JPH02221490A - Polyester synthetic paper - Google Patents
Polyester synthetic paperInfo
- Publication number
- JPH02221490A JPH02221490A JP3622989A JP3622989A JPH02221490A JP H02221490 A JPH02221490 A JP H02221490A JP 3622989 A JP3622989 A JP 3622989A JP 3622989 A JP3622989 A JP 3622989A JP H02221490 A JPH02221490 A JP H02221490A
- Authority
- JP
- Japan
- Prior art keywords
- polyester
- fiber
- paper
- strength
- fibers
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 125
- 239000000835 fiber Substances 0.000 claims abstract description 152
- 239000000853 adhesive Substances 0.000 claims description 20
- 230000001070 adhesive effect Effects 0.000 claims description 20
- -1 polyethylene terephthalate Polymers 0.000 abstract description 30
- 239000003513 alkali Substances 0.000 abstract description 16
- 239000007864 aqueous solution Substances 0.000 abstract description 14
- 239000003795 chemical substances by application Substances 0.000 abstract description 13
- 229920001131 Pulp (paper) Polymers 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 229920005989 resin Polymers 0.000 abstract description 5
- 239000011347 resin Substances 0.000 abstract description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 abstract description 3
- 239000005020 polyethylene terephthalate Substances 0.000 abstract description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 2
- 238000007598 dipping method Methods 0.000 abstract description 2
- 229920001225 polyester resin Polymers 0.000 abstract description 2
- 239000004645 polyester resin Substances 0.000 abstract description 2
- 239000011369 resultant mixture Substances 0.000 abstract 2
- 239000000123 paper Substances 0.000 description 72
- 238000000034 method Methods 0.000 description 28
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 229920002451 polyvinyl alcohol Polymers 0.000 description 21
- 239000004372 Polyvinyl alcohol Substances 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 19
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000007796 conventional method Methods 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 229910052698 phosphorus Inorganic materials 0.000 description 11
- 239000011574 phosphorus Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 230000007423 decrease Effects 0.000 description 9
- XQKKWWCELHKGKB-UHFFFAOYSA-L calcium acetate monohydrate Chemical compound O.[Ca+2].CC([O-])=O.CC([O-])=O XQKKWWCELHKGKB-UHFFFAOYSA-L 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000006068 polycondensation reaction Methods 0.000 description 7
- 235000011121 sodium hydroxide Nutrition 0.000 description 7
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000005809 transesterification reaction Methods 0.000 description 6
- 230000004580 weight loss Effects 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 238000002074 melt spinning Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 238000009987 spinning Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000004873 anchoring Methods 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 229940067460 calcium acetate monohydrate Drugs 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 229920000620 organic polymer Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000009832 plasma treatment Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 3
- 229920002994 synthetic fiber Polymers 0.000 description 3
- 239000012209 synthetic fiber Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 229920002978 Vinylon Polymers 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002964 rayon Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- CXOFVDLJLONNDW-UHFFFAOYSA-N Phenytoin Chemical group N1C(=O)NC(=O)C1(C=1C=CC=CC=1)C1=CC=CC=C1 CXOFVDLJLONNDW-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XDODWINGEHBYRT-UHFFFAOYSA-N [2-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCCCC1CO XDODWINGEHBYRT-UHFFFAOYSA-N 0.000 description 1
- XMUZQOKACOLCSS-UHFFFAOYSA-N [2-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC=C1CO XMUZQOKACOLCSS-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- IBBQVGDGTMTZRA-UHFFFAOYSA-N sodium;2-sulfobenzene-1,3-dicarboxylic acid Chemical compound [Na].OC(=O)C1=CC=CC(C(O)=O)=C1S(O)(=O)=O IBBQVGDGTMTZRA-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Landscapes
- Chemical Or Physical Treatment Of Fibers (AREA)
- Artificial Filaments (AREA)
- Paper (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、ポリエステル繊維を主体とした高引裂強力、
高引張強力を有する合成紙に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention provides high tear strength,
This invention relates to synthetic paper having high tensile strength.
［従来技術］
ポリエステル繊維は力学的特性、耐候性、電気絶縁性、
耐熱性２．耐薬品性、加工性０寸法安定性。[Prior art] Polyester fiber has excellent mechanical properties, weather resistance, electrical insulation,
Heat resistance 2. Chemical resistance, processability and dimensional stability.
耐湿性にすぐれ、またコストも低廉であることから、す
ぐれた紙素材として注目されている。しかし、ポリエス
テル繊維は疎水性が強く、木材パルプ、ビニロン繊維、
レーヨン繊維、あるいは熱水可溶性のポリビニルアルコ
ール系バインダー繊維などの汎用素材（いずれも親水性
）との親和性に乏しい。この為ポリエステル繊維とかか
る汎用原料との混抄紙は、汎用原料同志の混抄紙よりも
紙物性、待に引張強力、引裂強力が著しく低いという欠
点を有している。ざらにポリエステル繊維は疎水性が高
いため抄紙液中での分散性が悪いという欠点を有してい
る。It is attracting attention as an excellent paper material because of its excellent moisture resistance and low cost. However, polyester fiber has strong hydrophobicity, and it can be used for wood pulp, vinylon fiber, etc.
It has poor affinity with general-purpose materials such as rayon fibers or hot water-soluble polyvinyl alcohol binder fibers (both of which are hydrophilic). For this reason, paper made from a mixture of polyester fibers and such general-purpose raw materials has the disadvantage that paper properties, especially tensile strength and tear strength, are significantly lower than paper made from a mixture of general-purpose raw materials. Furthermore, polyester fibers have the disadvantage of poor dispersibility in papermaking liquids due to their high hydrophobicity.
かかる背景からポリエステル混抄紙の強力を高めるため
に種々の提案がなされているが、いまだ実用的に満足し
得るものは得られていない。Against this background, various proposals have been made to increase the strength of polyester blend paper, but so far nothing that is practically satisfactory has been achieved.
例えば特開昭６０−３４７００号公報では、ポリエステ
ルポリエーテルブロック共重合体で繊維表面を処理した
ポリエステル系繊維を用いる方法が開示されている。ま
た特開昭６２−１７０５８２号公報には繊維表面にポリ
ビニルアルコール系重合体を付着させる方法が開示され
ている。一方ポリエステル混抄紙用の接着性繊維に関す
る提案も種々なされている。例えば特開昭５９−１７５
号公報あるいは特開昭５９−１８７７８＠公報では共重
合ポリエステルバインダー繊維、特開昭５３−７４１０
７号公報では、ポリ酢酸ビニルグラフト天然パルプを部
分ケン化した半合成パルプなどが提案されているが満足
できるポリエステル混抄紙用バインダーは得られていな
い。For example, JP-A-60-34700 discloses a method using polyester fibers whose fiber surfaces have been treated with a polyester polyether block copolymer. Furthermore, Japanese Patent Application Laid-open No. 170582/1982 discloses a method for attaching a polyvinyl alcohol polymer to the surface of fibers. On the other hand, various proposals regarding adhesive fibers for polyester mixed paper have also been made. For example, JP-A-59-175
No. 59-18778 @ publication describes copolymerized polyester binder fiber, JP-A-53-7410
No. 7 proposes a semi-synthetic pulp obtained by partially saponifying polyvinyl acetate-grafted natural pulp, but a satisfactory binder for polyester-mixed papermaking has not been obtained.
一方合成繊維を抄紙する際に偏平糸を用いることに関し
ては、特公昭３９−２４８３０号公報あるいは特公昭３
９−１６２（）３＠公報において表面が平滑な偏平断面
の合成繊維を水の中に分散させ、カルボキシメチルセル
ロースを添加して抄紙することによって紙強力を向上せ
しめる方法が開示されている。また特開昭５８−２０４
４０６ ＠公報では、クラフトパルプと偏平プラスチッ
ク繊維とを混合抄紙することによって絶縁紙の強力を高
める方法が開示されている。しかるに、この方法におい
ても強力は不充分であった。また、紙の強力を高める別
の方法として、延伸ポリエステル繊維に未延伸ポリエス
テル繊維を併用し、抄紙したのち、熱圧加工する方法が
開示されている（特開昭５８−７６５９７号公報、特開
昭６３−２７５７９８号公報）。この方法の場合には熱
圧加工工程による製造コストの上昇を招くなどの欠点が
ある。On the other hand, regarding the use of flattened yarn when making paper from synthetic fibers, Japanese Patent Publication No. 39-24830 or Japanese Patent Publication No. 3
No. 9-162()3@ discloses a method of improving paper strength by dispersing synthetic fibers with flat cross sections with smooth surfaces in water and adding carboxymethyl cellulose to form paper. Also, JP-A-58-204
Publication No. 406@ discloses a method of increasing the strength of insulating paper by mixing kraft pulp and flat plastic fibers to form paper. However, even with this method, the strength was insufficient. In addition, as another method for increasing the strength of paper, a method has been disclosed in which drawn polyester fibers are used in combination with undrawn polyester fibers, paper is made, and then thermal pressure processing is performed (Japanese Patent Laid-Open No. 58-76597, (Sho 63-275798). This method has drawbacks such as an increase in manufacturing costs due to the hot-pressing process.
［発明の目的］
すなわら、従来、ポリエステル繊維を主体とする合成紙
においては、高い引裂強度、高い引張強度が達成されて
いない。そのためポリエステルのもつすぐれた特性にも
かかわらず、ポリエステル合成紙の展開が十分行なわれ
ていないのが瑛実である。本発明の目的は、ポリエステ
ル繊維を主体とした合成紙において、高い引裂強度、高
い引張強度を有するポリエステル合成紙を提供すること
にある。[Object of the Invention] Conventionally, high tear strength and high tensile strength have not been achieved in synthetic papers mainly composed of polyester fibers. For this reason, despite the excellent properties of polyester, polyester synthetic paper has not been sufficiently developed. An object of the present invention is to provide a synthetic paper mainly composed of polyester fibers, which has high tear strength and high tensile strength.
［発明の構成］
すなわち、本発明は、
［（１）主としてポリエステル繊維からなり接着性成分
を有する合成紙において、ポリエステル繊維がその表面
に直径０．００１〜５μの微細孔を有することを特徴と
するポリエステル合成紙。[Structure of the Invention] That is, the present invention provides the following features: [(1) A synthetic paper mainly composed of polyester fibers and having an adhesive component, characterized in that the polyester fibers have micropores with a diameter of 0.001 to 5 μm on the surface thereof. polyester synthetic paper.
（２）微細孔の直径が０．００５〜２μである請求項（
１）のポリエステル合成紙」である。(2) Claim in which the diameter of the micropores is 0.005-2μ
1) polyester synthetic paper.
ここにポリエステルとは例えばテレフタル酸。Polyester here is, for example, terephthalic acid.
イソフタル酸、ジフェニルジカルボン酸、ナフタリンジ
カルボン酸、ナトリウム・スルホイソフタル酸などの芳
香族ジカルボン酸、アジピン酸、セバシン酸、デカンジ
カルボン酸などの脂肪族ジカルボン酸またはへキサヒド
ロテレフタル酸の如き脂肪族ジカルボン酸を二塩基酸成
分とし、エチレングリコール、プロピレングリコール、
トリメチレングリコール、テトラメチレングリコール、
デカメチレングリコール、ジエチレングリコール。Aromatic dicarboxylic acids such as isophthalic acid, diphenyl dicarboxylic acid, naphthalene dicarboxylic acid, sodium sulfoisophthalic acid, aliphatic dicarboxylic acids such as adipic acid, sebacic acid, decane dicarboxylic acid, or aliphatic dicarboxylic acids such as hexahydroterephthalic acid. is the dibasic acid component, ethylene glycol, propylene glycol,
trimethylene glycol, tetramethylene glycol,
Decamethylene glycol, diethylene glycol.
２．２−ジメチルプロパンジオール、ヘキサヒドロキシ
リレングリコール、キシリレングリコールなどの脂肪族
、脂環族または芳香族グリコールあるいはポリエチレン
グリコールの如きポリオキシアルキレングリコールをグ
リコール成分とするポリエステルなどである。これら二
塩基酸成分またはグリコール成分をそれぞれ１種あるい
は２種以上組合せた共重合ポリエステルであってもよい
。特に好ましい例としてはポリエチレンテレフタレート
、ポリブチレンテレフタレートを挙げることができる。These include polyesters containing aliphatic, alicyclic or aromatic glycols such as 2.2-dimethylpropanediol, hexahydroxylylene glycol and xylylene glycol, or polyoxyalkylene glycols such as polyethylene glycol as a glycol component. A copolymerized polyester containing one type or a combination of two or more of these dibasic acid components or glycol components may also be used. Particularly preferred examples include polyethylene terephthalate and polybutylene terephthalate.
更に可塑性や溶融粘度を増大させるために重合体に可塑
剤、増粘剤などを添加してもよい。Furthermore, a plasticizer, a thickener, etc. may be added to the polymer in order to increase plasticity and melt viscosity.
また通常、繊維の添加剤として使用される光安定剤、顔
料、熱安定剤、難燃剤などが添加されていてもよい。Furthermore, light stabilizers, pigments, heat stabilizers, flame retardants, etc., which are usually used as additives for fibers, may be added.
直径０．００１〜５μの微細孔を有するポリエステル繊
維は、たとえば下記のごとき方法で得ることができる。Polyester fibers having micropores with a diameter of 0.001 to 5 microns can be obtained, for example, by the following method.
ａ、微細孔形成剤を含有せしめたポリエステル繊維をア
ルカリ水溶液で処理し、微細孔形成剤の１部を溶出せし
めることによって繊維表面に微細孔を形成させる。a. Polyester fibers containing a micropore-forming agent are treated with an alkaline aqueous solution to elute a portion of the micropore-forming agent, thereby forming micropores on the fiber surface.
ｂ、微細孔形成剤を用いない方法としては、グロー放電
プラズマ照射により繊維表面に微細孔を形成させること
ができる。b. As a method that does not use a micropore-forming agent, micropores can be formed on the fiber surface by glow discharge plasma irradiation.
たとえば、低温プラズマ加工をボ１去エステル繊維に適
用すれば、微細孔形成剤を含有せしめることなく、エツ
チングが可能である。具体的には、たとえば冷却ボック
ス、金網、電極群等からなる低温プラズマ装置において
、繊維長３〜３０ｍｍ程度のポリエステル短繊維を振動
する金網上に載置して低温プラズマ加工を行う。For example, if low-temperature plasma processing is applied to a voided ester fiber, etching is possible without incorporating a micropore-forming agent. Specifically, in a low-temperature plasma apparatus comprising, for example, a cooling box, a wire mesh, an electrode group, etc., short polyester fibers having a fiber length of about 3 to 30 mm are placed on a vibrating wire mesh and subjected to low-temperature plasma processing.
微細孔形成剤としては、例えば滑剤や艶消剤に使用され
る炭酸カルシウム、酸化チタン、硫酸バリウム、シリカ
、酸化ジルコニウムなどの無機化合物を用いることがで
きる。ざらには、ポリエステルの溶融、成型温度におい
てほとんど伸長変形されない有機高分子化合物でもよい
。As the micropore-forming agent, inorganic compounds such as calcium carbonate, titanium oxide, barium sulfate, silica, and zirconium oxide, which are used as lubricants and matting agents, can be used. In general, it may be an organic polymer compound that is hardly elongated and deformed at the melting and molding temperature of polyester.
これらの有機高分子化合物としては、ポリエステル溶融
温度においてポリエステルよりもはるかに高い粘性をも
つポリエチレン、ポリスチレン。These organic polymer compounds include polyethylene and polystyrene, which have a much higher viscosity than polyester at the polyester melting temperature.
ナイロン、ポリスルフォンなどである。これらは紡糸の
際、吐出糸が高い伸長変形応力を受けるにも拘らずこれ
らの化合物自身はほとんど伸長変形されないので微細孔
成形剤の役割を果たすことができる。These include nylon and polysulfone. Although these compounds are subjected to high elongation deformation stress during spinning, these compounds themselves are hardly elongated and deformed, so they can play the role of micropore forming agents.
ざらに、下記一般式
で表わされる有機スルホン酸化合物を共重合せしめたポ
リエステルを微細孔形成剤として用い、共重合しないポ
リエステルとブレンドして繊維化したのち該有機スルホ
ン酸化合物を共重合せしめたポリエステルの少なくとも
一部を例えばアルカリ処理により除去することによって
微細孔を形成せしめてもよい。In general, a polyester copolymerized with an organic sulfonic acid compound represented by the following general formula is used as a micropore forming agent, blended with a non-copolymerized polyester to form a fiber, and then the organic sulfonic acid compound is copolymerized with the polyester. The micropores may be formed by removing at least a portion of the pores by, for example, alkali treatment.
有機スルホン酸化合物の添加量は二官能性カルボン酸成
分に対し２〜１６モル％が好ましい。共重合体の混合割
合は、共重合しないポリエステル１００重量部に対し５
〜１００重量部が好ましい。The amount of the organic sulfonic acid compound added is preferably 2 to 16 mol % based on the bifunctional carboxylic acid component. The mixing ratio of the copolymer is 5 parts by weight per 100 parts by weight of the non-copolymerized polyester.
~100 parts by weight is preferred.
又、下記一般式
で表わされるスルホン酸金属塩をポリエステルの溶融紡
糸が終了するまでの任意の段階で添加し、得られた繊維
をアルカリ化合物の水溶液で処理してその一部を溶出す
ることにより微細孔を形成せしめてもよい。In addition, by adding a sulfonic acid metal salt represented by the general formula below at any stage until the completion of melt spinning of polyester, and treating the obtained fiber with an aqueous solution of an alkaline compound to elute a part of it, Fine pores may be formed.
ざらには、ポリエステルの合成が完了するまでの任意の
段階で、（ａ）ポリエステルを構成する酸成分に対して
０．５〜３モル％の下記一般式％式％（）
で表わされる含金属リン化合物及び（ｂ）該含金属リン
化合物に対して０．５〜１．２倍モルのアルカリ土類金
属化合物を（ａ）と（ｂ）とを予め反応させることなく
添加し、しかる後ポリエステルの合成を完了し、得られ
たポリエステルを溶融紡糸した後、アルカリ化合物の水
溶液によりその一部を溶出することにより形成せしめて
もよい。In general, at any stage until the synthesis of polyester is completed, (a) 0.5 to 3 mol % of the metal-containing compound represented by the following general formula % formula % () based on the acid component constituting the polyester. A phosphorus compound and (b) an alkaline earth metal compound in an amount of 0.5 to 1.2 times the mole of the metal-containing phosphorus compound are added without reacting (a) and (b) in advance, and then the polyester The polyester may be formed by completing the synthesis, melt-spinning the obtained polyester, and then eluting a part of it with an aqueous solution of an alkaline compound.
無機粒子の場合は、その粒子径として０．００１〜５μ
の粒径のものを用いるのが好ましい。粒径が０．００１
μ未満の場合は、繊維表面に形成される微細孔の径が接
着に有効ではない。一方粒径が５μを越える場合は、繊
維の形成時に異物として作用するため繊維の曳糸性が極
端に悪くなり有効でない。ざらに好ましい範囲としては
ｏ、 ｏｏｓ〜２μ、最も好ましい範囲としてはＯ，Ｏ
Ｓ〜１μである。微細孔形成剤をポリエステルに含有せ
しめるには、微粒子をポリエステルに直接添加する方法
、又はポリエステル重合反応時に、内部析出させて微粒
子を形成させる方法などを用いる。In the case of inorganic particles, the particle size is 0.001 to 5μ
It is preferable to use particles with a particle size of . Particle size is 0.001
When the diameter is less than μ, the diameter of micropores formed on the fiber surface is not effective for adhesion. On the other hand, if the particle size exceeds 5 μm, the particles act as foreign substances during fiber formation, resulting in extremely poor spinnability of the fibers and are not effective. Roughly preferred ranges are o, oos to 2μ, most preferred ranges are O, O
S~1μ. In order to incorporate the micropore-forming agent into the polyester, a method is used in which fine particles are directly added to the polyester, or a method in which fine particles are formed by internal precipitation during the polyester polymerization reaction.
微細孔形成剤の添加量は、ポリエステルに対して０．０
１〜１０重量％が好ましく、さらに好ましくは０．３〜
５重量％である。０．０１重量％未満では、その添加量
が不足のため接着に必要なだけの微細孔を得ることがで
きない。又１０重量％を越えると曳糸性が悪化し、ざら
に繊維強度も低下するので好ましくない。The amount of micropore forming agent added is 0.0 to polyester.
1 to 10% by weight is preferable, more preferably 0.3 to 10% by weight.
It is 5% by weight. If the amount is less than 0.01% by weight, the amount of addition is insufficient and it is not possible to obtain enough micropores for adhesion. Moreover, if it exceeds 10% by weight, the spinnability deteriorates and the fiber strength also deteriorates, which is not preferable.
高粘性有機高分子化合物を添加する場合には、少量の分
散助剤（ｃｏｍｐａｔｉｖｉｌｉｚｅｒ）を添加するこ
とにより、有機高分子を微細に分散させることができる
。添加量はポリエステルに対して０．１〜１５重量％が
好ましく、さらに好ましくは１〜５重ω％である。０．
１重量％未満では、その添加量が不足のため、接着に必
要なだけの微細孔を得ることができない。又１５重量％
を越えると曳糸性が悪化し、さらに繊維強度が低下して
好ましくない。このようにして１ｑられた繊維に対して
、アルカリ等で表面をエツチングすることにより微細孔
を得ることができる。When adding a highly viscous organic polymer compound, the organic polymer can be finely dispersed by adding a small amount of a dispersion aid (compatibilizer). The amount added is preferably 0.1 to 15% by weight, more preferably 1 to 5% by weight, based on the polyester. 0.
If the amount is less than 1% by weight, the amount of addition is insufficient and it is not possible to obtain sufficient micropores for adhesion. Also 15% by weight
Exceeding this is not preferable because the spinnability deteriorates and the fiber strength further decreases. Fine pores can be obtained by etching the surface of the fiber thus prepared by 1q with an alkali or the like.
スルホン酸金属塩の添加量は、あまりに少ないと、最終
的に得られるポリエステルｌｌｉ維表面に微細孔が不充
分になり、逆にあまりに多いと、その添加時期がポリエ
ステルの合成が終了する以前では、十分な重合度のポリ
エステルが得られ難く、またその添加時期が合成終了後
から溶融紡糸終了以前のときは紡糸時にトラブルを発生
し易い。このためスルホン酸金属塩の添加量は、添加す
べきポリエステルを構成する酸成分に対し０．１〜２５
モル％の範囲にすべきであり、０．３〜１５モル％の範
囲が好ましい。上記スルホン酸塩を添加した変性ポリエ
ステルを溶融紡糸するには特別な方法を採用する必要は
なく、通常のポリエステル繊維の溶融紡糸法を用いるこ
とができる。かくして得られたポリエステル繊維から添
加物の一部を除去するにはアルカリ化合物の水溶液に浸
漬処理することによって容易に行うことができる。If the amount of sulfonic acid metal salt added is too small, there will be insufficient micropores on the surface of the polyester LLI fibers finally obtained, and if it is too large, the addition time will be before the polyester synthesis is completed. It is difficult to obtain polyester with a sufficient degree of polymerization, and if it is added between after the completion of synthesis and before the completion of melt spinning, troubles are likely to occur during spinning. Therefore, the amount of sulfonic acid metal salt added is 0.1 to 25% of the acid component constituting the polyester to be added.
The range should be between 0.3 and 15 mol %, preferably between 0.3 and 15 mol %. There is no need to employ any special method to melt-spun the modified polyester to which the sulfonate has been added, and a normal melt-spinning method for polyester fibers can be used. Part of the additive can be easily removed from the polyester fiber thus obtained by dipping it in an aqueous solution of an alkaline compound.
また、このアルカリ化合物の水溶液の処理によって溶出
除去する量は、繊維重量に対して０．１〜２５重量％の
範囲が好ましい。Further, the amount of the alkaline compound eluted and removed by treatment with the aqueous solution is preferably in the range of 0.1 to 25% by weight based on the weight of the fiber.
含金属リン化合物の添加量はあまりに少ないと最終的に
１ｑられるポリエステル繊維の微細孔の量が不充分にな
り、この量を多くするに従って微細孔は増加するが、あ
まりに多くなると最早接着は著しい向上を示さず、かえ
って繊維強度低下が起り、その上十分な重合度と軟化点
とを有するポリエステルを得ることが困難となり、更に
紡糸時に糸切れが多発するというトラブルを発生する。If the amount of metal-containing phosphorus compound added is too small, the amount of micropores in the final 1q polyester fiber will be insufficient, and as this amount is increased, the number of micropores will increase, but if it is too large, the adhesion will no longer be significantly improved. Instead, fiber strength decreases, and furthermore, it becomes difficult to obtain a polyester having a sufficient degree of polymerization and softening point, and furthermore, trouble occurs in that yarn breakage occurs frequently during spinning.
このため、含金属リン化合物の添加量はポリエステルを
構成する酸成分に対して０．５〜３モル％の範囲にすべ
きであり、特に０．６〜２モル％の範囲が好ましい。ま
たアルカリ土類金属化合物の添加量が含金属リン化合物
の添加量に対して０．５倍モル゛より少ない量では、得
られるポリエステル繊維の微細孔が不充分であり、その
うえ重縮合速度が低下し高重合度のポリエステルを得る
ことが困難となり、又、生成ポリエステルの軟化点が大
幅に低下するようになる。逆に含金属リン化合物に対し
て１．２倍モルを越える量のアルカリ土類金属化合物を
使用すると、粗大粒子が生成し、接着性は改善される。Therefore, the amount of the metal-containing phosphorus compound added should be in the range of 0.5 to 3 mol%, particularly preferably in the range of 0.6 to 2 mol%, based on the acid component constituting the polyester. In addition, if the amount of the alkaline earth metal compound added is less than 0.5 times the amount of the metal-containing phosphorus compound added, the resulting polyester fibers will have insufficient micropores and the polycondensation rate will decrease. This makes it difficult to obtain a polyester with a high degree of polymerization, and the softening point of the resulting polyester is significantly lowered. On the other hand, when the alkaline earth metal compound is used in an amount exceeding 1.2 times the mole of the metal-containing phosphorus compound, coarse particles are formed and the adhesion is improved.
どころか、かえって繊維強度が低下するようになる。こ
のため、含金属リン化合物に対するアルカリ土類金属化
合物の添加量は、０．５〜１．２倍モルの範囲にすべき
であり、特に０．５〜１．０倍モルの範囲が好ましい。On the contrary, the fiber strength is reduced. Therefore, the amount of the alkaline earth metal compound added to the metal-containing phosphorus compound should be in the range of 0.5 to 1.2 times by mole, and particularly preferably in the range of 0.5 to 1.0 times by mole.
上記含金属リン化合物とアルカリ土類金属化合物とは予
め反応させることなくポリエステル反応系に添加する必
要がある。こうすることによって、不溶性粒子をポリエ
ステル中に均一な超微粒子状態で生成せしめることがで
きるようになる。予め外部で上記含金属リン化合物とア
ルカリ土類金属化合物とを反応させて不溶性粒子とした
後にポリエステル反応系に添加したのでは、ポリエステ
ル中での不溶性粒子の分散性が悪くなり、かつ粗大凝集
粒子が含有されるようになるため、最終的に１ｑられる
ポリエステル紙の強度を改善する効果は認められなくな
るので好ましくない。It is necessary to add the metal-containing phosphorus compound and the alkaline earth metal compound to the polyester reaction system without reacting them in advance. By doing so, the insoluble particles can be produced in the polyester in the form of uniform ultrafine particles. If the above-mentioned metal-containing phosphorus compound and alkaline earth metal compound are reacted externally in advance to form insoluble particles and then added to the polyester reaction system, the dispersibility of the insoluble particles in the polyester becomes poor and coarse agglomerated particles are formed. is contained, so that the effect of improving the strength of the polyester paper that is finally produced by 1q is no longer recognized, which is not preferable.
以上司明したように、上記の含金属リン化合物の特定量
と該リン化合物に対して特定量比のアルカリ土類金属化
合物とを予め反応させることなくポリエステル反応系に
添加し、しかる後ポリエステルの合成を完了することに
よって、高重合度。As explained above, a specific amount of the metal-containing phosphorus compound and an alkaline earth metal compound in a specific amount ratio to the phosphorus compound are added to the polyester reaction system without reacting in advance, and then the polyester is High degree of polymerization by completing the synthesis.
高軟化点及び良好な製糸化工程通過性を有し、かつ最終
的に紙の強度を高めることのできる繊維を与えることの
できるポリエステルを得ることができる。A polyester can be obtained which has a high softening point and good passability through the spinning process and is capable of giving fibers that can ultimately increase the strength of paper.
このようにして得られたポリエステルを溶融紡糸して繊
維とするには、格別な方法を採用する必要はなく、通常
のポリエステル繊維の溶融紡糸方法が任意に採用される
。There is no need to employ any special method to melt-spun the polyester obtained in this manner to form fibers, and any ordinary melt-spinning method for polyester fibers may be employed.
このようにして得られたポリエステル繊維はアルカリ化
合物の水溶液で処理することによりその繊維表面に微細
孔を形成せしめることができる。The polyester fiber thus obtained can be treated with an aqueous solution of an alkaline compound to form micropores on its surface.
アルカリ化合物の水溶液の処理によって溶出除去する量
は、繊維重量に対して０．１重量％以上の範囲にするの
が好ましい。The amount of alkaline compound eluted and removed by treatment with an aqueous solution is preferably in the range of 0.1% by weight or more based on the weight of the fiber.
本発明に使用するポリエステル繊維は、単糸繊度０．１
〜１０デニール、繊維長３〜３０ｍｍの範囲のものが好
ましい。単糸繊度が０．１デニ一ル未満の場合には、水
中分散性の悪化や紙の強度の低下をきたし、又１０デニ
ールを越える場合は、紙の強度の低下あるいは風合の硬
化を招くので好ましくない。The polyester fiber used in the present invention has a single yarn fineness of 0.1
-10 denier and fiber length of 3-30 mm are preferred. If the single yarn fineness is less than 0.1 denier, it will cause poor dispersibility in water and a decrease in paper strength, and if it exceeds 10 denier, it will cause a decrease in paper strength or harden the texture. So I don't like it.
繊維長が３ｍｍ未満の場合は、繊維の分散性はよいもの
の紙強力が不足し、かつ３０ＩＩＩｆｆｌを越える場合
は繊維の分散性が悪くなり品質斑が生じるので好ましく
ない。If the fiber length is less than 3 mm, the dispersibility of the fibers is good but the paper strength is insufficient, and if it exceeds 30IIIffl, the dispersibility of the fibers becomes poor and uneven quality occurs, which is not preferable.
本発明のポリエステル繊維の断面形状については、特に
制限はなく、例えば円、三角、四角、偏平、中空、星形
などを使用できるが、本発明において特に好ましい繊維
断面は偏平比が２．５〜１５の偏平糸である。ここで偏
平比とは、その繊維断面の長さと幅との比であり、特に
好ましい偏平比は３〜１０である。偏平比が２．５未満
では繊維間の接触が少なく紙の強度をざらに高くするこ
とはできない。一方偏平比が１５を越えるポリエステル
繊維を製糸することは一般に非常に困難であり、非常に
異形度の大きな紡糸口金を用いるか、又は紡糸中に口金
下で冷却風により急冷することが必要であるが、このよ
うな条件では、曳糸性が著しく悪くなるか及び／又はポ
リエステル繊維の強度が大巾に低くなり、ひいては紙の
強度が大巾に低下するので好ましくない。There is no particular restriction on the cross-sectional shape of the polyester fiber of the present invention, and for example, circular, triangular, square, flat, hollow, star-shaped, etc. can be used, but particularly preferred fiber cross-sections in the present invention have an aspect ratio of 2.5 to 2.5. 15 flat yarns. Here, the aspect ratio is the ratio between the length and width of the fiber cross section, and a particularly preferable aspect ratio is 3 to 10. When the aspect ratio is less than 2.5, there is little contact between the fibers and the strength of the paper cannot be significantly increased. On the other hand, it is generally very difficult to spin polyester fibers with an aspect ratio of more than 15, and it is necessary to use a spinneret with a very large degree of irregularity or to rapidly cool the yarn with cooling air under the spinneret during spinning. However, such conditions are not preferable because the spinnability will be significantly impaired and/or the strength of the polyester fibers will be greatly reduced, and the strength of the paper will be greatly reduced.
アルカリ性水溶液の濃度は通常ｏ、 ｏｉ〜４０％が用
いられ、特に０．１〜３０％の範囲が好ましく、処理温
度は常温〜１００″Ｃの範囲が好ましく、処理時間は１
分〜４時間の範囲が好ましい。The concentration of the alkaline aqueous solution is usually o, oi to 40%, particularly preferably in the range of 0.1 to 30%, the treatment temperature is preferably in the range of room temperature to 100''C, and the treatment time is 1.
A range of minutes to 4 hours is preferred.
アルカリ性水溶液によってポリエステル繊維より微細孔
形成剤を抽出除去するに際し、ポリエステル繊維の表面
自体も分解反応をうける。従って繊維の表面に親水性の
基、例えば水酸基あるいはカルボキシル基の量が大巾に
増大し、それらにより表面の親水性が大巾に向上するた
めポリエステル繊維の水分散性も向上するなどの効果も
有する。When the micropore-forming agent is extracted and removed from the polyester fiber using an alkaline aqueous solution, the surface of the polyester fiber itself also undergoes a decomposition reaction. Therefore, the amount of hydrophilic groups, such as hydroxyl groups or carboxyl groups, on the surface of the fibers greatly increases, which greatly improves the hydrophilicity of the surface, which also improves the water dispersibility of polyester fibers. have
一方アルカリ減量を過剰に行うと繊維全体の強度が低下
し、紙の強度は低下する。従って、アルカリによる繊維
の減量率は０．１〜２５％が好ましく、ざらには０．５
〜１５％が好ましい。On the other hand, if the alkali weight reduction is performed excessively, the strength of the entire fiber decreases, and the strength of the paper decreases. Therefore, the fiber loss rate due to alkali is preferably 0.1 to 25%, and roughly 0.5%.
~15% is preferred.
アルカリ処理によって繊維表面に得られる微細孔の直径
はｏ、 ｏｏｉ〜５μ、さらに好ましくは０、００５〜
２μ、最も好ましい範囲としては０．０５〜１μである
。The diameter of micropores obtained on the fiber surface by alkali treatment is o, ooi~5μ, more preferably 0,005~5μ.
2μ, most preferably 0.05 to 1μ.
微細孔の直径がｏ、 ｏｏｉ未満では合成紙の高強度化
に効果がない。又一方直径が５μを越えると高強度化に
寄与しないばかりか、繊維強度を大巾に低下せしめる。If the diameter of the micropores is less than o or ooi, it will not be effective in increasing the strength of synthetic paper. On the other hand, if the diameter exceeds 5μ, not only will it not contribute to increasing the strength, but it will also significantly reduce the fiber strength.
本発明のポリエステル繊維を相互に接着させる成分とし
て、接着性樹脂たとえば水可溶性ポリエステル樹脂、ポ
リビニルアルコール（ＰＶＡ）系樹脂あるいは低融点の
接着性繊維が混合されていることが必要である。その混
合量は０．０５〜２０重置％の範囲が好ましい。It is necessary that an adhesive resin such as a water-soluble polyester resin, a polyvinyl alcohol (PVA) resin, or a low melting point adhesive fiber be mixed as a component for adhering the polyester fibers of the present invention to each other. The mixing amount thereof is preferably in the range of 0.05 to 20% by weight.
ポリエステル繊維への付与量は本発明においては繊維重
量に対してＯ，ＯＳ〜２０重量％、特に好ましくは０．
１〜１５重量％の範囲である。In the present invention, the amount of O.OS applied to the polyester fiber is from 20% by weight to the weight of the fiber, particularly preferably 0.00% by weight.
It ranges from 1 to 15% by weight.
付与量が０．０５重量％未溝になると紙強力向上効果が
不足し、又２０重量％を越えると付着量が過大となって
ヤンキードライヤーへの紙の付着が発生するとともにコ
スト増となり好ましくない。If the applied amount is less than 0.05% by weight, the effect of improving paper strength will be insufficient, and if it exceeds 20% by weight, the applied amount will be excessive, causing paper to stick to the Yankee dryer and increasing costs, which is not desirable. .
ＰＶＡ系樹脂の付与方法については何ら制限されること
はないが、ＰＶＡ系樹脂単独又は他の加工剤が混合され
た水系液でもって付与するのが望ましい。There are no restrictions on the method of applying the PVA resin, but it is desirable to apply the PVA resin alone or with an aqueous solution mixed with other processing agents.
本発明の抄紙用ポリエステル繊維は公知の抄紙用素材（
例えば木材パルプ、麻、レーヨン繊維。The polyester fiber for papermaking of the present invention is a known material for papermaking (
For example, wood pulp, hemp, and rayon fibers.
ビニロン繊維、ＰＶＡバインダ繊維、ポリエステル未延
伸繊維、低融点ポリエステル繊維、その他の合成パルプ
合成繊維等）と組合せて公知の方法で湿式抄造できる。It can be wet-formed by a known method in combination with vinylon fiber, PVA binder fiber, undrawn polyester fiber, low melting point polyester fiber, other synthetic pulp, synthetic fiber, etc.
中でも木材パルプは安価であり、かつまた吸湿性にすぐ
れるなどポリエステルと補充関係にあり木材パルプを含
むポリエステル合成紙は巾広い用途に展開できるので特
に有用である。Among these, wood pulp is particularly useful because it is inexpensive, has excellent hygroscopicity, and has a complementary relationship with polyester, and polyester synthetic paper containing wood pulp can be used in a wide range of applications.
［作用及び効果］
本発明のポリエステル繊維を主とした合成紙は、下記の
効果を有する。[Actions and Effects] The synthetic paper mainly made of polyester fibers of the present invention has the following effects.
（１）ＰＶＡなどの混抄成分との接着力が高く、得られ
た紙の引張強力、引裂強力が大きい。(1) It has high adhesive strength with mixed paper components such as PVA, and the resulting paper has high tensile strength and tear strength.
（２）抄紙の分散性が向上する。(2) The dispersibility of papermaking is improved.
ポリエステル合成紙の強度が高まることに関するメカニ
ズムについては十分解明されてはいないが、次のように
推定することができる。Although the mechanism for increasing the strength of polyester synthetic paper has not been fully elucidated, it can be estimated as follows.
一般にポリエステル繊維中に添加物を入れることは、そ
の界面での接着性を低下せしめるとともに、強度も低下
せしめる。本発明の如く、その添加物を薬品処理によっ
て除去した場合、添加物の強度が繊維強度に寄与しない
こと及び薬品によるポリエステル繊維の浸蝕のためポリ
エステル繊維の強度、さらにはこれを用いて作製した合
成紙の強度が低下することが予想される。ところが、本
発明では、これらの予想に反して全く逆の結果が得られ
た。In general, adding additives to polyester fibers reduces the adhesion at the interface and also reduces the strength. When the additives are removed by chemical treatment as in the present invention, the strength of the additives does not contribute to the fiber strength, and the chemicals attack the polyester fibers, so the strength of the polyester fibers is affected. It is expected that the strength of the paper will decrease. However, in the present invention, contrary to these expectations, completely opposite results were obtained.
この事実はポリエステル繊維を主体とする合成紙の場合
、合成紙の強力がポリエステル繊維自体の強度に依存す
る度合は比較的小さくむしろ接着成分の強度あるいは、
ポリエステル繊維と接着成分間の接着力が支配的に紙の
強度を定めていることを示す。ところで接着成分として
一般に使用されるポリビニルアルコール系樹脂は、それ
らを膜状に成型し、その膜の強度を調べてみると十分に
高い強度が得られる。This fact shows that in the case of synthetic paper made mainly of polyester fibers, the strength of the synthetic paper does not depend on the strength of the polyester fibers themselves, but rather on the strength of the adhesive component or
This shows that the adhesive force between the polyester fiber and the adhesive component predominantly determines the strength of paper. By the way, when polyvinyl alcohol resins that are generally used as adhesive components are molded into a film and the strength of the film is examined, sufficiently high strength can be obtained.
従って、ポリエステル繊維を主体とした合成紙において
は合成紙の強度は、繊維と接着成分との間の接着に依存
しているといえる。Therefore, it can be said that the strength of synthetic paper mainly composed of polyester fibers depends on the adhesion between the fibers and the adhesive component.
ところで、ポリエステルとポリビニルアルコールはお互
いに親和性に乏しく、接着力は高くない。By the way, polyester and polyvinyl alcohol have poor affinity with each other and do not have high adhesive strength.
又例えばポリエーテルエステルブロック共重合体を接着
成分として用いる例もみられるが、同じポリエステルで
ありながら、接着力が十分高くないという欠点がみられ
る。すなわち従来の考え方はポリエステル繊維と接着成
分とを化学的に接着させようという努力にとどまり、そ
の結果、紙の強力向上には成功していない。For example, there are examples in which polyether ester block copolymers are used as the adhesive component, but although they are the same polyester, they have the disadvantage that the adhesive strength is not sufficiently high. That is, the conventional approach is limited to efforts to chemically bond polyester fibers and adhesive components, and as a result, it has not been successful in improving the strength of paper.
接着しようとする構成物（本発明の場合はポリエステル
繊維）の表面に微細孔を形成せしめた場合、比表面積が
増大すること及び機械的投錨効果（アンカー効果）が表
れて接着強度の向上が期待できることは一般によく知ら
れた事実である。そこでこれらの効果をポリエステル合
成紙に応用しようと試み、ポリエステル繊維に添加物を
添加し、それを除去することにより接着性向上に有効な
微細孔を形成せしめたものであるが、さらにはアルカリ
による繊維の浸漬のためその表面上に親水性の基、例え
ば水酸基やカルボキシル基が多量に形成され、これらが
水中への繊維分散性を向上せしめると共にこれらとポリ
ビニルアルコールとの親和性が接着に寄与することにな
ったと考えられる。When micropores are formed on the surface of the components to be bonded (polyester fibers in the case of the present invention), it is expected that the specific surface area will increase and a mechanical anchoring effect will appear, resulting in an improvement in adhesive strength. It is a well-known fact that this can be done. Therefore, we attempted to apply these effects to polyester synthetic paper, and by adding additives to polyester fibers and removing them, we formed micropores that were effective in improving adhesion. Due to the immersion of the fibers, a large amount of hydrophilic groups such as hydroxyl groups and carboxyl groups are formed on the surface of the fibers, which improve the dispersibility of the fibers in water, and the affinity of these groups with polyvinyl alcohol contributes to adhesion. It is thought that this happened.
［実施例］
以下、実施例により更に説明する。実施例における各測
定値は以下の方法で評価したものである。[Example] The following is a further explanation using Examples. Each measurement value in the examples was evaluated by the following method.
（１）裂断長
定速伸長型引張試験機を用い、ＪＩＳ Ｐ８１１３の方
法に従って引張強度を測定した。(1) Tensile strength was measured according to the method of JIS P8113 using a constant rate extension type tensile tester.
（２）伸度 上記方法に従って引張伸度を測定した。(2) Elongation Tensile elongation was measured according to the above method.
なお試料はいずれも方向性の低い混抄紙なので裂断長、
伸度については、経方向及び緯方向について測定し、そ
の平均値を測定値とした。Note that the samples are all mixed papers with low directionality, so the tearing length,
The elongation was measured in the longitudinal and latitudinal directions, and the average value was taken as the measured value.
実施例１〜４．比較例１〜２
ジメチルテレフタレート１９７１１部、エチレングリコ
ール１２４重量部及び酢酸カルシウム−水塩ｏ、ｉｉａ
重量部を精留塔付ガラスフラスコに入れ、常法に従って
エステル交換反応を行い、理論量のメタノール留出後、
反応生成物を精留塔付重縮合用フラスコに入れ、安定剤
としてトリメチルフォスフェート０．１１２重量部を添
加した。さらに、重縮合触媒として酢酸アンチモンＯ１
Ｏ乃重量部。Examples 1-4. Comparative Examples 1-2 19711 parts of dimethyl terephthalate, 124 parts by weight of ethylene glycol, and calcium acetate hydrate O, IIA
Part by weight was placed in a glass flask equipped with a rectifier, and transesterification was carried out according to a conventional method. After distilling off the theoretical amount of methanol,
The reaction product was placed in a polycondensation flask equipped with a rectification column, and 0.112 parts by weight of trimethyl phosphate was added as a stabilizer. Furthermore, antimony acetate O1 is used as a polycondensation catalyst.
Ono weight department.
次粒子径０，３２μのアナターゼ型酸化チタン（チタン
工業製）２．５重量部を添加した。ざらに温度を上昇さ
せ温度２８０℃、常圧で３０分間保持し、ざらに３０ｍ
１ｌｌ）ＩＱの減圧下で１５分間反応させ、次いで系内
を徐々に減圧し、攪拌下８００分間反応せた。最終内圧
は０．３２ｍ１ｌｌｔｌ（ｌであり、得られたポリマー
の極限粘度は０．８３５であった。反応終了後ポリマー
を常法によりチップ化し乾燥した。2.5 parts by weight of anatase-type titanium oxide (manufactured by Titan Kogyo) having a secondary particle size of 0.32 μm was added. Roughly raise the temperature to 280℃ and hold it at normal pressure for 30 minutes, then roughly 30m
1ll) IQ under reduced pressure for 15 minutes, then the pressure inside the system was gradually reduced and the reaction was continued for 800 minutes with stirring. The final internal pressure was 0.32 ml, and the intrinsic viscosity of the obtained polymer was 0.835. After the reaction was completed, the polymer was formed into chips by a conventional method and dried.
次にこの乾燥したチップを用い、紡糸口金として巾０．
１關×長さ０．８ｍｍの長方形の開口部を有するものを
使用し、常法に従って紡糸し、延伸を行い、長袖と短軸
との比が４．単糸デニールが２デニールの偏平糸を得た
（４０デニール／２０フイラメント）。このフィラメン
トをかぜ取り機により紹に取り数個所を結んで固定した
。このポリエステル繊維束１ｇに対して３５ｇ／ｉの苛
性ソーダ水溶液３００ｇを用意し、沸騰状態に加熱し、
繊維束を投入し一定時間攪拌したのち繊維束を取り出し
、水洗を数回行い、表面の苛性ソーダを除去した。これ
を風乾し、重量を測定し、最初の投入時の重量との比較
によってアルカリ減量率を締出した。Next, use this dried chip as a spinneret with a width of 0.
A fiber with a rectangular opening of 1 length x 0.8 mm in length was used, and the yarn was spun and stretched according to a conventional method, and the ratio of the long sleeve to the short axis was 4. A flat yarn with a single yarn denier of 2 denier was obtained (40 denier/20 filaments). This filament was taken out using a wind remover and tied in several places to fix it. Prepare 300 g of a 35 g/i caustic soda aqueous solution for 1 g of this polyester fiber bundle, heat it to a boiling state,
After the fiber bundle was put in and stirred for a certain period of time, the fiber bundle was taken out and washed with water several times to remove the caustic soda on the surface. This was air-dried, the weight was measured, and the alkali weight loss rate was determined by comparing the weight with the initial weight.
この際、アルカリ処理時間を種々変更して表−１のアル
カリ減ｍ率のサンプルを得た。このアルカリにより表面
処理されたポリエステル繊維束をカッターにより１ｃｍ
の長さに切断した。At this time, the alkali treatment time was variously changed to obtain samples having the alkali molar reduction rates shown in Table 1. This alkali-surface-treated polyester fiber bundle is cut into 1 cm by a cutter.
Cut to length.
切断されたポリエステル繊、！２２．５ｏを取り、ざら
に接着成分としてポリビニルアルコール繊維■ＰＢ−１
０１（クラレ製、熱水可溶性ポリビニルアルコール繊維
）２．５ｇを採取し、水１００１中に分散ざぜた。この
繊維分散液１０１を採取し、２５ｃｍｘ ２５ｃｎの大
きさの標準角型シートマシンを使用し、８゜メツシュの
金網上にサンプルを投入し脱水を行った（１０枚作製）
。このようにして抄造されたポリエステル合成紙を熊谷
理機工業株式会社製回転型乾燥機を用いて１２０℃で１
３秒間乾燥した。このようにして得られたポリエステル
合成紙の坪量を測定したところ約４０Ｍｍであり、厚み
はｏ、ｉｏ〜０、１５ｍｍであった。Cut polyester fiber! Take 22.5o and add polyvinyl alcohol fiber ■PB-1 as an adhesive component.
2.5 g of 01 (manufactured by Kuraray, hot water soluble polyvinyl alcohol fiber) was taken and dispersed in water 1001. This fiber dispersion liquid 101 was collected, and using a standard square sheet machine with a size of 25 cm x 25 cm, the sample was placed on an 8° mesh wire mesh and dehydrated (10 sheets were made).
. The polyester synthetic paper produced in this way was dried at 120°C using a rotary dryer manufactured by Kumagai Riki Kogyo Co., Ltd.
Dry for 3 seconds. The basis weight of the polyester synthetic paper thus obtained was measured to be about 40 mm, and the thickness was 0.io to 0.15 mm.
これを１５１１１ｍ巾Ｘ長ざ１０Ｃｍに切断し、さらに
９０゜方向を変えてサンプルを採取し、たてよこ方向同
一数のサンプルを採取した。This was cut to a width of 15,111 m and a length of 10 cm, and the direction was changed by 90° to take samples, and the same number of samples were taken in both the vertical and horizontal directions.
この試験片を用いＪＩＳ Ｐ−８１１３の方法にＩＨＩ
Ｌし、つかみ巾を５０ｍｍに設定し、５ ｃｍ／分の速
さで伸長する定速伸長型引張試験機により裂断長（Ｋｌ
ｌｌ）を測定した。サンプルは３０ケをとり平均値を採
用した。Using this test piece, IHI was applied to the method of JIS P-8113.
L, the grip width was set to 50 mm, and the tearing length (Kl
ll) was measured. Thirty samples were taken and the average value was used.
ここに裂断長は下式により求めた。Here, the fracture length was determined using the formula below.
引張強ざ（にｇ）ｘｌｏｏｏ
裂断長（にｍ） ＝
ＸＷ
Ｗ：試験片の坪量（ａ／ＴＩｔ＞
伸度は上記裂断長側定時の最高応力値に対応する伸度を
採用した。Tensile strength (g) .
比較例３〜９
実施例１において酸化チタンを添加しないで実施例１と
同じ方法でポリエステルを作製した。アルカリ減量率は
表−つのごとく変更した。極限粘度は０．６３８であっ
た。Comparative Examples 3 to 9 Polyesters were produced in the same manner as in Example 1 without adding titanium oxide. The alkali weight loss rate was changed as shown in the table. The intrinsic viscosity was 0.638.
実施例１と同様に製糸抄紙し、合成紙の裂断長。Paper was produced in the same manner as in Example 1, and the tearing length of the synthetic paper was measured.
伸度の測定を行った。The elongation was measured.
Ｂ：試験片の巾（ｍｍ）
表
ここで実施例１〜４．比較例２においてはその繊維表面
に多数の微細孔がみられ、実施例１〜４において裂断長
が２．０部ｍを越える高い紙強力が得られた。比較例２
の場合は繊維の強度が大巾に低下し、伸度が４．６％と
高い値が得られ、繊維とポリビニルアルコールとの良好
な接着が示唆されながらも紙強力としては低い値となっ
た。一方比較例１及び比較例３〜９においては繊維表面
に微細孔はみられず、紙の強度も低い値にとどまってい
る。B: Width of test piece (mm) Table Here, Examples 1 to 4. In Comparative Example 2, a large number of micropores were observed on the fiber surface, and in Examples 1 to 4, high paper strength with a tearing length exceeding 2.0 parts m was obtained. Comparative example 2
In the case of , the strength of the fibers decreased significantly, and the elongation was as high as 4.6%, indicating good adhesion between the fibers and polyvinyl alcohol, but the paper strength was low. . On the other hand, in Comparative Example 1 and Comparative Examples 3 to 9, no micropores were observed on the fiber surface, and the strength of the paper remained at a low value.
実施例５〜８．比較例１０〜１１
テレフタル酸ジメチル１９７部、エチレングリコール１
２４部、３−カルボメトキシ・ベンゼンスルホン酸ナト
リウム−５−カルボン酸ナトリウム４部（テレフタル酸
ジメチルに対して１３モル％）。Examples 5-8. Comparative Examples 10-11 197 parts of dimethyl terephthalate, 1 part of ethylene glycol
24 parts, 4 parts of sodium 3-carbomethoxybenzenesulfonate-5-sodium carboxylate (13 mol % based on dimethyl terephthalate).
酢酸カルシウム・１水塩０．１１８部を精留塔付反応槽
に入れ、常法に違ってエステル交換反応を行い、理論量
のメタノールが留出した後、反応生成物を精昭塔付重縮
合用反応槽に入れ、安定剤としてトリメチルホスフェー
ト０．１１２部及び重縮合触媒として三酸化アンチモン
０．０７９部を加え、温度２８０℃で、常圧下２０分、
３０ｍｍＨｇの減圧下１５分反応させた後、高真空下
で８０分間反応させた。最終内圧は０、３８ｍｍＨｇで
あり、得られた変性ポリエステルの極限粘度は０．６０
０ 、軟化点は２５８℃であった。反応終了後変性ポリ
エステルを常法に従いチップ化した。このチップを常法
に従い乾燥し、実施例１の方法に従って、繊維化を行い
単糸繊度が２デニルの偏平糸を１ｑ、アルカリ減量の債
、熱水可溶性ポリビニルアルコールと共に混抄してポリ
エステル合成紙サンプルを得た。アルカリ減量率は表２
のごとく変更した。Calcium acetate monohydrate (0.118 parts) was placed in a reaction tank equipped with a rectifying column, and transesterification was carried out in contrast to the conventional method. After the theoretical amount of methanol was distilled out, the reaction product was placed in a reaction tank equipped with a rectifying column. The mixture was placed in a condensation reaction tank, and 0.112 parts of trimethyl phosphate as a stabilizer and 0.079 parts of antimony trioxide as a polycondensation catalyst were added at a temperature of 280°C and under normal pressure for 20 minutes.
After reacting for 15 minutes under a reduced pressure of 30 mmHg, the reaction was carried out for 80 minutes under high vacuum. The final internal pressure was 0.38 mmHg, and the intrinsic viscosity of the obtained modified polyester was 0.60.
0, and the softening point was 258°C. After the reaction was completed, the modified polyester was made into chips according to a conventional method. The chips were dried according to a conventional method, and made into fibers according to the method of Example 1. A polyester synthetic paper sample was prepared by mixing 1 q of flat yarn with a single filament fineness of 2 denyl, an alkali weight loss bond, and hot water-soluble polyvinyl alcohol. I got it. Table 2 shows the alkali weight loss rate.
Changed as follows.
表−２
ここで実施例５〜８及び比較例１１において、その繊維
表面に多数の微細孔がみられ、実施例５〜８において裂
断長が２部ｍを越える高い紙強度が得られた。比較例１
１においては、繊維の強度が大巾に低下、伸度が３．９
％と高い値が得られ繊維とポリビニルアルコールとの良
好な接着が示唆されながらも紙強力としては低い値とな
った。一方比較例１０においては繊維表面に微細孔はみ
られず紙の強度も低い値にとどまった。Table 2 Here, in Examples 5 to 8 and Comparative Example 11, a large number of micropores were observed on the fiber surface, and in Examples 5 to 8, high paper strength with a tearing length exceeding 2 parts m was obtained. . Comparative example 1
In No. 1, the strength of the fibers decreased significantly and the elongation was 3.9.
Although a high value of % was obtained, suggesting good adhesion between the fiber and polyvinyl alcohol, the paper strength was low. On the other hand, in Comparative Example 10, no micropores were observed on the fiber surface and the strength of the paper remained at a low value.
実施例９〜１２．比較例１２〜１３
テレフタル酸ジメチル１００部、エチレングリコール６
０部、酢酸カルシウム１水塩０．０６部（テレフタル酸
ジメチルに対して０．０６６モル％〉をエステル交換色
に仕込み、窒素ガス雰囲気下４時間かけて１４０℃から
２３０℃まで昇温しで生成するメタノールを系外に留去
しながらエステル交換反応を行った。続いて得られた反
応生成物に、０．５部のリン酸トリメチル（テレフタル
酸ジメチルに対して０．６９３モル％）と０．３１部の
酢酸カルシウム１水塩（リン酸トリメチルに対して１７
２倍モル）とを８．５部のエチレングリコール中で１２
０℃の温度において全還流して６００分間反応しめて調
製したリン酸ジエステルカルシウム塩の透明溶液９．３
１部に室温下０．５７部の酢酸カルシウム１水塩（リン
酸トリメチルに対して０．９倍モル）を溶解せしめて得
たリン酸ジエステルカルシウム塩と酢酸カルシウムとの
混合透明溶液９．８８部を添加し、次いで三酸化アンチ
モン０．０４部を添加して重合化に移した。Examples 9-12. Comparative Examples 12-13 100 parts of dimethyl terephthalate, 6 parts of ethylene glycol
0 parts and 0.06 parts of calcium acetate monohydrate (0.066 mol% based on dimethyl terephthalate) were added to the transesterification color, and the temperature was raised from 140°C to 230°C over 4 hours under a nitrogen gas atmosphere. The transesterification reaction was carried out while the methanol produced was distilled out of the system. Subsequently, 0.5 part of trimethyl phosphate (0.693 mol % based on dimethyl terephthalate) was added to the obtained reaction product. 0.31 parts of calcium acetate monohydrate (17 parts per trimethyl phosphate)
2 times mole) in 8.5 parts of ethylene glycol.
Clear solution of phosphoric acid diester calcium salt prepared by reacting for 600 minutes under total reflux at a temperature of 0° C. 9.3
A mixed transparent solution of phosphoric acid diester calcium salt and calcium acetate obtained by dissolving 0.57 parts of calcium acetate monohydrate (0.9 times mole relative to trimethyl phosphate) in 1 part at room temperature 9.88 1 part, and then 0.04 part of antimony trioxide was added and the polymerization was carried out.
次いで１時間かけて７６０ｍｍＨｇからｉ ｍｍＨｇま
で減圧し、同時に１時間３０分かけて２３０℃から２８
５℃まで昇温した。１１ＩＩＩｌｌＨｇ以下の減圧下、
重合温度２８５℃で更に３時間、合計４時間３０分重合
して極限粘度０．６４１ 、軟化点２５９℃のポリマー
を得た。反応終了後ポリマーを常法に従いチップ化した
。The pressure was then reduced from 760 mmHg to 1 mmHg over 1 hour, and at the same time from 230°C to 28°C over 1 hour and 30 minutes.
The temperature was raised to 5°C. Under reduced pressure of 11IIIllHg or less,
Polymerization was carried out at a polymerization temperature of 285°C for an additional 3 hours, for a total of 4 hours and 30 minutes, to obtain a polymer having an intrinsic viscosity of 0.641 and a softening point of 259°C. After the reaction was completed, the polymer was made into chips according to a conventional method.
このチップを常法により乾燥し、実施例１の方法に従っ
て繊維化を行い、ざらにアルカリ減量後、熱水可溶性ポ
リビニルアルコールと共に混抄してサンプルを得た。The chips were dried in a conventional manner, and made into fibers according to the method of Example 1. After the chips were reduced in size with an alkali, they were mixed with hot water-soluble polyvinyl alcohol to obtain a sample.
ここで実施例９〜１２及び比較例１３において、その繊
維表面に多数の微細孔がみられ、実施例９〜１２におい
て裂断長が２Ｋｍを越える高い紙強度が得られた。比較
例１３においてはｍ維自体の強度が大巾に低下し、伸度
が６．３％と高い値が得られ、繊維とポリビニルアルコ
ールとの良好な接着が示唆されながらも紙強力としては
低い値となった。一方比較例、１２では、繊維表面に微
細孔はみられず紙の強度も低い値にとどまった。In Examples 9 to 12 and Comparative Example 13, a large number of micropores were observed on the fiber surface, and in Examples 9 to 12, high paper strength with a tearing length exceeding 2 km was obtained. In Comparative Example 13, the strength of the m-fibers themselves decreased significantly, and the elongation was as high as 6.3%, suggesting good adhesion between the fibers and polyvinyl alcohol, but the paper strength was low. It became the value. On the other hand, in Comparative Example 12, no micropores were observed on the fiber surface and the strength of the paper remained at a low value.
実施例１３〜１７．比較例１４〜１５
ジメチルテレフタレ一ト１９７部、エチレングリコール
１２４部及び酢酸カルシウム−水塩０．１１８部を精留
塔付ガラスフラスコに入れ、常法に従ってエステル交換
反応を行い、理論ｍのメタノール留出後、反応生成物を
精留塔付重縮合用フラスコに入れ、安定剤としてトリメ
チルホスフェート０．１１２重量部１重１含縮媒として
酸化アンチモン０、０７９部を加え、温度２８０℃、常
圧で３０分、’ ３部ｍｍＩＱの減圧下で１５分間反応
を進行させた後、−旦常圧にもどし、炭素数８〜２０で
平均炭素数が１４であるアルキルスルホン酸ソーダ混合
物を１０部添加した後、系内を徐々に減圧し、攪拌下８
００分間反応せた。最終内圧は０．３２ｍｍＨｇであり
、得られたポリマーの極限粘度は０．６３２であった。Examples 13-17. Comparative Examples 14 to 15 197 parts of dimethyl terephthalate, 124 parts of ethylene glycol, and 0.118 parts of calcium acetate hydrate were placed in a glass flask equipped with a rectification column, and a transesterification reaction was carried out according to a conventional method to obtain methanol of theoretical m. After distillation, the reaction product was placed in a polycondensation flask equipped with a rectification column, 0.112 parts by weight of trimethyl phosphate was added as a stabilizer, 0.079 parts of antimony oxide was added as a condensation medium containing 1 part by weight, and the mixture was heated at 280°C under normal conditions. After allowing the reaction to proceed for 15 minutes under a reduced pressure of 3 parts mmIQ, the reaction was returned to normal pressure and 10 parts of a sodium alkyl sulfonate mixture having 8 to 20 carbon atoms and an average carbon number of 14 was added. After the addition, the pressure inside the system was gradually reduced and the mixture was stirred for 8 hours.
The reaction was allowed to proceed for 00 minutes. The final internal pressure was 0.32 mmHg, and the resulting polymer had an intrinsic viscosity of 0.632.
反応終了後ポリマーを常法によりチップ化し、乾燥した
。After the reaction was completed, the polymer was formed into chips by a conventional method and dried.
次にこの乾燥したチップを用いて紡糸口金に巾０．１ｍ
１ｌｌ、長さ０．８ｍｍの長方形の開口部を有するもの
を使用し、常法に従って紡糸し、延伸を行い、長軸と短
軸との比が４、単糸繊度が２デニールの偏平糸を得た（
４０デニール／２０フイラメント）。Next, use this dried chip to attach a 0.1 m wide spinneret to a spinneret.
Using a 1 liter, rectangular opening with a length of 0.8 mm, the yarn was spun and drawn according to a conventional method to obtain a flat yarn with a long axis to short axis ratio of 4 and a single yarn fineness of 2 denier. Obtained(
40 denier/20 filament).
このフィラメントをかぜ取り機により総に取り数個所を
結んで固定した。このポリエステル繊維束１ｇに対して
３５Ｖ１の苛性ソーダ水溶液３００９を用意し、沸騰状
態に加熱し、繊維束を投入した。This filament was completely removed using a wind remover and tied in several places to secure it. A 35V1 caustic soda aqueous solution 3009 was prepared for 1 g of this polyester fiber bundle, heated to a boiling state, and the fiber bundle was introduced.
数分の攪拌の後、繊維束をとりだし、水洗を数回行い、
表面の苛性ソーダを除去した。これを風乾し、重量を測
定し、最初の投入時の重量との比較によってアルカリ減
量率を算出した。このアルカリにより表面処理されたポ
リエステル繊維束を力ツターにより１ｃｍの長さに切断
した。切断されたポリエステル繊維２２．５ｇを取り、
さらに接着成分としてポリエステルアルコール繊ＩＩＶ
ＰＢ−１０にクラレ製、熱水可溶性ポリビニルアルコー
ル繊維２．５ｇを採取し、水ｉｏｏ ｘ中に分散させた
。この繊維分散液１０１を採取し、縦２５Ｃｍ、横２５
ｃｍの大きさの標準角型シートマシンを使用し、８０メ
ツシユの金網上にサンプルを投入し脱水を行った（１０
枚作製）。After stirring for several minutes, the fiber bundle was taken out and washed several times with water.
The caustic soda on the surface was removed. This was air-dried, its weight was measured, and the alkali weight loss rate was calculated by comparing it with the weight at the time of initial addition. This alkali-surface-treated polyester fiber bundle was cut into a length of 1 cm using a power cutter. Take 22.5g of cut polyester fiber,
In addition, polyester alcohol fiber III is used as an adhesive component.
2.5 g of hot water soluble polyvinyl alcohol fiber manufactured by Kuraray was collected in PB-10 and dispersed in water ioox. This fiber dispersion liquid 101 was collected, and the length was 25 cm and the width was 25 cm.
Using a standard rectangular sheet machine with a size of
(manufactured in sheets).
このようにして抄製されたポリエステル紙を熊谷理機工
業株式会社製回転型乾燥機を用いて１２０℃で１３秒間
乾燥した。The polyester paper thus produced was dried at 120° C. for 13 seconds using a rotary dryer manufactured by Kumagai Riki Kogyo Co., Ltd.
このようにして得られたポリエステル紙の重量を測定し
たところ約４０ｇ／ｍであり、厚みはｏ、 ｉ。The weight of the polyester paper thus obtained was measured and was approximately 40 g/m, with thicknesses of o and i.
〜０．１５ｍｍであった。これを巾１５ｍｍ、長さ１０
ｃｍに切断し、さらに９０’方向を換えてサンプルを採
取し、縦横方向の同一数のサンプルを採取した。It was ~0.15 mm. This is 15mm wide and 10mm long.
The sample was cut into cm pieces, and the sample was taken in the 90' direction, and the same number of samples in the vertical and horizontal directions were taken.
比較例１６〜２２
実施例１３におけるアルキルスルホン酸ソーダを添加し
ないで、実施例１３と同様にポリエステルポリマーを作
製した。極限粘度は０．８４５であった。実施例１３と
同様に、製糸、抄紙した紙の強度（裂断長）の測定を行
った。結果を表−４に示した。Comparative Examples 16 to 22 Polyester polymers were produced in the same manner as in Example 13 without adding the sodium alkylsulfonate in Example 13. The intrinsic viscosity was 0.845. In the same manner as in Example 13, the strength (tear length) of the yarn-spun and paper-made paper was measured. The results are shown in Table-4.
表
＊目視判定 Ｏ：良 Δ：やヤ良
ここで実施例１３〜１７．比較例１５においては、その
繊維表面０．０１〜０．０８μｍの筋状凹部（マイクロ
グループ）がみられ、裂断長２．Ｏｋｍを超える高い強
力が得られた。比較例１５の場合は、繊維のフィブリル
化がおこりやすく、取扱い中に細かく割れてしまう現象
がおこり、又繊維強度も大巾に低くなり、紙の強度も高
くできない。但し、伸度は７．０％と高く、繊維と接着
成分との間の接着は凹部の投錨効果があったと考えられ
る。比較例１３．１６〜２２においてはアルキルスルホ
ン酸ソーダが添加されていないため、アルカリ減量によ
っても筋状凹部がなく、紙の強度も高くない。Table * Visual judgment O: Good Δ: Fairly good Here, Examples 13 to 17. In Comparative Example 15, streak-like recesses (micro groups) of 0.01 to 0.08 μm were observed on the fiber surface, and the tear length was 2.0 μm. High strength exceeding Okm was obtained. In the case of Comparative Example 15, the fibers tend to fibrillate and break into small pieces during handling, and the fiber strength is also significantly lowered, making it impossible to increase the strength of the paper. However, the elongation was as high as 7.0%, and it is thought that the adhesion between the fiber and the adhesive component had an anchoring effect in the recess. In Comparative Examples 13.16 to 22, no sodium alkylsulfonate was added, so there were no streaky depressions even after alkali weight loss, and the strength of the paper was not high.
実施例１８〜２５．比較例２３〜２５
極限粘度０．６３８のポリエチレンテレフタレートチッ
プ９５部に対して極限粘度１．０のナイロン６のチップ
５部を十分混合し、実施例１３に準じた方法を用いてポ
リエステル繊維を製造した。このようにして得られた繊
維束を沸騰状態に加熱した濃度１３５（Ｊ／ １の苛性
ソーダ及び濃度３０％の硫酸に数分間投入した。数分間
の攪拌ののち繊維束を取り出し、水洗をくりかえし表面
のアルカリ又は塩を除去した。Examples 18-25. Comparative Examples 23 to 25 Polyester fibers were produced by thoroughly mixing 5 parts of nylon 6 chips with an intrinsic viscosity of 1.0 with 95 parts of polyethylene terephthalate chips with an intrinsic viscosity of 0.638, and using a method similar to Example 13. did. The fiber bundle thus obtained was placed in caustic soda with a concentration of 135 (J/1) and sulfuric acid with a concentration of 30% heated to a boiling state for several minutes. After stirring for several minutes, the fiber bundle was taken out and washed repeatedly with water. alkalis or salts were removed.
さらに実施例１３で示す方法により抄造を行い、裂断長
、伸度を測定した。結果を表−５に示す。Furthermore, papermaking was performed by the method shown in Example 13, and the breaking length and elongation were measured. The results are shown in Table-5.
表−５
比較例２３．２５においては、繊維の減罹もなく、表面
に筋状凹部がみられず、紙の強度も低かった。Table 5 In Comparative Examples 23 and 25, there was no decrease in fiber morbidity, no streaky recesses were observed on the surface, and the strength of the paper was low.
実施例１８〜２２及び実施例２３〜２５においては、紙
の裂断長及び伸度が高く好ましい。実施例２３〜２５で
は硫酸水溶液による処理においては、硫酸によるポリエ
ステル繊維の浸蝕がほとんどないせいか、凹の大きさは
実施例１８〜２２に比べてやや細く、投錨効果が少なか
った。苛性ソーダ使用の実施例１８〜２２では裂断長、
伸度ともに優れており、苛性ソーダがより好ましいこと
を示す。比較例２４では伸度が高い（繊維と接着成分と
が投錨効果で十分に接着している）ものの繊維強度が低
く、ざらには紙の強度は低かった。In Examples 18 to 22 and Examples 23 to 25, the tearing length and elongation of the paper are high and are preferable. In Examples 23 to 25, in the treatment with the sulfuric acid aqueous solution, the size of the recesses was slightly smaller than in Examples 18 to 22, and the anchoring effect was small, probably because the polyester fibers were hardly eroded by the sulfuric acid. In Examples 18 to 22 using caustic soda, the breaking length,
Both elongation is excellent, indicating that caustic soda is more preferable. In Comparative Example 24, although the elongation was high (the fibers and the adhesive component were sufficiently bonded by the anchoring effect), the fiber strength was low, and the strength of the paper was generally low.
実施例２６
ジメチルテレフタレート１９７部、エチレングリコール
１２４部及び酢酸カルシウム−水塩０．１１８部を精留
塔付ガラスフラスコに入れ、常法にしだがって、エステ
ル交換反応を行い、理論量のメタノール留出後、反応生
成物を精留塔付重縮合用フラスコに入れ、安定剤として
トリメチルホスフェート０．１１２重囲部１重縮合触媒
として酸化アンチモン０．０７９部を加え、温度２８０
℃、常圧で３０分、 ３０ｍｍＨｇの減圧下で１５分間
反応を進行させた後、系内を徐々に減圧し、攪拌下８０
０分間反応せた。最終内圧は０．３２ｍｍＨａであり、
得られたポリマーの極限粘度は０．６３２であった。反
応終了後ポリマーを常法によりチップ化し、乾燥した。Example 26 197 parts of dimethyl terephthalate, 124 parts of ethylene glycol, and 0.118 parts of calcium acetate hydrate were placed in a glass flask equipped with a rectifying column, and a transesterification reaction was carried out according to a conventional method to distill a theoretical amount of methanol. After the reaction, the reaction product was placed in a polycondensation flask equipped with a rectification column, 0.112 parts of trimethyl phosphate was added as a stabilizer, and 0.079 parts of antimony oxide was added as a polycondensation catalyst.
After allowing the reaction to proceed for 30 minutes at ℃ and normal pressure, and for 15 minutes under a reduced pressure of 30 mmHg, the pressure inside the system was gradually reduced, and the reaction was carried out for 80 minutes under stirring.
The reaction was allowed to proceed for 0 minutes. The final internal pressure is 0.32 mmHa,
The intrinsic viscosity of the obtained polymer was 0.632. After the reaction was completed, the polymer was formed into chips by a conventional method and dried.
次に、この乾燥したチップを用いて、紡糸口金に巾０．
１ｍｍ ｘｏ、８ｍｍの長方形の開口部を有するものを
使用し、常法に従って紡糸し、延伸を行い、長軸と短軸
との比が４、単糸繊度が２デニールの偏平糸を得た（４
０デニール／２０フイラメント）。Next, using this dried chip, a width of 0.0 mm is applied to a spinneret.
Using a yarn with a rectangular opening of 1 mm xo and 8 mm, it was spun and drawn according to a conventional method to obtain a flat yarn with a long axis to short axis ratio of 4 and a single filament fineness of 2 denier ( 4
0 denier/20 filament).
得られたポリエステル繊維をカッターにより’１ｃｍの
長さに切断した。The obtained polyester fiber was cut into a length of 1 cm using a cutter.
電極間（小径の電極群と冷却ボックスとの間）が２ＣＩ
１１であり、冷却ボックスと接触しつつ振動する金網（
５０メツシユ）が配置されたプラズマ装置において、真
空度０．１ｎｍＨａ （空気）、電極間電圧５００Ｖ
、電流密度２．５１１Ａ ／Ｃｍ２ 、電源６０Ｈ２（
１００Ｖ）の発生条件で照射時間をかえてプラズマ処理
した。プラズマ処理効果を確認するために金網は同じ位
置での振動にとどめ、金網位置の移動はしなかった。The distance between the electrodes (between the small diameter electrode group and the cooling box) is 2CI.
11, and a wire mesh that vibrates while in contact with the cooling box (
In a plasma device equipped with 50 meshes, the degree of vacuum is 0.1 nmHa (air), and the voltage between the electrodes is 500 V.
, current density 2.511A/Cm2, power supply 60H2 (
Plasma treatment was performed under the generation condition of 100 V) while changing the irradiation time. In order to confirm the plasma treatment effect, the wire mesh was kept vibrating at the same position and the wire mesh position was not moved.
プラズマ処理されたポリエステル繊維２２．５！ＩＩを
取り、さらに接着成分としてポリビニルアルコール繊維
ＶＰＢ−１０に、クラレ製、熱水可溶性ポリビニルアル
コール繊維＞ ２．５ｇを採取し、水１００１中に分散
させた。この繊維分散液１０１Ｆを採取し、２５ｃｍｘ
２５ｃｍの大きざの標準角型シートマシンを使用し、
８Ｇメツシユの金網上にサンプルを投入し脱水を行った
（１０枚作製）。このようにして抄製されたポリエステ
ル紙を熊谷理機工業株式会社製回転型乾燥機を用いて１
２０℃で１３秒間乾燥した。得られたポリエステル紙の
重量は約４０（ＩＩ／Ｔｄ、厚みはｏ、 ｉ。Plasma treated polyester fiber 22.5! II was taken, and 2.5 g of hot water-soluble polyvinyl alcohol fiber manufactured by Kuraray Co., Ltd. was taken and dispersed in water 1001, and polyvinyl alcohol fiber VPB-10 was used as an adhesive component. Collect this fiber dispersion liquid 101F, and
Using a standard square sheet machine with a size of 25 cm,
The sample was placed on a wire mesh of 8G mesh and dehydrated (10 sheets were prepared). The polyester paper made in this way was dried using a rotary dryer manufactured by Kumagai Riki Kogyo Co., Ltd.
It was dried at 20°C for 13 seconds. The weight of the obtained polyester paper is approximately 40 (II/Td, thickness is o, i.
〜０．１５１ＩｌｌＩＩであった。これを１５ｍｍ巾ｘ
ｌｏｃｍの長さに切断し、ざらに９０°方向を換えてサ
ンプル採取し、縦横方向同一数のサンプルを採取した。~0.151IllII. This is 15mm wide x
The tube was cut to a length of 1.0 cm, and samples were collected by changing the direction by roughly 90°, and the same number of samples were collected in the vertical and horizontal directions.
表
プラズマ照射時間が未照射のもの、１５秒間照射したも
のについては繊維表面の微細孔がｏ、 ｏｏｉミクロン
以下であり、紙強度の向上はみられなかった。一方２分
を超える照射を行ったものは微細孔の径が０．１〜０．
８μとなり、裂断長も２．０ｋｍを超え高い値となり、
伸度も上昇する。一方６０分照射したものはプラズマ照
射による繊維表面のエツチングがすすみ、微細孔の輪郭
も５ミクロンをこえるが、その境界もややあいまいにな
り、かつ繊維強度は２ ａ／デニールと非常に低くなっ
た。これを用いて抄紙テストをした所、裂断長の上昇も
なく又伸度も低めであった。In the case where the surface plasma irradiation time was not irradiated and the case where the surface was irradiated for 15 seconds, the micropores on the fiber surface were less than 0,000 microns, and no improvement in paper strength was observed. On the other hand, those that were irradiated for more than 2 minutes had micropores with a diameter of 0.1 to 0.
8μ, and the fracture length was also high, exceeding 2.0km.
Elongation also increases. On the other hand, for those irradiated for 60 minutes, etching of the fiber surface due to plasma irradiation progressed, and the outline of micropores exceeded 5 microns, but the boundaries became somewhat vague and the fiber strength was extremely low at 2 a/denier. . When a paper making test was carried out using this material, there was no increase in the tearing length and the elongation was rather low.
実施例２７
実施例２６において、工程を連続化する目的で金網を移
動させ、プラズマの照射時間を金網移動速度で調節した
。得られた紙強度へのプラズマ効果を表−７に示した。Example 27 In Example 26, the wire mesh was moved for the purpose of making the process continuous, and the plasma irradiation time was adjusted by the wire mesh moving speed. Table 7 shows the plasma effect on the strength of the obtained paper.
表に示すように、プラズマ処理の効果は照射時間が２分
以上で確認された。但し、紙強力３．０ｋｍを超える高
強力紙を得るには３分以上が必要であった。As shown in the table, the effect of plasma treatment was confirmed when the irradiation time was 2 minutes or more. However, in order to obtain high-strength paper with a paper strength of over 3.0 km, 3 minutes or more was required.
表−６Table-6
Claims (2)
有する合成紙において、ポリエステル繊維がその表面に
直径０．００１〜５μの微細孔を有することを特徴とす
るポリエステル合成紙。(1) A synthetic paper consisting mainly of polyester fibers and having an adhesive component, characterized in that the polyester fibers have micropores with a diameter of 0.001 to 5 μm on their surface.
１）のポリエステル合成紙。(2) Claim in which the diameter of the micropores is 0.005-2μ
1) Polyester synthetic paper.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3622989A JPH02221490A (en) | 1989-02-17 | 1989-02-17 | Polyester synthetic paper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3622989A JPH02221490A (en) | 1989-02-17 | 1989-02-17 | Polyester synthetic paper |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02221490A true JPH02221490A (en) | 1990-09-04 |
Family
ID=12463945
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3622989A Pending JPH02221490A (en) | 1989-02-17 | 1989-02-17 | Polyester synthetic paper |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02221490A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0513781U (en) * | 1991-08-01 | 1993-02-23 | 株式会社リゾートメーシヨン・エンジニアリング | scorecard |
| JP2011236536A (en) * | 2009-05-25 | 2011-11-24 | Nippon Ester Co Ltd | Short-cut fiber for wet-laid staple fiber nonwoven fabric |
| JP2015052183A (en) * | 2013-09-06 | 2015-03-19 | 大王製紙株式会社 | Electric insulating paper and method of producing electric insulating paper |
| CN107141819A (en) * | 2017-05-14 | 2017-09-08 | 高昕文 | A kind of preparation method of stone paper |
-
1989
- 1989-02-17 JP JP3622989A patent/JPH02221490A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0513781U (en) * | 1991-08-01 | 1993-02-23 | 株式会社リゾートメーシヨン・エンジニアリング | scorecard |
| JP2011236536A (en) * | 2009-05-25 | 2011-11-24 | Nippon Ester Co Ltd | Short-cut fiber for wet-laid staple fiber nonwoven fabric |
| JP2015052183A (en) * | 2013-09-06 | 2015-03-19 | 大王製紙株式会社 | Electric insulating paper and method of producing electric insulating paper |
| CN107141819A (en) * | 2017-05-14 | 2017-09-08 | 高昕文 | A kind of preparation method of stone paper |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI362441B (en) | Para-aramid film-like fibrid particle | |
| TWI245821B (en) | The conjugate fiber | |
| EP0022182B1 (en) | Synthetic polyester pulp and process for preparing same | |
| KR101441723B1 (en) | Thin paper | |
| EP0117937A1 (en) | Polyester binder fibers | |
| WO2008130019A1 (en) | Wet-laid non-woven fabric and filter | |
| JPH02221490A (en) | Polyester synthetic paper | |
| JP4050000B2 (en) | Polyester binder fiber for wet papermaking and method for producing the same | |
| JPH09259856A (en) | Battery separator | |
| JP2006322090A (en) | Binder fiber | |
| JP6462368B2 (en) | Wet nonwovens and shoji paper and products | |
| JP2018189346A (en) | Water-absorptive and volatile material | |
| JP2004107860A (en) | Thermally adhesive sheath core type conjugated short fiber and non-woven fabric of the same | |
| JPH02210092A (en) | Wet non-woven fabric and production thereof | |
| JP2012067408A (en) | Wet type polyester nonwoven fabric | |
| JP2012067409A (en) | Heat-adhesive polyester composite fiber | |
| JP2004083651A (en) | Hygroscopic polyester composition and polyester fiber | |
| JP5071097B2 (en) | Sea-island polyester composite fiber | |
| JP2002151358A (en) | Separator for capacitor and manufacturing method thereof | |
| JP3736432B2 (en) | Highly hygroscopic polyester fiber | |
| JP2870712B2 (en) | Heat-fusible conjugate fiber with excellent durability and hydrophilicity | |
| JPH08209583A (en) | Paper made from aromatic polyester and its production | |
| JP4592948B2 (en) | Wiper | |
| US20220010461A1 (en) | Ultrafine fibers and liquid fiber dispersion | |
| JPS60246813A (en) | Production of ultrafine polyester yarn |