CN103347937A - Electrically insulating resin sheet - Google Patents

Electrically insulating resin sheet Download PDF

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Publication number
CN103347937A
CN103347937A CN2012800081830A CN201280008183A CN103347937A CN 103347937 A CN103347937 A CN 103347937A CN 2012800081830 A CN2012800081830 A CN 2012800081830A CN 201280008183 A CN201280008183 A CN 201280008183A CN 103347937 A CN103347937 A CN 103347937A
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CN
China
Prior art keywords
resin
insulating property
electrical insulating
sheet
property resin
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CN2012800081830A
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Chinese (zh)
Inventor
请井博一
笠置智之
吉良佳子
木原靖之
玉井彰
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Nitto Denko Corp
Nitto Shinko Corp
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Nitto Denko Corp
Nitto Shinko Corp
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Publication of CN103347937A publication Critical patent/CN103347937A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/286—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysulphones; polysulfides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • C08L81/06—Polysulfones; Polyethersulfones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2274/00—Thermoplastic elastomer material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/206—Insulating

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Insulating Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Insulating Materials (AREA)

Abstract

In order to address the problem of providing an electrically insulating resin sheet with excellent tear resistance and excellent heat resistance, an electrically insulating resin sheet is provided characterized by having a sheet-form electrically insulating resin layer with an edge-tear resistance of 220N/20mm or greater and a residual tensile strength ratio after 250 hours at 240 DEG C of 55% or greater.

Description

The electrical insulating property resin sheet
Technical field
The present invention relates to the electrical insulating property resin sheet.
Background technology
All the time, as the electrical insulating property resin sheet, known have various electrical insulating property resin sheets, for example, known have be disposed in the motor as the electrical insulating property resin sheet that uses around the winding wire of heating element etc.
As this electrical insulating property resin sheet, particularly, for example, known have an electrical insulating property resin sheet that only possesses the electrical insulating property resin layer, and this electrical insulating property resin layer comprises and has a plurality of aromatic hydrocarbonss and a plurality of sulfide linkage (polyphenylene sulfide S-) and vinyl based copolymer (patent documentation 1) in the molecule.
Yet, though above-mentioned electrical insulating property resin sheet has as the anti-electric trace voltinism that waits the electrical insulating property that requires between the winding wire of motor and winding wire, because by the heat of generations such as winding wire, tensile strengths etc. can reduce, and have not necessarily sufficient problem of thermotolerance.
In addition, there is the problem that tear edge is not necessarily had sufficient patience in above-mentioned electrical insulating property resin sheet, that is, exist as the tear strength of the necessary mechanical characteristic of resin sheet excellent problem not necessarily.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2007-186672 communique
Summary of the invention
The problem that invention will solve
The present invention waits in view of the above problems and forms, and its problem is to provide the electrical insulating property resin sheet of tear strength excellence and excellent heat resistance.
For the scheme of dealing with problems
Electrical insulating property resin sheet of the present invention is characterised in that, it is above and be the electrical insulating property resin layer of the sheet more than 55% at the strength retention ratio of the tensile strength after through 250 hours under 240 ℃ for 220N/20mm that it possesses end tearing resistance value (edge-tear resistance).
In electrical insulating property resin sheet of the present invention, preferably, aforementioned electric insulative resin layer comprises polysulfone resin and the thermoplastic resin except this polysulfone resin that has a plurality of alkylsulfonyls in the molecule.
In electrical insulating property resin sheet of the present invention, preferably, aforementioned electric insulative resin layer comprises aforementioned polysulfone resin and the thermoplastic resin except this polysulfone resin, as the thermoplastic resin except polysulfone resin, comprises polyamide resin and thermoplastic elastomer resin.By comprising aforementioned polysulfone resin, aforementioned polyamide resin and aforementioned thermoplastic elastomer resin, has the advantage that the tear strength of electrical insulating property resin sheet can become more excellent.
In electrical insulating property resin sheet of the present invention, preferably, aforementioned electric insulative resin layer comprises the aforementioned polyamide resin of aforementioned polysulfone resin, 1～30 weight % and the aforementioned thermoplastic elastomer resin of 0.1～5 weight %.
In electrical insulating property resin sheet of the present invention, preferably, aforementioned polyamide resin is the polyamide resin that has aromatic hydrocarbons in the molecule.Be the polyamide resin that has aromatic hydrocarbons in the molecule by aforementioned polyamide resin, have the advantage that the thermotolerance of electrical insulating property resin sheet can become more excellent.
In electrical insulating property resin sheet of the present invention, preferably, aforementioned thermoplastic elastomer resin is maleic anhydride modified polyolefin thermoplastic elastomer.
In electrical insulating property resin sheet of the present invention, preferably, aforementioned polysulfone resin is the polyethersulfone resin that also has a plurality of ehter bonds in the molecule.In addition, preferably, aforementioned polysulfone resin is the Polyphenylene Sulfone resin that also has a plurality of aromatic hydrocarbonss in the molecule.
Preferably, electrical insulating property resin sheet of the present invention also possesses at least a sheet material, and this sheet material is disposed at least one face side of aforementioned electric insulative resin layer.By above-mentioned formation, have the tear strength of electrical insulating property resin sheet and the advantage that thermotolerance can become more excellent.
In electrical insulating property resin sheet of the present invention, preferably, aforementioned sheet material comprises fully aromatic polyamide.In addition, preferably, aforementioned sheet material is non-woven fabrics.
In addition, preferably, aforementioned sheet material is for copying the paper that the paper method is made by wet type.In addition, preferably, aforementioned sheet material is the fully aromatic polyamide paper that comprises fully aromatic polyamide fiber.
Preferably, electrical insulating property resin sheet of the present invention was implemented corona treatment to the resin layer of the electrical insulating property at least side of aforementioned sheet material.
Preferably, electrical insulating property resin sheet of the present invention is used for the electrical isolation purposes.
The effect of invention
Electrical insulating property resin sheet of the present invention can be brought into play the effect of tear strength excellence and excellent heat resistance.
Description of drawings
Fig. 1 schematically illustratedly possesses the electrical insulating property resin sheet of two sheet materials by the sectional view in the cross section after cutting off along thickness direction.
Embodiment
Below an embodiment of electrical insulating property resin sheet of the present invention is described.
It is that 220N/20mm is above and be the electrical insulating property resin layer of the sheet more than 55% at the strength retention ratio of the tensile strength after through 250 hours under 240 ℃ that the electrical insulating property resin sheet of present embodiment possesses end tearing resistance value.
From tear strength and the more excellent aspect of thermotolerance of electrical insulating property resin sheet, preferably, aforementioned electric insulative resin sheet also possesses at least a sheet material, and this sheet material is disposed at least one face side of aforementioned electric insulative resin layer.
In addition, for aforementioned electric insulative resin sheet, preferably, aforementioned electric insulative resin layer comprises polysulfone resin and the thermoplastic resin except this polysulfone resin that has a plurality of alkylsulfonyls in the molecule.
Aforesaid end tearing resistance value is the index of tear strength, measures the value that obtains according to JIS C2151 " end tearing resistance (B method) " down at 23 ℃.Need to prove that aforesaid end tearing resistance value is generally below the 1000N/20mm.
The strength retention ratio of aforementioned tensile strength is stable on heating index.In addition, this strength retention ratio is following obtaining: with the electrical insulating property resin sheet 240 ℃ down place 250 hours before and afterwards, according to " tensile properties " of JIS C2151, under 23 ℃, carry out tension test, measure tensile strength, calculate by following formula.
Strength retention ratio (%)={ (tensile strength after the placement)/(tensile strength before placing) } * 100
Need to prove that this strength retention ratio specifically can be obtained by the method for putting down in writing among the embodiment.In addition, the common less than 100% of strength retention ratio.
Thickness to aforementioned electric insulative resin layer is not particularly limited, and is generally 1 μ m～500 μ m.
Aforementioned polysulfone resin has and comprises a plurality of alkylsulfonyl (SO 2-) molecular structure.
As this polysulfone resin, can list and also have a plurality of ehter bonds in the molecule and (also have the Polyphenylene Sulfone resin of a plurality of aromatic hydrocarbonss etc. in polyethersulfone resin O-) or the molecule.In addition, as this polysulfone resin, can list the polyethers Polyphenylene Sulfone resin that also has a plurality of ehter bonds and a plurality of aromatic hydrocarbonss in the molecule.
As aforementioned polysulfone resin, good from the plasticity of aforementioned electrical insulating property resin layer, and preferred, polyethers sulphone resin or Polyphenylene Sulfone resin, more preferably aforementioned polyethers Polyphenylene Sulfone resin are set out in the aspect that the thermotolerance of aforementioned electric insulative resin layer can become more excellent.
As aforementioned polyethers Polyphenylene Sulfone resin, preferably has the resin of the molecular structure of following formula (1).
Figure BDA00003638867800041
In the formula (1), n is the positive integer of the expression polymerization degree, usually in 10～5000 scope.
As aforementioned polyethers Polyphenylene Sulfone resin, commercially available product be can use, " ULTRASONE E Series ", " the RADEL A Series " that Solvay Advanced Polymers K.K. makes, " the SUMIKAEXCEL Series " that Sumitomo Chemical Co makes etc. that BASF AG makes for example can be listed.
In aforementioned electric insulative resin layer, the ratio that contains of aforementioned polysulfone resin is preferably more than the 50 weight %, more preferably more than the 70 weight %.In addition, the ratio that contains of aforementioned polysulfone resin is preferably below the 90 weight %, more preferably below the 80 weight %.
The ratio that contains by aforementioned polysulfone resin is more than the 50 weight %, has the advantage that the thermotolerance of electrical insulating property resin layer can become more excellent.In addition, the ratio that contains by aforementioned polysulfone resin is below the 90 weight %, has the advantage that the anti-electric trace voltinism of electrical insulating property resin layer can become more excellent.
As aforementioned thermoplastic resin except polysulfone resin, can list: polyamide resin; The multi-hydroxy polyether phenoxy resin that contains epoxy group(ing) that bisphenols and Epicholorohydrin reaction form; Have a plurality of oxygen methylene radical (CH in the molecule 2O-) polyacetal (POM) resin; Repeat polyphenylene oxide (the polyphenylene ether that the basic structure of aromatic hydrocarbons-ehter bond forms in the molecule; PPE) polyphenylene oxide (polyphenylene oxide such as resin; PPO) resin; Repeat aromatic polyether ketone (PEK) resin that the basic structure of aromatic hydrocarbons-ehter bond-aromatic hydrocarbons-ketonic bond forms in the molecule; Repeat aromatic polyether-ether ketone (PEEK) resin that the basic structure of aromatic hydrocarbons-ehter bond-aromatic hydrocarbons-ehter bond-aromatic hydrocarbons-ketonic bond forms in the molecule; Has a plurality of aromatic hydrocarbonss and a plurality of sulfide linkage (polyphenylene sulfide S-) (PPS) resin in the molecule; Polyetherimide (PEI) resin that has a plurality of aromatic hydrocarbonss, imide bond and ehter bond in the molecule; The polyamide thermoplastic imide resin that has a plurality of imide bonds and a plurality of amido linkages in the molecule; Polyolefin resines such as polyethylene, polypropylene, poly-cycloolefin; Vinyl cyanide, divinyl and cinnamic multipolymer (ABS resin) etc. contain aromatic vinyl resin; Vibrin such as PEN (PEN) resin, polybutylene terephthalate (PBT) resin, polyethylene terephthalate (PET) resin; Polycarbonate (PC) resin; Liquid crystalline polymers (LCP); Thermoplastic elastomer resin etc.
As aforementioned thermoplastic resin except polysulfone resin, from the tear strength of electrical insulating property resin layer and the thermotolerance aspect that electrical insulating properties such as more excellent and anti-electric trace voltinism can become more excellent that can become, preferred polyamide resin or thermoplastic elastomer resin, the more preferably mixture of polyamide resin and thermoplastic elastomer resin.
That is, from tear strength and the thermotolerance aspect that electrical insulating properties such as more excellent and anti-electric trace voltinism can become more excellent that can become, preferably, aforementioned electric insulative resin layer comprises aforementioned polysulfone resin and aforementioned polyamide resin.
For the resin sheet that possesses the electrical insulating property resin layer that comprises aforementioned polysulfone resin and aforementioned polyamide resin, for example, apply the excessive power that makes this resin sheet bending, when observing the resin sheet that is out of shape or breaks, can confirm following phenomenon.Particularly, for example, volume is had the winding wire of the motor of this resin sheet carry out bending process, when observing the destruction part of the resin sheet that destroys owing to excessive load, the polyamide resin that can confirm in the electrical insulating property resin layer partly destroys.
Can think that also polyamide resin contains the crystallinity composition, have the vulnerability that this crystallinity composition causes.And when inferring external force such as being subjected to tear edge at resin sheet, the destruction of resin sheet is from having the polyamide resin of above-mentioned vulnerability.In order to suppress this vulnerability, the electrical insulating property resin layer that comprises polysulfone resin and polyamide resin preferably further comprises aforementioned thermoplastic elastomer resin.Namely, aforementioned electric insulative resin layer also comprises aforementioned thermoplastic elastomer resin on the basis of aforementioned polysulfone resin and aforementioned polyamide resin, can suppress the vulnerability that polyamide resin can have by thermoplastic elastomer resin thus, have the electrical insulating property with excellent thermotolerance and excellence and the advantage that tear strength can become more excellent.
Particularly, aforementioned thermoplastic resin except polysulfone resin preferably comprises the aforementioned polyamide resin of 80～95 weight % concentration and the aforementioned thermoplastic elastomer resin of 5～20 weight % concentration.
In aforementioned electric insulative resin layer, aforementioned thermoplastic resin except polysulfone resin contain ratio be preferably 1 weight % above, more preferably 10 weight % above, more preferably more than the 20 weight %.In addition, be preferably below the 45 weight %, more preferably below the 30 weight %.
The ratio that contains by aforementioned thermoplastic resin except polysulfone resin is more than the 1 weight %, has the advantage that the anti-electric trace voltinism of electrical insulating property resin layer can become more excellent.In addition, the ratio that contains by aforementioned thermoplastic resin except polysulfone resin is below the 45 weight %, has the tear strength of electrical insulating property resin layer and the advantage that thermotolerance can become more excellent.
Aforementioned polyamide resin polyamine compound and polycarboxylic acid compound at least is polymerized by dehydrating condensation.
As aforementioned polyamide resin, can list in the polyamide resin that has aromatic hydrocarbons in the molecule, the molecule and only have aliphatic hydrocarbon as the fatty polyamide resin of hydrocarbon.Wherein, from the aspect that the thermotolerance of aforementioned electrical insulating property resin layer can become more excellent, has the polyamide resin of aromatic hydrocarbons in the preferred molecule.
In addition, as the polyamide resin that has aromatic hydrocarbons in the molecule, can list only have in the molecule aromatic hydrocarbons as have in the aromatic polyamide resin of hydrocarbon, the molecule aliphatic hydrocarbon and aromatic hydrocarbons the two as semiaromatic polyamide composition resin of hydrocarbon etc.
As the polyamide resin that has aromatic hydrocarbons in the molecule, from the aspect that excellent heat resistance and the anti-electric trace voltinism of electrical insulating property resin layer can become more excellent, preferred aforementioned semiaromatic polyamide composition resin.
Aforementioned polyamine compound as using in the polymerization of aforementioned polyamide resin particularly, for example can list diamine compound.
As this diamine compound, can list the alkyl that contains straight chain shape or chain aliphatie diamine, contain the saturated hydrocarbyl of ring-type alicyclic diamine, contain the aromatic diamine of aromatic hydrocarbyl etc.
As aforementioned aliphatie diamine, aforementioned alicyclic diamine or aforementioned aromatic diamine, for example can list the material shown in the following formula (2).Wherein, the R in the following formula (2) 1The aliphatic alkyl of expression carbon number 4～12 or contain the alicyclic alkyl of the carbon number 4～12 of cyclic saturated hydrocarbon, perhaps expression contains the alkyl of aromatic ring.
H 2N-R 1-NH 2…（2）
As aforementioned aliphatie diamine, from the aspect that the anti-electric trace voltinism of electrical insulating property resin layer can become more excellent, the R in the preferred formula (2) 1Carbon number be 9 nonamethylene diamine, more preferably with 1,9-nonamethylene diamine and 2-methyl isophthalic acid, the 8-octamethylenediamine mixes and the material that obtains.
As aforementioned aromatic diamine, can list phenylenediamine, benzene dimethylamine etc.
Aforementioned polycarboxylic acid compound as using in the polymerization of aforementioned polyamide resin particularly, for example can list the di-carboxylic acid compound.
As this di-carboxylic acid compound, can list the alkyl that contains straight chain shape or chain aliphatic dicarboxylic acid, contain the saturated hydrocarbyl of ring-type alicyclic di-carboxylic acid, contain the aromatic binary carboxylic acid of aromatic hydrocarbyl etc.
As aforementioned aliphatic dicarboxylic acid, aforementioned alicyclic di-carboxylic acid or aforementioned aromatic binary carboxylic acid, for example can list the material shown in the following formula (3).Wherein, the R in the following formula (3) 2The aliphatic alkyl of expression carbon number 4～25 or contain the alicyclic alkyl of the carbon number 4～12 of cyclic saturated hydrocarbon, perhaps expression contains the alkyl of aromatic ring.
HOOC-R 2-COOH…（3）
As aforementioned aliphatic dicarboxylic acid, can list hexanodioic acid, sebacic acid etc.
As aforementioned aromatic binary carboxylic acid, can list terephthalic acid, terephthalic acid methyl esters, naphthalic acid etc., as this aromatic binary carboxylic acid, from the aspect that the thermotolerance of aforementioned polyamide resin can become more excellent, preferred terephthalic acid.
Aforementioned polyamide resin can be the polyamide resin that above-mentioned a kind of diamine compound and a kind of di-carboxylic acid compound polymerization form, and also can be with each compound multiple combination and the polyamide resin that is polymerized respectively.In addition, if desired, also can be the polyamide resin that the material of further polymerization except diamine compound and di-carboxylic acid compound forms.
As aforementioned polyamide resin, preferred aforementioned semiaromatic polyamide composition resin as mentioned above, as this semiaromatic polyamide composition resin, more preferably will be as the aliphatie diamine of diamine compound and the material that is polymerized as the aromatic binary carboxylic acid of di-carboxylic acid compound, especially preferably will be as the nonamethylene diamine of aliphatie diamine and the material (PA9T) that is polymerized as the terephthalic acid of aromatic binary carboxylic acid.
In aforementioned electric insulative resin layer, the ratio that contains of aforementioned polyamide resin is preferably more than the 1 weight %, more preferably more than the 9 weight %.In addition, be preferably below the 30 weight %, more preferably below the 25 weight %.
The ratio that contains by aforementioned polyamide resin is more than the 1 weight %, has the advantage that the anti-electric trace voltinism of electrical insulating property resin layer can become more excellent.In addition, the ratio that contains by aforementioned polyamide resin is below the 30 weight %, has the tear strength of electrical insulating property resin layer and the advantage that thermotolerance can become more excellent.
Aforementioned thermoplastic elastomer resin is the thermoplastic resin that demonstrates rubber-like elasticity at normal temperatures.
Aforementioned thermoplastic elastomer resin is not particularly limited, as aforementioned thermoplastic elastomer resin, for example can list each thermoplastic elastomer resin of vinyl chloride, ethylene series, polyurethane series, polyester system, nitrile system, polyamide-based or fluorine system etc., particularly, for example can list polyhutadiene based thermoplastic elastomerics, styrene butadiene based thermoplastic elastomerics or styrene-isoprene block copolymer etc.
In addition, as aforementioned thermoplastic elastomer resin, can list thermoplastic elastomer resin that has polar functional group in the molecule etc.Has the thermoplastic elastomer resin of polar functional group in the molecule owing to have polar functional group and the affinity excellence of the polyamide resin with polarity.Therefore, in the electrical insulating property resin layer that comprises thermoplastic elastomer resin with polar functional group and polyamide resin, the associativity of these interlaminar resins becomes more firm.And the characteristic of the rubber-like elasticity of thermoplastic elastomer resin can suppress the vulnerability that polyamide resin shows more reliably, and is more excellent thereby tear strength can become.
As the thermoplastic elastomer resin that has polar functional group in the aforementioned molecule, particularly, for example can list the thermoplastic elastomer resin of anhydride group, epoxy group(ing) or halogen group isopolarity functional group with the functional group that contains active hydrogen functional group, nitrogen-containing functional group, contains active hydrogen and nitrogen, the functional group of containing carbonyl or thiocarbonyl, carboxyl.
As the aforementioned active hydrogen functional group that contains, can list-COOH ,-OH ,-SH ,-SO 3H ,-SO 2H ,-SOH etc.
As aforementioned nitrogen-containing functional group, can list-NRR ',＞C=N-,-CN ,-NCO ,-OCN ,-SCN ,-NO ,-NO 2Deng.
As the aforementioned functional group of containing active hydrogen and nitrogen, can list-NH 2,-NHR ,-CONH 2,-CONHR ,-CONH-,＞C=NH etc.
As the aforementioned functional group of containing carbonyl or thiocarbonyl, can list＞C=O,＞C=S ,-CH=O ,-CH=S ,-COOR ,-CSOR etc.
Wherein, the expression of R, the R ' in above-mentioned functional group hydrogen atom, alkyl, aryl etc.
As aforementioned polar functional group, the anhydride group of preferred carboxyl, carboxyl, hydroxyl (OH), epoxy group(ing), isocyanate group (NCO) or-NRR ' ,-NHR ,-NH 2Deng amino, the more preferably anhydride group of carboxyl, the acid anhydrides (maleic anhydride group) of further preferred toxilic acid.
Particularly, as aforementioned thermoplastic elastomer resin, from the aspect that the tear strength of electrical insulating property resin layer can become more excellent, has the thermoplastic elastomer resin of polar functional group in the preferred molecule, more preferably maleic anhydride modified polyolefin thermoplastic elastomer.
As aforementioned maleic anhydride modified polyolefin thermoplastic elastomer, from the aspect that the tear strength of electrical insulating property resin layer can become more excellent, the maleic anhydride modified multipolymer of optimal ethylene-propylene.
In aforementioned electric insulative resin layer, the ratio that contains of aforementioned thermoplastic elastomer resin is preferably more than the 0.1 weight %, more preferably more than the 0.5 weight %.In addition, the ratio that contains of aforementioned thermoplastic elastomer resin is preferably below the 5 weight %, more preferably below the 4 weight %.
The ratio that contains by aforementioned thermoplastic elastomer resin is more than the 0.1 weight %, has the advantage that the tear strength of electrical insulating property resin layer can become more excellent.In addition, the ratio that contains by aforementioned thermoplastic elastomer resin is below the 5 weight %, has the advantage that the thermotolerance of electrical insulating property resin layer can become more excellent.
In the scope of not damaging effect of the present invention, also can the various additives of compounding in the aforementioned electric insulative resin layer.
As this additive, for example can list alkyl phenolic resin, alkylphenol-acetylene resin, xylene resin, coumarone-indene resin, terpine resin, tackifier such as rosin, Poly Brominated Diphenyl Ethers, bromide fire retardants such as tetrabromo-bisphenol, clorafin, cross chlorine-based flame retardants such as chlorine cyclodecane, phosphoric acid ester, phosphorus flame retardants such as halogen-containing phosphoric acid ester, the boron flame retardant, oxide based fire retardant such as ANTIMONY TRIOXIDE SB 203 99.8 PCT, aluminium hydroxide, hydrated metal compounds such as magnesium hydroxide, phenol system, phosphorus system, the antioxidant of sulphur system, silicon-dioxide, clay, calcium carbonate, barium carbonate, Strontium carbonate powder, aluminum oxide, manganese oxide, boron nitride, silicon nitride, the mineral filler that aluminium nitride is such, thermo-stabilizer, photostabilizer, UV light absorber, lubricant, pigment, linking agent, crosslinking coagent, silane coupling agent, common plastics such as titanate coupling agent become to grade with compounding.In addition, can list the montmorillonite etc. of the particle diameter of aromatic polyamide fibre, a few nm～hundreds of nm.Comprise the resin compound of aforementioned polysulfone resin and aforementioned thermoplastic resin except polysulfone resin with respect to 100 weight parts, these additives for example can use 0.1～5 weight part.
Then, as the object lesson of aforementioned electric insulative resin sheet, can list the electrical insulating property resin sheet that disposes sheet material in the two sides side of aforementioned electric insulative resin layer, be elaborated with reference to accompanying drawing.
To be the schematically illustrated electrical insulating property resin sheet that will dispose sheet material 3 in the two sides side of aforementioned electric insulative resin layer 2 cut off and the sectional view in the cross section that obtains along thickness direction Fig. 1.
As shown in Figure 1, in above-mentioned electrical insulating property resin sheet 1, the electrical insulating property resin layer 2 that a plurality of sheet materials 3 clip sheet fits together.
Aforementioned sheet material 3 is as long as just be not particularly limited for sheet.In addition, the thickness of sheet material 3 is not particularly limited, is generally 10～100 μ m.
As aforementioned sheet material 3, for example can list non-woven fabrics, paper or film etc.As aforementioned sheet material 3, the aspect from the thermotolerance of electrical insulating property resin layer can become more excellent is preferably non-woven fabrics or paper.
As aforementioned sheet material 3, can list by wet type and copy the sheet material (Wet-laid non-woven fabric etc.) that the paper method makes, the sheet material of in atmosphere, making by drying process (dry type non-woven fabrics etc.) etc.
As aforementioned sheet material 3, from the aspect that the thermotolerance of electrical insulating property resin layer can become more excellent, preferably copy the paper that the paper method is made by wet type.
As the material of aforementioned sheet material 3, can list natural high moleculer eompounds such as synthetic macromolecular compounds such as polymeric amide, polyester, Mierocrystalline cellulose etc., from the aspect that the thermotolerance of electrical insulating property resin layer can become more excellent, preferred polyamide.
As this polymeric amide, can list whole formation monomers and all have the fully aromatic polyamide of aromatic hydrocarbons, all constitute the fatty polyamide that monomer all only has aliphatic hydrocarbon, the semiaromatic polyamide composition that comprises the formation monomer with aromatic hydrocarbons and the formation monomer with aliphatic hydrocarbon etc.As aforementioned polymeric amide, from the aspect that the thermotolerance of electrical insulating property resin layer can become more excellent, preferred fully aromatic polyamide.That is, preferably, aforementioned sheet material 3 comprises aforementioned fully aromatic polyamide.
In addition, as aforementioned sheet material 3, from the aspect that the thermotolerance of electrical insulating property resin layer can become more excellent, further preferably comprise the fully aromatic polyamide paper of fully aromatic polyamide fiber.That is, as sheet material 3, further the preferred fully aromatic polyamide fiber that uses is copied the fully aromatic polyamide paper that the paper method is made by wet type.
As aforementioned fully aromatic polyamide paper, for example can list following material: polycondensate (fully aromatic polyamide) fibrosis of the phenylenediamine that will be made of phenyl ring except amide group and phthalic acid is the fully aromatic polyamide paper that the main composition material forms with fiberized fully aromatic polyamide fiber.
The operation good aspect of aforementioned fully aromatic polyamide paper from the manufacturing process of mechanical characteristic excellence, electrical insulating property resin sheet, Substance is preferably 5g/m 2More than.Be 5g/m by Substance 2More than, the deficiency of mechanical strength is suppressed, and has in the manufacturing of electrical insulating property resin sheet the not advantage of easy fracture.
In addition, in the scope of not damaging effect of the present invention, the composition that in aforementioned fully aromatic polyamide paper, can add other, as this other composition, can list inorganic fibres such as organic fibres such as polyphenylene sulfide fibre, polyetheretherketonefiber fiber, trevira, aromatic ester fiber, liquid crystalline polyester fiber, polyethylene naphthalate fiber or glass fibre, rock wool, asbestos, boron fibre, sapphire whisker.
As aforementioned fully aromatic polyamide paper, for example can use the commercially available product etc. of the trade(brand)name " NOMEX " of E.I.Du Pont Company.
Preferably implement corona treatment in electrical insulating property resin layer 2 sides of aforementioned sheet material 3.By implementing this corona treatment, has the advantage that the splitting between sheet material and the electrical insulating property resin layer can further be suppressed.
Aforementioned corona treatment is that a face to the sheet material 3 that contacts with electrical insulating property resin layer 2 carries out discharge process, generates carboxyl, hydroxyl with polarity, makes the processing of the face roughening of sheet material 3.As aforementioned corona treatment, can adopt existing known usual method.
In aforementioned electric insulative resin sheet, be generally more than the 130V as the CTI value of the anti-electric trace test of the index of electrical insulating property.In addition, this CTI value is preferably below the 250V.Need to prove that anti-electric trace test can be undertaken by the method for putting down in writing among the embodiment.
Aforementioned electric insulative resin sheet is preferably as follows formation: the interlayer bonding force between aforementioned electric insulative resin layer and the aforementioned sheet material is greater than each cohesive failure power of aforementioned electric insulative resin layer and aforementioned sheet material, and making can splitting between aforementioned electric insulative resin layer and the aforementioned sheet material.
Then, the manufacture method to aforementioned electric insulative resin sheet describes.
The aforementioned electric insulative resin layer that aforementioned electric insulative resin sheet possesses can be made by utilizing existing known usual method that resin compound is configured as sheet, and described resin compound is with polysulfone resin and the thermoplastic resin except this polysulfone resin is heated to specified temperature and mixing obtains.Particularly, for example can utilize the forcing machine that the T mould is installed to be extruded into sheet by common mixing means heating such as kneader, pressure kneader, mixing roller, Banbury mixer, twin screw extruder and the resin compound that mixes waits to make.
In addition, for example, the electrical insulating property resin sheet that possesses two sheet materials specifically can be by pressing to make to the object with the state of two sheet material clamping electrical insulating property resin layers.
The utilization of aforementioned electric insulative resin sheet has the electrical insulating property this point, for example can be used for electrical isolation usefulness sheet that electrical isolation that the motor of automobile etc. uses uses with sheet, bus-bar with the electrical isolation of sheet, transformer (transformer) usefulness etc.
The electrical insulating property resin sheet of present embodiment such as above-mentioned illustration, but the present invention is not limited to above-mentioned illustrative electrical insulating property resin sheet.
In addition, in the scope of not damaging effect of the present invention, can adopt the various forms that in common electrical insulating property resin sheet, uses.
For example, in the above-described embodiment, be illustrated for respectively disposing the electrical insulating property resin sheet that a slice sheet material forms in the two sides side of the electrical insulating property resin layer of sheet among Fig. 1, but the present invention is not limited to this embodiment, also can be only forms at face side configuration a slice sheet material of the electrical insulating property resin layer of sheet.The electrical insulating property resin layer that also can only possess in addition, sheet.
Embodiment
Then, enumerate embodiment and further describe the present invention, but the present invention is not limited to this.
(embodiment 1)
At first, prepare following raw material.
Polysulfone resin: polyethers Polyphenylene Sulfone resin (PES) resin
(having a plurality of alkylsulfonyls, ehter bond and aromatic hydrocarbons in the molecule)
Use (Solvay Advanced Polymers K.K. trade(brand)name processed " RADEL A-300A ").
The mixture of the maleic anhydride modified polyolefin thermoplastic elastomer of 5 weight % concentration and the polyamide (PA) resin of 95 weight % concentration
(KURARAY CO., LTD trade(brand)name processed " Genestar N1001A ")
(maleic anhydride modified polyolefin thermoplastic elastomer; The maleic anhydride modified multipolymer of ethylene-propylene (EPMA))
(PA resin; The PA9T that has terephthalic acid units and nonamethylene diamine unit in the molecule)
Then, become the mode of the weight ratio of PES/PA/EPMA=90/9.5/0.5 with PES resin, PA resin and EPMA, utilize twin-screw mixer machine (Technovel Corp. system) to mix down at 310 ℃ the PES resin of 90 weight parts and " the Genestar N1001A " of 10 weight parts, the preparation resin compound.
Then, resin compound is configured as the thick sheet of 100 μ m by extrusion molding under 310 ℃, forms the electrical insulating property resin layer, make the electrical insulating property resin sheet of the electrical insulating property resin layer that only comprises sheet.
(embodiment 2)
Use the PES resin of 80 weight parts and " Genestar N1001A " preparation resin compound of 20 weight parts in the mode of the weight ratio that becomes PES/PA/EPMA=80/19/1, utilize this resin compound to form the electrical insulating property resin layer, except this point, the electrical insulating property resin sheet is made in operation similarly to Example 1.
(embodiment 3)
Use the PES resin of 70 weight parts and " Genestar N1001A " preparation resin compound of 30 weight parts in the mode of the weight ratio that becomes PES/PA/EPMA=70/28.5/1.5, utilize this resin compound to form the electrical insulating property resin layer, except this point, the electrical insulating property resin sheet is made in operation similarly to Example 1.
(embodiment 4)
Further prepare following raw material.
The mixture of the maleic anhydride modified polyolefin thermoplastic elastomer of 20 weight % concentration and the polyamide (PA) resin of 80 weight % concentration
(KURARAY CO., LTD trade(brand)name processed " Genestar N1006A ")
(maleic anhydride modified polyolefin thermoplastic elastomer; The maleic anhydride modified multipolymer of ethylene-propylene (EPMA))
(PA resin; The PA9T that has terephthalic acid units and nonamethylene diamine unit in the molecule)
Then, use the PES resin of 80 weight parts, " Genestar N1001A " and " Genestar N1006A " preparation resin compound of 7 weight parts of 13 weight parts in the mode of the weight ratio that becomes PES/PA/EPMA=80/17.9/2.1, utilize this resin compound to form the electrical insulating property resin layer, except this point, the electrical insulating property resin sheet is made in operation similarly to Example 1.
(embodiment 5)
Use the PES resin of 80 weight parts, " Genestar N1001A " and " Genestar N1006A " preparation resin compound of 13 weight parts of 7 weight parts in the mode of the weight ratio that becomes PES/PA/EPMA=80/17/3, utilize this resin compound to form the electrical insulating property resin layer, except this point, the electrical insulating property resin sheet is made in operation similarly to Example 1.
(embodiment 6)
Use the PES resin of 80 weight parts and " Genestar N1006A " preparation resin compound of 20 weight parts in the mode of the weight ratio that becomes PES/PA/EPMA=80/16/4, utilize this resin compound to form the electrical insulating property resin layer, except this point, the electrical insulating property resin sheet is made in operation similarly to Example 1.
(embodiment 7)
Use the PES resin of 80 weight parts and " Genestar N1001A " preparation resin compound of 20 weight parts in the mode of the weight ratio that becomes PES/PA/EPMA=80/19/1, utilize this resin compound to form the electrical insulating property resin layer, except this point, the electrical insulating property resin layer is made in operation similarly to Example 1.
On the other hand, prepare two fully aromatic polyamide paper (E.I.Du Pont Company's trade(brand)name processed " NOMEXT410 " thickness 50 μ m) as sheet material.And then, the face of the side that contacts with the electrical insulating property resin layer of each sheet material is implemented corona treatment.Corona treatment be to use " 500Series " that PILLAR TECHNOLOGIES company makes as equipment, under atmospheric pressure, under power 500W, processing speed 4m/ minute, the condition of specimen width 0.4m, carry out.
Then, will dispose the sample of state of two fully aromatic polyamide paper in the two sides side of the electrical insulating property resin layer made from two metal sheet clampings, use is heated to 350 ℃ thermocompressor, at pressure 200N/cm 2Under suppressed 60 seconds, the two sides side that is manufactured on the electrical insulating property resin layer possesses the thick electrical insulating property resin sheet of about 200 μ m of two sheet materials.
(embodiment 8)
Use the PES resin of 80 weight parts and " Genestar N1006A " preparation resin compound of 20 weight parts in the mode of the weight ratio that becomes PES/PA/EPMA=80/16/4, utilize this resin compound to form the electrical insulating property resin layer, except this point, the electrical insulating property resin layer is made in operation similarly to Example 1.
Then, further use two fully aromatic polyamide paper, with above-mentioned same operation, the two sides side that is manufactured on the electrical insulating property resin layer possesses the thick electrical insulating property resin sheet of about 200 μ m of two sheet materials.
(embodiment 9)
Further prepare following polyamide resin.
Polyamide resin: polyamide (PA) resin
(KURARAY CO., LTD trade(brand)name processed " Genestar N1000A ")
(PA9T that has a plurality of terephthalic acid units and nonamethylene diamine unit in the molecule)
Then, use the PES resin of 80 weight parts and " Genestar N1000A " preparation resin compound of 20 weight parts in the mode of the weight ratio that becomes PES/PA=80/20, utilize this resin compound to form the electrical insulating property resin layer, except this point, the electrical insulating property resin layer is made in operation similarly to Example 1.
Then, use two fully aromatic polyamide paper, with above-mentioned same operation, the two sides side that is manufactured on the electrical insulating property resin layer possesses the thick electrical insulating property resin sheet of about 200 μ m of two sheet materials.
(comparative example 1)
Except only using PES resin formation electrical insulating property resin layer this point, operation similarly to Example 1, manufacturing only comprises the electrical insulating property resin sheet of the electrical insulating property resin layer of sheet.
(comparative example 2)
Use the PES resin of 80 weight parts and " Genestar N1000A " preparation resin compound of 20 weight parts in the mode of the weight ratio that becomes PES/PA=80/20, utilize this resin compound to form the electrical insulating property resin layer, except this point, operation similarly to Example 1, manufacturing only comprises the electrical insulating property resin sheet of the electrical insulating property resin layer of sheet.
(comparative example 3)
Use the PES resin of 50 weight parts and " Genestar N1000A " preparation resin compound of 50 weight parts in the mode of the weight ratio that becomes PES/PA=50/50, utilize this resin compound to form the electrical insulating property resin layer, except this point, operation similarly to Example 1, manufacturing only comprises the electrical insulating property resin sheet of the electrical insulating property resin layer of sheet.
(comparative example 4)
Use the PES resin of 70 weight parts and " Genestar N1006A " preparation resin compound of 30 weight parts in the mode of the weight ratio that becomes PES/PA/EPMA=70/24/6, utilize this resin compound to form the electrical insulating property resin layer, except this point, operation similarly to Example 1, manufacturing only comprises the electrical insulating property resin sheet of the electrical insulating property resin layer of sheet.
(comparative example 5)
With PEN (PEN) film (Teijin DuPont Films Japan Limited trade(brand)name processed " Teonex100 μ m ") as the electrical insulating property resin sheet.
(comparative example 6)
With polyphenylene sulfide (PPS) film (Toray Industries, Inc. trade(brand)name processed " TORELINA100 μ m ") as the electrical insulating property resin sheet.
＜stable on heating evaluation＞
A plurality of test samples that the flow direction of the electrical insulating property resin layer of the electrical insulating property resin sheet that make on the manufacturing edge obtains with the width cut-out of 15mm.In addition, the test sample that a part is made was placed 250 hours in being heated to 240 ℃ thermostatic bath.According to " tensile properties " of JIS C2151, under 23 ℃, with 200mm/ minute, the test conditions of graticule 100mm to before in thermostatic bath, placing and test sample afterwards carry out tension test, measure tensile strength.Then, calculate strength retention ratio by following formula.
Strength retention ratio (%)={ (tensile strength after the placement)/(tensile strength before placing) } * 100
The evaluation of＜tear strength＞
According to " edge anti-tear (the B method) " of JIS C2151, under 23 ℃, measure respectively the electrical insulating property resin sheet along vertical (MD) to and horizontal (TD) end tearing resistance value when breaking.
The evaluation of＜anti-electric trace voltinism＞
According to JIS C2134, measure CTI(Comparative Tracking Index down at 23 ℃) value.
＜tensile elongation＞
According to JIS C2151, extrude direction (MD direction) and its orthogonal directions (TD direction) to the electrical insulating property resin sheet measured tensile elongation respectively under 23 ℃.
Thermotolerance (strength retention ratio), tear strength (end tearing resistance value), anti-electric trace voltinism (CTI value) and the evaluation result of tensile elongation of each embodiment and each comparative example are shown in table 1, table 2.
[table 1]
[table 2]
Figure BDA00003638867800201
Utilizability on the industry
Electrical insulating property resin sheet of the present invention can be used as the electrical isolation uses aptly such as sheet that need thermotolerance and electrical insulating property.Particularly, for example, in the purposes such as insulating film of electrical isolation with sheet material or electronic circuit board that the electrical isolation around the winding wire that is disposed at motor is used with sheet material, transformer, bus-bar, electrical condenser, cable, be fit to.
Description of reference numerals
1: electrical insulating property resin sheet, 2: electrical insulating property resin layer, 3: sheet material

Claims (18)

1. an electrical insulating property resin sheet is characterized in that, it possesses end tearing resistance value is that 220N/20mm is above and be the electrical insulating property resin layer of the sheet more than 55% at the strength retention ratio of the tensile strength after through 250 hours under 240 ℃.
2. electrical insulating property resin sheet according to claim 1, wherein, described electrical insulating property resin layer comprises polysulfone resin and the thermoplastic resin except this polysulfone resin that has a plurality of alkylsulfonyls in the molecule.
3. electrical insulating property resin sheet according to claim 2, wherein, described electrical insulating property resin layer comprises described polysulfone resin and the thermoplastic resin except this polysulfone resin, as the thermoplastic resin except this polysulfone resin, comprises polyamide resin and thermoplastic elastomer resin.
4. electrical insulating property resin sheet according to claim 3, wherein, described electrical insulating property resin layer comprises the described polyamide resin of described polysulfone resin, 1～30 weight % and the described thermoplastic elastomer resin of 0.1～5 weight %.
5. according to claim 3 or 4 described electrical insulating property resin sheets, wherein, described polyamide resin is the polyamide resin that has aromatic hydrocarbons in the molecule.
6. according to each the described electrical insulating property resin sheet in the claim 3～5, wherein, described thermoplastic elastomer resin is maleic anhydride modified polyolefin thermoplastic elastomer.
7. according to each the described electrical insulating property resin sheet in the claim 2～6, wherein, described polysulfone resin is the polyethersulfone resin that also has a plurality of ehter bonds in the molecule.
8. according to each the described electrical insulating property resin sheet in the claim 2～7, wherein, described polysulfone resin is the Polyphenylene Sulfone resin that also has a plurality of aromatic hydrocarbonss in the molecule.
9. according to each the described electrical insulating property resin sheet in the claim 1～8, wherein, it also possesses at least a sheet material, and this sheet material is disposed at least one face side of described electrical insulating property resin layer.
10. electrical insulating property resin sheet according to claim 9, wherein, described sheet material comprises fully aromatic polyamide.
11. according to claim 9 or 10 described electrical insulating property resin sheets, wherein, described sheet material is for copying the paper that the paper method is made by wet type.
12. according to each the described electrical insulating property resin sheet in the claim 9～11, wherein, described sheet material is the fully aromatic polyamide paper that comprises fully aromatic polyamide fiber.
13. according to claim 9 or 10 described electrical insulating property resin sheets, wherein, described sheet material is non-woven fabrics.
14. according to each the described electrical insulating property resin sheet in the claim 9～13, wherein, the resin layer of the electrical insulating property at least side of described sheet material was implemented corona treatment.
15. according to each the described electrical insulating property resin sheet in the claim 9～14, it is following formation: the interlayer bonding force between described electrical insulating property resin layer and the described sheet material is greater than each cohesive failure power of described electrical insulating property resin layer and described sheet material, and making can splitting between described electrical insulating property resin layer and the described sheet material.
16. according to each the described electrical insulating property resin sheet in the claim 1～15, wherein, the CTI value of anti-electric trace test is more than the 130V.
17. according to each the described electrical insulating property resin sheet in the claim 1～16, it is used for the electrical isolation purposes.
18. according to each the described electrical insulating property resin sheet in the claim 1～17, it is used for the purposes that motor coil is used insulating trip.
CN2012800081830A 2011-02-09 2012-02-07 Electrically insulating resin sheet Pending CN103347937A (en)

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