JP2014201856A - Heat-adhesive composite fiber - Google Patents
Heat-adhesive composite fiber Download PDFInfo
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- JP2014201856A JP2014201856A JP2013079616A JP2013079616A JP2014201856A JP 2014201856 A JP2014201856 A JP 2014201856A JP 2013079616 A JP2013079616 A JP 2013079616A JP 2013079616 A JP2013079616 A JP 2013079616A JP 2014201856 A JP2014201856 A JP 2014201856A
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- 239000000835 fiber Substances 0.000 title claims abstract description 94
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 239000000853 adhesive Substances 0.000 title claims abstract description 45
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000002844 melting Methods 0.000 claims abstract description 19
- 230000008018 melting Effects 0.000 claims abstract description 19
- 229920001283 Polyalkylene terephthalate Polymers 0.000 claims abstract description 11
- 230000009477 glass transition Effects 0.000 claims abstract description 8
- 230000001070 adhesive effect Effects 0.000 claims description 12
- -1 polyethylene terephthalate Polymers 0.000 claims description 10
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 10
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 10
- 229920001634 Copolyester Polymers 0.000 claims description 6
- 239000004745 nonwoven fabric Substances 0.000 abstract description 17
- 238000005520 cutting process Methods 0.000 abstract description 13
- 229920000728 polyester Polymers 0.000 abstract description 13
- 239000002253 acid Substances 0.000 abstract description 3
- 239000000306 component Substances 0.000 description 78
- 229920000642 polymer Polymers 0.000 description 33
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 18
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 18
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 9
- 239000008358 core component Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000009987 spinning Methods 0.000 description 4
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000006224 matting agent Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- CNGYZEMWVAWWOB-VAWYXSNFSA-N 5-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-[(e)-2-[4-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound N=1C(NC=2C=C(C(\C=C\C=3C(=CC(NC=4N=C(N=C(NC=5C=CC=CC=5)N=4)N(CCO)CCO)=CC=3)S(O)(=O)=O)=CC=2)S(O)(=O)=O)=NC(N(CCO)CCO)=NC=1NC1=CC=CC=C1 CNGYZEMWVAWWOB-VAWYXSNFSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000013021 overheating Methods 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
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- YXTFRJVQOWZDPP-UHFFFAOYSA-M sodium;3,5-dicarboxybenzenesulfonate Chemical compound [Na+].OC(=O)C1=CC(C(O)=O)=CC(S([O-])(=O)=O)=C1 YXTFRJVQOWZDPP-UHFFFAOYSA-M 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
Landscapes
- Multicomponent Fibers (AREA)
Abstract
Description
本発明は、湿式および乾式不織布の接着用として好適なポリエステル系の熱接着性複合繊維に関するものである。 The present invention relates to a polyester-based heat-adhesive conjugate fiber suitable for bonding wet and dry nonwoven fabrics.
従来、ポリエステル系熱接着性複合繊維としては、ポリエチレンテレフタレート（ＰＥＴ）等のポリアルキレンテレフタレートを芯成分とし、イソフタル酸成分やテレフタル酸成分等を構成成分とするポリエステル系重合体を鞘成分とした繊維が、樹脂バインダー等を使用せず、熱処理のみによって、成形できることから、広く使用されている。 Conventionally, as a polyester-based heat-adhesive conjugate fiber, a fiber having a polyalkylene terephthalate such as polyethylene terephthalate (PET) as a core component and a polyester polymer having an isophthalic acid component or a terephthalic acid component as a sheath component as a sheath component. However, it is widely used because it can be molded only by heat treatment without using a resin binder or the like.
このような不織布を基材として使用した、例えば、粘着テープのような一部の用途においては、作業性の観点から、特定の切断のための器具を使用することなく、指先でテープを容易に切断することができる、手切れ性が求められる場合がある。例えば、熱可塑性樹脂からなる配向網状体を、配向軸が交差するように積層した積層体により、手切れ性の良好な粘着テープが提案されている（例えば、特許文献１参照。）。従来、手切れ性の改良に対しては、不織布やテープの構成面から提案がなされているが、材料となるシート状物を構成する熱可塑性樹脂等の機械的物性が強すぎるために手切れ性が十分に良好なシート状物が提案できていないのが現状である。 In some applications, such as adhesive tape, using such a non-woven fabric as a base material, from the viewpoint of workability, the tape can be easily made with a fingertip without using a specific cutting tool. There is a case where hand cutting ability that can be cut is required. For example, a pressure-sensitive adhesive tape with good hand cutting properties has been proposed by using a laminate in which oriented networks made of a thermoplastic resin are laminated so that the orientation axes cross each other (see, for example, Patent Document 1). Conventionally, improvements in hand cutting properties have been proposed from the viewpoint of the composition of nonwoven fabrics and tapes, but the mechanical properties such as the thermoplastic resin that constitutes the sheet material used as the material are too strong, so that the hand cutting occurs. At present, no sheet-like material having sufficiently good properties has been proposed.
本発明は、かかる背景に基づき、手切れ性の良好な不織布を得るために好適なポリエステル系熱接着性複合繊維を提供することを課題とする。 Based on this background, an object of the present invention is to provide a polyester-based heat-adhesive conjugate fiber suitable for obtaining a nonwoven fabric with good hand cutting properties.
本発明者は、上記課題を解決するため鋭意検討を重ねた結果、所定の繊度のポリエステル系熱接着性複合繊維において、特定の構成を採用することで、上記課題を解決できることを見出した。 As a result of intensive studies to solve the above problems, the present inventor has found that the above problems can be solved by adopting a specific configuration in a polyester-based heat-adhesive conjugate fiber having a predetermined fineness.
すなわち本発明は、繊維軸方向に連続している繊維形成性成分と、繊維軸方向に連続している熱接着性成分とからなる複合繊維であり、前記繊維形成性成分が融点２２０℃以上で、固有粘度０．３０〜０．５５ｄＬ／ｇのポリアルキレンテレフタレートからなり、前記熱接着性成分が融点１１０〜２００℃またはガラス転移温度５０〜１１０℃の共重合ポリエステルからなり、少なくとも前記熱接着性成分が表面に露出するように前記繊維形成性成分と前記熱接着性成分が複合化された複合繊維であって、単糸繊度が０．０１〜１．５ｄｔｅｘである複合繊維であり、そのような複合繊維により上記課題を解決することができる。 That is, the present invention is a composite fiber composed of a fiber-forming component continuous in the fiber axis direction and a heat-adhesive component continuous in the fiber axis direction, and the fiber-forming component has a melting point of 220 ° C. or higher. , Composed of polyalkylene terephthalate having an intrinsic viscosity of 0.30 to 0.55 dL / g, wherein the thermal adhesive component is composed of a copolyester having a melting point of 110 to 200 ° C. or a glass transition temperature of 50 to 110 ° C., and at least the thermal adhesive property A composite fiber in which the fiber-forming component and the heat-adhesive component are combined such that the component is exposed on the surface, and the single fiber fineness is 0.01 to 1.5 dtex, and so on The above-mentioned problem can be solved by a simple composite fiber.
本発明の熱接着性複合繊維によれば、手切れ性の良好な不織布を提供することができる。 According to the heat-adhesive conjugate fiber of the present invention, it is possible to provide a nonwoven fabric with good hand cutting properties.
本発明の複合繊維は、繊維軸方向に連続している繊維形成性成分と、繊維軸方向に連続している熱接着性成分からなる複合繊維であり、繊維形成性成分として融点２２０℃以上のポリアルキレンテレフタレートを用いる。繊維形成性成分のポリエステルの融点が２２０℃未満になると、複合繊維を安定して製糸することが困難となるばかりでなく、熱接着処理時に熱接着性成分と同時に繊維形成性成分の少なくとも一部も溶融してしまうことがあり、熱接着処理が安定して行うことができず、操作性が低下するので好ましくない。ポリアルキレンテレフタレートの具体例としては、ＰＥＴ、ポリトリメチレンテレフタレート（ＰＴＴ）、ポリブチレンテレフタレート（ＰＢＴ）が好ましく、ＰＥＴまたはＰＢＴがより好ましい。更に、その特性を損なわない範囲であれば少量の共重合成分や艶消剤、着色剤、滑剤等の添加剤を含有していてもよい。中でも、ポリエチレンテレフタレートは安価で汎用であるため、より好ましい。 The composite fiber of the present invention is a composite fiber composed of a fiber-forming component continuous in the fiber axis direction and a heat-adhesive component continuous in the fiber axis direction, and has a melting point of 220 ° C. or more as the fiber-forming component. Polyalkylene terephthalate is used. When the melting point of the polyester of the fiber-forming component is less than 220 ° C., not only is it difficult to stably produce the composite fiber, but at least a part of the fiber-forming component simultaneously with the heat-adhesive component during the heat-bonding process. May be melted, the heat bonding treatment cannot be performed stably, and the operability is lowered, which is not preferable. Specific examples of the polyalkylene terephthalate are preferably PET, polytrimethylene terephthalate (PTT), and polybutylene terephthalate (PBT), and more preferably PET or PBT. Furthermore, a small amount of a copolymer component, an additive such as a matting agent, a coloring agent, and a lubricant may be contained as long as the characteristics are not impaired. Among these, polyethylene terephthalate is more preferable because it is inexpensive and widely used.
本発明の複合繊維の繊維形成性成分として使用するポリアルキレンテレフタレートの固有粘度は、０．３０〜０．５５ｄＬ／ｇであり、好ましくは、０．３５〜０．５０ｄＬ／ｇである。０．３０ｄＬ／ｇより小さいと、繊維形成性成分として十分な機械強度が得られないため、複合繊維自身が脆弱となり過ぎるため、不織布として成形する工程での破断や劣化を招き、不織布を得ることが極めて困難となる。０．５５ｄＬ／ｇより大きいと、適度な脆性を有する繊維が得られず、その結果、粘着テープに求められる所期の手切れ性良好な不織布を得ることができない。さらに、繊維形成性成分の固有粘度を上述の範囲とすることで、良好な曳糸性が得られるため、後述するような、本発明における細い繊度領域の複合繊維を得るためにも有利となる。 The intrinsic viscosity of the polyalkylene terephthalate used as the fiber-forming component of the conjugate fiber of the present invention is 0.30 to 0.55 dL / g, preferably 0.35 to 0.50 dL / g. If it is less than 0.30 dL / g, sufficient mechanical strength as a fiber-forming component cannot be obtained, and the composite fiber itself becomes too brittle, leading to breakage and deterioration in the process of forming the nonwoven fabric, thereby obtaining a nonwoven fabric. Is extremely difficult. When it is larger than 0.55 dL / g, fibers having moderate brittleness cannot be obtained, and as a result, a desired non-woven fabric with good hand cutting properties required for an adhesive tape cannot be obtained. Furthermore, by setting the intrinsic viscosity of the fiber-forming component in the above range, good spinnability can be obtained, which is advantageous for obtaining a composite fiber having a fine fineness region in the present invention as described later. .
一方、熱接着性成分となるポリエステルとしては、融点が１１０〜２００℃またはガラス転移温度が５０〜１１０℃の範囲の共重合ポリエステルが適用される。例えば、テレフタル酸、イソフタル酸、２，６−ナフタレンジカルボン酸、アジピン酸、セバシン酸、アゼライン酸、ドデカン二酸、１，４−シクロヘキサンジカルボン酸等のジカルボン酸もしくはこれらのジカルボン酸の炭素数１〜６個のジアルキルエステル、ジフェニルエステルであるジカルボン酸成分と、エチレングリコール、１，３−プロパンジオール、１，４−ブタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオール、ジエチレングリコール、１，４−シクロヘキサンジオール、１，４−シクロヘキサンジメタノール等のジオール成分のランダムまたはブロック共重合体があげられる。中でも、従来広く用いられている、イソフタル酸が共重合された共重合ポリエチレンテレフタレートを主成分とすることが、繊維形成性成分であるポリアルキレンテレフタレートと複合した場合に、曳糸性が良好な複合繊維を構成することができ、粘着テープに求められる熱接着性を充足できるという観点から好ましい。更には、テレフタル酸成分、イソフタル酸成分、エチレングリコール成分およびジエチレングリコール成分から構成された共重合ポリエステルが、コスト面や取扱い性の点でより好ましい。 On the other hand, as the polyester serving as the heat-adhesive component, a copolyester having a melting point of 110 to 200 ° C. or a glass transition temperature of 50 to 110 ° C. is applied. For example, dicarboxylic acids such as terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, 1,4-cyclohexanedicarboxylic acid, or these dicarboxylic acids having 1 to 1 carbon atoms 6 dialkyl esters, a dicarboxylic acid component which is a diphenyl ester, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, 1, Examples thereof include random or block copolymers of diol components such as 4-cyclohexanediol and 1,4-cyclohexanedimethanol. Among them, a composite having good spinnability when it is combined with polyalkylene terephthalate, which is a fiber-forming component, which has been widely used in the past, which is mainly composed of copolymerized polyethylene terephthalate copolymerized with isophthalic acid. It is preferable from the viewpoint that the fiber can be formed and the thermal adhesiveness required for the pressure-sensitive adhesive tape can be satisfied. Furthermore, a copolymer polyester composed of a terephthalic acid component, an isophthalic acid component, an ethylene glycol component, and a diethylene glycol component is more preferable in terms of cost and handling.
熱接着性成分として、上記のようなテレフタル酸成分、イソフタル酸成分、エチレングリコール成分およびジエチレングリコール成分からなる共重合ポリエステルを使用する場合には、テレフタル酸成分とイソフタル酸成分のモル比は５０：５０〜９０：１０の範囲が適当である。共重合ポリエステルを構成する酸成分全体に対する、イソフタル酸成分の割合は、１０〜５０モル％であることが好ましく、より好ましくは１５〜４５モル％である。イソフタル酸の割合が１０モル％より小さいと融点が高くなり、熱接着性が不十分となり、好ましくない。５０％モルより大きいと、紡糸後の固化が遅くなり、繊維同士が膠着するため、好ましくない。一方、エチレングリコールとジエチレングリコールのモル比は、０：１００〜１００：０の範囲で任意に選ぶことができる。好ましくはエチレングリコールとジエチレングリコールのモル比は、６０：４０〜９９：１の範囲である。この範囲であると曳糸性および熱接着性が共により良好である。ここで主成分とするとは、全熱接着性成分の８０重量％、好ましくは９０重量％が共重合ポリエステルから構成されていることを表す。このような構成を採用することによって、本発明の複合繊維は熱接着性複合繊維としての特性を有することがある。 In the case where a copolymerized polyester composed of the terephthalic acid component, isophthalic acid component, ethylene glycol component and diethylene glycol component as described above is used as the thermal adhesive component, the molar ratio of the terephthalic acid component to the isophthalic acid component is 50:50. A range of ~ 90: 10 is suitable. The ratio of the isophthalic acid component to the entire acid component constituting the copolymer polyester is preferably 10 to 50 mol%, more preferably 15 to 45 mol%. If the proportion of isophthalic acid is less than 10 mol%, the melting point becomes high and the thermal adhesiveness becomes insufficient, which is not preferable. If it is larger than 50% mol, solidification after spinning is delayed and the fibers stick together, which is not preferable. On the other hand, the molar ratio of ethylene glycol and diethylene glycol can be arbitrarily selected within the range of 0: 100 to 100: 0. Preferably the molar ratio of ethylene glycol to diethylene glycol is in the range of 60:40 to 99: 1. Within this range, both the spinnability and the thermal adhesiveness are better. Here, the main component means that 80% by weight, preferably 90% by weight of the total heat-adhesive component is composed of a copolyester. By employ | adopting such a structure, the composite fiber of this invention may have the characteristic as a heat bondable composite fiber.
上記の繊維形成性成分を構成するポリマー、または、熱接着性成分を主として構成するポリマーには、必要に応じて、各種の添加剤、例えば、艶消し剤、熱安定剤、消泡剤、整色剤、難燃剤、酸化防止剤、紫外線吸収剤、蛍光増白剤、着色顔料などが含有されているようなポリマー組成物であってもよい。 For the polymer constituting the above-mentioned fiber-forming component or the polymer mainly constituting the heat-adhesive component, various additives such as a matting agent, a heat stabilizer, an antifoaming agent, a regulating agent are used as necessary. It may be a polymer composition containing a colorant, a flame retardant, an antioxidant, an ultraviolet absorber, a fluorescent brightener, a color pigment, and the like.
本発明の複合繊維は、少なくとも熱接着性成分が該複合繊維の表面に露出するように複合化されている複合繊維であり、熱接着性成分と繊維形成性成分が並列型（サイドバイサイド型）に複合化されたもの、熱接着性成分を鞘成分とし繊維形成性成分を芯成分とし、両成分が同芯鞘芯型または偏芯鞘芯型に複合化されたもの、又は熱接着性成分が海成分繊維形成性成分を島成分として海島型に複合化された複合繊維を例示することができるが、なかでも複合繊維の表面全体が熱接着性成分に覆われ、紡糸がより容易に行う事ができる観点から鞘芯型に複合化させるのが特に好ましい。なお、お互いに非相溶である２種類以上のポリマー成分をブレンドして紡糸して得られた繊維は、複数種のポリマー成分の少なくとも１種が繊維軸方向に連続していない態様であり、繊維軸方向に沿って機械的強度にバラツキが生じ本発明の効果を奏さないと考えられる。 The composite fiber of the present invention is a composite fiber in which at least the heat-adhesive component is composited so as to be exposed on the surface of the composite fiber, and the heat-adhesive component and the fiber-forming component are in a parallel type (side-by-side type). A composite, a thermal adhesive component as a sheath component and a fiber-forming component as a core component, both components combined into a concentric sheath core type or an eccentric sheath core type, or a thermal adhesive component Examples of the composite fiber can be illustrated as a sea-island type compound using the sea component fiber-forming component as an island component. Among them, the entire surface of the composite fiber is covered with the heat-adhesive component, making spinning easier. It is particularly preferable to make a composite with a sheath core type from the viewpoint of being able to achieve this. The fiber obtained by blending and spinning two or more polymer components that are incompatible with each other is an embodiment in which at least one of the plurality of polymer components is not continuous in the fiber axis direction, It is considered that the mechanical strength varies along the fiber axis direction and the effect of the present invention is not achieved.
熱接着性成分の複合繊維に占める重量割合は、４０〜９５重量％とすることが望ましい。４０重量％未満では、熱接着性成分を含まない他の繊維（主体繊維）と不織布を形成する際に、主体繊維と接着するのに十分なポリマー量がないため、該主体繊維との熱接着性が不十分となり、十分な強力の湿式不織布が得られない。また、９５重量％を超えると、複合繊維の安定した溶融紡糸が困難となる。上記熱接着性成分の複合繊維に占める重量割合としては４５〜９０重量％の範囲が好ましく、より好ましくは５０〜８０重量％の範囲である。 The weight ratio of the heat-adhesive component to the composite fiber is preferably 40 to 95% by weight. If it is less than 40% by weight, there is not a sufficient amount of polymer to adhere to the main fiber when forming a non-woven fabric with other fibers (main fiber) that do not contain a heat-adhesive component. The properties become insufficient, and a sufficiently strong wet nonwoven fabric cannot be obtained. On the other hand, if it exceeds 95% by weight, stable melt spinning of the composite fiber becomes difficult. The weight ratio of the thermal adhesive component to the composite fiber is preferably in the range of 45 to 90% by weight, more preferably in the range of 50 to 80% by weight.
本発明における複合繊維の単糸繊度は、０．０１〜１．５ｄｔｅｘの範囲にある必要がある。０．０１ｄｔｅｘより小さいと、実用に耐える強度を有する不織布を得難くなる。１．５ｄｔｅｘより大きいと、単糸1本当たりの強力が大きくなり、手切れ性の不良となるため、好ましくない。好ましい単糸繊度は０．１〜１．０ｄｔｅｘである。 The single yarn fineness of the composite fiber in the present invention needs to be in the range of 0.01 to 1.5 dtex. When it is smaller than 0.01 dtex, it is difficult to obtain a nonwoven fabric having a strength that can withstand practical use. If it is larger than 1.5 dtex, the strength per single yarn is increased, resulting in poor hand cutting properties, which is not preferable. A preferable single yarn fineness is 0.1 to 1.0 dtex.
上述のように、繊維形成性成分として融点が２２０℃以上で０．３０〜０．５５ｄＬ／ｇの低固有粘度のポリアルキレンテレフタレートを採用し、複合繊維全体としての引張破断強度、破断伸度が高くならないように構成し、熱接着性成分に融点またはガラス転移温度が規定された共重合ポリエステルを採用し、その熱接着性成分が表面に露出するように配置することにより、繊維形成性成分の融点よりも低い温度で他の繊維等と融着できる複合繊維を構成し、更に１．５ｄｔｅｘ以下の細繊度とすることによっても更に繊維としての破断強度の増加を抑えることができる。このような繊維は繊維としての強度伸度が高くないために、タフネスで表される（［タフネス］＝［破断強度］×√［破断伸度］）＝（［破断強度］×［破断伸度］＾０．５）の値が低く、不織布等の繊維構造体を形成した際に手切れ性が良好とすることができる。 As described above, a polyalkylene terephthalate having a melting point of 220 ° C. or higher and a low intrinsic viscosity of 0.30 to 0.55 dL / g is employed as the fiber-forming component, and the tensile breaking strength and breaking elongation of the composite fiber as a whole are By adopting a copolyester having a melting point or glass transition temperature defined as the heat-adhesive component and arranging it so that the heat-adhesive component is exposed on the surface, the fiber-forming component An increase in breaking strength as a fiber can be further suppressed by forming a composite fiber that can be fused with other fibers at a temperature lower than the melting point, and by setting the fineness to 1.5 dtex or less. Since such a fiber does not have a high strength elongation as a fiber, it is represented by toughness ([Toughness] = [Break strength] × √ [Break elongation]) = ([Break strength] × [Break elongation] ] 0.5) is low, and when a fiber structure such as a non-woven fabric is formed, it is possible to improve hand cutting.
本発明の熱接着性複合繊維は、たとえば、以下の方法により製造することができる。すなわち、前述した熱接着性成分および繊維形成性成分を構成するポリマーをチップ状とし、これらをそれぞれ乾燥した後、溶融して公知に複合紡糸口金に導入し、溶融複合繊維糸条として押し出し、口金下１５〜１００ｍｍの位置で冷却固化し紡糸速度３００〜２０００ｍ／分で巻き取り未延伸糸を得る。得られた未延伸糸を、熱接着性成分のガラス転移温度Ｔｇとして、Ｔｇ〜Ｔｇ＋３０℃の温水中で、１．５〜３０．０倍に延伸し、２５〜１３０℃で定長熱処理もしくはオーバーフィード熱処理または弛緩熱処理を行って熱接着性複合繊維とすることができる。 The thermoadhesive conjugate fiber of the present invention can be produced, for example, by the following method. That is, the above-mentioned polymers constituting the heat-adhesive component and the fiber-forming component are made into chips, dried, melted and introduced into a known composite spinneret, extruded as a melted composite fiber yarn, It is cooled and solidified at a position of 15 to 100 mm below to obtain an undrawn yarn wound at a spinning speed of 300 to 2000 m / min. The obtained unstretched yarn was stretched 1.5 to 30.0 times in warm water of Tg to Tg + 30 ° C. as the glass transition temperature Tg of the heat-adhesive component, and was subjected to constant length heat treatment or overheating at 25 to 130 ° C. A heat-adhesive conjugate fiber can be obtained by performing feed heat treatment or relaxation heat treatment.
上記複合繊維は、湿式不織布用として使用する場合は、その繊維長を１．０〜３０ｍｍ、好ましくは２．０〜２０ｍｍとする必要がある。繊維長が１．０ｍｍより短くなると、切断抵抗が大きくなり、繊維同士の絡みが起こり易く、繊維の品質斑が発生する。一方、繊維長が３０ｍｍを超えて長くなると、抄紙時、繊維の水中分散性が悪化するので好ましくない。また、乾式不織布用として用いる場合は、その繊維長を、３０〜８０ｍｍ、好ましくは、４０〜７０ｍｍとする必要がある。３０ｍｍより短いと繊維の絡合性が低下し、カードに掛かり難くなり、好ましくない。８０ｍｍより長いとネップを形成し、不織布の品位を損なうため、好ましくない。 When the composite fiber is used for a wet nonwoven fabric, the fiber length needs to be 1.0 to 30 mm, preferably 2.0 to 20 mm. When the fiber length is shorter than 1.0 mm, the cutting resistance increases, the fibers tend to be entangled with each other, and fiber quality spots occur. On the other hand, if the fiber length exceeds 30 mm, it is not preferable because the dispersibility of the fiber in water deteriorates during papermaking. Moreover, when using it for dry-type nonwoven fabrics, the fiber length needs to be 30-80 mm, Preferably, it is 40-70 mm. If it is shorter than 30 mm, the entanglement of the fibers is lowered, and it is difficult to hang the card. If it is longer than 80 mm, a nep is formed, and the quality of the nonwoven fabric is impaired.
以下に本発明の構成及び効果を具体的にするため、実施例等を挙げるが、本発明は、これら実施例になんら限定を受けるものではない。なお、実施例中の各値は、以下の方法に従って求めた。 In order to make the configuration and effects of the present invention concrete, examples and the like are given below, but the present invention is not limited to these examples. In addition, each value in an Example was calculated | required according to the following method.
（１）固有粘度［η］
ポリマーサンプル０．１２ｇを１０ｍＬのテトラクロロエタン／フェノール混合溶媒（容量比１／１）に溶解し、３５℃における固有粘度（ｄＬ／ｇ）を測定した。
(1) Intrinsic viscosity [η]
0.12 g of a polymer sample was dissolved in 10 mL of a tetrachloroethane / phenol mixed solvent (volume ratio 1/1), and the intrinsic viscosity (dL / g) at 35 ° C. was measured.
（２）ガラス転移温度、融点
ＴＡインストルメンツ製 ＴＡ−２９２０示差走査熱量測定計ＤＳＣを用いた。測定は、試料１０ｍｇを窒素雰囲気下、昇温速度１０℃／分で室温から２６０℃まで昇温し、結晶融解吸熱ピーク及び結晶化発熱ピークのピークトップ温度を各々融点及び結晶化点と定義した。
(2) Glass transition temperature, melting point TA-2920 differential scanning calorimeter DSC manufactured by TA Instruments was used. In the measurement, 10 mg of a sample was heated from room temperature to 260 ° C. at a heating rate of 10 ° C./min in a nitrogen atmosphere, and the peak top temperatures of the crystal melting endothermic peak and the crystallization exothermic peak were defined as the melting point and the crystallization point, respectively. .
（３）単糸繊度
ＪＩＳ Ｌ １０１５：２００５ ８．５．１ Ａ法に記載の方法により測定した。
(3) Single yarn fineness It measured by the method as described in JIS L 1015: 2005 8.5.1 A method.
（４）破断強度・破断伸度
ＪＩＳ Ｌ １０１５：２００５ ８．７．１法に記載の方法により測定した。
(4) Breaking strength and breaking elongation It measured by the method as described in JIS L 1015: 2005 8.7.1 method.
（５）タフネス
（４）に記載の方法で得られた破断強度と破断伸度から、下式で定義する。
タフネス＝強度×√（伸度）
タフネスが２２より小さい繊維が、本願で想定している発明の目的として好適に用いることができる。
(5) Toughness From the breaking strength and breaking elongation obtained by the method described in (4), the following formula is used.
Toughness = Strength x √ (Elongation)
A fiber having a toughness smaller than 22 can be suitably used for the purpose of the invention assumed in the present application.
（６）繊維を構成しているポリマー種類
本発明の複合繊維の芯成分、鞘成分のポリマー種類は、複合繊維中から取り出した試料をＩＲ，１Ｈ−ＮＭＲ、ＤＳＣ等の各種の機器分析を行う事で特定することができる。
(6) Type of polymer constituting the fiber The core type and the sheath type of the composite fiber of the present invention are obtained by conducting various instrumental analyzes such as IR, 1 H-NMR, DSC on samples taken from the composite fiber. It can be specified by doing.
（７）複合繊維の断面形状の観察
得られた繊維の繊維表面または断面を、光学顕微鏡または電子顕微鏡で観察することにより、複合繊維の熱接着性成分が表面に露出するように複合化されている態様を確認することができる。
(7) Observation of the cross-sectional shape of the composite fiber By observing the fiber surface or cross-section of the obtained fiber with an optical microscope or an electron microscope, the composite fiber is composited so that the thermal adhesive component is exposed on the surface. Can be confirmed.
実施例および比較例において使用したポリマーの固有粘度、組成及び熱特性は以下の通りである。
１）ポリマーＡ
構成： 酸成分がモル比でテレフタル酸が６０モル％、イソフタル酸が４０モル％であり、ジオール成分がモル比でエチレングリコールが９５モル％、ジエチレングリコールが５％モルの割合で共重合された非晶性共重合ポリエステル
固有粘度［η］：０．５６ｄＬ／ｇ
ガラス転移温度：６４℃
２）ポリマーＢ
種類： ポリエチレンテレフタレート
固有粘度：０．４７ｄＬ／ｇ
融点：２５６℃
３）ポリマーＣ
種類：ポリエチレンテレフタレート
固有粘度：０．６４ｄＬ／ｇ
融点：２５６℃
４）ポリマーＤ
構成：５−スルホイソフタル酸ナトリウムを４．５モル％共重合したポリエチレンテレフタレート
固有粘度：０．３６５ｄＬ／ｇ
融点：２４９℃
The intrinsic viscosity, composition and thermal properties of the polymers used in the examples and comparative examples are as follows.
1) Polymer A
Constitution: 60% by mole of terephthalic acid and 40% by mole of isophthalic acid in molar ratio of acid component, non-copolymerized in a ratio of 95% by mole of ethylene glycol and 5% of diethylene glycol in molar ratio of diol component Crystalline copolyester intrinsic viscosity [η]: 0.56 dL / g
Glass transition temperature: 64 ° C
2) Polymer B
Type: Polyethylene terephthalate Intrinsic viscosity: 0.47 dL / g
Melting point: 256 ° C
3) Polymer C
Type: Polyethylene terephthalate Intrinsic viscosity: 0.64 dL / g
Melting point: 256 ° C
4) Polymer D
Composition: Polyethylene terephthalate copolymerized with 4.5 mol% sodium 5-sulfoisophthalate Inherent viscosity: 0.365 dL / g
Melting point: 249 ° C
［実施例１］
ポリマーＡを二軸エクストルーダーで溶融して溶融ポリマー（熱接着性成分）とし、ポリマーＢを一軸エクストルーダーで溶融して溶融ポリマー（繊維形成性成分）とした。両溶融ポリマーを、前者を鞘成分、後者を芯成分とし、かつ重量比が鞘：芯＝５５：４５となるように、直径０．３ｍｍの丸穴キャピラリーを１３３６孔有する公知の芯鞘型複合紡糸口金から、複合化して溶融吐出させた。この際、口金温度は２８０℃、吐出量は３６０ｇ／分とした。さらに吐出ポリマーを冷却風で冷却し、１３００ｍ／分で巻き取り、未延伸糸を得た。この未延伸糸を６４℃の温水中で３．８倍に延伸した。繊維表面に界面活性剤を付与した後、５ｍｍの繊維長にカットし、熱接着性複合繊維を得た。結果を表１に示した。
[Example 1]
Polymer A was melted with a biaxial extruder to form a molten polymer (thermal adhesive component), and polymer B was melted with a uniaxial extruder to form a molten polymer (fiber-forming component). A known core-sheath type composite comprising both molten polymers, the former being a sheath component, the latter being a core component, and 1336 round hole capillaries having a diameter of 0.3 mm so that the weight ratio is sheath: core = 55: 45 From the spinneret, it was compounded and melted and discharged. At this time, the die temperature was 280 ° C., and the discharge rate was 360 g / min. Further, the discharged polymer was cooled with cooling air and wound at 1300 m / min to obtain an undrawn yarn. This undrawn yarn was drawn 3.8 times in warm water at 64 ° C. After imparting a surfactant to the fiber surface, it was cut into a fiber length of 5 mm to obtain a heat-adhesive conjugate fiber. The results are shown in Table 1.
［実施例２］
ポリマーＡを二軸エクストルーダーで溶融して溶融ポリマー（熱接着性成分）とし、ポリマーＤを一軸エクストルーダーで溶融して溶融ポリマー（繊維形成性成分）とした。両溶融ポリマーを、前者を鞘成分、後者を芯成分とし、かつ重量比が鞘：芯＝５５：４５となるように、直径０．３ｍｍの丸穴キャピラリーを１３３６孔有する公知の芯鞘型複合紡糸口金から、複合化して溶融吐出させた。この際、口金温度は２８０℃、吐出量は７４０ｇ／分とした。さらに吐出ポリマーを冷却風で冷却し、５００ｍ／分で巻き取り、未延伸糸を得た。この未延伸糸を９０℃の温水中で２５倍に延伸した。繊維表面に界面活性剤を付与した後、５ｍｍの繊維長にカットし、熱接着性複合繊維を得た。結果を表１に示した。
[Example 2]
Polymer A was melted with a biaxial extruder to form a molten polymer (thermal adhesive component), and polymer D was melted with a uniaxial extruder to form a molten polymer (fiber-forming component). A known core-sheath type composite comprising both molten polymers, the former being a sheath component, the latter being a core component, and 1336 round hole capillaries having a diameter of 0.3 mm so that the weight ratio is sheath: core = 55: 45 From the spinneret, it was compounded and melted and discharged. At this time, the die temperature was 280 ° C., and the discharge rate was 740 g / min. Further, the discharged polymer was cooled with cooling air and wound at 500 m / min to obtain an undrawn yarn. This undrawn yarn was drawn 25 times in warm water at 90 ° C. After imparting a surfactant to the fiber surface, it was cut into a fiber length of 5 mm to obtain a heat-adhesive conjugate fiber. The results are shown in Table 1.
［比較例１］
ポリマーＡを二軸エクストルーダーで溶融して溶融ポリマー（熱接着性成分）とし、ポリマーＣを一軸エクストルーダーで溶融して溶融ポリマー（繊維形成性成分）とした。両溶融ポリマーを、前者を鞘成分、後者を芯成分とし、かつ重量比が鞘：芯＝５５：４５となるように、直径０．３ｍｍの丸穴キャピラリーを１３３６孔有する公知の芯鞘型複合紡糸口金から、複合化して溶融吐出させた。この際、口金温度は２８０℃、吐出量は６４０ｇ／分とした。さらに吐出ポリマーを冷却風で冷却し、１３２０ｍ／分で巻き取り、未延伸糸を得た。この未延伸糸を６４℃の温水中で３．２４倍に延伸した。繊維表面に界面活性剤を付与した後、５ｍｍの繊維長にカットし、熱接着性複合繊維を得た。結果を表１に示した。
[Comparative Example 1]
Polymer A was melted with a biaxial extruder to obtain a molten polymer (thermal adhesive component), and polymer C was melted with a uniaxial extruder to obtain a molten polymer (fiber-forming component). A known core-sheath type composite comprising both molten polymers, the former being a sheath component, the latter being a core component, and 1336 round hole capillaries having a diameter of 0.3 mm so that the weight ratio is sheath: core = 55: 45 From the spinneret, it was compounded and melted and discharged. At this time, the die temperature was 280 ° C., and the discharge rate was 640 g / min. Further, the discharged polymer was cooled with cooling air and wound up at 1320 m / min to obtain an undrawn yarn. The undrawn yarn was drawn 3.24 times in warm water at 64 ° C. After imparting a surfactant to the fiber surface, it was cut into a fiber length of 5 mm to obtain a heat-adhesive conjugate fiber. The results are shown in Table 1.
［比較例２］
１０３２孔有する複合紡糸口金を使用する以外は、比較例１と同様にして、複合繊維を得た。結果を表１に示した。
[Comparative Example 2]
A composite fiber was obtained in the same manner as in Comparative Example 1 except that a composite spinneret having 1032 holes was used. The results are shown in Table 1.
本発明に基づくポリエステル系熱接着性複合繊維を使用することにより、粘着テープのような良好な手切れ性の要求される用途において好適に用いられる、不織布を製造することができる。 By using the polyester-based heat-adhesive conjugate fiber according to the present invention, it is possible to produce a non-woven fabric that is suitably used in applications that require good hand cutting properties such as pressure-sensitive adhesive tapes.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001226830A (en) * | 2000-02-09 | 2001-08-21 | Teijin Ltd | Hot-melt type conjugated fiber and structured fiber product composed thereof |
| JP2002030555A (en) * | 2000-07-18 | 2002-01-31 | Nippon Ester Co Ltd | Ball-like staple fiber comprising thermally adhesive fiber and fiber structure |
| JP2004027377A (en) * | 2002-06-21 | 2004-01-29 | Teijin Fibers Ltd | Polyester staple fiber and nonwoven fabric composed thereof |
| WO2006088163A1 (en) * | 2005-02-18 | 2006-08-24 | Kb Seiren, Ltd. | Woven structure of belt form and method for production thereof |
| JP2009057654A (en) * | 2007-08-31 | 2009-03-19 | Toray Ind Inc | Pressure-resistant sheet and fluid separation element using the same |
| JP2009061373A (en) * | 2007-09-05 | 2009-03-26 | Toray Ind Inc | Separation membrane support body |
-
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001226830A (en) * | 2000-02-09 | 2001-08-21 | Teijin Ltd | Hot-melt type conjugated fiber and structured fiber product composed thereof |
| JP2002030555A (en) * | 2000-07-18 | 2002-01-31 | Nippon Ester Co Ltd | Ball-like staple fiber comprising thermally adhesive fiber and fiber structure |
| JP2004027377A (en) * | 2002-06-21 | 2004-01-29 | Teijin Fibers Ltd | Polyester staple fiber and nonwoven fabric composed thereof |
| US20040265577A1 (en) * | 2002-06-21 | 2004-12-30 | Hironori Goda | Polyester staple fiber and nonwoven fabric comprising same |
| WO2006088163A1 (en) * | 2005-02-18 | 2006-08-24 | Kb Seiren, Ltd. | Woven structure of belt form and method for production thereof |
| JP2009057654A (en) * | 2007-08-31 | 2009-03-19 | Toray Ind Inc | Pressure-resistant sheet and fluid separation element using the same |
| JP2009061373A (en) * | 2007-09-05 | 2009-03-26 | Toray Ind Inc | Separation membrane support body |
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