts according to claim 2, wherein have two shown in the following general formula (20) in main chain
It imports univalent perssad shown in following formula (6) or (7) to the polyarylene sulfide resin of sulfide linkage in the end group of main chain,
In formula, R5And R6Respectively indicate general formula (a), (b) or (c) shown in univalent perssad,
Wherein, the X in general formula (a)~(c) is hydrogen atom or alkali metal atom, in general formula (b), R10Indicate carbon atom number 1~6
Alkylidene, in general formula (c), R11Indicate the alkylidene of hydrogen atom or carbon atom number 1~3, R12Indicate the alkane of carbon atom number 1~5
Base.
4. surface mounted electronic parts according to claim 1, wherein the polyarylene sulfide resin has 0.80~1.70
Mw/Mtop,
The Mw and Mtop is the weight average molecular weight and peak molecular weight using gel permeation chromatography measurement respectively.
5. surface mounted electronic parts according to claim 1, wherein the polyarylene sulfide resin has at 300 DEG C
0.95~1.75 non-newtonian index and 0.80~1.70 Mw/Mtop,
The Mw and Mtop is the weight average molecular weight and peak molecular weight using gel permeation chromatography measurement respectively.
6. surface mounted electronic parts according to claim 1, wherein at least one kind of other ingredients are polyamide resin
Rouge.
7. a kind of manufacturing method of surface mounted electronic parts is the manufacturing method of following surface mounted electronic parts: electricity
The metal terminal of subassembly is placed in substrate surface in a manner of contacting with the conducting parts on substrate by soft solder ball, is flowing back
Heating in furnace, thus by the electronic component solder on substrate,
The surface mounted electronic parts, which have, obtains the forming of surface mounted electronic parts polyarylene sulfide resin composition
Surface mounted electronic parts formed products and metal terminal,
The surface mounted electronic parts polyarylene sulfide resin composition contains: polyarylene sulfide resin；It is filled out with being selected from by inorganic
Fill agent, the thermoplastic resin in addition to the polyarylene sulfide resin, elastomer and the crosslinking with 2 or more cross-linking functional groups
Property resin composition group at least one kind of other ingredients,
It includes making diiodo- aromatic compound, elemental sulfur and polymerization inhibitor comprising the diiodo- virtue that the polyarylene sulfide resin, which utilizes,
The method reacted in the molten mixture of fragrant compounds of group, the elemental sulfur and the polymerization inhibitor obtains,
The polyarylene sulfide resin has disulfide bond shown in the following general formula (20) in main chain:
The polyarylene sulfide resin has in the group for selecting the salt of free carboxyl group and carboxyl to form from the polymerization inhibitor at least
A kind of group.
8. the manufacturing method of surface mounted electronic parts according to claim 7, wherein the polyarylene sulfide resin be with
Ratio relative to the range that the polyarylene sulfide resin is 0.01~10000ppm includes the mixture of iodine atom.
9. the manufacturing method of surface mounted electronic parts according to claim 7, wherein have the following general formula in main chain
(20) polyarylene sulfide resin of disulfide bond shown in imports monovalence shown in following formula (6) or (7) in the end group of main chain
Group,
In formula, R5And R6Respectively indicate general formula (a), (b) or (c) shown in univalent perssad,
Wherein, the X in general formula (a)~(c) is hydrogen atom or alkali metal atom, in general formula (b), R10Indicate carbon atom number 1~6
Alkylidene, in general formula (c), R11Indicate the alkylidene of hydrogen atom or carbon atom number 1~3, R12Indicate the alkane of carbon atom number 1~5
Base.
10. the manufacturing method of surface mounted electronic parts according to claim 7, wherein at least one kind of other ingredients
For polyamide.
11. a kind of polyarylene sulfide resin composition of surface mounted electronic parts, wherein the polyarylene sulfide resin composition
For the polyarylene sulfide resin composition in claim 1.
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| PCT/JP2014/072640 WO2015045724A1 (en) | 2013-09-26 | 2014-08-28 | Polyarylene sulfide resin composition and molded product thereof, and surface-mount electronic component |
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| CN108473766A (en) * | 2015-11-23 | 2018-08-31 | Sk化学株式会社 | Poly (arylene sulfide) resin composition and molded articles |
| KR20170059897A (en) * | 2015-11-23 | 2017-05-31 | 에스케이케미칼주식회사 | Polyarylene sulfide and preparation method thereof |
| WO2017161537A1 (en) * | 2016-03-24 | 2017-09-28 | Ticona Llc | Polyarylene sulfide composition with improved adhesion to metal components |
| CN110225821B (en) * | 2017-01-27 | 2021-06-25 | Dic株式会社 | Metal/resin composite structure and method for producing same |
| KR101887654B1 (en) * | 2017-04-28 | 2018-08-10 | 한국화학연구원 | Preparation method of polyphenylene sulfide copolymer and copolymer prepared using the same |
| WO2019151184A1 (en) * | 2018-01-31 | 2019-08-08 | 住友化学株式会社 | Resin composition |
| EP3778219A4 (en) * | 2018-04-10 | 2021-12-29 | DIC Corporation | Composite structure and manufacturing method therefor |
| JP7156872B2 (en) * | 2018-09-07 | 2022-10-19 | 帝人株式会社 | resin composition |
| TW202035569A (en) * | 2019-02-19 | 2020-10-01 | 日商Ｄｉｃ股份有限公司 | Film and layered body |
| KR20210100814A (en) * | 2020-02-07 | 2021-08-18 | 에스케이케미칼 주식회사 | Polymerization inhibitor for a polyarylene sulfide resin |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0424447A1 (en) * | 1988-07-15 | 1991-05-02 | Eastman Kodak Company | Terminated copoly(arylene sulfide) |
| JPH06172489A (en) * | 1992-12-08 | 1994-06-21 | Mitsubishi Petrochem Co Ltd | Thermoplastic resin composition |
| CN1703445A (en) * | 2002-10-04 | 2005-11-30 | 出光兴产株式会社 | Process for producing polyarylene sulfide |
| CN1856545A (en) * | 2003-08-18 | 2006-11-01 | 切夫里昂菲利普化学有限责任公司 | Polyphenylene sulfide composition and application |
| CN101194048A (en) * | 2005-04-12 | 2008-06-04 | 通用电气公司 | Electrochemical cell structure |
| JP2008247955A (en) * | 2007-03-29 | 2008-10-16 | Dic Corp | Polyarylene sulfide resin composition |
| WO2009096400A1 (en) * | 2008-01-30 | 2009-08-06 | Dic Corporation | Poly(arylene sulfide) resin composition, process for production thereof, and surface mount electronic component |
| CN101578322A (en) * | 2007-01-05 | 2009-11-11 | Sk化学株式会社 | Method for production of polyarylene sulfide resin with excellent luminosity and the polyarylene sulfide resin |
| CN102791773A (en) * | 2010-03-09 | 2012-11-21 | Sk化学株式会社 | Reusable polyarylene sulfide and method for preparing same |
| CN102822240A (en) * | 2010-03-10 | 2012-12-12 | Sk化学株式会社 | Polyarylene sulfide having reduced outgassing and preparation method thereof |
| CN104364316A (en) * | 2012-06-11 | 2015-02-18 | Sk化学株式会社 | Polyarylene sulfide resin composition and method for preparing same |
| CN104520352A (en) * | 2012-08-07 | 2015-04-15 | Sk化学株式会社 | Polyarylene sulfide resin and method for preparing same |
| CN105492538A (en) * | 2013-08-30 | 2016-04-13 | Dic株式会社 | Resin composition for water-related component, and pipeline for fluid |
| CN105493310A (en) * | 2013-08-30 | 2016-04-13 | Dic株式会社 | Resin composition for gasket, production method therefor, and gasket for secondary battery |
| CN105517797A (en) * | 2013-08-30 | 2016-04-20 | Dic株式会社 | Multilayer moulded body, and component for fuel using same |
Family Cites Families (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6172489A (en) * | 1984-09-17 | 1986-04-14 | Mitsubishi Electric Corp | Picture area detecting device |
| US4792600A (en) * | 1987-11-09 | 1988-12-20 | Eastman Kodak Company | Process for the preparation of copoly(arylene sulfide) with aromatic nitro compound catalyst |
| JP3339027B2 (en) * | 1993-04-05 | 2002-10-28 | 出光石油化学株式会社 | Polyarylene sulfide resin composition, protection / supporting member for integrated module of electric / electronic component, and protection / supporting member for electric / electronic component corresponding to SMT |
| JP5428335B2 (en) * | 2006-05-10 | 2014-02-26 | 東レ株式会社 | Biaxially oriented polyarylene sulfide film |
| KR101183780B1 (en) * | 2006-08-24 | 2012-09-17 | 에스케이케미칼주식회사 | Manufacturing process for Polyarylene sulfide |
| JP2008231140A (en) * | 2007-03-16 | 2008-10-02 | Toray Ind Inc | Polyphenylene sulfide resin composition for sealing electronic component, and method for producing tablet for sealing electronic component and molded article |
| JP5024071B2 (en) * | 2008-01-18 | 2012-09-12 | テクノポリマー株式会社 | Heat dissipation resin composition |
| JP5257778B2 (en) * | 2008-01-31 | 2013-08-07 | Ｄｉｃ株式会社 | Polyarylene sulfide resin composition, method for producing the same, and electronic component for surface mounting |
| TWI428394B (en) | 2008-01-31 | 2014-03-01 | Dainippon Ink & Chemicals | Polyarylene sulfide resin composition, manufacturing method thereof and surface-mount electronic element |
| JP2009263635A (en) * | 2008-04-03 | 2009-11-12 | Dic Corp | Thermoplastic resin composition, process for producing the same, and electronic component for surface mounting |
| US8263734B2 (en) * | 2009-02-13 | 2012-09-11 | Chevron Phillips Chemical Company Lp | System and method for reducing off-gassing of polyphenylene sulfide |
| WO2011111982A2 (en) * | 2010-03-10 | 2011-09-15 | 에스케이케미칼주식회사 | Polyarylene sulfide, and preparation method thereof |
| CN102939340B (en) * | 2010-04-23 | 2014-10-08 | 宝理塑料株式会社 | Polyarylene sulfide resin composition |
| KR101750014B1 (en) * | 2010-05-12 | 2017-06-23 | 에스케이케미칼 주식회사 | Polyarylene sulfide having excellent formability and preparation method threrof |
| KR20160042939A (en) * | 2013-08-09 | 2016-04-20 | 디아이씨 가부시끼가이샤 | Polyarylene sulfide resin composition and molded article of same |
| JP6655392B2 (en) * | 2013-08-09 | 2020-02-26 | Dic株式会社 | Polyarylene sulfide resin composition and molded article thereof |
| JP6287450B2 (en) | 2014-03-26 | 2018-03-07 | 富士通株式会社 | Portable information processing apparatus and program |
| JP6970698B2 (en) * | 2017-08-10 | 2021-11-24 | 水ｉｎｇ株式会社 | Disinfection method for ammonia-containing nitrogen-containing wastewater |
-
2014
- 2014-08-28 KR KR1020167007980A patent/KR102570299B1/en active IP Right Grant
- 2014-08-28 CN CN201910508931.5A patent/CN110283457B/en active Active
- 2014-08-28 CN CN201480053300.4A patent/CN105579529A/en active Pending
- 2014-08-28 WO PCT/JP2014/072640 patent/WO2015045724A1/en active Application Filing
- 2014-08-28 JP JP2015539034A patent/JP6718232B2/en active Active
-
2019
- 2019-04-05 JP JP2019072718A patent/JP7257855B2/en active Active
-
2021
- 2021-04-01 JP JP2021062730A patent/JP7375787B2/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0424447A1 (en) * | 1988-07-15 | 1991-05-02 | Eastman Kodak Company | Terminated copoly(arylene sulfide) |
| JPH06172489A (en) * | 1992-12-08 | 1994-06-21 | Mitsubishi Petrochem Co Ltd | Thermoplastic resin composition |
| CN1703445A (en) * | 2002-10-04 | 2005-11-30 | 出光兴产株式会社 | Process for producing polyarylene sulfide |
| CN1856545A (en) * | 2003-08-18 | 2006-11-01 | 切夫里昂菲利普化学有限责任公司 | Polyphenylene sulfide composition and application |
| CN101194048A (en) * | 2005-04-12 | 2008-06-04 | 通用电气公司 | Electrochemical cell structure |
| CN101578322A (en) * | 2007-01-05 | 2009-11-11 | Sk化学株式会社 | Method for production of polyarylene sulfide resin with excellent luminosity and the polyarylene sulfide resin |
| JP2008247955A (en) * | 2007-03-29 | 2008-10-16 | Dic Corp | Polyarylene sulfide resin composition |
| WO2009096400A1 (en) * | 2008-01-30 | 2009-08-06 | Dic Corporation | Poly(arylene sulfide) resin composition, process for production thereof, and surface mount electronic component |
| CN102791773A (en) * | 2010-03-09 | 2012-11-21 | Sk化学株式会社 | Reusable polyarylene sulfide and method for preparing same |
| CN102822240A (en) * | 2010-03-10 | 2012-12-12 | Sk化学株式会社 | Polyarylene sulfide having reduced outgassing and preparation method thereof |
| CN104364316A (en) * | 2012-06-11 | 2015-02-18 | Sk化学株式会社 | Polyarylene sulfide resin composition and method for preparing same |
| CN104520352A (en) * | 2012-08-07 | 2015-04-15 | Sk化学株式会社 | Polyarylene sulfide resin and method for preparing same |
| CN105492538A (en) * | 2013-08-30 | 2016-04-13 | Dic株式会社 | Resin composition for water-related component, and pipeline for fluid |
| CN105493310A (en) * | 2013-08-30 | 2016-04-13 | Dic株式会社 | Resin composition for gasket, production method therefor, and gasket for secondary battery |
| CN105517797A (en) * | 2013-08-30 | 2016-04-20 | Dic株式会社 | Multilayer moulded body, and component for fuel using same |
Non-Patent Citations (3)
| Title |
|---|
| 石安富等: "《工程塑料-性能﹒成型﹒应用》", 30 September 1986, 上海科学技术出版社, pages: 482 - 486 * |
| 许健南: "《塑料材料》", 31 January 1999, 中国轻工业出版社, pages: 293 - 296 * |
| 黄锐等: "《塑料工程手册.上册》", 30 April 2000, 机械工业出版社, pages: 579 - 582 * |
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| Publication number | Publication date |
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| JP2019137868A (en) | 2019-08-22 |
| KR102570299B1 (en) | 2023-08-24 |
| KR20160065835A (en) | 2016-06-09 |
| JP6718232B2 (en) | 2020-07-08 |
| CN110283457B (en) | 2023-03-31 |
| JP7257855B2 (en) | 2023-04-14 |
| JPWO2015045724A1 (en) | 2017-03-09 |
| WO2015045724A1 (en) | 2015-04-02 |
| JP2021113319A (en) | 2021-08-05 |
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| JP7375787B2 (en) | 2023-11-08 |
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