JP2012233266A - Organic fiber fibrid, sheet material using the same, and sound absorbing structural material in which the sheet material is arranged - Google Patents
Organic fiber fibrid, sheet material using the same, and sound absorbing structural material in which the sheet material is arranged Download PDFInfo
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- 239000000835 fiber Substances 0.000 title claims abstract description 47
- 239000000463 material Substances 0.000 title claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000004760 aramid Substances 0.000 claims abstract description 18
- 229920003235 aromatic polyamide Polymers 0.000 claims abstract description 18
- 239000010419 fine particle Substances 0.000 claims abstract description 18
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 150000001408 amides Chemical class 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 5
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 claims abstract description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000015271 coagulation Effects 0.000 claims abstract description 4
- 238000005345 coagulation Methods 0.000 claims abstract description 4
- 229920006158 high molecular weight polymer Polymers 0.000 claims abstract 3
- 229920000642 polymer Polymers 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 8
- 238000010009 beating Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 230000004580 weight loss Effects 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims 1
- 239000006185 dispersion Substances 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 claims 1
- 239000011358 absorbing material Substances 0.000 abstract description 14
- 229940113088 dimethylacetamide Drugs 0.000 abstract 1
- 238000001035 drying Methods 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 10
- 239000002657 fibrous material Substances 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- -1 polypropylene Polymers 0.000 description 6
- 239000005995 Aluminium silicate Substances 0.000 description 5
- 235000012211 aluminium silicate Nutrition 0.000 description 5
- 238000007731 hot pressing Methods 0.000 description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 5
- WRDNCFQZLUCIRH-UHFFFAOYSA-N 4-(7-azabicyclo[2.2.1]hepta-1,3,5-triene-7-carbonyl)benzamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)N1C2=CC=C1C=C2 WRDNCFQZLUCIRH-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000001112 coagulating effect Effects 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 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 2
- ICXAPFWGVRTEKV-UHFFFAOYSA-N 2-[4-(1,3-benzoxazol-2-yl)phenyl]-1,3-benzoxazole Chemical compound C1=CC=C2OC(C3=CC=C(C=C3)C=3OC4=CC=CC=C4N=3)=NC2=C1 ICXAPFWGVRTEKV-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229920000561 Twaron Polymers 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
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 239000004762 twaron Substances 0.000 description 2
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000037396 body weight Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000011491 glass wool Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- SNICXCGAKADSCV-UHFFFAOYSA-N nicotine Chemical compound CN1CCCC1C1=CC=CN=C1 SNICXCGAKADSCV-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Abstract
Description
本発明は、耐熱性、吸音性に優れた吸音材を提供することが可能な有機繊維フィブリッド、これを用いたシート材、このシート材を配してなる、耐熱性に優れた吸音用構造材に関する。 The present invention relates to an organic fiber fibrid that can provide a sound-absorbing material having excellent heat resistance and sound-absorbing property, a sheet material using the same, and a structural material for sound-absorbing excellent in heat resistance, comprising the sheet material. About.
従来、車輌や住宅あるいは高速道路などの吸音、遮音材として、ガラスウール、ウレタンフォーム、ポリエステル繊維、さらには高融点熱可塑性繊維と低融点熱可塑性繊維を用いたもの（例えば、特許文献１参照）など、各種繊維を用いた吸音材が多数提案されている。かかる吸音材に要求される特性としては、吸音性、軽量性、形態安定性などがあげられる。特に、吸音性においては、低周波から高周波にかけて広くかつ良好な吸音特性が求められている。吸音材の吸音性を高める方法としては、従来、繊維径を細くしたり、目付けを大きくするなどの方法が採用されてきた。しかるに、単に繊維径を細くするだけでは、低周波から高周波にかけて広くかつ良好な吸音特性は十分には得られず、形態安定性も損なわれるという問題があった。他方、単に目付けを大きくするだけでは、軽量性が損なわれるという問題があった。 Conventionally, glass wool, urethane foam, polyester fiber, and high-melting thermoplastic fiber and low-melting thermoplastic fiber are used as sound absorbing and sound insulating materials for vehicles, houses, and highways (see, for example, Patent Document 1). Many sound absorbing materials using various fibers have been proposed. The properties required for such a sound absorbing material include sound absorbing properties, light weight, and form stability. In particular, in sound absorption, wide and good sound absorption characteristics are required from low to high frequencies. Conventionally, methods for increasing the sound absorbing property of the sound absorbing material, such as reducing the fiber diameter or increasing the basis weight, have been employed. However, if the fiber diameter is simply reduced, a wide and good sound absorption characteristic from low frequency to high frequency cannot be obtained sufficiently, and the form stability is also impaired. On the other hand, there is a problem in that lightness is impaired simply by increasing the basis weight.
また、近年、自動車性能の高度化・乗心地の快適さを追求する動きが急速に高まって来ており、中でも自動車エンジンの高性能化は目覚しいものがある。他方、エンジンルームの高温化、騒音の拡大、難燃規制の強化等大型自動車を中心として問題が健在化しつつある。従来、エンジンの騒音を低減するためボンネット裏に難燃化したポリプロピレン繊維あるいはポリエチレンテレフタレート繊維の不織布やガラス繊維マットが吸音材として用いられていたが、エンジンルームの高温化が進むに従い、これら素材の耐熱・難燃性は限度に達しつつある。吸音材の耐熱・難燃性向上技術として、無機繊維質を結合剤にて結着させる方法（特許文献２）などが提案されている。しかしながら、無機質を通常の結合剤にて結着するには無機質の脱落の問題などで配合量に限界があること、また、無機質が吸音材表面に存在することにより音の反射割合が高くなり、良質な吸音材を得ることは困難であった。 In recent years, there has been a rapid increase in the pursuit of sophistication of automobile performance and comfort of riding, and in particular, the performance improvement of automobile engines is remarkable. On the other hand, problems are becoming more prevalent, especially in large vehicles, such as high engine room temperatures, increased noise, and stricter flame retardant regulations. Conventionally, non-woven fabrics or glass fiber mats made of flame-retardant polypropylene fiber or polyethylene terephthalate fiber have been used as sound absorbing material on the back of the bonnet to reduce engine noise. Heat resistance and flame retardancy are reaching their limits. As a technique for improving the heat resistance and flame retardancy of a sound absorbing material, a method of binding an inorganic fiber with a binder (Patent Document 2) has been proposed. However, in order to bind the inorganic material with a normal binder, there is a limit to the amount of blending due to the problem of the removal of the inorganic material, etc., and because the inorganic material is present on the surface of the sound absorbing material, the sound reflection ratio is increased, It was difficult to obtain a good sound absorbing material.
本発明の目的は、耐熱性・難燃性に優れた吸音材を提供することにある。 An object of the present invention is to provide a sound-absorbing material excellent in heat resistance and flame retardancy.
本発明は、耐熱性を向上するために無機微粒子を添加した吸音性のシート材を作製するにあたり、音の反射を抑制するため無機微粒子の表面を非晶質含水フィブリッドにて覆うことを特徴とする。
すなわち、本発明は、パラ型全芳香族ポリアミドおよび／またはメタ型全芳香族ポリアミドからなる高分子重合体をＮ−メチル−２−ピロリドン、Ｎ，Ｎ’−ジメチルホルムアミド、Ｎ，Ｎ’−ジメチルアセトアミド、またはテトラメチルウレアおよびこれらの混合物から選択される極性アミド溶媒に溶解した溶液に上記高分子重合体に対して、１０〜９０重量％となるよう無機微粒子を添加した混合液を水系凝固液に導入して得られる無機微粒子を内包した非晶質含水成形物からなる有機繊維フィブリッド、該有機繊維フィブリッドからなるシート材、および該シート材を配した吸音用構造材である。
The present invention is characterized in that in producing a sound-absorbing sheet material to which inorganic fine particles are added in order to improve heat resistance, the surface of the inorganic fine particles is covered with amorphous water-containing fibrids in order to suppress sound reflection. To do.
That is, the present invention relates to a polymer comprising a para-type wholly aromatic polyamide and / or a meta-type wholly aromatic polyamide as N-methyl-2-pyrrolidone, N, N′-dimethylformamide, N, N′-dimethyl. A mixture obtained by adding inorganic fine particles to a solution dissolved in a polar amide solvent selected from acetamide or tetramethylurea and a mixture thereof in an amount of 10 to 90% by weight with respect to the polymer is an aqueous coagulation solution. An organic fiber fibrid composed of an amorphous water-containing molded article encapsulating inorganic fine particles obtained by introducing into the above, a sheet material composed of the organic fiber fibrid, and a sound absorbing structural material provided with the sheet material.
本発明によれば、耐熱性・難燃性に優れた吸音材を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the sound-absorbing material excellent in heat resistance and a flame retardance can be provided.
本発明の無機微粒子を内包した非晶質含水構造物からなる有機繊維フィブリッドに用いられるポリマー（高分子重合体）としては、ポリ−ｐ−フェニレンテレフタルアミドに代表されるパラ型全芳香族ポリアミドや、その共重合体、メタ型全芳香族ポリアミド、ポリ−ｐ−フェニレンベンゾビスオキサゾール（ＰＢＯ）ホモポリマーなど、ポリマーの種類や、ポリマーの構造や重合度などは特に限定されるものではなく、ポリマー自身の耐熱性や製造工程などを考慮するとパラ型全芳香族ポリアミドやメタ型全芳香族ポリアミドが好ましく、最も好ましくはパラ型全芳香族ポリアミドである。 Examples of the polymer (polymer) used for the organic fiber fibrid composed of the amorphous water-containing structure encapsulating the inorganic fine particles of the present invention include para-type wholly aromatic polyamides represented by poly-p-phenylene terephthalamide, , Its copolymer, meta-type wholly aromatic polyamide, poly-p-phenylenebenzobisoxazole (PBO) homopolymer, and the like, the type of polymer, the structure and degree of polymerization of the polymer are not particularly limited, and the polymer In view of its own heat resistance and production process, para-type wholly aromatic polyamides and meta-type wholly aromatic polyamides are preferred, and para-type wholly aromatic polyamides are most preferred.
また、本発明の有機繊維フィブリッドの製造に用いられる溶媒としては、Ｎ−メチル−２−ピロリドン、Ｎ，Ｎ’−ジメチルホルムアミド、Ｎ，Ｎ’−ジメチルアセトアミド、またはテトラメチルウレアおよびこれらの混合物から選択される極性アミド溶媒が挙げられる。
極性アミド溶媒の使用量は、高分子重合体の濃度が好ましくは２〜２０重量％、さらに好ましくは4〜１０重量％となる量である。
The solvent used in the production of the organic fiber fibrids of the present invention includes N-methyl-2-pyrrolidone, N, N′-dimethylformamide, N, N′-dimethylacetamide, tetramethylurea and mixtures thereof. Examples include selected polar amide solvents.
The amount of the polar amide solvent used is such that the concentration of the polymer is preferably 2 to 20% by weight, more preferably 4 to 10% by weight.
さらに、本発明の有機繊維フィブリッドに用いられる無機微粒子とは、耐熱・難燃性に優れたものであればいかようにも使用できるが、クレイ、タルク、硫酸バリウム、カオリン、シリカ、ウォラストナイト、オスモス・雲母などが使用できる。
無機微粒子の粒子径は、２０μｍ以下のものが好ましく、さらに好ましくは５μｍ以下である。２０μｍを超えると、パルプへの内包性が悪くなるため、吸音性を阻害する。
また、無機微粒子は、その比表面積が２g／ｍ２以上、かつ７００℃にて５時間焼結した際の重量減少が１０％以下である。
無機微粒子の添加量は、高分子重合体に対して、１０重量％から９０重量％の範囲である。１０重量％未満では、耐熱・難燃性を発現しにくく、一方９０重量％を超えると、非晶質含水フィブリッド内に無機微粒子を内包できず、吸音性が悪くなるとともに、粉落ちなどの原因となる。
Furthermore, the inorganic fine particles used in the organic fiber fibrids of the present invention can be used in any way as long as they have excellent heat resistance and flame retardancy. Clay, talc, barium sulfate, kaolin, silica, wollastonite , Osmos, mica, etc. can be used.
The particle diameter of the inorganic fine particles is preferably 20 μm or less, more preferably 5 μm or less. If it exceeds 20 μm, the sound-absorbing property will be hindered because the inclusion in the pulp is deteriorated.
The inorganic fine particles have a specific surface area of 2 g / m 2 or more and a weight loss of 10% or less when sintered at 700 ° C. for 5 hours.
The addition amount of the inorganic fine particles is in the range of 10% by weight to 90% by weight with respect to the polymer. If it is less than 10% by weight, it is difficult to develop heat resistance and flame retardancy. On the other hand, if it exceeds 90% by weight, inorganic fine particles cannot be encapsulated in the amorphous hydrous fibrids, resulting in poor sound absorption and causes of powder falling off. It becomes.
本発明の無機微粒子を内包した非晶質含水成形体からなる有機繊維フィブリッドは、例えば、例えば、ＷＯ ２００４／０９９４７６ Ａ１〔特表２００６−５２５３９１号公報〕、特公昭３５−１１８５１号公報、特公昭３７−５７３２号公報などに記載されているような、有機系高分子重合体溶液を、該高分子重合体溶液の凝固液と剪断力とが存在する系において混合するなどの方法より作製される、微小のフィブリルを有する薄葉状、鱗片状の小片、ランダムにフィブリル化した微小短繊維、または粒状の粒子状物を指す。ここで非晶質とは、一般に水素結合に基づく結晶構造を形成する前の構造物を指す。さらに非結晶構造中に水分が含まれたものを非晶質含水成形物と総称する。一般にポリマーは凝固後、乾燥や延伸することにより結晶化が進行するが、凝固ポリマー中にある程度の水を含むことによりその結晶化が抑制され、それゆえ該非晶質含水フィブリッドの結晶化度は含水率とある程度相関しているといえる。一概には言えないが、含水率が高いほど結晶化度は低く、含水率が低いほど結晶化度は高いと推定される。低結晶化度であるほど柔軟であり、かつ他の繊維材料との絡み合いにおいてバインダー的な特性を有するものとなり、乾燥プレス工程で結晶化が進むことにより、耐熱性のある高強度バインダーとなる。
一旦乾燥工程等を経て該非晶質含水フィブリッドの水が除去された場合、ポリマーの結晶化が進行することにより、再びポリマー中へ大量の水が存在することが困難となり、その結果、本発明で期待されるような、バインダー的な特性は示せず、高強度が発現しないため好ましくない。
Organic fiber fibrids made of an amorphous water-containing molded article encapsulating inorganic fine particles of the present invention include, for example, WO 2004/099476 A1 (Japanese Patent Publication No. 2006-525391), Japanese Patent Publication No. 35-11851, Japanese Patent Publication No. Sho. It is prepared by a method such as mixing an organic polymer solution in a system in which a coagulating solution and a shearing force of the polymer solution are present, as described in JP-A-37-5732. , Refers to thin-leafed, flaky small pieces having small fibrils, short fibers randomly fibrillated, or granular particles. Here, the term “amorphous” generally refers to a structure before a crystal structure based on hydrogen bonds is formed. Further, a material in which moisture is contained in an amorphous structure is collectively referred to as an amorphous water-containing molded product. In general, crystallization proceeds by drying or stretching after solidification of the polymer, but the crystallization is suppressed by containing a certain amount of water in the solidified polymer. It can be said that there is some correlation with the rate. Although it cannot be generally stated, it is estimated that the higher the water content, the lower the crystallinity, and the lower the water content, the higher the crystallinity. The lower the degree of crystallinity, the more flexible and the binder property in the entanglement with other fiber materials, and the crystallization proceeds in the drying press step, whereby a heat-resistant high-strength binder is obtained.
Once the water of the amorphous hydrous fibrid is removed through a drying process or the like, it becomes difficult for a large amount of water to exist again in the polymer due to the progress of crystallization of the polymer. As expected, the binder-like characteristics cannot be shown, and high strength is not exhibited.
以上により、該非晶質含水フィブリッドは一般には有機高分子重合体溶液を水系凝固液に導入後、急激な剪断力をかけて微小なフィブリッドとした後、水洗後／又は水洗することなく、かつ乾燥することなくして得ることが好ましい。また、非晶質含水フィブリッドとしては、有機系高分子重合体溶液を、水系凝固液で凝固して作製された非晶質含水成形物を湿潤状態で粘状叩解用リファイナリーやビーターを使用して更にフィブリル化したものを乾燥工程等を経ることなく回収されたものでも良い。
さらに、非晶質含水フィブリッド中に水分が存在することにより、ポリマーの結晶化が抑制されてポリマー自体があまり剛直にならずに柔軟であり、この状態で抄造等によりビーターシートガスケットの基となるシート状物を得た後、乾燥や熱プレスを行った場合、シート状物中の非晶質含水成形体有機繊維フィブリッドから水が除去されてポリマーの結晶化が進行し、且つその過程で平滑に変形するために、その結果として得られた吸音用シート材に高強度が発現するという効果も考えられる。
As described above, the amorphous water-containing fibrid is generally dried after the organic polymer solution is introduced into the water-based coagulation liquid and then subjected to a rapid shearing force to form a fine fibrid, and then washed with water and / or without washing with water. It is preferable to obtain without doing. In addition, as the amorphous hydrous fibrid, an amorphous hydrous molded product prepared by coagulating an organic polymer solution with an aqueous coagulating liquid is used in a wet state using a refiner or beater for viscous beating. Furthermore, what was collect | recovered without passing through a drying process etc. may be sufficient as what was fibrillated.
Furthermore, the presence of moisture in the amorphous water-containing fibrid suppresses the crystallization of the polymer, so that the polymer itself is not stiff and is flexible and becomes a basis for the beater sheet gasket by papermaking or the like in this state. When drying or hot pressing is carried out after obtaining a sheet-like material, water is removed from the amorphous water-containing molded organic fiber fibrids in the sheet-like material, and the crystallization of the polymer proceeds, and in the process smooth In order to deform | transform into this, the effect that high intensity | strength expresses in the sheet material for sound absorption obtained as a result is also considered.
以上のことから、非晶質含水フィブリッドの水分率としては、１０〜９９重量％であることが好ましく、１０重量％未満では結晶化度が高くなり、本発明の高強度は得られない。一方、９９重量％を超えると、水分が殆んどで効率が悪くなり好ましくない。好ましくは２０重量％以上、最も好ましくは５０重量％以上である。 From the above, the moisture content of the amorphous hydrated fibrid is preferably 10 to 99% by weight, and if it is less than 10% by weight, the degree of crystallinity becomes high and the high strength of the present invention cannot be obtained. On the other hand, if it exceeds 99% by weight, the water content is almost undesirably reduced. Preferably it is 20 weight% or more, Most preferably, it is 50 weight% or more.
次に、本発明のシート材は、以上の有機繊維フィブリッドを用いた吸音シートである。
本発明におけるシート材（吸音シート）には、無機微粒子を内包した非晶質含水成形体からなる有機繊維フィブリッドのほかに任意の繊維材料を併用することが出来る。繊維材料を併用することにより、シート材の強度が高まるほか、シート製造時の濾水時間が短くなり、生産性向上に繋がる。
この繊維材料としては、パラ型全芳香族ポリアミド繊維、アクリル繊維、ポリ−ｐ−フェニレンベンゾビスオキサゾール繊維、セルロース繊維、ポリプロピレン繊維、ポリエチレン繊維、芳香族ポリエステル繊維などの有機繊維の短繊維や高度にフィブリル化したパルプ状繊維、好ましくはパラ型全芳香族ポリアミド繊維の高度にフィブリル化したアラミドパルプが挙げられる。また、単一または複数種組み合わせて用いることができ、その種類や組合せ、配合比率等は特に限定されるものではない。
Next, the sheet material of the present invention is a sound-absorbing sheet using the above organic fiber fibrids.
In the sheet material (sound-absorbing sheet) in the present invention, any fiber material can be used in addition to the organic fiber fibrid made of an amorphous water-containing molded body encapsulating inorganic fine particles. By using the fiber material in combination, the strength of the sheet material is increased and the drainage time at the time of sheet production is shortened, leading to an improvement in productivity.
These fiber materials include para-type wholly aromatic polyamide fibers, acrylic fibers, poly-p-phenylene benzobisoxazole fibers, cellulose fibers, polypropylene fibers, polyethylene fibers, aromatic polyester fibers, and other organic fiber short fibers. Mention may be made of fibrillated pulp fibers, preferably highly fibrillated aramid pulp of para-type wholly aromatic polyamide fibers. Moreover, it can be used combining single or multiple types, The kind, combination, compounding ratio, etc. are not specifically limited.
シート材における本発明の有機繊維フィブリッドの配合量としては、２０〜１００ 重量％、好ましくは３０〜１００ 重量％、さらに好ましくは４０〜１００重量％
である。配合量が２０重量％未満の場合、配合量が少なすぎるために、本発明の有機繊維フィブリッドを添加することによる明確な耐熱・難燃性の向上効果は得られない。
As a compounding quantity of the organic fiber fibrid of this invention in a sheet | seat material, 20 to 100 weight%, Preferably it is 30 to 100 weight%, More preferably, it is 40 to 100 weight%
It is. When the blending amount is less than 20% by weight, the blending amount is too small, so that it is not possible to obtain a clear effect of improving heat resistance and flame retardancy by adding the organic fiber fibrid of the present invention.
本発明におけるシート材（吸音材シート）の製造工程として、まず原料のスラリーを調製する。このスラリーの水への投入順序等に特に規定はなく、繊維材料や有機繊維フィブリッド（非晶質含水フィブリッド）、必要に応じて分散剤などを投入し、例えばナイアガラビーターやディスクリファイナーなどの公知の叩解機を用いることができる。なお、叩解により形状が変わるなどの支障がある材料の場合は、繊維材料等を予め叩解した後に添加しても特に差し支えない。
混合は、パルパーなどの公知のミキサーを用いることができる。これらの工程で、混合や叩解の際、気泡の発生を抑制する目的で、一般の抄造の際に用いられる公知の消泡剤を用いることができる。
As a manufacturing process of the sheet material (sound absorbing material sheet) in the present invention, first, a raw material slurry is prepared. There is no particular restriction on the order of adding the slurry into water, and fiber materials, organic fiber fibrids (amorphous water-containing fibrids), a dispersing agent, etc., are added as necessary. For example, Niagara beaters and disc refiners are known. A beater can be used. In addition, in the case of a material having a hindrance such as a shape change by beating, there is no problem even if a fiber material or the like is added after beating in advance.
For the mixing, a known mixer such as a pulper can be used. In these steps, a known antifoaming agent used in general papermaking can be used for the purpose of suppressing the generation of bubbles during mixing and beating.
次に、このスラリーを抄造し、シート状物を得る。抄造は、長網抄紙機や丸網抄紙機といった連続抄紙機や、ＴＡＰＰＩ箱型抄紙機など公知の抄造装置を用いて抄造することができ、また抄造後、連続抄紙機の場合はそのまま乾燥工程を経てローラーへ巻き取る。箱型抄紙機などのバッチ式での抄紙機の場合は、抄造後の紙を金枠等に保持し、乾燥機などで乾燥する。乾燥温度は、水が十分に除去できる温度であれば特に制限は無いが、原料の劣化等を考慮すると、８０℃〜１５０℃が好ましいが、この温度に限定されるものではない。その後、必要に応じて熱プレスを行う。熱プレスの圧力や温度は、特に限定されるものではなく、原料の種類や最終製品の厚みなどにより適宜調節することができ、カレンダーなどの公知の熱プレス機を用いることができる。なお、乾燥と熱プレスを同時に行っても特に差し支えは無い。この乾燥および熱プレス工程において、該非晶質含水フィブリッドは、ポリマー中から水が除去され、シートの平滑性や高強度が発現するものと考えられる。さらに必要に応じて任意の大きさや形状に裁断し、吸音材シートを得る。 Next, the slurry is made to obtain a sheet. Paper making can be carried out using a continuous paper machine such as a long paper machine or a round paper machine, or a known paper making machine such as a TAPPI box paper machine. After that, take it up on a roller. In the case of a batch type paper machine such as a box type paper machine, the paper after the paper making is held on a metal frame or the like and dried with a dryer or the like. The drying temperature is not particularly limited as long as it is a temperature at which water can be sufficiently removed. However, considering the deterioration of the raw material and the like, it is preferably 80 ° C. to 150 ° C., but is not limited to this temperature. Thereafter, hot pressing is performed as necessary. The pressure and temperature of the hot press are not particularly limited and can be appropriately adjusted depending on the type of raw material and the thickness of the final product, and a known hot press such as a calendar can be used. Note that there is no particular problem even if drying and hot pressing are performed simultaneously. In this drying and hot pressing process, it is considered that the amorphous hydrous fibrid exhibits water smoothness and high strength by removing water from the polymer. Furthermore, it cuts into arbitrary magnitude | sizes and shapes as needed, and obtains a sound-absorbing material sheet.
以上のような本発明のシート材（吸音材シート）は、耐熱性ボード上の表面に単独で／または積層して張り合わせるなどすることにより、車輌内装、住宅、高速道路壁面などの吸音用構造材として用いられる。 The sheet material (sound-absorbing material sheet) of the present invention as described above is a structure for sound absorption of vehicle interiors, houses, highway wall surfaces, etc. by being attached to the surface of the heat-resistant board alone or / or laminated. Used as a material.
以下に本発明を実施例に基づき具体的に説明するが、これらに限定されるものではない。
なお、実施例においては下記の測定方法に従って各種の物性測定を実施した。
１）長さ加重平均繊維長
パルプエキスパート試験機により計測、平均繊維長を測定した。
２）水分率（重量％）
ＪＩＳ Ｌ１０１３に準拠して測定し下記の式で算出した。
水分率（重量％）＝〔（Ｗ０−Ｗ）／Ｗ０〕×１００
ここで、Ｗ０は乾燥前重量、Ｗは乾燥後重量である。
３）厚さ
寸法測定器：ＳＴ−０２２ゲージスタンド（(株)小野測器製）を用いて測定した。
４）難燃性
限界酸素指数(ＬＯＩ値) ＪＩＳ Ｌ１０９１ Ｅ法に準拠した測定法にて測定を実施した。
５）吸音性
ＪＩＳ Ａ１４０５に基づき、管内法による建築材料の垂直入射吸音率を１／３オクターブ中心周波数１０００―６３００Ｈｚで測定した。ｎ数５でその平均値を算出した。なお、本発明の吸音シート材が音源側に位置するよう配して測定をおこなった。
ブランク用基材として、メタ型全芳香族ポリアミド（帝人テクノプロダクツ社製、コーネックス（ポリメタフェニレンイソフタルアミド）のフェルト 目付４５g／ｍ２を使用して測定した。）
６）シートからの粉落ち
得られた吸音シート材を黒色台紙の上高さ３cmの位置にて、シート材の両端を把持し、１分間手動にて浸透させた後の、黒色台紙上の粉体量を目視にて観察した。
The present invention will be specifically described below based on examples, but is not limited thereto.
In the examples, various physical properties were measured according to the following measurement methods.
1) Length-weighted average fiber length Measured by a pulp expert tester, and the average fiber length was measured.
2) Moisture content (wt%)
It measured based on JISL1013 and computed with the following formula.
Moisture content (% by weight) = [(W0−W) / W0] × 100
Here, W0 is the weight before drying, and W is the weight after drying.
3) Thickness Measured using a dimension measuring device: ST-022 gauge stand (manufactured by Ono Sokki Co., Ltd.).
4) Flame retardancy Limiting oxygen index (LOI value) Measurement was performed by a measurement method based on JIS L1091 E method.
5) Sound absorption Based on JIS A1405, the normal incident sound absorption coefficient of the building material by the pipe inner method was measured at a 1/3 octave center frequency of 1000-6300 Hz. The average value was calculated with n number of 5. The measurement was performed with the sound-absorbing sheet material of the present invention placed on the sound source side.
Meta-type wholly aromatic polyamide (measured by using 45 g / m 2 felt weight of Conex (polymetaphenylene isophthalamide) manufactured by Teijin Techno Products Co., Ltd.) as a blank substrate.
6) Powder fall off from the sheet The powder on the black mount after the sound-absorbing sheet material obtained was gripped at both ends of the black mount at a position 3 cm above and manually infiltrated for 1 minute. The body weight was observed visually.
［実施例１〜６］
「ＷＯ ２００４／０９９４７６ Ａ１」の実施例１に記載の手順に従い、ポリ−ｐ−フェニレンテレフタルアミドの非晶質含水フィブリッドを作製した。その際、非晶質含水フィブリッドの４０〜８０重量％となるようカオリンを添加し、上記手順にてカオリンを内包した非晶質含水フィブリッド（有機繊維フィブリッド）を得た。得られた非晶質含水フィブリッドの長さ加重平均繊維長、水分率を表１〜２に示す。
次に、その他の繊維材料として、ポリ−ｐ−フェニレンテレフタルアミド繊維を高度にフィブリル化させたアラミドパルプ（商品名「トワロン１０９４」、帝人トワロン製、長さ加重平均繊維長：０．９１ｍｍ、以下アラミドパルプと略称）を、それぞれ表１〜２のような組成で、吸音シート材を次のような工程を経て作製した。
まず、ポリ−ｐ−フェニレンテレフタルアミドの非晶質含水フィブリッドとアラミドパを水に分散させ、パルパーにて混合した。そして、抄紙機を用いて抄造した後、カレンダーを用いて乾燥・熱プレスを行って吸音シート材を得た。得られた吸音シート材の物性を同じく表１〜２に示す。
[Examples 1 to 6]
An amorphous water-containing fibrid of poly-p-phenylene terephthalamide was prepared according to the procedure described in Example 1 of “WO 2004/099476 A1”. At that time, kaolin was added so as to be 40 to 80% by weight of the amorphous water-containing fibrid, and amorphous water-containing fibrid (organic fiber fibrid) containing kaolin was obtained by the above procedure. Tables 1 and 2 show the length-weighted average fiber length and moisture content of the obtained amorphous water-containing fibrids.
Next, as other fiber materials, aramid pulp (trade name “Twaron 1094”, made by Teijin Twaron, length-weighted average fiber length: 0.91 mm, below, highly fibrillated poly-p-phenylene terephthalamide fiber Abbreviated as aramid pulp), each having a composition as shown in Tables 1 and 2, and a sound-absorbing sheet material was produced through the following steps.
First, an amorphous water-containing fibrid of poly-p-phenylene terephthalamide and aramidpa were dispersed in water and mixed with a pulper. Then, after making paper using a paper machine, drying and hot pressing were performed using a calendar to obtain a sound absorbing sheet material. The physical properties of the obtained sound absorbing sheet material are also shown in Tables 1-2.
［比較例１］
非晶質含水フィブリッドを作製する際にカオリンを添加しなかった他は、実施例１と同様に非晶質含水フィブリッドを作製し、評価した。結果を表２に示す。
[Comparative Example 1]
An amorphous water-containing fibrid was prepared and evaluated in the same manner as in Example 1 except that kaolin was not added when preparing the amorphous water-containing fibrid. The results are shown in Table 2.
［比較例２］
非晶質含水フィブリッドの代わりにアラミドパルプとカオリンを表１に示す割合で抄紙時に配合してシート材を作製し、評価した。結果を表２に示す。
[Comparative Example 2]
A sheet material was prepared and evaluated by blending aramid pulp and kaolin in the ratio shown in Table 1 at the time of papermaking instead of the amorphous water-containing fibrid. The results are shown in Table 2.
本発明の有機繊維フィブリッドを用いたシート材は、吸音性、耐熱性に優れ、自動車などの車輌や住宅あるいは高速道路などの吸音、遮音材として有用である。 The sheet material using the organic fiber fibrids of the present invention is excellent in sound absorption and heat resistance, and is useful as a sound absorption and sound insulation material for vehicles such as automobiles, houses, and highways.
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| CN113668089B (en) * | 2020-05-13 | 2023-07-28 | 中蓝晨光化工有限公司 | Preparation method of aromatic polyamide membranous fibrid |
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