WO2016190163A1 - Aramid paper sheet and method for producing same - Google Patents
Aramid paper sheet and method for producing same Download PDFInfo
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- WO2016190163A1 WO2016190163A1 PCT/JP2016/064567 JP2016064567W WO2016190163A1 WO 2016190163 A1 WO2016190163 A1 WO 2016190163A1 JP 2016064567 W JP2016064567 W JP 2016064567W WO 2016190163 A1 WO2016190163 A1 WO 2016190163A1
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- WIPO (PCT)
- Prior art keywords
- aramid paper
- aramid
- paper
- fibrid
- fibrids
- Prior art date
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- 229920003235 aromatic polyamide Polymers 0.000 title claims abstract description 113
- 239000004760 aramid Substances 0.000 title claims abstract description 111
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000000835 fiber Substances 0.000 claims abstract description 49
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000007731 hot pressing Methods 0.000 claims description 8
- 230000009477 glass transition Effects 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 230000014509 gene expression Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 230000035699 permeability Effects 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 238000010292 electrical insulation Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- -1 polymetaphenylene isophthalamide Polymers 0.000 description 6
- 239000011810 insulating material Substances 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000003490 calendering Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229920000784 Nomex Polymers 0.000 description 3
- 238000010009 beating Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000004763 nomex Substances 0.000 description 3
- 230000002093 peripheral effect Effects 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 229920006231 aramid fiber Polymers 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 229920003367 Teijinconex Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 239000012777 electrically insulating material Substances 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- QZUPTXGVPYNUIT-UHFFFAOYSA-N isophthalamide Chemical compound NC(=O)C1=CC=CC(C(N)=O)=C1 QZUPTXGVPYNUIT-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000004765 teijinconex Substances 0.000 description 1
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/10—Organic non-cellulose fibres
- D21H13/20—Organic non-cellulose fibres from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H13/26—Polyamides; Polyimides
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
- D21F5/00—Dryer section of machines for making continuous webs of paper
- D21F5/004—Drying webs by contact with heated surfaces or materials
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
- D21H25/04—Physical treatment, e.g. heating, irradiating
Definitions
- the present invention relates to an electrically insulating material having high heat resistance. More specifically, the present invention relates to aramid paper that is thin and has high strength.
- aramid paper is a synthetic paper made of aromatic polyamide and has been used as an electrical insulating material and aircraft honeycomb base due to its excellent heat resistance, flame resistance, electrical insulation, toughness and flexibility.
- DuPont (USA) Nomex (R) fiber paper comprises mixing poly (metaphenylene isophthalamide) staple fibers and fibrids in water, It is manufactured by calendering the paper mixed with the slurry. This paper is known to still have high strength and toughness and excellent electrical insulation even at high temperatures.
- insulating materials such as transformers and motors
- An object of the present invention is to provide a thin heat insulating sheet material having high heat resistance. Another object of the present invention is to provide a method for producing the above electric insulating sheet material.
- the present invention is an aramid paper formed from a mixture of a fibrid formed from an aromatic polyamide and a short fiber, and the following inequalities (1) and (2) 40 ⁇ [FB] ⁇ 90 (1) [Thickness] / ([Fiber diameter of short fiber] ⁇ 2) ⁇ 1.25 (2) [Wherein [FB] is the fibrid content (% by weight) in the aramid paper] An aramid paper having a satisfying fibrid content and thickness is provided.
- the present invention includes hot pressing with an aramid paper formed from a mixture of a fibrid formed from an aromatic polyamide and a short fiber between at least a pair of heating elements.
- the method for producing aramid paper according to the first aspect is provided, wherein the shrinkage rate of the aramid paper after hot pressing with the heating element is 3% or less.
- the present invention sandwiches an aramid paper formed from a mixture of a fibrid formed from an aromatic polyamide and a short fiber between at least a pair of heating elements, and has a weight of 1000 kg / cm 2 or more.
- aramid means a linear polymer compound (aromatic polyamide) in which 60% or more of amide bonds are directly bonded to an aromatic ring.
- aromatic polyamide examples include polymetaphenylene isophthalamide and copolymers thereof, polyparaphenylene terephthalamide and copolymers thereof, poly (paraphenylene) -copoly (3,4 diphenyl ether) terephthalamide, and the like.
- These aramids are industrially produced by, for example, conventionally known interfacial polymerization methods, solution polymerization methods and the like using isophthalic acid chloride and metaphenylenediamine, and can be obtained as commercial products. Is not to be done.
- polymetaphenylene isophthalamide is preferably used in that it has characteristics such as good moldability, thermal adhesiveness, flame retardancy, and heat resistance.
- aramid fibrids are film-form aramid particles having paper-making properties and are also called aramid pulp (see Japanese Patent Publication No. 35-11851, Japanese Patent Publication No. 37-5732, etc.).
- Aramid fibrids are widely known to be used as a papermaking raw material after being disaggregated and beaten in the same manner as ordinary wood pulp, and can be subjected to so-called beating treatment for the purpose of maintaining quality suitable for papermaking. This beating process can be performed by a disk refiner, a beater, or other papermaking raw material processing equipment that exerts a mechanical cutting action.
- the shape change of the fibrid can be monitored by the freeness test method stipulated in Japanese Industrial Standard P8121.
- the freeness of the aramid fibrid after the beating treatment is preferably in the range of 10 to 300 cm 3 (Canadian Standard Freeness).
- the strength of the multi-thermal electrical insulation sheet material formed therefrom may be reduced.
- the utilization efficiency of the mechanical power to be input becomes small, the processing amount per unit time is often reduced, and further refinement of the fibrid is reduced. Since it proceeds too much, the so-called binder function is likely to deteriorate.
- the aramid fibrid has excellent properties as a binder, so it can efficiently supplement fine particles and other additive components, and at the same time the raw material yield is improved in the production of the aramid paper of the present invention. It is possible to reduce the number of through-holes in layers in the sheet, and the electrical insulation is improved.
- an aramid short fiber is obtained by cutting a fiber made of aramid.
- aramid registered trademark
- examples of such a fiber include “Teijin Conex (registered trademark)” by Teijin Limited, “ Although what can be obtained by brand names, such as "NOMEX (trademark)", is mentioned, It is not limited to these.
- the length of the aramid short fibers can be selected from the range of generally 1 mm or more and less than 50 mm, preferably 2 to 10 mm. If the length of the short fiber is less than 1 mm, the mechanical properties of the sheet material are deteriorated.
- the fiber diameter of the aramid short fibers can be selected from the range of preferably 0.1 to 25 ⁇ m, more preferably 1 to 20 ⁇ m.
- the aramid paper is a sheet-like material mainly composed of the aramid fibrid and the aramid short fibers, and the following inequalities (1) and (2) 40 ⁇ [FB] ⁇ 90 (1) [Thickness] / ([Fiber diameter of short fiber] ⁇ 2) ⁇ 1.25 (2) [Wherein [FB] is the fibrid content (% by weight) in the aramid paper) And satisfying the fibrid content and thickness.
- the aramid paper has a more porous structure and tends to cause a problem in electrical insulation.
- Aramid paper is generally produced by a method of mixing the above-mentioned aramid fibrid and aramid short fibers and then forming a sheet.
- a method of forming a sheet using an air flow after dry blending the aramid fibrid and the aramid short fiber, a method of forming a sheet using an air flow, after the aramid fibrid and the aramid short fiber are dispersed and mixed in a liquid medium, the liquid permeation is performed.
- a so-called wet papermaking method using water as a medium is preferably selected.
- a single or mixed aqueous slurry containing at least aramid fibrids and short aramid fibers is fed to a paper machine and dispersed, and then dewatered, squeezed and dried to be wound up as a sheet. The method is common.
- a long paper machine a circular paper machine, an inclined paper machine, and a combination paper machine combining these are used.
- a composite sheet composed of a plurality of paper layers can be obtained by forming and combining slurry having different blending ratios.
- Additives such as a dispersibility improver, an antifoaming agent, and a paper strength enhancer are used as necessary during papermaking.
- Aramid paper generally has a basis weight in the range of 5 to 1000 g / m 2 , preferably 15 to 200 g / m 2 .
- the tensile strength of the aramid paper is preferably in the range of 0.5 kgf / 15 mm or more, more preferably 1 kgf / 15 mm or more.
- the air permeability of the aramid paper is preferably in the range of 3000 seconds or more, more preferably 4000 seconds or more.
- the aramid paper obtained as described above is known to be improved in density, crystallinity, heat resistance, dimensional stability, and mechanical strength by hot pressing at a high temperature and high pressure between a pair of heating elements. ing.
- the heat pressure condition is preferably such that the shrinkage rate of the aramid paper after being hot-pressed between the heating elements is 3% or less. When the shrinkage rate exceeds 3%, it becomes difficult to have a thickness in the range of the above formula (2) due to an increase in thickness due to shrinkage.
- the shrinkage rate is more preferably 2% or less, and further preferably 1.5% or less.
- the aramid paper is sandwiched between at least a pair of heating elements and a pressure of 1000 kg / cm 2 or more is applied.
- the amount of heat Q (J / m 2 ) expressed by the following is supplied per unit area of the aramid paper, the shrinkage rate is suppressed to within 3%, and the short fiber itself is deformed by sufficient heat pressure, and the thinner sheet Fabrication is possible.
- the basis weight of the aramid paper is 20 g / m 2
- the specific heat is 1.89 J / g / K
- the glass transition temperature is 275 ° C.
- the temperature before being sandwiched between metal rolls is 20 ° C.
- the surface temperature is 100 to 275 ° C.
- the linear heat pressure is 100 kg / cm or more.
- / M 2 or more can be exemplified, but is not limited thereto.
- the above hot pressing can be performed a plurality of times in an arbitrary order.
- the glass transition temperature is determined by raising the temperature of the test piece from room temperature at a rate of 3 ° C./min, measuring the calorific value with a differential scanning calorimeter, and drawing two extension lines on the endothermic curve. The value obtained from the intersection of the 1/2 straight line and the endothermic curve between them, and the glass transition temperature of the aramid paper used in the examples was 275 ° C.
- a polymetaphenylene isophthalamide fibrid was manufactured using a pulp particle manufacturing apparatus (wet precipitator) composed of a combination of a stator and a rotor described in JP-A-52-15621. This was treated with a disaggregator and a beater to adjust the length weighted average fiber length to 0.9 mm (freeness of aramid fibrid: 100 ml (Canadian Freeness)).
- aramid short fiber Nomex (registered trademark), single yarn fineness 2 denier, fiber diameter 15 ⁇ m
- Examples 1 to 4 (Manufacture of aramid paper) Aramid fibrids and aramid short fibers prepared as described above were each dispersed in water to prepare a slurry. These slurries are mixed so that the aramid fibrids and aramid short fibers have the blending ratios (weight ratios) shown in Table 1, and a sheet-like material is produced with a tappy hand machine (cross-sectional area of 625 cm 2 ). did.
- a metal calender roll the outer peripheral length where the roll and the aramid paper contact each other is adjusted to 1 mm and subjected to hot pressing under the calender conditions shown in Table 1 (the aramid paper before being sandwiched between the heating elements). The temperature is 20 ° C.) to obtain an aramid paper. Table 1 shows the main characteristic values of the aramid paper thus obtained.
- the thickness is expressed by the following formula (2) [Thickness] / ([Fiber diameter of short fiber] ⁇ 2) ⁇ 1.25 (2) It is thin enough to meet the requirements, and it uses high aramid material with high strength, high air permeability, and essentially high heat resistance, so it can be used as an insulating material for transformers, motors, etc. Useful.
- the outer peripheral length where the roll and the aramid paper contact each other is adjusted to 1 mm and subjected to hot pressing under the calender conditions shown in Table 2 (the aramid paper before being sandwiched between the heating elements).
- the temperature is 20 ° C.) to obtain an aramid paper.
- Table 2 shows the main characteristic values of the aramid paper thus obtained.
- the aramid paper of Comparative Examples 1 to 3 has a low air permeability. Furthermore, the aramid paper of Comparative Example 1 has a low strength, and the aramid papers of Comparative Examples 2 and 3 have a large shrinkage due to high shrinkage. It seems difficult to cope with the change.
Abstract
An aramid paper sheet which is formed from a mixture of short fibers and fibrids formed from an aromatic polyamide, and which has a content of the fibrids and a thickness satisfying inequality expressions (1) and (2).
40 ≤ (FB) ≤ 90 (1)
(Thickness)/((Fiber diameter of short fibers) × 2) ≤ 1.25 (2)
(In the formulae, (FB) represents the content (wt%) of the fibrids in the aramid paper sheet.)
Description
本発明は、耐熱性の高い電気絶縁材料に関する。さらに詳しくは、薄くて、強度が高いアラミド紙に関する。
The present invention relates to an electrically insulating material having high heat resistance. More specifically, the present invention relates to aramid paper that is thin and has high strength.
改善された強度及び／又は熱安定性を紙に付与できる高性能材料から製造された紙が開発されてきた。例えば、アラミド紙は、芳香族ポリアミドよりなる合成紙であり、その優れた耐熱性、耐燃性、電気絶縁性、強靱性および可撓性により、電気絶縁材料および航空機ハニカム用ベースとして使用されてきた。これらの材料のうち、デュポン（ＤｕＰｏｎｔ）（米国）のノーメックス（Ｎｏｍｅｘ）（登録商標）繊維を含んでなる紙は、ポリ（メタフェニレンイソフタルアミド）短繊維とファイブリッドとを水中で混合し、次に混合したスラリーを抄紙した後、カレンダー加工することによって製造されている。この紙は、高温においてさえ、依然として高い強度及び強靱性を有すると共に優れた電気絶縁性を有することが知られている。
近年、変圧器、モータなど絶縁材料を必要とする機器の小型化、軽量化により、さらに耐熱性が高く薄い絶縁材料が求められている。 Papers made from high performance materials that can impart to papers improved strength and / or thermal stability have been developed. For example, aramid paper is a synthetic paper made of aromatic polyamide and has been used as an electrical insulating material and aircraft honeycomb base due to its excellent heat resistance, flame resistance, electrical insulation, toughness and flexibility. . Of these materials, DuPont (USA) Nomex (R) fiber paper comprises mixing poly (metaphenylene isophthalamide) staple fibers and fibrids in water, It is manufactured by calendering the paper mixed with the slurry. This paper is known to still have high strength and toughness and excellent electrical insulation even at high temperatures.
In recent years, with the miniaturization and weight reduction of devices that require insulating materials such as transformers and motors, there is a demand for thin insulating materials with higher heat resistance.
近年、変圧器、モータなど絶縁材料を必要とする機器の小型化、軽量化により、さらに耐熱性が高く薄い絶縁材料が求められている。 Papers made from high performance materials that can impart to papers improved strength and / or thermal stability have been developed. For example, aramid paper is a synthetic paper made of aromatic polyamide and has been used as an electrical insulating material and aircraft honeycomb base due to its excellent heat resistance, flame resistance, electrical insulation, toughness and flexibility. . Of these materials, DuPont (USA) Nomex (R) fiber paper comprises mixing poly (metaphenylene isophthalamide) staple fibers and fibrids in water, It is manufactured by calendering the paper mixed with the slurry. This paper is known to still have high strength and toughness and excellent electrical insulation even at high temperatures.
In recent years, with the miniaturization and weight reduction of devices that require insulating materials such as transformers and motors, there is a demand for thin insulating materials with higher heat resistance.
本発明は、耐熱性の高く、薄い電気絶縁シート材料を提供することを目的とする。
本発明は、又、上記電気絶縁シート材料の製造方法を提供することを目的とする。 An object of the present invention is to provide a thin heat insulating sheet material having high heat resistance.
Another object of the present invention is to provide a method for producing the above electric insulating sheet material.
本発明は、又、上記電気絶縁シート材料の製造方法を提供することを目的とする。 An object of the present invention is to provide a thin heat insulating sheet material having high heat resistance.
Another object of the present invention is to provide a method for producing the above electric insulating sheet material.
本発明者らはかかる状況に鑑み、変圧器、モータなどの小型化、軽量化に対応した、耐熱性が高く薄い絶縁材料を開発すべく、鋭意検討を進めた結果、本発明に到達した。
すなわち、第一の態様において、本発明は、芳香族ポリアミドから形成されるファイブリッド及び短繊維との混合物から形成されたアラミド紙であり、下記不等式（１）及び（２）
４０≦［ＦＢ］ ≦９０ （１）
［厚み］／（［短繊維の繊維径］×２）≦１．２５ （２）
〔式中、［ＦＢ］はアラミド紙中のファイブリッドの含量（重量％）である〕
を満たすファイブリッド含量及び厚みを有するアラミド紙を提供する。
また、第二の態様において、本発明は、少なくとも一対の発熱体の間に芳香族ポリアミドから形成されるファイブリッド及び短繊維との混合物から形成されたアラミド紙を挟んで熱圧加工することを含み、上記発熱体による熱圧加工後の上記アラミド紙の収縮率が３％以下である、第一の態様に記載のアラミド紙の製造方法を提供する。
さらに、第三の態様において、本発明は、少なくとも一対の発熱体の間に芳香族ポリアミドから形成されるファイブリッド及び短繊維との混合物から形成されたアラミド紙を挟み、１０００ｋｇ／ｃｍ2以上の圧力を加えると同時に、上記発熱体より、下式（３）
Ｑ≧ ［ＢＷ］×ｃ×（Ｔｇ－ｔ） （３）
〔式中、［ＢＷ］は樹脂シートの坪量（ｇ／ｍ2）であり、ｃは上記アラミド紙の比熱（Ｊ／ｇ／Ｋ）であり、Ｔｇは上記アラミド紙のガラス転移温度（℃）であり、ｔは発熱体に挟まれる前の上記アラミド紙の温度（℃）であり、上記発熱体の表面の温度はＴｇ以下である〕
で表される熱量Ｑ（Ｊ／ｍ2）を供給することを含む、第一の態様に記載のアラミド紙の製造方法を提供する。
以下、本発明について詳細に説明する。 In view of such a situation, the inventors of the present invention have arrived at the present invention as a result of diligent investigation to develop a thin insulating material having high heat resistance corresponding to miniaturization and weight reduction of a transformer and a motor.
That is, in the first aspect, the present invention is an aramid paper formed from a mixture of a fibrid formed from an aromatic polyamide and a short fiber, and the following inequalities (1) and (2)
40 ≦ [FB] ≦ 90 (1)
[Thickness] / ([Fiber diameter of short fiber] × 2) ≦ 1.25 (2)
[Wherein [FB] is the fibrid content (% by weight) in the aramid paper]
An aramid paper having a satisfying fibrid content and thickness is provided.
Further, in the second aspect, the present invention includes hot pressing with an aramid paper formed from a mixture of a fibrid formed from an aromatic polyamide and a short fiber between at least a pair of heating elements. In addition, the method for producing aramid paper according to the first aspect is provided, wherein the shrinkage rate of the aramid paper after hot pressing with the heating element is 3% or less.
Furthermore, in the third aspect, the present invention sandwiches an aramid paper formed from a mixture of a fibrid formed from an aromatic polyamide and a short fiber between at least a pair of heating elements, and has a weight of 1000 kg / cm 2 or more. At the same time as the pressure is applied, from the heating element, the following formula (3)
Q ≧ [BW] × c × (Tg−t) (3)
[Wherein [BW] is the basis weight (g / m 2 ) of the resin sheet, c is the specific heat (J / g / K) of the aramid paper, and Tg is the glass transition temperature (° C.) of the aramid paper. And t is the temperature (° C.) of the aramid paper before being sandwiched by the heating element, and the temperature of the surface of the heating element is Tg or less.
The method for producing aramid paper according to the first aspect, comprising supplying a heat quantity Q (J / m 2 ) represented by:
Hereinafter, the present invention will be described in detail.
すなわち、第一の態様において、本発明は、芳香族ポリアミドから形成されるファイブリッド及び短繊維との混合物から形成されたアラミド紙であり、下記不等式（１）及び（２）
４０≦［ＦＢ］ ≦９０ （１）
［厚み］／（［短繊維の繊維径］×２）≦１．２５ （２）
〔式中、［ＦＢ］はアラミド紙中のファイブリッドの含量（重量％）である〕
を満たすファイブリッド含量及び厚みを有するアラミド紙を提供する。
また、第二の態様において、本発明は、少なくとも一対の発熱体の間に芳香族ポリアミドから形成されるファイブリッド及び短繊維との混合物から形成されたアラミド紙を挟んで熱圧加工することを含み、上記発熱体による熱圧加工後の上記アラミド紙の収縮率が３％以下である、第一の態様に記載のアラミド紙の製造方法を提供する。
さらに、第三の態様において、本発明は、少なくとも一対の発熱体の間に芳香族ポリアミドから形成されるファイブリッド及び短繊維との混合物から形成されたアラミド紙を挟み、１０００ｋｇ／ｃｍ2以上の圧力を加えると同時に、上記発熱体より、下式（３）
Ｑ≧ ［ＢＷ］×ｃ×（Ｔｇ－ｔ） （３）
〔式中、［ＢＷ］は樹脂シートの坪量（ｇ／ｍ2）であり、ｃは上記アラミド紙の比熱（Ｊ／ｇ／Ｋ）であり、Ｔｇは上記アラミド紙のガラス転移温度（℃）であり、ｔは発熱体に挟まれる前の上記アラミド紙の温度（℃）であり、上記発熱体の表面の温度はＴｇ以下である〕
で表される熱量Ｑ（Ｊ／ｍ2）を供給することを含む、第一の態様に記載のアラミド紙の製造方法を提供する。
以下、本発明について詳細に説明する。 In view of such a situation, the inventors of the present invention have arrived at the present invention as a result of diligent investigation to develop a thin insulating material having high heat resistance corresponding to miniaturization and weight reduction of a transformer and a motor.
That is, in the first aspect, the present invention is an aramid paper formed from a mixture of a fibrid formed from an aromatic polyamide and a short fiber, and the following inequalities (1) and (2)
40 ≦ [FB] ≦ 90 (1)
[Thickness] / ([Fiber diameter of short fiber] × 2) ≦ 1.25 (2)
[Wherein [FB] is the fibrid content (% by weight) in the aramid paper]
An aramid paper having a satisfying fibrid content and thickness is provided.
Further, in the second aspect, the present invention includes hot pressing with an aramid paper formed from a mixture of a fibrid formed from an aromatic polyamide and a short fiber between at least a pair of heating elements. In addition, the method for producing aramid paper according to the first aspect is provided, wherein the shrinkage rate of the aramid paper after hot pressing with the heating element is 3% or less.
Furthermore, in the third aspect, the present invention sandwiches an aramid paper formed from a mixture of a fibrid formed from an aromatic polyamide and a short fiber between at least a pair of heating elements, and has a weight of 1000 kg / cm 2 or more. At the same time as the pressure is applied, from the heating element, the following formula (3)
Q ≧ [BW] × c × (Tg−t) (3)
[Wherein [BW] is the basis weight (g / m 2 ) of the resin sheet, c is the specific heat (J / g / K) of the aramid paper, and Tg is the glass transition temperature (° C.) of the aramid paper. And t is the temperature (° C.) of the aramid paper before being sandwiched by the heating element, and the temperature of the surface of the heating element is Tg or less.
The method for producing aramid paper according to the first aspect, comprising supplying a heat quantity Q (J / m 2 ) represented by:
Hereinafter, the present invention will be described in detail.
（アラミド）
本発明において、アラミドとは、アミド結合の６０％以上が芳香環に直接結合した線状高分子化合物（芳香族ポリアミド）を意味する。このようなアラミドとしては、例えばポリメタフェニレンイソフタルアミド及びその共重合体、ポリパラフェニレンテレフタルアミド及びその共重合体、ポリ（パラフェニレン）－コポリ（３，４ジフェニルエーテル）テレフタルアミドなどが挙げられる。これらのアラミドは、例えばイソフタル酸塩化物およびメタフェニレンジアミンを用いた従来既知の界面重合法、溶液重合法等により工業的に製造されており、市販品として入手することができるが、これに限定されるものではない。これらのアラミドの中では、ポリメタフェニレンイソフタルアミドが、良好な成型加工性、熱接着性、難燃性、耐熱性などの特性を備えている点で好ましく用いられる。 (Aramid)
In the present invention, aramid means a linear polymer compound (aromatic polyamide) in which 60% or more of amide bonds are directly bonded to an aromatic ring. Examples of such aramids include polymetaphenylene isophthalamide and copolymers thereof, polyparaphenylene terephthalamide and copolymers thereof, poly (paraphenylene) -copoly (3,4 diphenyl ether) terephthalamide, and the like. These aramids are industrially produced by, for example, conventionally known interfacial polymerization methods, solution polymerization methods and the like using isophthalic acid chloride and metaphenylenediamine, and can be obtained as commercial products. Is not to be done. Among these aramids, polymetaphenylene isophthalamide is preferably used in that it has characteristics such as good moldability, thermal adhesiveness, flame retardancy, and heat resistance.
本発明において、アラミドとは、アミド結合の６０％以上が芳香環に直接結合した線状高分子化合物（芳香族ポリアミド）を意味する。このようなアラミドとしては、例えばポリメタフェニレンイソフタルアミド及びその共重合体、ポリパラフェニレンテレフタルアミド及びその共重合体、ポリ（パラフェニレン）－コポリ（３，４ジフェニルエーテル）テレフタルアミドなどが挙げられる。これらのアラミドは、例えばイソフタル酸塩化物およびメタフェニレンジアミンを用いた従来既知の界面重合法、溶液重合法等により工業的に製造されており、市販品として入手することができるが、これに限定されるものではない。これらのアラミドの中では、ポリメタフェニレンイソフタルアミドが、良好な成型加工性、熱接着性、難燃性、耐熱性などの特性を備えている点で好ましく用いられる。 (Aramid)
In the present invention, aramid means a linear polymer compound (aromatic polyamide) in which 60% or more of amide bonds are directly bonded to an aromatic ring. Examples of such aramids include polymetaphenylene isophthalamide and copolymers thereof, polyparaphenylene terephthalamide and copolymers thereof, poly (paraphenylene) -copoly (3,4 diphenyl ether) terephthalamide, and the like. These aramids are industrially produced by, for example, conventionally known interfacial polymerization methods, solution polymerization methods and the like using isophthalic acid chloride and metaphenylenediamine, and can be obtained as commercial products. Is not to be done. Among these aramids, polymetaphenylene isophthalamide is preferably used in that it has characteristics such as good moldability, thermal adhesiveness, flame retardancy, and heat resistance.
（アラミドファイブリッド）
本発明において、アラミドファイブリッドとは、抄紙性を有するフィルム状のアラミド粒子であり、アラミドパルプとも呼ばれる（特公昭３５－１１８５１号公報、特公昭３７－５７３２号公報等参照）。
アラミドファイブリッドは、通常の木材パルプと同様に、離解、叩解処理を施し抄紙原料として用いることが広く知られており、抄紙に適した品質を保つ目的でいわゆる叩解処理を施すことができる。この叩解処理は、ディスクリファイナー、ビーター、その他の機械的切断作用を及ぼす抄紙原料処理機器によって実施することができる。この操作において、ファイブリッドの形態変化は、日本工業規格Ｐ８１２１に規定の濾水度試験方法（フリーネス）でモニターすることができる。本発明において、叩解処理を施した後のアラミドファイブリッドの濾水度は、１０～３００ｃｍ3（カナディアンスタンダードフリーネス）の範囲内にあることが好ましい。この範囲より大きな濾水度のファイブリッドでは、それから成形される多熱性電気絶縁シート材料の強度が低下する可能性がある。他方、１０ｃｍ3よりも小さな濾水度を得ようとすると、投入する機械動力の利用効率が小さくなり、また、単位時間当たりの処理量が少なくなることが多く、さらに、ファイブリッドの微細化が進行しすぎるため、いわゆるバインダー機能の低下を招きやすい。したがって、１０ｃｍ3よりも小さな濾水度を得ようとしても、格段の利点が認められない。
本発明のアラミド紙において、アラミドファイブリッドは、バインダーとして優れた特性を有しているため微粒子及び他の添加成分を効率的に補足でき、本発明のアラミド紙製造において原料歩留まりが良好となると同時にシート内で層状に重なり、貫通孔を減少させることが可能で、電気絶縁性が向上する。 (Aramid Five Brid)
In the present invention, aramid fibrids are film-form aramid particles having paper-making properties and are also called aramid pulp (see Japanese Patent Publication No. 35-11851, Japanese Patent Publication No. 37-5732, etc.).
Aramid fibrids are widely known to be used as a papermaking raw material after being disaggregated and beaten in the same manner as ordinary wood pulp, and can be subjected to so-called beating treatment for the purpose of maintaining quality suitable for papermaking. This beating process can be performed by a disk refiner, a beater, or other papermaking raw material processing equipment that exerts a mechanical cutting action. In this operation, the shape change of the fibrid can be monitored by the freeness test method stipulated in Japanese Industrial Standard P8121. In the present invention, the freeness of the aramid fibrid after the beating treatment is preferably in the range of 10 to 300 cm 3 (Canadian Standard Freeness). For fibrids with a freeness greater than this range, the strength of the multi-thermal electrical insulation sheet material formed therefrom may be reduced. On the other hand, if it is desired to obtain a freeness smaller than 10 cm 3 , the utilization efficiency of the mechanical power to be input becomes small, the processing amount per unit time is often reduced, and further refinement of the fibrid is reduced. Since it proceeds too much, the so-called binder function is likely to deteriorate. Therefore, no particular advantage is recognized even when trying to obtain a freeness smaller than 10 cm 3 .
In the aramid paper of the present invention, the aramid fibrid has excellent properties as a binder, so it can efficiently supplement fine particles and other additive components, and at the same time the raw material yield is improved in the production of the aramid paper of the present invention. It is possible to reduce the number of through-holes in layers in the sheet, and the electrical insulation is improved.
本発明において、アラミドファイブリッドとは、抄紙性を有するフィルム状のアラミド粒子であり、アラミドパルプとも呼ばれる（特公昭３５－１１８５１号公報、特公昭３７－５７３２号公報等参照）。
アラミドファイブリッドは、通常の木材パルプと同様に、離解、叩解処理を施し抄紙原料として用いることが広く知られており、抄紙に適した品質を保つ目的でいわゆる叩解処理を施すことができる。この叩解処理は、ディスクリファイナー、ビーター、その他の機械的切断作用を及ぼす抄紙原料処理機器によって実施することができる。この操作において、ファイブリッドの形態変化は、日本工業規格Ｐ８１２１に規定の濾水度試験方法（フリーネス）でモニターすることができる。本発明において、叩解処理を施した後のアラミドファイブリッドの濾水度は、１０～３００ｃｍ3（カナディアンスタンダードフリーネス）の範囲内にあることが好ましい。この範囲より大きな濾水度のファイブリッドでは、それから成形される多熱性電気絶縁シート材料の強度が低下する可能性がある。他方、１０ｃｍ3よりも小さな濾水度を得ようとすると、投入する機械動力の利用効率が小さくなり、また、単位時間当たりの処理量が少なくなることが多く、さらに、ファイブリッドの微細化が進行しすぎるため、いわゆるバインダー機能の低下を招きやすい。したがって、１０ｃｍ3よりも小さな濾水度を得ようとしても、格段の利点が認められない。
本発明のアラミド紙において、アラミドファイブリッドは、バインダーとして優れた特性を有しているため微粒子及び他の添加成分を効率的に補足でき、本発明のアラミド紙製造において原料歩留まりが良好となると同時にシート内で層状に重なり、貫通孔を減少させることが可能で、電気絶縁性が向上する。 (Aramid Five Brid)
In the present invention, aramid fibrids are film-form aramid particles having paper-making properties and are also called aramid pulp (see Japanese Patent Publication No. 35-11851, Japanese Patent Publication No. 37-5732, etc.).
Aramid fibrids are widely known to be used as a papermaking raw material after being disaggregated and beaten in the same manner as ordinary wood pulp, and can be subjected to so-called beating treatment for the purpose of maintaining quality suitable for papermaking. This beating process can be performed by a disk refiner, a beater, or other papermaking raw material processing equipment that exerts a mechanical cutting action. In this operation, the shape change of the fibrid can be monitored by the freeness test method stipulated in Japanese Industrial Standard P8121. In the present invention, the freeness of the aramid fibrid after the beating treatment is preferably in the range of 10 to 300 cm 3 (Canadian Standard Freeness). For fibrids with a freeness greater than this range, the strength of the multi-thermal electrical insulation sheet material formed therefrom may be reduced. On the other hand, if it is desired to obtain a freeness smaller than 10 cm 3 , the utilization efficiency of the mechanical power to be input becomes small, the processing amount per unit time is often reduced, and further refinement of the fibrid is reduced. Since it proceeds too much, the so-called binder function is likely to deteriorate. Therefore, no particular advantage is recognized even when trying to obtain a freeness smaller than 10 cm 3 .
In the aramid paper of the present invention, the aramid fibrid has excellent properties as a binder, so it can efficiently supplement fine particles and other additive components, and at the same time the raw material yield is improved in the production of the aramid paper of the present invention. It is possible to reduce the number of through-holes in layers in the sheet, and the electrical insulation is improved.
（アラミド短繊維）
本発明において、アラミド短繊維とは、アラミドを材料とする繊維を切断したものであり、そのような繊維としては、例えば帝人（株）の「テイジンコーネックス（登録商標）」、デュポン社の「ノーメックス（登録商標）」などの商品名で入手することができるものが挙げられるが、これらに限定されるものではない。
アラミド短繊維の長さは、一般に１ｍｍ以上５０ｍｍ未満、好ましくは２～１０ｍｍの範囲から選ぶことができる。短繊維の長さが１ｍｍよりも小さいと、シート材料の力学特性が低下し、他方、５０ｍｍ以上のものは、湿式法でのアラミド紙の製造に際して「からみ」「結束」などが発生しやすく欠陥の原因となりやすい。
アラミド短繊維の繊維径は、好ましくは０．１～２５μｍ、より好ましくは１～２０μｍの範囲から選ぶことができる。 (Aramid short fiber)
In the present invention, an aramid short fiber is obtained by cutting a fiber made of aramid. Examples of such a fiber include “Teijin Conex (registered trademark)” by Teijin Limited, “ Although what can be obtained by brand names, such as "NOMEX (trademark)", is mentioned, It is not limited to these.
The length of the aramid short fibers can be selected from the range of generally 1 mm or more and less than 50 mm, preferably 2 to 10 mm. If the length of the short fiber is less than 1 mm, the mechanical properties of the sheet material are deteriorated. On the other hand, if the length is 50 mm or more, defects such as “entanglement” and “bonding” are likely to occur during the production of aramid paper by the wet method. It is easy to cause.
The fiber diameter of the aramid short fibers can be selected from the range of preferably 0.1 to 25 μm, more preferably 1 to 20 μm.
本発明において、アラミド短繊維とは、アラミドを材料とする繊維を切断したものであり、そのような繊維としては、例えば帝人（株）の「テイジンコーネックス（登録商標）」、デュポン社の「ノーメックス（登録商標）」などの商品名で入手することができるものが挙げられるが、これらに限定されるものではない。
アラミド短繊維の長さは、一般に１ｍｍ以上５０ｍｍ未満、好ましくは２～１０ｍｍの範囲から選ぶことができる。短繊維の長さが１ｍｍよりも小さいと、シート材料の力学特性が低下し、他方、５０ｍｍ以上のものは、湿式法でのアラミド紙の製造に際して「からみ」「結束」などが発生しやすく欠陥の原因となりやすい。
アラミド短繊維の繊維径は、好ましくは０．１～２５μｍ、より好ましくは１～２０μｍの範囲から選ぶことができる。 (Aramid short fiber)
In the present invention, an aramid short fiber is obtained by cutting a fiber made of aramid. Examples of such a fiber include “Teijin Conex (registered trademark)” by Teijin Limited, “ Although what can be obtained by brand names, such as "NOMEX (trademark)", is mentioned, It is not limited to these.
The length of the aramid short fibers can be selected from the range of generally 1 mm or more and less than 50 mm, preferably 2 to 10 mm. If the length of the short fiber is less than 1 mm, the mechanical properties of the sheet material are deteriorated. On the other hand, if the length is 50 mm or more, defects such as “entanglement” and “bonding” are likely to occur during the production of aramid paper by the wet method. It is easy to cause.
The fiber diameter of the aramid short fibers can be selected from the range of preferably 0.1 to 25 μm, more preferably 1 to 20 μm.
（アラミド紙）
本発明において、アラミド紙とは、前記のアラミドファイブリッド及びアラミド短繊維から主として構成されるシート状物であり、下記不等式（１）及び（２）
４０≦[ＦＢ] ≦９０ （１）
[厚み]／（[短繊維の繊維径]×２）≦１．２５ （２）
〔式中、[ＦＢ]はアラミド紙中のファイブリッドの含量（重量％）である〕
を満たす、ファイブリッド含量及び厚みを有している。ファイブリッドの含量が４０重量％より少なくなると、アラミド紙はより多孔質な構造となり、電気絶縁性に支障をきたす原因となりやすい。また、９０重量％より大きくなると、相対的に短繊維の含量が少なくなり、後述する少なくとも一対の発熱体の間に挟んで熱圧加工した後の上記のアラミド紙の収縮率が３％を越え、収縮による厚み増加により、上記（２）式の範囲の厚みを有することが困難となる。
アラミド紙は、一般に、前述したアラミドファイブリッドとアラミド短繊維とを混合した後シート化する方法により製造される。具体的には、例えば上記アラミドファイブリッド及びアラミド短繊維を乾式ブレンドした後に、気流を利用してシートを形成する方法、アラミドファイブリッド及びアラミド短繊維を液体媒体中で分散混合した後、液体透過性の支持体、例えば網またはベルト上に吐出してシート化し、液体を除いて乾燥する方法などが適用できるが、これらのなかでも水を媒体として使用する、いわゆる湿式抄造法が好ましく選択される。
湿式抄造法では、少なくともアラミドファイブリッド、アラミド短繊維を含有する単一または混合物の水性スラリーを、抄紙機に送液し分散した後、脱水、搾水及び乾燥操作することによって、シートとして巻き取る方法が一般的である。抄紙機としては長網抄紙機、円網抄紙機、傾斜型抄紙機及びこれらを組み合わせたコンビネーション抄紙機などが利用される。コンビネーション抄紙機での製造の場合、配合比率の異なるスラリーをシート成形し合一することで複数の紙層からなる複合体シートを得ることができる。抄造の際に必要に応じて分散性向上剤、消泡剤、紙力増強剤などの添加剤が使用される。
また、これ以外にその他の繊維状成分（例えば、ポリフェニレンスルフィド繊維、ポリエーテルエーテルケトン繊維、セルロース系繊維、ＰＶＡ系繊維、ポリエステル繊維、アリレート繊維、液晶ポリエステル繊維、ポリエチレンナフタレート繊維などの有機繊維、ガラス繊維、ロックウール、アスベスト、ボロン繊維などの無機繊維ガラス繊維）を添加することができる。
アラミド紙は、一般に５～１０００ｇ／ｍ2、好ましくは１５～２００ｇ／ｍ2の範囲内の坪量を有している。
アラミド紙の引張強度は、好ましくは０．５ｋｇｆ／１５ｍｍ以上、より好ましくは１ｋｇｆ／１５ｍｍ以上の範囲内である。さらに、アラミド紙の透気度は、好ましくは３０００秒以上、より好ましくは４０００秒以上の範囲内である。 (Aramid paper)
In the present invention, the aramid paper is a sheet-like material mainly composed of the aramid fibrid and the aramid short fibers, and the following inequalities (1) and (2)
40 ≦ [FB] ≦ 90 (1)
[Thickness] / ([Fiber diameter of short fiber] × 2) ≦ 1.25 (2)
[Wherein [FB] is the fibrid content (% by weight) in the aramid paper)
And satisfying the fibrid content and thickness. When the content of fibrid is less than 40% by weight, the aramid paper has a more porous structure and tends to cause a problem in electrical insulation. On the other hand, when the content exceeds 90% by weight, the content of short fibers is relatively reduced, and the shrinkage ratio of the aramid paper after hot pressing is sandwiched between at least a pair of heating elements described later exceeds 3%. Due to the increase in thickness due to shrinkage, it becomes difficult to have a thickness in the range of the above formula (2).
Aramid paper is generally produced by a method of mixing the above-mentioned aramid fibrid and aramid short fibers and then forming a sheet. Specifically, for example, after dry blending the aramid fibrid and the aramid short fiber, a method of forming a sheet using an air flow, after the aramid fibrid and the aramid short fiber are dispersed and mixed in a liquid medium, the liquid permeation is performed. For example, a so-called wet papermaking method using water as a medium is preferably selected. .
In the wet papermaking method, a single or mixed aqueous slurry containing at least aramid fibrids and short aramid fibers is fed to a paper machine and dispersed, and then dewatered, squeezed and dried to be wound up as a sheet. The method is common. As the paper machine, a long paper machine, a circular paper machine, an inclined paper machine, and a combination paper machine combining these are used. In the case of production with a combination paper machine, a composite sheet composed of a plurality of paper layers can be obtained by forming and combining slurry having different blending ratios. Additives such as a dispersibility improver, an antifoaming agent, and a paper strength enhancer are used as necessary during papermaking.
In addition to this, other fibrous components (for example, polyphenylene sulfide fibers, polyether ether ketone fibers, cellulose fibers, PVA fibers, polyester fibers, arylate fibers, liquid crystal polyester fibers, organic fibers such as polyethylene naphthalate fibers, Glass fiber, rock wool, asbestos, boron fiber and other inorganic fiber glass fibers) can be added.
Aramid paper generally has a basis weight in the range of 5 to 1000 g / m 2 , preferably 15 to 200 g / m 2 .
The tensile strength of the aramid paper is preferably in the range of 0.5 kgf / 15 mm or more, more preferably 1 kgf / 15 mm or more. Furthermore, the air permeability of the aramid paper is preferably in the range of 3000 seconds or more, more preferably 4000 seconds or more.
本発明において、アラミド紙とは、前記のアラミドファイブリッド及びアラミド短繊維から主として構成されるシート状物であり、下記不等式（１）及び（２）
４０≦[ＦＢ] ≦９０ （１）
[厚み]／（[短繊維の繊維径]×２）≦１．２５ （２）
〔式中、[ＦＢ]はアラミド紙中のファイブリッドの含量（重量％）である〕
を満たす、ファイブリッド含量及び厚みを有している。ファイブリッドの含量が４０重量％より少なくなると、アラミド紙はより多孔質な構造となり、電気絶縁性に支障をきたす原因となりやすい。また、９０重量％より大きくなると、相対的に短繊維の含量が少なくなり、後述する少なくとも一対の発熱体の間に挟んで熱圧加工した後の上記のアラミド紙の収縮率が３％を越え、収縮による厚み増加により、上記（２）式の範囲の厚みを有することが困難となる。
アラミド紙は、一般に、前述したアラミドファイブリッドとアラミド短繊維とを混合した後シート化する方法により製造される。具体的には、例えば上記アラミドファイブリッド及びアラミド短繊維を乾式ブレンドした後に、気流を利用してシートを形成する方法、アラミドファイブリッド及びアラミド短繊維を液体媒体中で分散混合した後、液体透過性の支持体、例えば網またはベルト上に吐出してシート化し、液体を除いて乾燥する方法などが適用できるが、これらのなかでも水を媒体として使用する、いわゆる湿式抄造法が好ましく選択される。
湿式抄造法では、少なくともアラミドファイブリッド、アラミド短繊維を含有する単一または混合物の水性スラリーを、抄紙機に送液し分散した後、脱水、搾水及び乾燥操作することによって、シートとして巻き取る方法が一般的である。抄紙機としては長網抄紙機、円網抄紙機、傾斜型抄紙機及びこれらを組み合わせたコンビネーション抄紙機などが利用される。コンビネーション抄紙機での製造の場合、配合比率の異なるスラリーをシート成形し合一することで複数の紙層からなる複合体シートを得ることができる。抄造の際に必要に応じて分散性向上剤、消泡剤、紙力増強剤などの添加剤が使用される。
また、これ以外にその他の繊維状成分（例えば、ポリフェニレンスルフィド繊維、ポリエーテルエーテルケトン繊維、セルロース系繊維、ＰＶＡ系繊維、ポリエステル繊維、アリレート繊維、液晶ポリエステル繊維、ポリエチレンナフタレート繊維などの有機繊維、ガラス繊維、ロックウール、アスベスト、ボロン繊維などの無機繊維ガラス繊維）を添加することができる。
アラミド紙は、一般に５～１０００ｇ／ｍ2、好ましくは１５～２００ｇ／ｍ2の範囲内の坪量を有している。
アラミド紙の引張強度は、好ましくは０．５ｋｇｆ／１５ｍｍ以上、より好ましくは１ｋｇｆ／１５ｍｍ以上の範囲内である。さらに、アラミド紙の透気度は、好ましくは３０００秒以上、より好ましくは４０００秒以上の範囲内である。 (Aramid paper)
In the present invention, the aramid paper is a sheet-like material mainly composed of the aramid fibrid and the aramid short fibers, and the following inequalities (1) and (2)
40 ≦ [FB] ≦ 90 (1)
[Thickness] / ([Fiber diameter of short fiber] × 2) ≦ 1.25 (2)
[Wherein [FB] is the fibrid content (% by weight) in the aramid paper)
And satisfying the fibrid content and thickness. When the content of fibrid is less than 40% by weight, the aramid paper has a more porous structure and tends to cause a problem in electrical insulation. On the other hand, when the content exceeds 90% by weight, the content of short fibers is relatively reduced, and the shrinkage ratio of the aramid paper after hot pressing is sandwiched between at least a pair of heating elements described later exceeds 3%. Due to the increase in thickness due to shrinkage, it becomes difficult to have a thickness in the range of the above formula (2).
Aramid paper is generally produced by a method of mixing the above-mentioned aramid fibrid and aramid short fibers and then forming a sheet. Specifically, for example, after dry blending the aramid fibrid and the aramid short fiber, a method of forming a sheet using an air flow, after the aramid fibrid and the aramid short fiber are dispersed and mixed in a liquid medium, the liquid permeation is performed. For example, a so-called wet papermaking method using water as a medium is preferably selected. .
In the wet papermaking method, a single or mixed aqueous slurry containing at least aramid fibrids and short aramid fibers is fed to a paper machine and dispersed, and then dewatered, squeezed and dried to be wound up as a sheet. The method is common. As the paper machine, a long paper machine, a circular paper machine, an inclined paper machine, and a combination paper machine combining these are used. In the case of production with a combination paper machine, a composite sheet composed of a plurality of paper layers can be obtained by forming and combining slurry having different blending ratios. Additives such as a dispersibility improver, an antifoaming agent, and a paper strength enhancer are used as necessary during papermaking.
In addition to this, other fibrous components (for example, polyphenylene sulfide fibers, polyether ether ketone fibers, cellulose fibers, PVA fibers, polyester fibers, arylate fibers, liquid crystal polyester fibers, organic fibers such as polyethylene naphthalate fibers, Glass fiber, rock wool, asbestos, boron fiber and other inorganic fiber glass fibers) can be added.
Aramid paper generally has a basis weight in the range of 5 to 1000 g / m 2 , preferably 15 to 200 g / m 2 .
The tensile strength of the aramid paper is preferably in the range of 0.5 kgf / 15 mm or more, more preferably 1 kgf / 15 mm or more. Furthermore, the air permeability of the aramid paper is preferably in the range of 3000 seconds or more, more preferably 4000 seconds or more.
（熱圧加工）
上記のようにして得られたアラミド紙は、一対の発熱体間にて高温高圧で熱圧することにより、密度、結晶化度、耐熱性、寸法安定性、及び機械強度が向上することが知られている。熱圧の条件は、上記発熱体間に挟んで熱圧加工した後の上記のアラミド紙の収縮率が３％以下であることが好ましい。上記収縮率が３％を越えると、収縮による厚み増加により、上記（２）式の範囲の厚みを有することが困難となる。上記収縮率は、より好ましくは２％以下であり、さらに好ましくは１．５％以下である。
さらに、好ましくは少なくとも一対の発熱体の間に上記アラミド紙を挟み、１０００ｋｇ／ｃｍ2以上の圧力を加えると同時に、上記発熱体より、下式（３）
Ｑ≧ ［ＢＷ］×ｃ×（Ｔｇ－ｔ） （３）
〔式中、［ＢＷ］は樹脂シートの坪量（ｇ／ｍ2）であり、ｃは上記アラミド紙の比熱（Ｊ／ｇ／Ｋ）であり、Ｔｇは上記アラミド紙のガラス転移温度（℃）であり、ｔは発熱体に挟まれる前の上記アラミド紙の温度（℃）であり、上記発熱体の表面の温度はＴｇ以下である〕
で表される熱量Ｑ（Ｊ／ｍ2）をアラミド紙単位面積あたりへ供給すると上記収縮率も３％以内に抑えられ、かつ充分な熱圧により、短繊維自身も変形し、より薄いシートの作製が可能となる。
上記熱圧加工として、例えば、上記アラミド紙の坪量が２０ｇ／ｍ2、比熱１．８９Ｊ／ｇ／Ｋ、ガラス転移温度２７５℃、金属ロールに挟まれる前の温度が２０℃のとき、発熱体として、金属製ロール使用の場合、表面温度１００～２７５℃、金属ロールがアラミド紙に接する外周長を例えば１ｍｍとすれば線圧１００ｋｇ／ｃｍ以上、の金属ロールからアラミド紙への供給熱量９６４０Ｊ／ｍ2以上を例示することができるが、これらに限定されるものではない。上記の熱圧加工を任意の順に複数回行うこともできる。 (Hot pressure processing)
The aramid paper obtained as described above is known to be improved in density, crystallinity, heat resistance, dimensional stability, and mechanical strength by hot pressing at a high temperature and high pressure between a pair of heating elements. ing. The heat pressure condition is preferably such that the shrinkage rate of the aramid paper after being hot-pressed between the heating elements is 3% or less. When the shrinkage rate exceeds 3%, it becomes difficult to have a thickness in the range of the above formula (2) due to an increase in thickness due to shrinkage. The shrinkage rate is more preferably 2% or less, and further preferably 1.5% or less.
Further, preferably, the aramid paper is sandwiched between at least a pair of heating elements and a pressure of 1000 kg / cm 2 or more is applied.
Q ≧ [BW] × c × (Tg−t) (3)
[Wherein [BW] is the basis weight (g / m 2 ) of the resin sheet, c is the specific heat (J / g / K) of the aramid paper, and Tg is the glass transition temperature (° C.) of the aramid paper. And t is the temperature (° C.) of the aramid paper before being sandwiched by the heating element, and the temperature of the surface of the heating element is Tg or less.
When the amount of heat Q (J / m 2 ) expressed by the following is supplied per unit area of the aramid paper, the shrinkage rate is suppressed to within 3%, and the short fiber itself is deformed by sufficient heat pressure, and the thinner sheet Fabrication is possible.
For example, when the basis weight of the aramid paper is 20 g / m 2 , the specific heat is 1.89 J / g / K, the glass transition temperature is 275 ° C., and the temperature before being sandwiched between metal rolls is 20 ° C. In the case of using a metal roll as the body, if the surface temperature is 100 to 275 ° C. and the outer peripheral length where the metal roll is in contact with the aramid paper is 1 mm, for example, the linear heat pressure is 100 kg / cm or more. / M 2 or more can be exemplified, but is not limited thereto. The above hot pressing can be performed a plurality of times in an arbitrary order.
上記のようにして得られたアラミド紙は、一対の発熱体間にて高温高圧で熱圧することにより、密度、結晶化度、耐熱性、寸法安定性、及び機械強度が向上することが知られている。熱圧の条件は、上記発熱体間に挟んで熱圧加工した後の上記のアラミド紙の収縮率が３％以下であることが好ましい。上記収縮率が３％を越えると、収縮による厚み増加により、上記（２）式の範囲の厚みを有することが困難となる。上記収縮率は、より好ましくは２％以下であり、さらに好ましくは１．５％以下である。
さらに、好ましくは少なくとも一対の発熱体の間に上記アラミド紙を挟み、１０００ｋｇ／ｃｍ2以上の圧力を加えると同時に、上記発熱体より、下式（３）
Ｑ≧ ［ＢＷ］×ｃ×（Ｔｇ－ｔ） （３）
〔式中、［ＢＷ］は樹脂シートの坪量（ｇ／ｍ2）であり、ｃは上記アラミド紙の比熱（Ｊ／ｇ／Ｋ）であり、Ｔｇは上記アラミド紙のガラス転移温度（℃）であり、ｔは発熱体に挟まれる前の上記アラミド紙の温度（℃）であり、上記発熱体の表面の温度はＴｇ以下である〕
で表される熱量Ｑ（Ｊ／ｍ2）をアラミド紙単位面積あたりへ供給すると上記収縮率も３％以内に抑えられ、かつ充分な熱圧により、短繊維自身も変形し、より薄いシートの作製が可能となる。
上記熱圧加工として、例えば、上記アラミド紙の坪量が２０ｇ／ｍ2、比熱１．８９Ｊ／ｇ／Ｋ、ガラス転移温度２７５℃、金属ロールに挟まれる前の温度が２０℃のとき、発熱体として、金属製ロール使用の場合、表面温度１００～２７５℃、金属ロールがアラミド紙に接する外周長を例えば１ｍｍとすれば線圧１００ｋｇ／ｃｍ以上、の金属ロールからアラミド紙への供給熱量９６４０Ｊ／ｍ2以上を例示することができるが、これらに限定されるものではない。上記の熱圧加工を任意の順に複数回行うこともできる。 (Hot pressure processing)
The aramid paper obtained as described above is known to be improved in density, crystallinity, heat resistance, dimensional stability, and mechanical strength by hot pressing at a high temperature and high pressure between a pair of heating elements. ing. The heat pressure condition is preferably such that the shrinkage rate of the aramid paper after being hot-pressed between the heating elements is 3% or less. When the shrinkage rate exceeds 3%, it becomes difficult to have a thickness in the range of the above formula (2) due to an increase in thickness due to shrinkage. The shrinkage rate is more preferably 2% or less, and further preferably 1.5% or less.
Further, preferably, the aramid paper is sandwiched between at least a pair of heating elements and a pressure of 1000 kg / cm 2 or more is applied.
Q ≧ [BW] × c × (Tg−t) (3)
[Wherein [BW] is the basis weight (g / m 2 ) of the resin sheet, c is the specific heat (J / g / K) of the aramid paper, and Tg is the glass transition temperature (° C.) of the aramid paper. And t is the temperature (° C.) of the aramid paper before being sandwiched by the heating element, and the temperature of the surface of the heating element is Tg or less.
When the amount of heat Q (J / m 2 ) expressed by the following is supplied per unit area of the aramid paper, the shrinkage rate is suppressed to within 3%, and the short fiber itself is deformed by sufficient heat pressure, and the thinner sheet Fabrication is possible.
For example, when the basis weight of the aramid paper is 20 g / m 2 , the specific heat is 1.89 J / g / K, the glass transition temperature is 275 ° C., and the temperature before being sandwiched between metal rolls is 20 ° C. In the case of using a metal roll as the body, if the surface temperature is 100 to 275 ° C. and the outer peripheral length where the metal roll is in contact with the aramid paper is 1 mm, for example, the linear heat pressure is 100 kg / cm or more. / M 2 or more can be exemplified, but is not limited thereto. The above hot pressing can be performed a plurality of times in an arbitrary order.
（ガラス転移温度）
本発明において、ガラス転移温度は、試験片を室温から３℃／分の割合で昇温させ、示差走査熱量計にて発熱量を測定し、吸熱曲線に２本の延長練を引き、延長線間の１／２直線と吸熱曲線の交点から求められる値であり、実施例で用いたアラミド紙のガラス転移温度は２７５℃であった。 (Glass-transition temperature)
In the present invention, the glass transition temperature is determined by raising the temperature of the test piece from room temperature at a rate of 3 ° C./min, measuring the calorific value with a differential scanning calorimeter, and drawing two extension lines on the endothermic curve. The value obtained from the intersection of the 1/2 straight line and the endothermic curve between them, and the glass transition temperature of the aramid paper used in the examples was 275 ° C.
本発明において、ガラス転移温度は、試験片を室温から３℃／分の割合で昇温させ、示差走査熱量計にて発熱量を測定し、吸熱曲線に２本の延長練を引き、延長線間の１／２直線と吸熱曲線の交点から求められる値であり、実施例で用いたアラミド紙のガラス転移温度は２７５℃であった。 (Glass-transition temperature)
In the present invention, the glass transition temperature is determined by raising the temperature of the test piece from room temperature at a rate of 3 ° C./min, measuring the calorific value with a differential scanning calorimeter, and drawing two extension lines on the endothermic curve. The value obtained from the intersection of the 1/2 straight line and the endothermic curve between them, and the glass transition temperature of the aramid paper used in the examples was 275 ° C.
（比熱）
本発明において、比熱は、試験片を室温から３℃／分の割合で昇温させ、示差走査熱量計にて比熱を測定した。実施例で用いたアラミド紙の比熱は１．８９Ｊ／ｇ／Ｋであった。
以下、本発明を、実施例を挙げてさらに具体的に説明する。なお、これらの実施例は、単なる例示であり、本発明の内容を何ら限定するためのものではない。 (specific heat)
In the present invention, the specific heat was measured by heating the test piece at a rate of 3 ° C./min from room temperature and measuring the specific heat with a differential scanning calorimeter. The specific heat of the aramid paper used in the examples was 1.89 J / g / K.
Hereinafter, the present invention will be described more specifically with reference to examples. These examples are merely illustrative and are not intended to limit the content of the present invention.
本発明において、比熱は、試験片を室温から３℃／分の割合で昇温させ、示差走査熱量計にて比熱を測定した。実施例で用いたアラミド紙の比熱は１．８９Ｊ／ｇ／Ｋであった。
以下、本発明を、実施例を挙げてさらに具体的に説明する。なお、これらの実施例は、単なる例示であり、本発明の内容を何ら限定するためのものではない。 (specific heat)
In the present invention, the specific heat was measured by heating the test piece at a rate of 3 ° C./min from room temperature and measuring the specific heat with a differential scanning calorimeter. The specific heat of the aramid paper used in the examples was 1.89 J / g / K.
Hereinafter, the present invention will be described more specifically with reference to examples. These examples are merely illustrative and are not intended to limit the content of the present invention.
（測定方法）
（１）収縮率
カレンダー加工前後のアラミド紙の幅を測定し、下記の式で計算した。
［カレンダー加工後のアラミド紙の幅］／［カレンダー加工前のアラミド紙の幅］×１００％
（２）坪量、厚みの測定
ＪＩＳ Ｃ２３００－２に準じて実施した。
厚みむらに関しては連続した４０点の厚みを測定し、その標準偏差を厚みむらとした。
（３）密度の計算
坪量÷厚みで計算した。
（４）引張強度の測定
テンシロン引張試験機を幅１５ｍｍ、チャック間隔５０ｍｍ、引張速度５０ｍｍ／分で実施した。
（５）透気度
王研式透気度計（旭精工社製ＫＧ－２）を用いて測定した透気度をガーレー式透気度に換算した。一連のシートについては、この時間が短いほど多孔質で、電気絶縁性が低いと言える。 (Measuring method)
(1) Shrinkage The width of the aramid paper before and after calendering was measured and calculated by the following formula.
[Width of aramid paper after calendering] / [Width of aramid paper before calendering] x 100%
(2) Measurement of basis weight and thickness The measurement was performed according to JIS C2300-2.
Regarding the thickness unevenness, 40 consecutive thicknesses were measured, and the standard deviation was defined as the thickness unevenness.
(3) Calculation of density It calculated by basic weight ÷ thickness.
(4) Measurement of tensile strength A Tensilon tensile tester was carried out at a width of 15 mm, a chuck interval of 50 mm, and a tensile speed of 50 mm / min.
(5) Air Permeability The air permeability measured using a Oken type air permeability meter (KG-2 manufactured by Asahi Seiko Co., Ltd.) was converted to Gurley air permeability. For a series of sheets, it can be said that the shorter this time, the more porous and the lower the electrical insulation.
（１）収縮率
カレンダー加工前後のアラミド紙の幅を測定し、下記の式で計算した。
［カレンダー加工後のアラミド紙の幅］／［カレンダー加工前のアラミド紙の幅］×１００％
（２）坪量、厚みの測定
ＪＩＳ Ｃ２３００－２に準じて実施した。
厚みむらに関しては連続した４０点の厚みを測定し、その標準偏差を厚みむらとした。
（３）密度の計算
坪量÷厚みで計算した。
（４）引張強度の測定
テンシロン引張試験機を幅１５ｍｍ、チャック間隔５０ｍｍ、引張速度５０ｍｍ／分で実施した。
（５）透気度
王研式透気度計（旭精工社製ＫＧ－２）を用いて測定した透気度をガーレー式透気度に換算した。一連のシートについては、この時間が短いほど多孔質で、電気絶縁性が低いと言える。 (Measuring method)
(1) Shrinkage The width of the aramid paper before and after calendering was measured and calculated by the following formula.
[Width of aramid paper after calendering] / [Width of aramid paper before calendering] x 100%
(2) Measurement of basis weight and thickness The measurement was performed according to JIS C2300-2.
Regarding the thickness unevenness, 40 consecutive thicknesses were measured, and the standard deviation was defined as the thickness unevenness.
(3) Calculation of density It calculated by basic weight ÷ thickness.
(4) Measurement of tensile strength A Tensilon tensile tester was carried out at a width of 15 mm, a chuck interval of 50 mm, and a tensile speed of 50 mm / min.
(5) Air Permeability The air permeability measured using a Oken type air permeability meter (KG-2 manufactured by Asahi Seiko Co., Ltd.) was converted to Gurley air permeability. For a series of sheets, it can be said that the shorter this time, the more porous and the lower the electrical insulation.
（原料調製）
特開昭５２－１５６２１号公報に記載の、ステーターとローターの組み合わせで構成されるパルプ粒子の製造装置（湿式沈殿機）を用いて、ポリメタフェニレンイソフタルアミドのファイブリッドを製造した。これを、離解機、叩解機で処理し長さ加重平均繊維長を０．９ｍｍに調節した（アラミドファイブリッドの濾水度：１００ml（カナディアンフリーネス））。一方、デュポン社製メタアラミド繊維（ノーメックス（登録商標）、単糸繊度２デニール、繊維径１５μｍ）を、長さ６ｍｍに切断（以下「アラミド短繊維」と記載）した。 (Raw material preparation)
A polymetaphenylene isophthalamide fibrid was manufactured using a pulp particle manufacturing apparatus (wet precipitator) composed of a combination of a stator and a rotor described in JP-A-52-15621. This was treated with a disaggregator and a beater to adjust the length weighted average fiber length to 0.9 mm (freeness of aramid fibrid: 100 ml (Canadian Freeness)). On the other hand, meta-aramid fiber (Nomex (registered trademark), single yarn fineness 2 denier, fiber diameter 15 μm) manufactured by DuPont was cut into a length of 6 mm (hereinafter referred to as “aramid short fiber”).
特開昭５２－１５６２１号公報に記載の、ステーターとローターの組み合わせで構成されるパルプ粒子の製造装置（湿式沈殿機）を用いて、ポリメタフェニレンイソフタルアミドのファイブリッドを製造した。これを、離解機、叩解機で処理し長さ加重平均繊維長を０．９ｍｍに調節した（アラミドファイブリッドの濾水度：１００ml（カナディアンフリーネス））。一方、デュポン社製メタアラミド繊維（ノーメックス（登録商標）、単糸繊度２デニール、繊維径１５μｍ）を、長さ６ｍｍに切断（以下「アラミド短繊維」と記載）した。 (Raw material preparation)
A polymetaphenylene isophthalamide fibrid was manufactured using a pulp particle manufacturing apparatus (wet precipitator) composed of a combination of a stator and a rotor described in JP-A-52-15621. This was treated with a disaggregator and a beater to adjust the length weighted average fiber length to 0.9 mm (freeness of aramid fibrid: 100 ml (Canadian Freeness)). On the other hand, meta-aramid fiber (Nomex (registered trademark), single yarn fineness 2 denier, fiber diameter 15 μm) manufactured by DuPont was cut into a length of 6 mm (hereinafter referred to as “aramid short fiber”).
（実施例１～４）
（アラミド紙の製造）
上記のとおり調製したアラミドファイブリッドとアラミド短繊維をおのおの水中で分散しスラリーを作製した。これらのスラリーを、アラミドファイブリッドとアラミド短繊維が表１に示す各配合比率（重量比）となるように混合し、タッピー式手抄き機（断面積６２５ｃｍ2）にてシート状物を作製した。次いで、これを金属製カレンダーロールにおいて、ロールとアラミド紙が接する外周長を１ｍｍとなるように調整し、表１に示す各カレンダー条件で熱圧加工し（発熱体に挟まれる前のアラミド紙の温度は２０℃である）、アラミド紙を得た。このようにして得られたアラミド紙の主要特性値を表１に示す。 (Examples 1 to 4)
(Manufacture of aramid paper)
Aramid fibrids and aramid short fibers prepared as described above were each dispersed in water to prepare a slurry. These slurries are mixed so that the aramid fibrids and aramid short fibers have the blending ratios (weight ratios) shown in Table 1, and a sheet-like material is produced with a tappy hand machine (cross-sectional area of 625 cm 2 ). did. Next, in a metal calender roll, the outer peripheral length where the roll and the aramid paper contact each other is adjusted to 1 mm and subjected to hot pressing under the calender conditions shown in Table 1 (the aramid paper before being sandwiched between the heating elements). The temperature is 20 ° C.) to obtain an aramid paper. Table 1 shows the main characteristic values of the aramid paper thus obtained.
（アラミド紙の製造）
上記のとおり調製したアラミドファイブリッドとアラミド短繊維をおのおの水中で分散しスラリーを作製した。これらのスラリーを、アラミドファイブリッドとアラミド短繊維が表１に示す各配合比率（重量比）となるように混合し、タッピー式手抄き機（断面積６２５ｃｍ2）にてシート状物を作製した。次いで、これを金属製カレンダーロールにおいて、ロールとアラミド紙が接する外周長を１ｍｍとなるように調整し、表１に示す各カレンダー条件で熱圧加工し（発熱体に挟まれる前のアラミド紙の温度は２０℃である）、アラミド紙を得た。このようにして得られたアラミド紙の主要特性値を表１に示す。 (Examples 1 to 4)
(Manufacture of aramid paper)
Aramid fibrids and aramid short fibers prepared as described above were each dispersed in water to prepare a slurry. These slurries are mixed so that the aramid fibrids and aramid short fibers have the blending ratios (weight ratios) shown in Table 1, and a sheet-like material is produced with a tappy hand machine (cross-sectional area of 625 cm 2 ). did. Next, in a metal calender roll, the outer peripheral length where the roll and the aramid paper contact each other is adjusted to 1 mm and subjected to hot pressing under the calender conditions shown in Table 1 (the aramid paper before being sandwiched between the heating elements). The temperature is 20 ° C.) to obtain an aramid paper. Table 1 shows the main characteristic values of the aramid paper thus obtained.
表１の結果から、本発明（実施例１～４）のアラミド紙は、収縮率が３％以内に抑えられているので、厚みが下式（２）
［厚み］／（［短繊維の繊維径］×２）≦１．２５ （２）
を満たすほど、充分に薄くなっており、また、強度も高く、透気度も充分に高く、耐熱性が本質的に高いアラミド素材を使用しているので、変圧器、モータなどの絶縁材料として有用である。 From the results in Table 1, since the aramid paper of the present invention (Examples 1 to 4) has a shrinkage rate of 3% or less, the thickness is expressed by the following formula (2)
[Thickness] / ([Fiber diameter of short fiber] × 2) ≦ 1.25 (2)
It is thin enough to meet the requirements, and it uses high aramid material with high strength, high air permeability, and essentially high heat resistance, so it can be used as an insulating material for transformers, motors, etc. Useful.
［厚み］／（［短繊維の繊維径］×２）≦１．２５ （２）
を満たすほど、充分に薄くなっており、また、強度も高く、透気度も充分に高く、耐熱性が本質的に高いアラミド素材を使用しているので、変圧器、モータなどの絶縁材料として有用である。 From the results in Table 1, since the aramid paper of the present invention (Examples 1 to 4) has a shrinkage rate of 3% or less, the thickness is expressed by the following formula (2)
[Thickness] / ([Fiber diameter of short fiber] × 2) ≦ 1.25 (2)
It is thin enough to meet the requirements, and it uses high aramid material with high strength, high air permeability, and essentially high heat resistance, so it can be used as an insulating material for transformers, motors, etc. Useful.
（比較例１～３）
（アラミド紙の製造）
上記のとおり調製したアラミドファイブリッドとアラミド短繊維をおのおの水中で分散しスラリーを作製した。これらのスラリーを、アラミドファイブリッドとアラミド短繊維が表２に示す各配合比率（質量比）となるように混合し、タッピー式手抄き機（断面積６２５ｃｍ2）にてシート状物を作製した。次いで、これを金属製カレンダーロールにおいて、ロールとアラミド紙が接する外周長を１ｍｍとなるように調整し、表２に示す各カレンダー条件で熱圧加工し（発熱体に挟まれる前のアラミド紙の温度は２０℃である）、アラミド紙を得た。このようにして得られたアラミド紙の主要特性値を表２に示す。 (Comparative Examples 1 to 3)
(Manufacture of aramid paper)
Aramid fibrids and aramid short fibers prepared as described above were each dispersed in water to prepare a slurry. These slurries are mixed so that the aramid fibrids and the aramid short fibers have the respective blending ratios (mass ratios) shown in Table 2, and a sheet-like material is produced with a tappy hand machine (cross-sectional area of 625 cm 2 ). did. Next, in a metal calender roll, the outer peripheral length where the roll and the aramid paper contact each other is adjusted to 1 mm and subjected to hot pressing under the calender conditions shown in Table 2 (the aramid paper before being sandwiched between the heating elements). The temperature is 20 ° C.) to obtain an aramid paper. Table 2 shows the main characteristic values of the aramid paper thus obtained.
（アラミド紙の製造）
上記のとおり調製したアラミドファイブリッドとアラミド短繊維をおのおの水中で分散しスラリーを作製した。これらのスラリーを、アラミドファイブリッドとアラミド短繊維が表２に示す各配合比率（質量比）となるように混合し、タッピー式手抄き機（断面積６２５ｃｍ2）にてシート状物を作製した。次いで、これを金属製カレンダーロールにおいて、ロールとアラミド紙が接する外周長を１ｍｍとなるように調整し、表２に示す各カレンダー条件で熱圧加工し（発熱体に挟まれる前のアラミド紙の温度は２０℃である）、アラミド紙を得た。このようにして得られたアラミド紙の主要特性値を表２に示す。 (Comparative Examples 1 to 3)
(Manufacture of aramid paper)
Aramid fibrids and aramid short fibers prepared as described above were each dispersed in water to prepare a slurry. These slurries are mixed so that the aramid fibrids and the aramid short fibers have the respective blending ratios (mass ratios) shown in Table 2, and a sheet-like material is produced with a tappy hand machine (cross-sectional area of 625 cm 2 ). did. Next, in a metal calender roll, the outer peripheral length where the roll and the aramid paper contact each other is adjusted to 1 mm and subjected to hot pressing under the calender conditions shown in Table 2 (the aramid paper before being sandwiched between the heating elements). The temperature is 20 ° C.) to obtain an aramid paper. Table 2 shows the main characteristic values of the aramid paper thus obtained.
上記表２から明らかなように、比較例１～３のアラミド紙は透気度が小さい。さらに、比較例１のアラミド紙は強度が小さく、比較例２及び３のアラミド紙は収縮率が高いため厚みが大きくなっており、絶縁材料としては変圧器、モータなどの機器の小型化、軽量化に対応することは困難であると考えられる。
As is clear from Table 2 above, the aramid paper of Comparative Examples 1 to 3 has a low air permeability. Furthermore, the aramid paper of Comparative Example 1 has a low strength, and the aramid papers of Comparative Examples 2 and 3 have a large shrinkage due to high shrinkage. It seems difficult to cope with the change.
Claims (3)
- 芳香族ポリアミドから形成されるファイブリッド及び短繊維との混合物から形成されたアラミド紙であり、下記不等式（１）及び（２）
４０≦［ＦＢ］ ≦９０ （１）
［厚み］／（［短繊維の繊維径］×２）≦１．２５ （２）
〔式中、［ＦＢ］はアラミド紙中のファイブリッドの含量（重量％）である〕
を満たすファイブリッド含量及び厚みを有するアラミド紙。 Aramid paper formed from a mixture of fibrids and short fibers formed from an aromatic polyamide, the following inequalities (1) and (2)
40 ≦ [FB] ≦ 90 (1)
[Thickness] / ([Fiber diameter of short fiber] × 2) ≦ 1.25 (2)
[Wherein [FB] is the fibrid content (% by weight) in the aramid paper]
Aramid paper having a fibrid content and thickness satisfying - 少なくとも一対の発熱体の間に芳香族ポリアミドから形成されるファイブリッド及び短繊維との混合物から形成されたアラミド紙を挟んで熱圧加工することを含み、上記発熱体による熱圧加工後の上記アラミド紙の収縮率が３％以下である、請求項１に記載のアラミド紙の製造方法。 Including aramid paper formed from a mixture of a fibrid formed from an aromatic polyamide and a short fiber between at least a pair of heating elements, and hot-pressing, and after the hot-pressure processing by the heating element The method for producing aramid paper according to claim 1, wherein the shrinkage rate of the aramid paper is 3% or less.
- 少なくとも一対の発熱体の間に芳香族ポリアミドから形成されるファイブリッド及び短繊維との混合物から形成されたアラミド紙を挟み、１０００ｋｇ／ｃｍ2以上の圧力を加えると同時に、上記発熱体より、下式（３）
Ｑ≧ ［ＢＷ］×ｃ×（Ｔｇ－ｔ） （３）
〔式中、［ＢＷ］は樹脂シートの坪量（ｇ／ｍ2）であり、ｃは上記アラミド紙の比熱（Ｊ／ｇ／Ｋ）であり、Ｔｇは上記アラミド紙のガラス転移温度（℃）であり、ｔは発熱体に挟まれる前の上記アラミド紙の温度（℃）であり、上記発熱体の表面の温度はＴｇ以下である〕
で表される熱量Ｑ（Ｊ／ｍ2）を供給することを含む、請求項１に記載のアラミド紙の製造方法。 Aramid paper formed from a mixture of fibrids and short fibers formed from aromatic polyamide is sandwiched between at least a pair of heating elements, and at the same time as applying a pressure of 1000 kg / cm 2 or more, Formula (3)
Q ≧ [BW] × c × (Tg−t) (3)
[Wherein [BW] is the basis weight (g / m 2 ) of the resin sheet, c is the specific heat (J / g / K) of the aramid paper, and Tg is the glass transition temperature (° C.) of the aramid paper. And t is the temperature (° C.) of the aramid paper before being sandwiched by the heating element, and the temperature of the surface of the heating element is Tg or less.
The manufacturing method of the aramid paper of Claim 1 including supplying calorie | heat amount Q (J / m < 2 >) represented by these.
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| CN202310418992.9A CN116516718A (en) | 2015-05-28 | 2016-05-17 | Aramid paper and preparation method thereof |
| CN201680031183.0A CN107636226A (en) | 2015-05-28 | 2016-05-17 | Aramid paper and preparation method thereof |
| KR1020177029459A KR20180012743A (en) | 2015-05-28 | 2016-05-17 | Aramid paper and its manufacturing method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018188778A1 (en) * | 2017-04-12 | 2018-10-18 | Diehl Aviation Laupheim Gmbh | Paper and thus produced honeycomb structure |
| WO2020170902A1 (en) * | 2019-02-22 | 2020-08-27 | デュポン帝人アドバンスドペーパー株式会社 | Method for producing aramid paper |
| US20220184538A1 (en) * | 2019-04-05 | 2022-06-16 | Ahlstrom-Munksjö Oyj | Flue gas filtration media |
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| CN115897292A (en) * | 2022-10-28 | 2023-04-04 | 株洲时代华先材料科技有限公司 | Aramid crepe paper and preparation method thereof |
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- 2016-05-17 CN CN201680031183.0A patent/CN107636226A/en active Pending
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- 2016-05-17 WO PCT/JP2016/064567 patent/WO2016190163A1/en active Application Filing
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| WO2018188778A1 (en) * | 2017-04-12 | 2018-10-18 | Diehl Aviation Laupheim Gmbh | Paper and thus produced honeycomb structure |
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| JP2016223021A (en) | 2016-12-28 |
| CN107636226A (en) | 2018-01-26 |
| CN116516718A (en) | 2023-08-01 |
| TW201704591A (en) | 2017-02-01 |
| JP6649701B2 (en) | 2020-02-19 |
| KR20180012743A (en) | 2018-02-06 |
| TWI702326B (en) | 2020-08-21 |
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