JP6236666B2 - Brush containing monofilament containing polyamide-410 - Google Patents
Brush containing monofilament containing polyamide-410 Download PDFInfo
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- JP6236666B2 JP6236666B2 JP2014535121A JP2014535121A JP6236666B2 JP 6236666 B2 JP6236666 B2 JP 6236666B2 JP 2014535121 A JP2014535121 A JP 2014535121A JP 2014535121 A JP2014535121 A JP 2014535121A JP 6236666 B2 JP6236666 B2 JP 6236666B2
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- polyamide
- monofilament
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- monofilaments
- wet
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Links
- 229920006394 polyamide 410 Polymers 0.000 title claims description 16
- 229920002647 polyamide Polymers 0.000 claims description 21
- 239000004952 Polyamide Substances 0.000 claims description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 238000011084 recovery Methods 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 229920000305 Nylon 6,10 Polymers 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 229920000572 Nylon 6/12 Polymers 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 230000001680 brushing effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000005700 Putrescine Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- PFBWBEXCUGKYKO-UHFFFAOYSA-N ethene;n-octadecyloctadecan-1-amine Chemical compound C=C.CCCCCCCCCCCCCCCCCCNCCCCCCCCCCCCCCCCCC PFBWBEXCUGKYKO-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
-
- A—HUMAN NECESSITIES
- A46—BRUSHWARE
- A46D—MANUFACTURE OF BRUSHES
- A46D1/00—Bristles; Selection of materials for bristles
- A46D1/02—Bristles details
- A46D1/0207—Bristles characterised by the choice of material, e.g. metal
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/96—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from other synthetic polymers
Description
本発明は、ポリアミド含有モノフィラメントを含むブラシ、特にこれらのモノフィラメントを含む歯ブラシに関する。 The present invention relates to brushes comprising polyamide-containing monofilaments, and in particular to toothbrushes comprising these monofilaments.
ナイロンとしても知られているポリアミドを含有するモノフィラメントを含むブラシは知られており、例えば英国特許出願公開第８００６１０Ａ号明細書に記載されている。英国特許出願公開第８００６１０Ａ号明細書には、ナイロンモノフィラメントを含むブラシが記載されており、この用途のためのナイロン−６６およびナイロン−６１０に言及している。ブラシ、特に歯ブラシでの用途では、所謂「湿潤時曲げ回復性」がモノフィラメントにとって必須の特性である。「湿潤時曲げ回復性」とは、濡れている間の変形後、元の形に戻る材料の能力のことをいう。湿潤時曲げ回復性が高いということは、モノフィラメントが容易に元の形に戻ることを意味し、例えば、これらのモノフィラメントを含むブラシをより長期間使用することが可能になる。 Brushes comprising monofilaments containing polyamide, also known as nylon, are known and are described, for example, in GB-A 800610A. GB 800610A describes a brush comprising nylon monofilaments and refers to nylon-66 and nylon-610 for this application. For applications in brushes, especially toothbrushes, so-called “bend recovery when wet” is an essential property for monofilaments. “Bend recovery when wet” refers to the ability of a material to return to its original shape after deformation while wet. The high bend recovery when wet means that the monofilament easily returns to its original shape, and for example, a brush containing these monofilaments can be used for a longer period of time.
したがって、本発明の目的は、高い湿潤時曲げ回復性を示す、ポリアミドからなるモノフィラメントを含むブラシを提供することにある。 Accordingly, an object of the present invention is to provide a brush including a monofilament made of polyamide and exhibiting high bend recovery when wet.
驚いたことに、この目的は、ポリアミド−４１０を含むポリアミドを含有するモノフィラメントを含むブラシを提供することにより達成された。ＰＡ−４１０を含むポリアミドを含有するモノフィラメントは、国際公開第００／０９５８６号パンフレットで知られている。しかしながら、国際公開第００／０９５８６号パンフレットには、湿潤状態でのフィラメントの特性について記載されておらず、またそれらをブラシで使用することについて記載されていない。 Surprisingly, this object has been achieved by providing a brush comprising monofilaments containing polyamide, including polyamide-410. Monofilaments containing polyamides including PA-410 are known from WO 00/09586. However, WO 00/09586 does not describe the properties of the filaments in the wet state and does not describe their use in brushes.
［ポリアミド−４１０］
本明細書では、ポリアミド−４１０は、１０個の炭素原子を有するジカルボン酸と４個の炭素原子を有するジアミンから誘導されるモノマー単位を含むポリアミドであると理解される。ジカルボン酸としては、１，１０デカン二酸の使用が好ましい。ジアミンとしては、１，４−ブタンジアミンの使用が好ましい。ＰＡ−４１０は、さらに他のモノマー単位、例えば、１０個未満の炭素原子を有するジカルボン酸、または４個超の炭素原子を有するジアミンを、ポリアミド全量に対し最大３０重量％まで含んでもよい。本発明のブラシに使用されるモノフィラメントに使用されるＰＡ−４１０は、カルボキシル基間に１０個の炭素原子からなる原子鎖を有するジカルボン酸と、４個の炭素原子を有するジアミンを、ポリアミドの全量に対して少なくとも８０重量％含むことが好ましく、ポリアミドの全量に対して少なくとも９０重量％含むことがより好ましく、ポリアミドの全量に対して少なくとも９５重量％含むことがより一層好ましく、少なくとも９９重量％含むことがより一層好ましく、ポリアミドの全量に対して少なくとも９９．９重量％含むことが最も好ましい。
[Polyamide-410]
As used herein, polyamide-410 is understood to be a polyamide comprising monomer units derived from a dicarboxylic acid having 10 carbon atoms and a diamine having 4 carbon atoms. As the dicarboxylic acid, use of 1,10 decanedioic acid is preferred. As the diamine, 1,4-butanediamine is preferably used. PA-410 may further contain other monomer units, for example, dicarboxylic acids having less than 10 carbon atoms, or diamines having more than 4 carbon atoms, up to 30% by weight based on the total amount of polyamide. PA-410 used for the monofilament used for the brush of the present invention is a dicarboxylic acid having an atomic chain consisting of 10 carbon atoms between carboxyl groups and a diamine having 4 carbon atoms, and the total amount of polyamide. Preferably at least 80% by weight, more preferably at least 90% by weight, more preferably at least 95% by weight, more preferably at least 99% by weight, based on the total amount of polyamide. It is even more preferred that it comprises at least 99.9% by weight based on the total amount of polyamide.
本発明のブラシで使用するモノフィラメントは、ポリアミドの全量に対して、好ましくは少なくとも４０重量％のポリアミド−４１０、より好ましくは少なくとも５０重量％のポリアミド−４１０、最も好ましくは少なくとも６０重量％のポリアミド−４１０を含むポリアミドから製造される。ポリアミドは実質的にＰＡ−４１０からなることが最も好ましい。好ましい実施形態では、ポリアミド含有モノフィラメントは他のポリマーを含まない。 The monofilament used in the brush of the invention is preferably at least 40% by weight polyamide-410, more preferably at least 50% by weight polyamide-410, most preferably at least 60% by weight polyamide-based on the total amount of polyamide. Manufactured from polyamide containing 410. Most preferably, the polyamide consists essentially of PA-410. In a preferred embodiment, the polyamide-containing monofilament is free of other polymers.
他の重要な改良点は、ポリアミド−４１０が少なくとも部分的に再生可能資源をベースとし得るため、本発明のモノフィラメントが、もはや完全には化石系炭素をベースとしないことである。モノフィラメントのポリアミドが、たとえ、ほんのわずかのポリアミド−４１０を含有し、そしてまた他ポリマーを含有するにしても、このことは特に有利である。少なくとも部分的に天然資源由来のモノマーをベースとするＰＡ４１０をモノフィラメントに使用することにより、特にモノフィラメント工業、およびその用途では、既に地球温暖化ガスおよびＣＯ２の重要な削減をもたらしている。 Another important improvement is that the monofilaments of the invention are no longer completely based on fossil carbon, since polyamide-410 can be based at least in part on renewable resources. This is particularly advantageous even if the monofilament polyamide contains only a small amount of polyamide-410 and also contains other polymers. The use of at least partially PA410 that the monomers derived from natural resources based on the monofilament, particularly monofilaments industry, and in its application, has already resulted in a significant reduction of greenhouse gases and CO 2.
本発明のブラシに使用するモノフィラメントの他の利点は、湿潤時の剛性保持力が良好なことである。本明細書では、「湿潤時剛性保持力」は、通常、ＩＳＯ５２７１Ａにしたがって、例えば相対湿度０％などの乾燥条件と比較した、高湿下、すなわち相対湿度５０％下で、引張弾性率としてＭＰａの単位で測定される剛性を保持する能力であると理解される。湿潤時の高い剛性保持力を歯ブラシに適用すると、歯磨きは湿潤状態で行われるものであるため、快適な歯磨き感が得られる。このように、モノフィラメントは、非常に良好な湿潤時曲げ回復性と良好な湿潤時剛性保持力とを併せ持つとき、歯ブラシの毛として有利に使用できる。 Another advantage of the monofilament used in the brush of the present invention is that it has good stiffness retention when wet. In the present specification, “rigid retention force when wet” is generally expressed as MPa in terms of tensile elastic modulus under high humidity, that is, under 50% relative humidity, according to ISO 5271A, for example, compared to drying conditions such as 0% relative humidity. It is understood that this is the ability to retain stiffness measured in units. When high rigidity retention force when wet is applied to the toothbrush, tooth brushing is performed in a wet state, so that a comfortable tooth brushing feeling can be obtained. Thus, the monofilament can be advantageously used as toothbrush bristles when it has both a very good wet bending recovery and a good wet stiffness retention.
ポリアミド−４１０は、例えば、実施例に記載するようにして調製することができる。モノフィラメントは、ポリアミド−４１０の粘度数（ＶＮ）が少なくとも１００ｍｌ／ｇであることが好ましく、少なくとも１１０ｍｌ／ｇであることがより好ましく、少なくとも１２０ｍｌ／ｇであることがより一層好ましく、少なくとも１４０ｍｌ／ｇであることが最も好ましい。粘度が高いほど、モノフィラメントの機械的特性が改善されるであろう。粘度数は高くとも２００ｍｌ／ｇであることが好ましい。粘度数が高すぎると、紡糸機の処理能力が限定される。粘度数は、ＩＳＯ ３０７、２００７年版にしたがい、ギ酸（９０重量％）中、濃度０．００５ｇ／ｍｌで、２５℃で測定される。 Polyamide-410 can be prepared, for example, as described in the examples. The monofilament preferably has a polyamide-410 viscosity number (VN) of at least 100 ml / g, more preferably at least 110 ml / g, even more preferably at least 120 ml / g, at least 140 ml / g. Most preferably. The higher the viscosity, the better the mechanical properties of the monofilament. The viscosity number is preferably at most 200 ml / g. If the viscosity number is too high, the throughput of the spinning machine is limited. The viscosity number is measured at 25 ° C. at a concentration of 0.005 g / ml in formic acid (90% by weight) according to ISO 307, 2007 edition.
［モノフィラメント］
本発明のブラシに使用するモノフィラメントは、１マイクロメートル〜１．５ｍｍの平均直径を有することが好ましい。モノフィラメントは、１５マイクロメートル〜１．２ｍｍの平均直径を有することが好ましい。モノフィラメントは、ポリアミドを溶融させ、その後、ダイスに通して押し出すことにより製造できる。ダイスを出た後、モノフィラメントは急冷浴で冷却されることが好ましい。高品質のモノフィラメントを製造するために、糸を互いに離れた状態に維持することが好ましい。これは、分離ガイドまたは櫛によりなし得る。エアーギャップの長さ、すなわち紡糸板と水表面の距離は、モノフィラメントの表面および機械的特性に影響し得る。モノフィラメントに要求される特性に応じて、少なくとも単段または少なくとも２段の延伸工程を、例えば温浴中、または熱風炉もしくは赤外線加熱炉オーブン中で行うことができる。２段延伸プロセスの第２段は、通常、熱風炉中で行われ、第１段の温度より高い温度が要求される。非常に精密な交差が要求される場合、第１段に水浴を使用することが好ましい。
[Monofilament]
The monofilament used in the brush of the present invention preferably has an average diameter of 1 micrometer to 1.5 mm. The monofilament preferably has an average diameter of 15 micrometers to 1.2 mm. Monofilaments can be made by melting the polyamide and then extruding it through a die. After exiting the die, the monofilament is preferably cooled in a quench bath. In order to produce high quality monofilaments, it is preferred to keep the yarns separated from one another. This can be done with a separation guide or a comb. The length of the air gap, ie the distance between the spinning plate and the water surface, can affect the surface and mechanical properties of the monofilament. Depending on the properties required for the monofilament, at least a single-stage or at least two-stage drawing process can be carried out, for example, in a warm bath, or in a hot or infrared furnace oven. The second stage of the two-stage drawing process is usually performed in a hot stove and requires a temperature higher than the temperature of the first stage. If very precise crossing is required, it is preferable to use a water bath in the first stage.
延伸比および適用する温度は、モノフィラメントの分子の物理的構造に影響する。引張強さ、伸び、弾性率、耐熱性および非反応性染料による染色性などの多くの特性が物理的構造に依存するため、延伸プロセスはモノフィラメントの特性に広く、かつ多様な影響を及ぼす。 The draw ratio and applied temperature affect the physical structure of the monofilament molecule. Since many properties, such as tensile strength, elongation, elastic modulus, heat resistance and dyeability with non-reactive dyes, depend on the physical structure, the drawing process has a wide and varied influence on the properties of the monofilament.
任意選択による第３の工程として、熱安定性、引張強さ、破断伸びおよび染色性などのモノフィラメントの特性は、固定または緩和により所望のレベルに調整することができる。許容される緩和の割合および適用する温度は、最終的に要求される特性に大きく依存する。適切な固定／緩和を達成するには、第３工程におけるモノフィラメントの温度は、延伸過程での温度に少なくとも等しくすべきであり、むしろ通常はそれより高くすべきである。加熱炉の温度設定は、ライン速度、モノフィラメントの直径、炉長および気流速度に大きく依存する。 As an optional third step, the properties of the monofilament such as thermal stability, tensile strength, elongation at break and dyeability can be adjusted to a desired level by fixation or relaxation. The rate of relaxation allowed and the temperature applied will depend greatly on the properties ultimately required. In order to achieve proper fixation / relaxation, the temperature of the monofilament in the third step should be at least equal to the temperature during the stretching process, but rather usually higher. The furnace temperature setting is highly dependent on line speed, monofilament diameter, furnace length and airflow speed.
本発明のブラシに使用するモノフィラメントは、白色の外観を与えるために、二酸化チタンなどの顔料を含むことが好ましい。本発明のモノフィラメントはまた、透明性をより高めるために、エチレンビスステアリルアミン（ＥＢＡ）などの潤滑剤を含んでもよい。 The monofilament used in the brush of the present invention preferably contains a pigment such as titanium dioxide in order to give a white appearance. The monofilament of the present invention may also contain a lubricant such as ethylene bisstearylamine (EBA) to further increase transparency.
モノフィラメントは、毛、好ましくは歯ブラシの毛に有利に使用することができる。このように、本発明はまた、モノフィラメントを含む歯ブラシに関する。歯ブラシは良好な湿潤時曲げ回復性と良好な湿潤時剛性保持力を併せ持つ。これにより、歯ブラシを廃棄する必要が生じるまでに、より長期に亘る使用が可能になる。さらにこれは、より長期間使用できることと、ブラシの少なくとも一部が再生可能資源から作られていることの両方から、ＣＯ２削減においても有利である。 Monofilaments can advantageously be used for bristles, preferably toothbrush bristles. Thus, the present invention also relates to a toothbrush that includes a monofilament. Toothbrushes have both good bend recovery when wet and good stiffness retention when wet. This allows longer term use before the toothbrush needs to be discarded. This is also advantageous in reducing CO 2 because it can be used for a longer period of time and at least a portion of the brush is made from renewable resources.
［実施例］
［ＰＡ−４１０の調製］
不活性な２Ｌのオートクレーブ反応器中で、４１０塩の４５％溶液を調製した。３４８．２ｇの固体１，１０−デカン二酸を加える前に、１，４−ジアミノブタンの６７．５％溶液２３０ｍｌを６５℃で５４０ｍｌの水に加えた。反応器の最大圧力を２ｂａｒＡに設定した。塩溶液を６０分で１５３℃まで加熱した。この過程で、水の濃度が１５３℃で１０％になるよう、過剰の水を蒸留除去した。反応器の圧力を１２ｂａｒＡに設定した。４１０塩溶液を１５分以内に加熱して圧力を１２ｂａｒＡとし、それにより塩溶液を重合させた。溶融ポリマーが得られ、かつ温度が２５０℃に達するまで、１２ｂａｒＡを維持しながら、さらに多くの水を蒸留除去する。２５０℃に達すると、６０分で２６５℃へと加熱しながら、また溶融ポリマーをさらに重合させながら、反応器を１．０２ｂａｒＡまで減圧した。溶融ポリマーをさらに２９０℃に加熱し、１．０２ｂａｒＡで１６時間その温度に維持した。溶融ポリマーの水を少量の窒素流れにより除去した。重縮合段階の終了後、水浴中へ内容物を注いで反応器を空にしてポリマーのストランドを得、これを切断して粒状とした。ＰＡ−４１０ポリマーは、９０％ギ酸中、１７９ｍｌ／ｇの溶液粘度を有していた。
[Example]
[Preparation of PA-410]
A 45% solution of 410 salt was prepared in an inert 2 L autoclave reactor. Before adding 348.2 g of solid 1,10-decanedioic acid, 230 ml of a 67.5% solution of 1,4-diaminobutane was added to 540 ml of water at 65 ° C. The maximum pressure in the reactor was set at 2 barA. The salt solution was heated to 153 ° C. in 60 minutes. During this process, excess water was distilled off so that the concentration of water was 10% at 153 ° C. The reactor pressure was set at 12 barA. The 410 salt solution was heated within 15 minutes to a pressure of 12 barA, thereby polymerizing the salt solution. More water is distilled off while maintaining 12 barA until a molten polymer is obtained and the temperature reaches 250 ° C. Upon reaching 250 ° C., the reactor was depressurized to 1.02 bar A while heating to 265 ° C. in 60 minutes and further polymerizing the molten polymer. The molten polymer was further heated to 290 ° C. and maintained at that temperature at 1.02 bar A for 16 hours. The molten polymer water was removed with a small stream of nitrogen. After completion of the polycondensation stage, the contents were poured into a water bath to empty the reactor to obtain polymer strands which were cut into granules. The PA-410 polymer had a solution viscosity of 179 ml / g in 90% formic acid.
ＰＡ−４１０を２７０℃の温度にして溶融させ、その後、ダイスに通して押し出すことにより、直径０．２ｍｍのモノフィラメントを得た。 PA-410 was melted at a temperature of 270 ° C., and then extruded through a die to obtain a monofilament having a diameter of 0.2 mm.
［測定］
［粘度数（ＶＮ）］
ＩＳＯ ３０７ ２００７年版にしたがい、ＰＡ−４１０試料を０．００５ｇ／ｍｌの濃度でギ酸（９０重量％）に溶解させ、ウベローデ（Ｕｂｅｌｏｈｄｅ）粘度計により、溶媒の流下時間（ｔ０）と溶液の流下時間（ｔ１）を２５℃で測定し、式ＶＮ＝［（ｔ１／ｔ０）−１］×２００ｍｌ／グラムから粘度数を計算することにより、粘度数を求めた。
[Measurement]
[Viscosity number (VN)]
According to ISO 307 2007 edition, PA-410 sample was dissolved in formic acid (90 wt%) at a concentration of 0.005 g / ml, and the solvent flow time (t0) and the solution flow time were measured by Ubelohde viscometer. (T1) was measured at 25 ° C., and the viscosity number was calculated by calculating the viscosity number from the formula VN = [(t1 / t0) −1] × 200 ml / gram.
［ピンチ曲げ回復試験］
所謂、ピンチ穴曲げ回復法により、各種モノフィラメントについて曲げ回復試験を行った。この方法は、各種サイズの金属板の穴を使用する（それぞれ、１．５ｍｍ、２．５ｍｍおよび３．５ｍｍの穴を有する板Ａ、ＢおよびＣ）。以下の手順を用いた。
[Pinch bending recovery test]
A bending recovery test was performed on various monofilaments by a so-called pinch hole bending recovery method. This method uses metal plate holes of various sizes (plates A, B and C with 1.5 mm, 2.5 mm and 3.5 mm holes, respectively). The following procedure was used.
２０±１℃の温度の水にモノフィラメントを１８時間浸漬した。穴の中央にモノフィラメントを置き、モノフィラメントをもつれさせないように、鈍器を用いて穴の中に静かに押し込んだ。モノフィラメントが穴の半径からはみ出さないように位置決めした。 The monofilament was immersed in water at a temperature of 20 ± 1 ° C. for 18 hours. A monofilament was placed in the center of the hole and gently pushed into the hole using a blunt so as not to entangle the monofilament. The monofilament was positioned so as not to protrude from the hole radius.
モノフィラメントを含む金属板を５０±２℃の水に２分間、その後２０±２℃の水に３０秒間浸漬した。板を水から取り出し、モノフィラメントを穴から取り出した。２０±２℃の水を満たしたペトリ皿の中にモノフィラメントを入れた。１５分間の浸漬後、モノフィラメントを取り出し、モノフィラメントが平滑面上に横にして置かれているのを確認しながら、夾角を測定した。 The metal plate containing the monofilament was immersed in water at 50 ± 2 ° C. for 2 minutes and then in water at 20 ± 2 ° C. for 30 seconds. The plate was removed from the water and the monofilament was removed from the hole. The monofilament was placed in a petri dish filled with 20 ± 2 ° C. water. After immersion for 15 minutes, the monofilament was taken out, and the depression angle was measured while confirming that the monofilament was placed on a smooth surface.
回復率を式［１］により算出した。
回復率＝夾角×１００／１８０％ ［式１］
結果を表１に示す。
The recovery rate was calculated by the formula [1].
Recovery rate = depression angle x 100/180% [Formula 1]
The results are shown in Table 1.
驚いたことに、表１は、歯ブラシ用繊維に通常使用されている、特にＰＡ−６１０およびＰＡ−６１２と比べて、ＰＡ−４１０が３つの全ての径で高い回復率を有することを示している。 Surprisingly, Table 1 shows that PA-410 has a high recovery rate in all three diameters, as compared to PA-610 and PA-612, which are commonly used for toothbrush fibers. Yes.
［マンドレル湾曲回復試験］
直径２．５ｍｍの心棒に繊維を接着し、１０回巻き付ける心棒回復試験も行った。この後、心棒に巻いた繊維をその位置のまま室温で１時間放置し、その後心棒から繊維を切り離して、水が入った皿の中で１時間回復させた。％で表される心棒湾曲回復性は、回復期間の最後における繊維の巻き数に対する心棒に巻きつけた巻き数である。結果を表２に示す。
[Mandrel curvature recovery test]
A mandrel recovery test was also conducted in which the fiber was bonded to a mandrel with a diameter of 2.5 mm and wound 10 times. Thereafter, the fiber wound around the mandrel was left at that position at room temperature for 1 hour, and then the fiber was separated from the mandrel and allowed to recover for 1 hour in a dish containing water. The mandrel curvature recovery expressed in% is the number of turns wound on the mandrel relative to the number of turns of fiber at the end of the recovery period. The results are shown in Table 2.
これらの試験はまた、特に、歯ブラシ用繊維に通常使用されているポリアミド−６１０およびポリアミド−６１２と比較して、ＰＡ−４１０からなるモノフィラメントが非常に高い回復性を有することを示している。 These tests also show that monofilaments made of PA-410 have a very high recovery, especially compared to polyamide-610 and polyamide-612, which are commonly used for toothbrush fibers.
ＩＳＯ ５２７ １Ａにしたがって、ＰＡ−４１０板の引張弾性率を測定し、他のポリアミドと比較した。結果を表３に示す。 According to ISO 527 1A, the tensile modulus of the PA-410 plate was measured and compared with other polyamides. The results are shown in Table 3.
ＰＡ−４１０の剛性保持率は、ＰＡ−６およびＰＡ−６６より高いことが示されている。しかしながら、ＰＡ−４１０の本質的により高い剛性のために、湿潤状態でのＰＡ−４１０の剛性もまたＰＡ−６１０およびＰＡ−６１２の剛性より高い。これらのデータは、湿潤時曲げ回復性の結果と併せて、本発明のモノフィラメントが、例えば歯ブラシ用の毛の用途で要求される、これらの特性の最良の組み合わせを与えることを示している。 The stiffness retention of PA-410 has been shown to be higher than PA-6 and PA-66. However, due to the inherently higher stiffness of PA-410, the stiffness of PA-410 in the wet state is also higher than that of PA-610 and PA-612. These data, along with wet bend recovery results, show that the monofilaments of the present invention provide the best combination of these properties required, for example, in bristle applications for toothbrushes.
Claims (6)
前記ポリアミド−４１０の粘度数が１００〜２００ｍｌ／ｇである、ブラシ。 Comprising a monofilament containing polyamide comprising at least 80% by weight of polyamide-410 relative to the total amount of polyamide;
The brush whose viscosity number of the said polyamide-410 is 100-200 ml / g .
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP11185487.3 | 2011-10-17 | ||
| EP11185487 | 2011-10-17 | ||
| PCT/EP2012/070487 WO2013057102A1 (en) | 2011-10-17 | 2012-10-16 | Brush containing mono-filaments containing polyamide-410 |
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| Publication Number | Publication Date |
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| JP2014528338A JP2014528338A (en) | 2014-10-27 |
| JP6236666B2 true JP6236666B2 (en) | 2017-11-29 |
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| JP2014535121A Active JP6236666B2 (en) | 2011-10-17 | 2012-10-16 | Brush containing monofilament containing polyamide-410 |
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| Country | Link |
|---|---|
| US (1) | US20140259487A1 (en) |
| EP (1) | EP2769009B1 (en) |
| JP (1) | JP6236666B2 (en) |
| CN (1) | CN103890248A (en) |
| BR (1) | BR112014009132A8 (en) |
| CA (1) | CA2851766A1 (en) |
| MX (1) | MX2014004568A (en) |
| WO (1) | WO2013057102A1 (en) |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2836516A (en) | 1955-05-02 | 1958-05-27 | Weco Products Company | Method of treating nylon bristles and products produced thereby |
| JPS61231214A (en) * | 1985-04-05 | 1986-10-15 | Toray Monofilament Co Ltd | Polyamide monofilament |
| DE19640726A1 (en) * | 1996-10-02 | 1998-04-23 | Braun Ag | Bristle for a toothbrush |
| JPH10201538A (en) * | 1997-01-20 | 1998-08-04 | Lion Corp | Tooth brush |
| NL1009846C2 (en) * | 1998-08-12 | 2000-02-15 | Dsm Nv | Polyamide product from polytetramethylene diacid amide. |
| BR0109612A (en) * | 2000-03-30 | 2004-01-13 | Asahi Chemical Ind | Monofilament yarn and method for its production |
| US8695148B2 (en) * | 2002-08-09 | 2014-04-15 | Colgate-Palmolive Company | Toothbrush |
| EP1805232B1 (en) * | 2004-09-30 | 2009-12-30 | Chemtura Corporation | Improved polymers of bromostyrenes having controlled molecular weight |
| US7550551B2 (en) * | 2006-08-22 | 2009-06-23 | Chemtura Corporation | Brominated flame retardant |
| JP5760405B2 (en) * | 2009-11-30 | 2015-08-12 | 東レ株式会社 | Polyamide resin composition and molded article comprising the same |
| JP2011200352A (en) * | 2010-03-25 | 2011-10-13 | Toray Monofilament Co Ltd | Tapered bristle and brush |
| CN102884104B (en) * | 2010-05-06 | 2015-05-20 | 帝斯曼知识产权资产管理有限公司 | Process for preparing PA-4X, and PA-410 obtainable by the process |
| US8845934B2 (en) * | 2011-09-12 | 2014-09-30 | Sabic Global Technologies B.V. | Compatibilized biopolyamide-poly(arylene ether) thermoplastic resin |
-
2012
- 2012-10-16 EP EP12772338.5A patent/EP2769009B1/en active Active
- 2012-10-16 CN CN201280050893.XA patent/CN103890248A/en active Pending
- 2012-10-16 BR BR112014009132A patent/BR112014009132A8/en not_active Application Discontinuation
- 2012-10-16 WO PCT/EP2012/070487 patent/WO2013057102A1/en active Application Filing
- 2012-10-16 US US14/350,457 patent/US20140259487A1/en not_active Abandoned
- 2012-10-16 MX MX2014004568A patent/MX2014004568A/en unknown
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| Publication number | Publication date |
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| CA2851766A1 (en) | 2013-04-25 |
| BR112014009132A2 (en) | 2017-06-13 |
| JP2014528338A (en) | 2014-10-27 |
| US20140259487A1 (en) | 2014-09-18 |
| BR112014009132A8 (en) | 2017-06-20 |
| WO2013057102A1 (en) | 2013-04-25 |
| CN103890248A (en) | 2014-06-25 |
| MX2014004568A (en) | 2014-07-09 |
| EP2769009A1 (en) | 2014-08-27 |
| EP2769009B1 (en) | 2016-12-21 |
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