CN107849340A - Anti-static resin composition - Google Patents
Anti-static resin composition Download PDFInfo
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- CN107849340A CN107849340A CN201680044661.1A CN201680044661A CN107849340A CN 107849340 A CN107849340 A CN 107849340A CN 201680044661 A CN201680044661 A CN 201680044661A CN 107849340 A CN107849340 A CN 107849340A
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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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6886—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The problem of the present invention is that providing antistatic behaviour is particularly anlistatig continuation, heat resistance and anti-static resin composition transparent excellent and that diverging gas problem is not present.The anti-static resin composition includes the polyester resin (A) with following characteristics (a1) and (a2) of 100 mass parts and the polyetherester resins (B) with the construction unit for deriving from the aromatic polycarboxylic acid substituted by sulphonate-base of 7~25 mass parts.(a1) using from the summation of the construction unit of polybasic carboxylic acid as 100 moles of %, then comprising 90~100 moles of % from the construction unit of terephthalic acid (TPA) and 0~10 mole of % construction unit from M-phthalic acid.(a2) as 100 moles of %, then 2 are derived from from the construction unit of Isosorbide-5-Nitrae cyclohexanedimethanol and 10~50 moles of % comprising 50~90 moles of % using from the summation of the construction unit of polyalcohol, 2, the construction unit of the cyclobutanediol of 4,4 tetramethyl 1,3.
Description
Technical field
The present invention relates to anti-static resin composition.More particularly, it is related to the polyester resin group with antistatic behaviour
Compound.
Background technology
Precision electronic components such as semiconductor wafer, semiconductor element and integrated circuit sometimes due to it is micro it is powered just
Function can be caused to damage (described electrostatic breakdown.), it is therefore desirable to pallet, packaging material, storage keeping for carrying them
The volumetric resistivity value of material used in instrument and external packing component etc. is 109~1010Ω·cm.Furthermore, it desired to above-mentioned bag
Package material has the transparency (haze value is less than 50%) that can at least confirm degree existing for inclusion by visual observation, preferably
With the transparency that can carry out the degree such as product inspection, the identification mark for confirming apposition in inclusion by visual observation, (haze value is
Less than 15%).Also, require the heat resistance for tackling following situations：When manufacturing precision electronic components, the production such as drying process
Raw heat；In the article of manufacture assembling precision electronic components, heat caused by drying process；(the assembling of precise electronic machine
The article of precision electronic components) for example, the transport of the truck mounted machine of sound machine, information communication machine etc., keeping, Yi Jishi
Environment temperature when border uses；And heat caused by above-mentioned machine run, it is therefore desirable to which at least 80 DEG C of temperature is heat-resisting
Property.
Because thermoplastic resin has many excellent characteristics, therefore, it is proposed to much be used for the volume of thermoplastic resin
Resistance value is arranged to 109~1010Ω cm technology, and practical application, to cause generally regardless of whether for electric insulating quality
Higher material, the related field of precision electronic components can be applied to.
As above-mentioned technology, such as propose thermoplastic resin and alkylsulfonate, alkylbenzenesulfonate plasma surface
The resin combination (for example, patent document 1 and 2) of the surfactant of activating agent particularly alkyl (aryl) Sulfonates.
But this technology is to reduce resistance value by making the surfactant of low molecule amount be oozed out from the surface of products formed, therefore,
In the presence of wipe, washing surface surfactant and cause antistatic behaviour reduce (resistance value risings) the problem of and produce dissipate
The problem of gas.
As above-mentioned technology, such as, it is proposed that comprising the thermoplastic resin with antistatic behaviour (for example, polyether ester amides
(patent document 3), Main chain copolymers are made up of polyamide, branch polymer is gathered by the block of polyalkylene ether and thermoplastic polyester
Graft polymers (patent document 4) that compound is formed, specific polyamidoimide elastomer (patent document 5) and specific
Polyethylene glycol, specific unimpeded diisocyanate and specific aliphatic chain extender ethylene glycol reaction product (specially
Sharp document 6) etc.) resin combination.But in these techniques, in order to obtain sufficient antistatic behaviour, it is sometimes desirable to a large amount of
Coordinate the thermoplastic resin with antistatic behaviour.In addition, its heat resistance, the transparency can not be met.In addition, these have it is antistatic
Property thermoplastic resin have and promote polyester resin deterioration, the property of low molecule quantization, polyester resin has anti-with these
It is bad the shaping such as being easy to burr, shrink mark occur in ejection formed piece to be present in the resin combination of the thermoplastic resin of static behaviour
The problem of.
In addition, as the thermoplastic resin with above-mentioned antistatic behaviour, it is proposed that using polyether ester (for example, by specific point
Polybasic carboxylic acid of poly- (oxyalkylene) glycol of son amount, the glycol of carbon number 2~8 and carbon number 4~20 etc. is condensed to yield
Polyether ester (patent document 7), by poly- (oxyalkylene) glycol of aromatic dicarboxylic acid of carbon number 4~20 etc., specified molecular weight with
And the glycol polycondensation of carbon number 4~10 obtain polyether ester (patent document 8), will be substituted containing specified quantitative by specific sulphonate-base
The aromatic dicarboxylic acid of carbon number 6~20 of aromatic dicarboxylic acid, specified molecular weight poly- (oxyalkylene) glycol and carbon number 2~
The polyether ester (patent document 9) that 10 glycol polycondensation obtains, and aromatic dicarboxylic acid by carbon number 4~20 etc., specific molecular
Polyether ester (patent document 10) that the glycol polycondensation of poly- (oxyalkylene) glycol and carbon number 4~10 of amount obtains etc.).It is but poly-
The single antistatic behaviour of ether-ether is insufficient.
Therefore, it is proposed to ionic surface active agent (for example, 0031 section of patent document 7, patent document 11) is used simultaneously
Scheme, still, in these techniques in the presence of washing, wipe cause antistatic behaviour reduce and produce diverging gas the problem of.
Therefore, proposed in patent document 12 using from molten condition to the polyesters of at least 5 minutes half an hour of crystallization
The scheme of resin based on resin.But base resin causes heat resistance not high due to this characteristic.
Not yet propose antistatic behaviour be particularly anlistatig continuation, heat resistance and the transparency it is excellent and in the absence of hair
Dissipate the anti-static resin composition of gas problem.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 5-222241 publications
Patent document 2：Japanese Unexamined Patent Application 62-230835 publications
Patent document 3：Japanese Unexamined Patent Application 62-273252 publications
Patent document 4：Japanese Unexamined Patent Publication 5-97984 publications
Patent document 5：Japanese Unexamined Patent Publication 3-255161 publications
Patent document 6：Japanese Unexamined Patent Publication 5-222289 publications
Patent document 7：Japanese Unexamined Patent Publication 6-57153 publications
Patent document 8：Japanese Unexamined Patent Publication 8-283548 publications
Patent document 9：Japanese Unexamined Patent Publication 10-219095 publications
Patent document 10：Japanese Unexamined Patent Publication 2006-022232 publications
Patent document 11：Japanese Unexamined Patent Publication 8-283548 publications
Patent document 12：Japanese Unexamined Patent Publication 2009-001618 publications
The content of the invention
The present invention problem be to provide antistatic behaviour be particularly anlistatig continuation, heat resistance and the transparency it is excellent and
In the absence of the anti-static resin composition of diverging gas problem.Another problem of the present invention is to provide following antistatic resin groups
Compound：Specific insulation is 109~1010Ω cm, above-mentioned antistatic behaviour can also be kept even if being washed, being wiped, it is heat-resisting
Property, the transparency and mouldability it is excellent, and in the absence of diverging gas problem.
The present inventor passes through the tree of specific polyester resin and specific polyether ester by conscientiously studying discovery
Oil/fat composition can realize above-mentioned problem.
That is, anti-static resin composition of the invention includes：
100 mass parts have following characteristics (a1) and the polyester resin (A) of (a2)；And
The polyether ester of the construction unit with the aromatic polycarboxylic acid from sulphonate-base substitution of 7~25 mass parts
Resin (B),
(a1) using from the summation of the construction unit of polybasic carboxylic acid as 100 moles of %, then comprising 90~100 moles of %
From the construction unit of terephthalic acid (TPA) and 0~10 mole of % construction unit from M-phthalic acid,
(a2) using from the summation of the construction unit of polyalcohol as 100 moles of %, then comprising 50~90 moles of %
2,2,4,4- tetramethyl -1,3- rings are derived from from the construction unit of 1,4 cyclohexane dimethanol and 10~50 moles of %
The construction unit of butanediol.
Second invention is that the composition (B) is polyetherester resins according to the first invention described anti-static resin composition,
Comprising：
From from terephthalic acid (TPA), 2,6 naphthalene dicarboxylic acid, 2,7- naphthalene dicarboxylic acids, biphenyl -4,4'- dicarboxylic acids and they
Formation ester the group that is formed of derivative in the construction unit of more than one aromatic dicarboxylic acid (b1) that selects；
From following chemical formula (1) represent by sulphonate-base substitution aromatic polycarboxylic acid and/or its form ester
Derivative (b2) construction unit；
From the construction unit of the PAG (b3) of number-average molecular weight 200~50000；And
From the construction unit of the glycol (b4) of carbon number 2~10,
Wherein, the content of the construction unit of the composition (b1) and the structure list from the composition (b2) will be derived from
Member content and be used as 100 moles of %, then the construction unit from the composition (b1) comprising 70~98 moles of % with
And 2~30 moles of % construction unit from the composition (b2),
Content from the construction unit of the composition (b1), the construction unit from the composition (b2) are contained
Amount, the content of construction unit and the content of construction unit from the composition (b4) from the composition (b3)
With as 100 mass %, then the content from the construction unit of the composition (b3) is 10~60 mass %.
Chemical formula 1
In chemical formula 1,
Ar represents the group of the aromatic ring structure with least three hydrogen atoms of substitution；
R1 and R2 represents the aryl of hydrogen atom, the alkyl of carbon number 1~6 or carbon number 6~12 independently of one another；
M+Represent metal ion, Si Wan Ji Phosphonium ions or tetraalkyl ammonium ion.
3rd invention is according to the described anti-static resin composition of the first invention or the second invention, relative to 100 mass parts
The composition (A), the ionic surface active agent (C) also containing 0.5~5 mass parts.
Anti-static resin composition of 4th invention according to any one of the first~the 3rd invention, specific insulation are
109~1010Ω·cm。
5th invention is to include the article of the anti-static resin composition any one of the first~the 4th invention.
6th invention is to include the precise electronic of the anti-static resin composition any one of the first~the 4th invention
Machine.
As the present invention anti-static resin composition, antistatic behaviour be particularly anlistatig continuation, heat resistance and
The transparency is excellent, and in the absence of diverging gas problem.As the preferred anti-static resin composition of the present invention, specific insulation
For 109~1010Ω cm, above-mentioned antistatic behaviour can also be kept even if being washed, being wiped, heat resistance, the transparency and into
Type is excellent, and in the absence of diverging gas problem.It can act as precision electronic components such as semiconductor wafer, semiconductor element
And the transportation tray of integrated circuit etc., packaging material, storage keeping instrument and external packing component etc. material, be assembled with
External packing component of precise electronic machine of precision electronic components etc..
Brief description of the drawings
Fig. 1 is polyester resin1H-NMR measurement example.
Embodiment
The anti-static resin composition of the present invention includes the polyester with following characteristics (a1) and (a2) of 100 mass parts
Resinoid (A) and 7~25 mass parts have the construction unit for deriving from the aromatic polycarboxylic acid by sulphonate-base substitution
Polyetherester resins (B).
(a1) using from the summation of the construction unit of polybasic carboxylic acid as 100 moles of %, then comprising 90~100 moles of %
From the construction unit of terephthalic acid (TPA) and 0~10 mole of % construction unit from M-phthalic acid.
(a2) using from the summation of the construction unit of polyalcohol as 100 moles of %, then comprising 50~90 moles of %
2,2,4,4- tetramethyl -1,3- rings are derived from from the construction unit of 1,4 cyclohexane dimethanol and 10~50 moles of %
The construction unit of butanediol.
(A) polyester resin：
The composition (A) is polyester resin, comprising (a1) using from the summation of the construction unit of polybasic carboxylic acid as
100 moles of %, then come comprising 90~100 moles of % from the construction unit of terephthalic acid (TPA) and 0~10 mole of %
Come from the construction unit of M-phthalic acid；(a2) as 100 moles of %, then wrapped from the summation of the construction unit of polyalcohol
The % containing the %, more preferably 60~80 moles of 50~90 moles of %, preferably 55~85 moles from 1,4 cyclohexane dimethanol
Construction unit and the %, more preferably 20~40 moles of 10~50 moles of %, preferably 15~45 moles %'s derives from 2,2,4,4-
The construction unit of tetramethyl -1,3- cyclobutanediols.Wherein, polybasic carboxylic acid includes it and forms the derivative of ester.That is, terephthalic acid (TPA)
The derivative of ester is formed comprising it.Equally, M-phthalic acid includes it and forms the derivative of ester.Wherein, polyalcohol includes its shape
Into the derivative of ester.That is, 1,4-CHDM includes it and forms the derivative of ester.Equally, 2,2,4,4- tetramethyls -1,3-
Cyclobutanediol includes it and forms the derivative of ester.
As the composition (A), in the limit for not violating the purpose of the present invention, can also include except terephthalic acid (TPA)
And the construction unit from other polybasic carboxylic acids beyond M-phthalic acid.As other above-mentioned polybasic carboxylic acids, for example, can
To enumerate phthalic acid, naphthalene dicarboxylic acids, diphenyl -4,4'- dicarboxylic acids, diphenoxyethanedicarboxylic acid, diphenyl -3,3'-
The aromatic polycarboxylic acids such as dicarboxylic acids, diphenyl -4,4'- dicarboxylic acids and anthracene dicarboxylic acids；1,2- cyclohexane dicarboxylic acids, 1,3- rings
The alicyclic polycarboxylic acid such as hexane dicarboxylic acid and 1,4- cyclohexane dicarboxylic acids；Malonic acid, butanedioic acid, glutaric acid, adipic acid, heptan
The aliphatic polycarboxylic acids such as diacid, suberic acid, azelaic acid and decanedioic acid；And their derivative of formation ester etc..As
Other above-mentioned polybasic carboxylic acids, can use it is therein more than one.
As the composition (A), in the limit for not violating the purpose of the present invention, can also include except Isosorbide-5-Nitrae-hexamethylene
The construction unit from other polyalcohols beyond dimethanol and 2,2,4,4- tetramethyl -1,3- cyclobutanediols.As upper
State other polyalcohols, for example, can enumerate ethylene glycol, diethylene glycol, trimethylene, tetramethylene glycol, neopentyl glycol,
Polyethylene glycol, 1,2- propane diols, 1,3- propane diols, polypropylene glycol, 1,2- butanediols, 1,3 butylene glycol, 1,4- butanediols, 1,5-
Pentanediol, 1,6-HD, neopentyl glycol, dodecanediol, 3- methyl isophthalic acids, 5- pentanediols, 2- methyl-1,3-propanediols, 1,
The aliphatic polyols such as 2- cyclohexanediols, 1,4- cyclohexanediols, glycerine and trimethylolpropane；Xylene glycol, 4,4'- bis-
Double (4- hydroxy phenyls) propane of xenol, 2,2-, double (4- hydroxy phenyls) sulfones, bisphenol-A, the oxyalkylene addition compound etc. of bisphenol-A
Aromatic polyol；And their derivative of formation ester etc..As above-mentioned polyalcohol, can use it is therein it is a kind of with
On.
Due to the glass transition temperature of the composition (A) it is higher (usual more than 90 DEG C, preferably more than 100 DEG C, more preferably
More than 110 DEG C), therefore, the excellent heat resistance of anti-static resin composition of the invention.In addition, composition (A) height is thoroughly
It is bright, and there is amorphism or low-crystalline, good with the Combination of the composition (B), therefore, of the invention is antistatic
Resin combination it is transparent excellent.
In this manual, will be logical using the Diamond DSC type differential scanning calorimetry (DSC)s of PerkinElmer Co., Ltd.
The melting caloric for crossing the second melting curve (melting curve that last temperature-rise period measures) that following temperature program(me)s measure is
Below 10J/g polyester resin is defined as amorphism, and the polyester resin more than 10J/g and below 60J/g is defined as low
Crystallinity, the temperature program(me) are：By sample after 320 DEG C are kept for 5 minutes, -50 are cooled to 20 DEG C/min of cooling rate
DEG C, after -50 DEG C are kept for 5 minutes, 320 DEG C are heated to 20 DEG C/min of programming rate.
In this manual, using the Diamond DSC type differential scanning calorimetry (DSC)s of PerkinElmer Co., Ltd., under
The Glass Transition occurred in the curve that the last temperature-rise period of temperature program(me) measures is stated, according to ASTM D3418 figure
The 2 intermediate point glass transition temperatures that calculate of drawing are as glass transition temperature, the temperature program(me)：By sample with 50
DEG C/min programming rate be warming up to 200 DEG C, 200 DEG C keep 10 minutes after, be cooled to 20 DEG C/min of cooling rate
50 DEG C, after 50 DEG C are kept for 10 minutes, 200 DEG C are heated to 20 DEG C/min of programming rate.
It can use13C-NMR、1H-NMR obtains the ratio for the structural units that each composition is derived from above-mentioned polyester resin
Example.Shown in Fig. 11H-NMR measurement example.
For example, sample 20mg can be dissolved in chloroform-d1In solvent 0.6mL, using 125MHz nuclear magnetic resonance device,
Pass through following conditioned measurement13C-NMR spectrum.
Chemical shift reference chloroform-d1：77ppm
Measurement pattern pulse proton wideband decouples
45 ° of pulse width (5.00 μ seconds)
Count 64K
Observation scope 250ppm (- 25~225ppm)
5.5 seconds repetition times
Cumulative frequency 256 times
23 DEG C of measurement temperature
Window function exponential (BF：1.0Hz)
For example, sample 20mg can be dissolved in chloroform-d1In solvent 0.6mL, using 400MHz nuclear magnetic resonance device,
Pass through following conditioned measurement1H-NMR spectrum.
Chemical shift reference chloroform：7.24ppm
Measurement pattern pulse
45 ° of pulse width (5.14 μ seconds)
Count 16k
Measurement range 15ppm (- 2.5~12.5ppm)
7.8 seconds repetition times
Cumulative frequency 64 times
23 DEG C of measurement temperature
Window function exponential (BF：0.18Hz)
It may be referred to " macromolecule analysis handbook (the first edition first printing on the 20th of September in 2008, the analysis of Japan of civic organization
Chemistry can macromolecule analysis and research forum compile, towards storehouse Co., Ltd. of bookstore) page 496~503 ", " independent administrative corporation's thing
Matter, the NMR data storehouse (http at Materials Research Institution material information station://polymer.nims.go.jp/NMR/) " carry out peak return
Category, the ratio of each composition in the composition (a) is calculated according to peak area ratio.Furthermore, it is possible in the strain of Mitsui Chemicals analysis center
The analysis office such as formula commercial firm is carried out13C-NMR、1H-NMR measurement.
(B) polyetherester resins：
The composition (B) is the polyethers with the construction unit for deriving from the aromatic polycarboxylic acid by sulphonate-base substitution
Ester resin.From the aspect of antistatic behaviour and the transparency, the composition (B) preferably comprises：
From from terephthalic acid (TPA), 2,6 naphthalene dicarboxylic acid, 2,7- naphthalene dicarboxylic acids, biphenyl -4,4'- dicarboxylic acids and it
Formation ester the group that is formed of derivative in the construction unit of more than one aromatic dicarboxylic acid (b1) that selects；
By following chemical formula (1) represent derive from by sulphonate-base substitution aromatic polycarboxylic acid and/or its formed
The construction unit of the derivative (b2) of ester；
From the construction unit of the PAG (b3) of number-average molecular weight 200~50000；And
From the construction unit of the glycol (b4) of carbon number 2~10,
Wherein, the content of the construction unit of the composition (b1) and the structure list from the composition (b2) will be derived from
Member content and be used as 100 moles of %, then the construction unit from the composition (b1) comprising 70~98 moles of % with
And 2~30 moles of % construction unit from the composition (b2), the construction unit of the composition (b1) will be derived from
Content, from the composition (b2) construction unit content, from the construction unit of the composition (b3) content with
And the content and 100 mass % of conduct of the construction unit from the composition (b4), then from the composition (b3)
The content of construction unit is 10~60 mass %.
Chemical formula 1
In chemical formula (1), Ar represents the group of the aromatic ring structure with least three hydrogen atoms of substitution, R1 and R2
Hydrogen atom, the alkyl of carbon number 1~6 or the aryl of carbon number 6~12, M are represented independently of one another+Represent metal ion, tetraalkyl
Phosphonium ion or tetraalkyl ammonium ion.
Derived from when the composition (B) includes from above-mentioned terephthalic acid (TPA), 2,6 naphthalene dicarboxylic acid, 2,7- naphthalene dicarboxylic acids, connection
More than one the aromatic series dicarboxyl selected in the group that the derivative of benzene -4,4'- dicarboxylic acids and their formation ester is formed
During the construction unit of sour (b1), heat resistance is better, is preferred scheme therefore.
Represent more from the aromatic series by sulphonate-base substitution when the composition (B) includes above-mentioned chemical formula (1)
During the construction unit of the derivative (b2) of first carboxylic acid and/or its formation ester, antistatic behaviour is better, is preferred scheme therefore.
For the Ar in above-mentioned chemical formula (1), Ar is the group of the aromatic ring structure with least three hydrogen atoms of substitution.
As the Ar in above-mentioned chemical formula (1), for example, the group for the benzene ring structure being substituted with least three hydrogen atoms can be enumerated
And the group for the naphthalene ring being substituted with least three hydrogen atoms.Three hydrogen atoms are not limited to by above-mentioned chemical formula (1)
The specific three substituents substitution of institute or more than one hydrogen atom are taken by alkyl, phenyl, halogen and alkoxy etc.
Substitute for base.The position of substitution is not limited, can arbitrarily be selected.It is special from polymerism, machinery for the Ar in above-mentioned chemical formula (1)
Property and tone from the aspect of, preferably have substitution three hydrogen atoms benzene ring structure group.
R1 in above-mentioned chemical formula (1) is the aryl of hydrogen atom, the alkyl of carbon number 1~6 or carbon number 6~12.It is preferred that hydrogen
The alkyl of the carbon numbers such as atom, methyl, ethyl and propyl group 1~3.Wherein, for the R1 in above-mentioned chemical formula (1), from polymerism,
From the aspect of mechanical property and tone, preferably methyl and ethyl.
R2 in above-mentioned chemical formula (1) is the aryl of hydrogen atom, the alkyl of carbon number 1~6 or carbon number 6~12.It is preferred that hydrogen
The alkyl of the carbon numbers such as atom, methyl, ethyl and propyl group 1~3.Wherein, for the R2 in above-mentioned chemical formula (1), from polymerism,
From the aspect of mechanical property and tone, preferably methyl and ethyl.
R1 and R2 in above-mentioned chemical formula (1) can be identical structure or different structure.Above-mentioned chemical formula (1)
In R1 and R2 it is each independent, can be arbitrary structures within the above range.
M in above-mentioned chemical formula (1)+It is metal ion, Si Wan Ji Phosphonium ions or tetraalkyl ammonium ion.In addition, upper
State the M in chemical formula (1)+In the case of for multivalence, the sulfonic group of respective amount therewith is corresponding with (in above-mentioned chemical formula (1)
Except M+Part in addition).For example, the M in above-mentioned chemical formula (1)+In the case of for divalent metal ion, relative to 1 gold
Category ion be corresponding with 2 sulfonic groups (in above-mentioned chemical formula (1) except M+Part in addition).
As above-mentioned metal ion, for example, sodium ion, potassium ion can be enumerated, and the alkali metal ion such as lithium ion；Calcium
The alkaline-earth metal ion such as ion and magnesium ion；And zinc ion etc..As above-mentioned Si Wan Ji Phosphonium ions, four fourths can be enumerated
Ji Phosphonium ion and tetramethyl phosphonium ion etc..As above-mentioned tetraalkyl ammonium ion, potassium ion and tetramethyl can be enumerated
Base ammonium ion etc..Wherein, as the M in above-mentioned chemical formula (1)+, from polymerism, mechanical property, antistatic behaviour and tone side
Face consideration, preferred as alkali ion, potassium ion and 4-butyl-phosphonium ion.More preferably alkali metal ion and the tetrabutyl
Phosphonium ion.
As the composition (b2), i.e., the aromatic polycarboxylic acid substituted by sulphonate-base of above-mentioned chemical formula (1) expression
And/or its formed ester derivative, for example, can enumerate M-phthalic acid -4- sodium sulfonates, 5-sodium sulfo isophthalate,
Phthalic acid -4- potassium sulfonates, M-phthalic acid -5- potassium sulfonates, terephthalic acid (TPA) -2- sodium sulfonates, terephthalic acid (TPA) -2- sulfonic acid
Potassium, M-phthalic acid -4- sulfonic acid zinc, M-phthalic acid -5- sulfonic acid zinc, sulfo group-terephthalic acid (TPA) -2- sulfonic acid zinc, isophthalic diformazan
Acid -4- sulfonic acid Si Wan Ji phosphonium salts, M-phthalic acid -5- sulfonic acid Si Wan Ji phosphonium salts, M-phthalic acid -4- sulfonic acid tetraalkylammonium salt,
M-phthalic acid -5- sulfonic acid tetraalkylammonium salt, terephthalic acid (TPA) -2- sulfonic acid Si Wan Ji phosphonium salts, the alkane of terephthalic acid (TPA) -2- sulfonic acid four
Base ammonium salt, 2,6 naphthalene dicarboxylic acid -4- sodium sulfonates, 2,7- naphthalene dicarboxylic acids -4- sodium sulfonates, 2,6 naphthalene dicarboxylic acid -4- potassium sulfonates, 2,6-
Naphthalene dicarboxylic acids -4- zinc sulfonates, 2,6 naphthalene dicarboxylic acid -4- sulfonic acid Si Wan Ji phosphonium salts, 2,7- naphthalene dicarboxylic acids -4- sulfonic acid Si Wan Ji Phosphonium
Salt, their dimethyl ester and their diethylester etc..
Wherein, as the composition (b2), from the aspect of polymerism, mechanical property and tone, preferred isophthalic diformazan
Dimethyl phthalate -4- sodium sulfonates, Sodium Dimethyl Isophthalate-5-sulfonate, DMIP -4- potassium sulfonates, isophthalic two
Formic acid dimethyl ester -5- potassium sulfonates, dimethyl terephthalate (DMT) -2- sodium sulfonates and dimethyl terephthalate (DMT) -2- potassium sulfonates.
As the composition (B), the content of the construction unit of the composition (b1) will be derived from and derive from the composition
(b2) construction unit content and 100 moles of % are used as, then comprising the % of 70~98 moles of %, preferably 71~97 moles, more
It is preferred that 73~95 moles of %, further preferred 75~91 moles of % construction unit from the composition (b1), comprising 2~
The %, more preferably 5~27 moles of 30 moles of %, preferably 3~29 moles %, further preferred 9~25 moles of % from described
The construction unit of composition (b2).
When the composition (B) include above range in from the construction unit of the composition (b1) and from institute
When stating the construction unit of composition (b2), the antistatic behaviour of anti-static resin composition of the invention is better.In addition, even if enter
Water-filling washes, wipes and can also keep good antistatic behaviour.In addition, molecular weight and crystallinity with abundance, operability are good
It is good.
When the composition (B) includes the structure list of the PAG (b3) from number-average molecular weight 200~50000
When first, antistatic behaviour is better, therefore is preferred scheme.
It is the PAG of number-average molecular weight 200~50000 as the composition (b3), for example, can enumerate poly-
Ethylene glycol, polypropylene glycol, using ethylene glycol as principal monomer (usual 60 moles of more than %, preferably 80 moles of more than %) and by third
Glycol etc. as principal monomer and is incited somebody to action a small amount of as the copolymer of comonomer, using the aklylene glycol of ethylene glycol, propane diols etc.
(usual 10 moles of below %, preferably 5 moles of below %, more preferably 1 mole of below %.) aromatic polyol is as comonomer
Copolymer and their mixture etc..
, can be with from the aspect of antistatic behaviour, dispersiveness and heat resistance for the composition (b3) number-average molecular weight
It is 200~50000, preferably 500~30000, more preferably 1000~20000.
For the content of the construction unit from the composition (b3) of the composition (B), from antistatic behaviour, operability
And can be 10~60 mass % from the aspect of heat resistance, preferably 15~55 mass %, more preferably 20~50 mass %.Its
In, content from the construction unit of the composition (b1), the content of construction unit from the composition (b2), source
Content in the construction unit of the composition (b3) and the content of the construction unit from the composition (b4) and be 100
Quality %.
When the composition (B) is included from the construction unit of the ethylene glycol (b4) of carbon number 2~10, antistatic behaviour, behaviour
The property made and heat resistance are better, therefore are preferred schemes.
It is the glycol of carbon number 2~10 as the composition (b4), ethylene glycol, propane diols, 1,2- butanediols, 1 can be enumerated,
3- butanediols, 1,4- butanediols, 1,6-HD, 3- methyl isophthalic acids, 5- pentanediols, 2- methyl-1,3-propanediols, 1,2- hexamethylenes two
The aliphatic ethylene glycol such as alcohol and 1,4- cyclohexanediols；Diethylene glycol etc. has the ethylene glycol of ehter bond；And thiodiethanol etc.
Ethylene glycol with thioether bond etc..It is excellent from the aspect of antistatic behaviour, crystallinity and operability as the composition (b4)
Select 1,6-HD, ethylene glycol and diethylene glycol.As the composition (b4), can use it is therein more than one.
As the composition (B), according to JIS K7367-1：2002, use specification Fig. 2 DIN Ubbelohde viscometer (hairs
Capillary diameter 0.63mm), the mixed solvent of phenol/tetrachloroethanes (mass ratio 60/40), in concentration 1.2g/dl, 35 DEG C of temperature
Under the conditions of the reduced viscosity that measures from the aspect of antistatic behaviour, heat resistance and machine performance, preferably 0.2cm3/ more than g,
More preferably 0.25cm3/ more than g, further preferred 0.3cm3/ more than g, on the other hand, can also from the aspect of antistatic behaviour
It is 1.8cm3/ below g.
It is not particularly limited and obtains the composition (B) method using the composition (b1)~(b4), any side can be used
Method.150~300 are melted to for example, can heat the composition (b1)~(b4) under the conditions of existing for ester exchange catalyst
DEG C, polycondensation reaction is brought it about so as to obtain the composition (B).
Above-mentioned ester exchange catalyst is not particularly limited, any ester exchange catalyst can be used.Urged as above-mentioned ester exchange
Agent, for example, the antimonials such as antimony oxide can be enumerated；Stannous acetate, Dibutyltin oxide and oxalic acid dibutyl
The tin compounds such as tin；The titanium compounds such as butyl titanate；The zinc compounds such as zinc acetate；The calcium compounds such as calcium acetate；Sodium carbonate with
And alkali metal salt such as potassium carbonate etc..Wherein, preferred butyl titanate.As above-mentioned ester exchange catalyst, can use therein
More than one.
The dosage of above-mentioned ester exchange catalyst is not particularly limited, still, relative to 1 mole of mentioned component (b1), generally
Can be 0.01~0.5 mole of %, preferably 0.03~0.3 mole of %.
Additionally, it is preferred that in above-mentioned polycondensation reaction simultaneously using various stabilizers such as antioxidants.
As above-mentioned polycondensation reaction, preferably enter while distillate is evaporated in 150~250 DEG C, preferably 150~200 DEG C
After row 1~20 hour or so, temperature is risen to 180~300 DEG C, preferably 200~280 DEG C, more preferably 220~260 DEG C, then
Carry out 1~20 hour or so.The composition (B) can be arranged to the reduced viscosity with preferred scope.
As the example for the composition (B) sold on the market, Zhu Ben's Oil Corporation can be enumerated
" ELECUTR02 (trade name) " etc..
As the composition (B) use level, relative to the composition (A) of 100 mass parts, examined in terms of antistatic behaviour
Consider, can be more than 7 mass parts, preferably more than 9 mass parts, more preferably more than 12 mass parts.On the other hand, from anti-diverging gas
Can be below 25 mass parts, preferably below 22 mass parts, more preferably below 20 mass parts from the aspect of property and the transparency.
(C) ionic surface active agent (any condition)：
The anti-static resin composition of the present invention is as described above, even if without using ionic surface active agent it is also seen that abundance
Antistatic behaviour, but be not precluded from using ionic surface active agent.It is special anti-static resin composition is used for into such as initial stage
Pay attention to antistatic behaviour purposes, it is relatively low consider diverging gas, the necessity for oozing out problem purposes in the case of, it is of the invention anti-
Electrostatic resin combination can include ionic surface active agent.
Using in the case of composition (C) ionic surface active agent, use level can be possessed by any condition, not special
Do not limit, can be 0.5~5 mass parts relative to the composition (A) of 100 mass parts still.
As the composition (C), for example, the organic sulfonic acid type surface-active being made up of organic sulfonic acid and alkali can be enumerated
Agent.
As above-mentioned organic sulfonic acid, for example, can enumerate octyl benzene sulfonic acid, DBSA, dibutyl benzene sulfonic acid,
And the alkyl benzene sulphonate that the carbon number of the alkyl such as dinonyl benzene sulfonic acid is 6~18；And dimethylnaphthalene sulfonic acid, diisopropyl naphthalene sulphur
The carbon number of the alkyl such as acid and dibutyl naphthalenesulfonic acid is 2~18 alkyl naphthalene sulfonic acid etc..Wherein, preferred DBSA
And dimethylnaphthalene sulfonic acid.As above-mentioned organic sulfonic acid, can use it is therein more than one.
As above-mentioned alkali, for example, the alkali metal such as lithium, sodium and potassium can be enumerated；4-butyl-phosphonium, tributyl Bian Ji Phosphonium, three
Ethyl Shi Liu Wan Ji Phosphonium and tetraphenylphosphoniphenolate Deng phosphonium compounds；And tetrabutylammonium, tributyl benzyl ammonium chloride and triphen
Ammonium compounds such as base hexadecyldimethyl benzyl ammonium etc..Wherein, preferably sodium, potassium, tetramethyl phosphonium, Si Yi Ji Phosphonium, Si Ji Ji Phosphonium, Si Xin Ji Phosphonium, four fourths
Ji Phosphonium, tributyl benzyl phosphorus, triethyl group Shi Liu Wan Ji Phosphonium and tetraphenylphosphoniphenolate.As above-mentioned alkali, one kind therein can be used
More than.
As the composition (C), from the aspect of the inhibition and antistatic behaviour of diverging gas, preferably above-mentioned alkali is
Phosphonium compounds, for example, DBSA 4-butyl-phosphonium etc. can be enumerated.
The specific insulation preferably 10 of the anti-static resin composition of the present invention10Below Ω cm, more preferably 109~1010
Ω·cm.Further preferred specific insulation is 109~1010Ω cm, it can also keep above-mentioned anti-even if being washed, being wiped
Static behaviour.
In this manual, specific insulation is the value according to following experiment (2) measurements.
The diverging gas flow of the anti-static resin composition of the present invention is preferably below 2 μ g/g, more preferably below 1 μ g/g.Such as
Fruit is usual purposes, and diverging gas flow is that below 2 μ g/g can be used well.Even precise electronic machine etc. particularly requires
The purposes of relatively low diverging gas flow, by the way that diverging gas flow is arranged to below 1 μ g/g, also can well it use.In this specification
In, diverging gas flow is the amount (μ g) of caused diverging gas from sample 1g measured according to following experiments (5).
The present invention anti-static resin composition in, can be as needed, in addition to mentioned component, also include except
Surfactant, thermostabilization beyond the thermoplastic resin and the composition (C) of the composition (A) and the composition (B)
Agent, antioxidant, hydrolysis inhibitor, matal deactivator, ultra-violet absorber, antistatic additive, lubricant and colouring agent etc..
In the anti-static resin composition of the present invention, heat stabilizer, antioxidant are preferably comprised.Can be larger in shaping
Products formed when the formation problems such as prevent from colouring, burn.In the anti-static resin composition of the present invention, metallic blunt is preferably comprised
Agent.In the case of the part for being contacted with metal, it can also prevent the burn into of the contact portion from changing colour.
As above-mentioned antioxidant, for example, BHT, 2,6- DI-tert-butylphenol compounds, 2 can be enumerated,
4- dimethyl -6- tert-butyl phenols, 4,4- dihydroxydiphenyls and three (2- methyl -4- hydroxyl -5- tert-butyl-phenyls) butane etc.
Phenolic antioxidants, phosphorous acid salt antioxidant and thioether antioxidants etc..Wherein, preferably phenol is anti-oxidant
Agent and phosphorous acid salt antioxidant.
Can by the composition (A), the composition (B) and any condition in any order or simultaneously melting mixing
To manufacture the anti-static resin composition of the present invention.The method of melting mixing is not particularly limited, known method can be used.Example
Such as, single axle extruding machine, biaxial extruder, roller, mixer or various kneaders can be used.Using mixer or kneading
In the case of machine, for example, it is preferable to carry out melting mixing under conditions of being 240~260 DEG C in discharge temperature.It is kneaded using twin shaft
In the case of machine, for example, it is preferable to enter under conditions of agitating paddle rotation number is 50~500rpm, melting temperature is 240~260 DEG C
Row melting mixing.
The anti-static resin composition of the present invention can be molded by known forming method processing and forming to be arbitrary
Product.As above-mentioned forming method, for example, common jet forming method, insert molding method, dual-color forming method, interlayer can be enumerated
The method of forming, gas jet method, special-shaped extrusion moulding, double-colored extrusion moulding, the covering method of forming and thin slice, film extrusion
Method of forming etc..
Embodiment
Below, the present invention is illustrated by embodiment, but the invention is not restricted to this.
Measuring method
(1) mouldability：
Using 120 tons of Jet forming machine of mold closing power, in 240~260 DEG C of barrel temperature, 50 DEG C of mold temperature, cooling
Between longitudinal 64.4mmm, horizontal 64.4mm, thickness 3mm ejection formation plate is molded under conditions of 5 minutes.What visual observations obtained
Plate, assessed according to following benchmark.
○：Shrink mark and warpage are not confirmed.
×：Confirm shrink mark and either warpage or confirm shrink mark and warpage
(2) specific insulation (antistatic behaviour)：
According to ASTMD257 specifications (version in 1987), measured by bicyclic sonde method (ring sonde method).That is, will pass through
The ejection formation plate that the method for above-mentioned experiment (1) obtains is as experiment slice, in 23 ± 2 DEG C of temperature, the reality of relative humidity 50 ± 5%
Test in room carry out more than 40 hours state adjustment after, use resistivity meter " the HIRESTA UP of Mitsubishi chemical Co., Ltd
MCP-HT450 types (trade name) ", Mitsubishi chemical Co., Ltd bicyclic probe (as ring-type, main electrode external diameter is 0.59cm,
Guard electrode internal diameter is 1.1cm) calculating platform " UFL (business of " URS PROBE (trade name) " and Mitsubishi chemical Co., Ltd
The name of an article) ", measured applying voltage 500V, time of measuring under conditions of 60 seconds.To measurement position of 1 experiment slice at 2 positions
Measure, 3 experiment slices are measured, the average value of 6 measured values will be added up to as the specific insulation of the sample.
In addition, the measuring method of resistivity and its theoretical webpage (http that may be referred to Mitsubishi chemical Co., Ltd：//
Www.mccat.co.jp/3seihin/genri/ghlup2.htm) etc..
(3) specific insulation (durability 1 of antistatic behaviour) after water cleaning：
Method by above-mentioned experiment (1) is obtained into ejection formation plate to use in the tank filled with 25 DEG C of distilled water
The surface of gauze (gauze of medical kind 1 of this Industry Co., Ltd of river) clean plate 10 minutes, moisture is wiped using clean paper
Afterwards, 23 ± 2 DEG C of temperature, relative humidity 50 ± 5% laboratory in dry more than 24 hours, according to the side of above-mentioned experiment (2)
Method measures specific insulation.
(4) specific insulation (durability 2 of antistatic behaviour) after wiping：
The ejection formation plate that method by above-mentioned experiment (1) is obtained is placed on JISL0849 tester for friction between,
Installed on the friction terminal of tester for friction between overlapping covered with 4 pieces of gauzes (yarn of medical kind 1 of this Industry Co., Ltd of river
Cloth) stainless steel plate (longitudinal 10mm, horizontal 10mm, thickness 1mm), set the length and width face of the stainless steel plate to be contacted with experiment slice,
350g load-carryings are carried, under conditions of being 1 back and forth/second as 60mm, speed using the displacement for the terminal that rubs by experiment slice back and forth
After wiping 300 times, according to the specific insulation at the wiping position of the method measurement experiment piece of above-mentioned experiment (2).
(5) gas flow is dissipated：
The thermal desorption formula gas chromatograph quality analysis apparatus of Perkinelmer Inc. can be used to measure.
(5-1) traps diverging gas by thermal desorption method：
Resin combination Freezing smashing is formed into 2mm with the crushed material of lower block, crushed material will be obtained through the above way
0.1g is put into the sample tray of the capture unit of said apparatus, is heated 10 minutes at 120 DEG C, caused volatile materials is made
By the use of helium as vector gas, trap in the cold-trap pipe for remaining 5 DEG C.
(5-2) volatile materials (diverging gas) quantifies：
The cold-trap pipe for having volatile materials by above-mentioned (5-1) trapping is heated to 40 DEG C/sec of programming rate
300 DEG C, the gas that will be disengaged from is supplied to the gas chromatograph mass analysis cell of said apparatus, and its yield is quantified.This
When, using standard sample (GL sciences Co., Ltd. based on 2,6- diphenyl to the porous of the low pole of penylene oxide
A certain amount of n-decane of impregnation in polymer beads adsorbent " TenaxTA (trade name) "), measured using same with the above method
Manufactured detection line.
(6) haze value (transparency)：
Using 120 tons of Jet forming machine of mold closing power, in 240~260 DEG C of barrel temperature, 50 DEG C of mold temperature, cooling
Between longitudinal 60mm, horizontal 60mm, thickness 0.5mm ejection formation piece is molded under conditions of 5 minutes, according to JIS K 7136：
2000, measure obtained matrix band using the transmissometer " NDH2000 (trade name) " of Nippon Denshoku Industries Co., Ltd.
Haze value.Assessed with following benchmark.
◎：Less than 5%
○：More than 5%, less than 50%
×：More than 50%
(7) heat distortion temperature (heat resistance)：
According to ASTMD648-07, using 120 tons of Jet forming machine of mold closing power, in 240~260 DEG C of barrel temperature, mould
Temperature 50 C, length 127mm, height 13mm, thickness 6mm experiment slice are molded under conditions of 5 minutes cool times, use the examination
Piece is tested to measure under conditions of distance between the fulcrum 100.0mm (B methods), load-carrying 1.82MPa, 2 DEG C of programming rate.
The raw material used
(A) polyester resin：
(A-1) polyester resin, wherein, using from the summation of the construction unit of polybasic carboxylic acid as 100 moles of %, then
Include the 100 moles of % construction unit from terephthalic acid (TPA), using from the summation of the construction unit of polyalcohol as
100 moles of %, then comprising 77 moles of % from the source of the construction unit of 1,4-CHDM and 23 moles of %
In the construction unit of 2,2,4,4- tetramethyl -1,3- cyclobutanediols.108 DEG C of glass transition temperature, heat of fusion 0J/g (DSC
Do not occur obvious melting peakss in two melting curves).
(A-2) polyester resin, wherein, using from the summation of the construction unit of polybasic carboxylic acid as 100 moles of %, then
Include the 100 moles of % construction unit from terephthalic acid (TPA), using from the summation of the construction unit of polyalcohol as
100 moles of %, then comprising 64 moles of % from the source of the construction unit of 1,4-CHDM and 36 moles of %
In the construction unit of 2,2,4,4- tetramethyl -1,3- cyclobutanediols.119 DEG C of glass transition temperature, heat of fusion 0J/g (DSC
Do not occur obvious melting peakss in two melting curves).
(A ') compares resin：
(A ' -1) polyester resin, wherein, using from the summation of the construction unit of polybasic carboxylic acid as 100 moles of %,
The 100 moles of % construction unit from terephthalic acid (TPA) is then included, by the summation work from the construction unit of polyalcohol
For 100 moles of %, then come comprising 34 moles of % from the construction unit of 1,4-CHDM and 66 moles of %
Come from the construction unit of ethylene glycol.81 DEG C of glass transition temperature, heat of fusion 0J/g (do not occur bright in the melting curves of DSC second
Aobvious melting peakss).
The polycarbonate resin " IUPILON3000 (trade name) " of (A ' -2) Mitsubishi engineering Plastics Co., Ltd.Glass
Change 143 DEG C of transition temperature.
(B) polyetherester resins：
(B-1) the polyether ester tree obtained according to the content of 0063 section of Japanese Unexamined Patent Publication 8-283548 publications, reference example 1
Fat.The composition (b1) is dimethyl terephthalate (DMT), and the composition (b2) is Sodium Dimethyl Isophthalate-5-sulfonate, institute
It is polyethylene glycol (number-average molecular weight 20000) to state composition (b3), and the composition (b4) is BDO.Will derive from it is described into
Divide the content of construction unit of the content of the construction unit of (b1) with deriving from the composition (b2) and be used as 100 moles of %,
Then the construction unit from the composition (b1) is arranged to 75 moles of %, will be set from the construction unit of the composition (b2)
It is set to 25 moles of %.The content of the construction unit of the composition (b1), the structure list from the composition (b2) will be derived from
Member content, from the composition (b3) construction unit content and the construction unit from the composition (b4)
It is content and be used as 100 mass %, then the content from the construction unit of the composition (b3) is 11 mass %.
(B-2) the polyether ester tree obtained according to the content of 0064 section of Japanese Unexamined Patent Publication 8-283548 publications, reference example 2
Fat.The composition (b1) is dimethyl terephthalate (DMT), and the composition (b2) is Sodium Dimethyl Isophthalate-5-sulfonate, institute
It is polyethylene glycol (number-average molecular weight 20000) to state composition (b3), and the composition (b4) is BDO.Will derive from it is described into
Divide the content of construction unit of the content of the construction unit of (b1) with deriving from the composition (b2) and be used as 100 moles of %,
Then the construction unit from the composition (b1) is arranged to 85 moles of %, and the construction unit from the composition (b2) is set
For 15 moles of %.The content of the construction unit of the composition (b1), the construction unit from the composition (b2) will be derived from
Content, from the composition (b3) construction unit content and contain from the construction unit of the composition (b4)
Measure and 100 mass % of conduct, then the content from the construction unit of the composition (b3) is 20 mass %.
(B-3) the polyether ester tree obtained according to the content of 0065 section of Japanese Unexamined Patent Publication 8-283548 publications, reference example 3
Fat.The composition (b1) is dimethyl terephthalate (DMT), and the composition (b2) is Sodium Dimethyl Isophthalate-5-sulfonate, institute
It is polyethylene glycol (number-average molecular weight 20000) to state composition (b3), and the composition (b4) is BDO.Will derive from it is described into
Divide the content of construction unit of the content of the construction unit of (b1) with deriving from the composition (b2) and be used as 100 moles of %,
Then the construction unit from the composition (b1) is arranged to 75 moles of %, and the construction unit from the composition (b2) is set
For 25 moles of %.The content of the construction unit of the composition (b1), the construction unit from the composition (b2) will be derived from
Content, from the composition (b3) construction unit content and the construction unit from the composition (b4)
Content and be used as 100 mass %, then the content from the construction unit of the composition (b3) is 20 mass %.
(B-4) the polyether ester tree obtained according to the content of 0066 section of Japanese Unexamined Patent Publication 8-283548 publications, reference example 4
Fat.The composition (b1) is dimethyl terephthalate (DMT), and the composition (b2) is Sodium Dimethyl Isophthalate-5-sulfonate, institute
It is polyethylene glycol (number-average molecular weight 4000) to state composition (b3), and the composition (b4) is BDO.Will derive from it is described into
Divide the content of construction unit of the content of the construction unit of (b1) with deriving from the composition (b2) and be used as 100 moles of %,
Then the construction unit from the composition (b1) is arranged to 75 moles of %, and the construction unit from the composition (b2) is set
For 25 moles of %.The content of the construction unit of the composition (b1), the construction unit from the composition (b2) will be derived from
Content, from the composition (b3) construction unit content and the construction unit from the composition (b4)
Content and be used as 100 mass %, then the content from the construction unit of the composition (b3) is 20 mass %.
(B ') compares polyetherester resins：
The polyether ester amides resin " PELESTAT 6321NC (trade name) " of (B ' -1) Sanyo Chemical Industries Co., Ltd..Do not have
There is the construction unit from the aromatic polycarboxylic acid by sulphonate-base substitution.
(C) ionic surface active agent
(C-1) Kanto Kagaku K. K.Neopelex.
Example 1~11, example 1C~7C
UseTwin shaft kneading machine in the same direction, the complex of the match ratio in table 1~3 shown in either table is being set
240~260 DEG C of progress melting mixings of constant temperature degree, obtain resin combination.Carry out above-mentioned experiment (1)~(7).Represented in table 1~3
As a result.
Table 1
Table 2
Table 3
It is the mouldability of resin combination of the present invention, antistatic behaviour, anlistatig durability, low diverging gaseousness, transparent
Property and excellent heat resistance.
Claims (6)
1. a kind of anti-static resin composition, it is characterised in that include：
100 mass parts have following characteristics (a1) and the polyester resin (A) of (a2)；And
The polyether ester tree with the construction unit for deriving from the aromatic polycarboxylic acid by sulphonate-base substitution of 7~25 mass parts
Fat (B),
(a1) as 100 moles of %, then come from the summation of the construction unit of polybasic carboxylic acid comprising 90~100 moles of %
The construction unit of terephthalic acid (TPA) and 0~10 mole of % construction unit from M-phthalic acid are come from,
(a2) as 100 moles of %, then 50~90 moles of % source is included using from the summation of the construction unit of polyalcohol
2,2,4,4- tetramethyl -1,3- rings fourth two is derived from the construction unit of 1,4 cyclohexane dimethanol and 10~50 moles of %
The construction unit of alcohol.
2. anti-static resin composition according to claim 1, it is characterised in that
The composition (B) is polyetherester resins, comprising：
From from terephthalic acid (TPA), 2,6 naphthalene dicarboxylic acid, 2,7- naphthalene dicarboxylic acids, biphenyl -4,4'- dicarboxylic acids and they
The construction unit of more than one the aromatic dicarboxylic acid (b1) selected in the group that the derivative of formation ester is formed；
From following chemical formula (1) represent by sulphonate-base substitution aromatic polycarboxylic acid and/or its form spreading out for ester
The construction unit of biological (b2)；
From the construction unit of the PAG (b3) of number-average molecular weight 200~50000；And
From the construction unit of the glycol (b4) of carbon number 2~10,
Wherein, the content of the construction unit of the composition (b1) and the construction unit from the composition (b2) will be derived from
Content and be used as 100 moles of %, then comprising 70~98 moles of % from the construction unit of the composition (b1) and 2~
The 30 moles of % construction unit from the composition (b2),
Will derive from the composition (b1) construction unit content, from the composition (b2) construction unit content,
The sum of content from the construction unit of the composition (b3) and the content of the construction unit from the composition (b4)
As 100 mass %,
Then the content from the construction unit of the composition (b3) is 10~60 mass %,
Chemical formula 1
In chemical formula 1,
Ar represents the group of the aromatic ring structure with least three hydrogen atoms of substitution；
R1 and R2 represents the aryl of hydrogen atom, the alkyl of carbon number 1~6 or carbon number 6~12 independently of one another；
M+Represent metal ion, Si Wan Ji Phosphonium ions or tetraalkyl ammonium ion.
3. anti-static resin composition according to claim 1 or 2, it is characterised in that
Relative to the composition (A) of 100 mass parts, the ionic surface active agent (C) also containing 0.5~5 mass parts.
4. anti-static resin composition according to any one of claim 1 to 3, it is characterised in that
Specific insulation is 109~1010Ω·cm。
5. a kind of article, it is characterised in that the article includes antistatic resin group according to any one of claims 1 to 4
Compound.
6. a kind of precise electronic machine, it is characterised in that the precise electronic machine includes any one of Claims 1 to 4 institute
The anti-static resin composition stated.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015154830 | 2015-08-05 | ||
| JP2015-154830 | 2015-08-05 | ||
| PCT/JP2016/072211 WO2017022637A1 (en) | 2015-08-05 | 2016-07-28 | Antistatic resin composition |
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| Publication Number | Publication Date |
|---|---|
| CN107849340A true CN107849340A (en) | 2018-03-27 |
| CN107849340B CN107849340B (en) | 2020-08-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201680044661.1A Active CN107849340B (en) | 2015-08-05 | 2016-07-28 | Antistatic resin composition |
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| Country | Link |
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| JP (1) | JP6656253B2 (en) |
| KR (1) | KR102513777B1 (en) |
| CN (1) | CN107849340B (en) |
| TW (1) | TWI715604B (en) |
| WO (1) | WO2017022637A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114437518A (en) * | 2021-12-29 | 2022-05-06 | 金发科技股份有限公司 | Low-warpage glass fiber reinforced PBT composition and preparation method and application thereof |
| CN115996981A (en) * | 2020-09-24 | 2023-04-21 | 理研科技株式会社 | Antistatic resin composition, resin film, and base film for antistatic dicing tape |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP7148301B2 (en) * | 2017-07-14 | 2022-10-05 | 花王株式会社 | Method for producing thermoplastic resin composition |
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| CN1882649A (en) * | 2003-11-26 | 2006-12-20 | 伊斯曼化学公司 | Polyester compositions for calendering |
| JP2009001618A (en) * | 2007-06-19 | 2009-01-08 | Riken Technos Corp | Antistatic polyester resin composition |
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| CN115996981A (en) * | 2020-09-24 | 2023-04-21 | 理研科技株式会社 | Antistatic resin composition, resin film, and base film for antistatic dicing tape |
| CN114437518A (en) * | 2021-12-29 | 2022-05-06 | 金发科技股份有限公司 | Low-warpage glass fiber reinforced PBT composition and preparation method and application thereof |
| CN114437518B (en) * | 2021-12-29 | 2023-11-24 | 金发科技股份有限公司 | Low-warpage glass fiber reinforced PBT composition and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
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| TWI715604B (en) | 2021-01-11 |
| KR102513777B1 (en) | 2023-03-24 |
| JPWO2017022637A1 (en) | 2018-06-07 |
| TW201718760A (en) | 2017-06-01 |
| WO2017022637A1 (en) | 2017-02-09 |
| CN107849340B (en) | 2020-08-04 |
| JP6656253B2 (en) | 2020-03-04 |
| KR20180037214A (en) | 2018-04-11 |
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