JP5853065B1 - Gather material - Google Patents

Abstract

Provided is a gather member suitable as a base material for medical materials such as absorbent articles represented by sanitary products and disposable paper diapers, masks, bandages and the like. A gathering member containing elastic fibers, and the elastic fiber constituting the gathering member has a stress (cN / dT) at the time of 300% stretching in a third repetition in a 300% stretching recovery repeated test. It is 0.050 or more and 0.150 or less, and the 200% stress retention (%) of the third repetition in the 300% stretch recovery repeat test is 65 or more and 95 or less, and the third repeat in the 300% stretch recovery repeat test. The gather member having a later residual strain (%) of 42 or less. [Selection figure] None

Description

  The present invention relates to a gather member containing specific elastic fibers, which is suitable as a base material for medical materials such as absorbent articles typified by sanitary products and disposable paper diapers, masks, and bandages.

Conventionally, a waist part, a leg part, and the like of a paper diaper are provided with a gathered part having elasticity to improve fit and prevent leakage of urine and the like. In such a gathered portion, rubber or polyurethane elastic fiber is used to obtain stretchability. Usually, the rubber or polyurethane elastic fiber is stretched and bonded to a non-woven fabric with a hot melt adhesive or the like. It is composed.
For this reason, the characteristic as a stretchable material of rubber or polyurethane elastic fiber after being bonded to the nonwoven fabric by a hot melt adhesive or the like greatly affects the fit feeling of a paper diaper, urine leakage, and the like.

Various proposals have been made for gathered parts such as disposable diapers.
For example, Patent Document 1 below proposes a polyurethane elastic yarn that is easy to attach and detach and has a comfortable fit by attaching a specific treatment agent to a polyurethane elastic fiber made of a specific polyalkylene ether diol. However, since the elastic fiber undergoes a stretching process, a hot melt bonding process, and the like in the diaper manufacturing process, the physical properties change during the process, and the degree of the effect varies depending on the method of use.
Also, in Patent Document 2 below, by specifying the physical properties of the gathered portion in which elastic fibers are arranged at a constant interval between two sheets, deviation at the time of wearing is less likely to occur, and rubber marks can be suppressed. Pants-type diapers have been proposed, but elastic fibers for obtaining these effects are not disclosed.

JP 2005-344214 A JP 2004-81365 A

  It is an object of the present invention to provide hygiene products, medical products, and the like that are easy to attach and detach, have a good fit, and are difficult to slip off by specifying elastic fibers in the gather member.

As a result of intensive studies and repeated experiments to solve the above-mentioned problems, the present inventors solved the above-mentioned problems by the elastic fibers constituting the gather member having a specific elongation stress, recovery force, and residual strain physical properties. The present inventors have found out what can be done and have completed the present invention.
That is, the present invention is as follows.

｛式中、Ｒ _１ 〜Ｒ _３ は有機基である。｝中のソフトセグメント部分の平均繰り返し数ｍを、下記式（９）：
ｍ＝２×（Ｆ１／Ｆ２） …式（９）
により求め、さらに、ソフトセグメント部分の数平均分子量Ｍｓとして下記式（１０）：
Ｍｓ＝（Ｍｄｏ＋Ｍｄｉ）×ｍ＋Ｍｄｏ …式（１０）
｛式中、Ｍｄｏ：ポリアルキレンエーテルジオールの数平均分子量、Ｍｄｉ：有機ジイソシアネートの分子量、ｍ：前記式（９）により求めた、前記構造式中のソフトセグメント部分の平均繰り返し数ｍである。｝により求めたものであり、かつ、前記弾性繊維を構成するポリマーのソフトセグメント部分に含まれるポリアルキレンエーテルジオールの側鎖メチル基の平均個数Ｎｍｍｓは、前記式（１０）により求めたソフトセグメント部分の数平均分子量Ｍｓを、下記式（５）：
Ｎｍｍｓ＝Ｎｍｄ×{（Ｍｓ−Ｍｄｏ）／（Ｍｄｏ＋Ｍｄｉ）＋１} …式（５）
｛式中、Ｎｍｄ：ポリアルキレンエーテルジオール１分子に含まれる側鎖メチル基の平均個数、Ｍｓ：ソフトセグメント部分の数平均分子量、Ｍｄｏ：ポリアルキレンエーテルジオールの数平均分子量、Ｍｄｉ：有機ジイソシアネートの分子量である。｝に代入して求めたものである。 [1] A gathering member containing a polyurethane elastic fiber obtained from a polyalkylene ether diol, an organic diisocyanate compound, and an active hydrogen atom-containing compound that reacts with an isocyanate group, and the softening of the elastic fiber taken out from the gathering member The number average molecular weight Ms of the segment part is 4800 or more and 11000 or less, and the stress (cN / dT) at the time of 300% elongation in the third repetition in the 300% elongation recovery repeated test of the elastic fiber is 0.050 or more and 0.150 or less. , and the repeated third 200% stress retention of at 300% elongation recovery repetition test (%) is 65 or more 95 or less, 3 100% elongation recovery repetition residual strain of repeated after the third in the test (%) 42 hereinafter der is, and software of the polymer constituting the elastic fibers The average number Nmms of side chain methyl groups of the polyalkylene ether diol contained in the segment portion is represented by the following formula (1):
3.8 ≦ Nmms ≦ 35 (1)
Meeting said gathering member. However, the number average molecular weight Ms of the soft segment portion of the elastic fiber is the peak of the methylene group of the organic diisocyanate whose both ends are urethane bonds in the NMR spectrum of the polyurethane elastic fiber composed of the polyalkylene ether diol and the organic diisocyanate ( f1) and the integral curve height of the methylene group peak (f2) of the organic diisocyanate, one of which is a urethane bond and the other is a urea bond, are F1 and F2, respectively.

{Wherein R _{1 to} R ₃ are organic groups. } The average number of repetitions m of the soft segment portion in the following formula (9):
m = 2 × (F1 / F2) Equation (9)
And the following formula (10) as the number average molecular weight Ms of the soft segment portion:
Ms = (Mdo + Mdi) × m + Mdo Equation (10)
{In the formula, Mdo: number average molecular weight of polyalkylene ether diol, Mdi: molecular weight of organic diisocyanate, m: average repeat number m of the soft segment portion in the structural formula determined by the above formula (9). } And the average number Nmms of side chain methyl groups of the polyalkylene ether diol contained in the soft segment portion of the polymer constituting the elastic fiber is the soft segment portion determined by the formula (10). The number average molecular weight Ms of the following formula (5):
Nmms = Nmd × {(Ms−Mdo) / (Mdo + Mdi) +1} (5)
{In the formula, Nmd: average number of side chain methyl groups contained in one molecule of polyalkylene ether diol, Ms: number average molecular weight of soft segment portion, Mdo: number average molecular weight of polyalkylene ether diol, Mdi: molecular weight of organic diisocyanate It is. } Is obtained by substituting for.

[ 2 ] An absorbent article including the gather member according to [1 ] .

[ 3 ] A medical material including the gather member according to [1 ] .

  Sanitary products, medical products, and the like using the gather members of the present invention are easy to attach and detach, have a good fit, and are difficult to slip off.

The chemical structural formula of an example of the structural formula of the soft segment part of the polyurethane elastic fiber which comprises the gather member of this invention, and a hard segment part. The chemical structural formula of an example of the structural formula of the polyalkylene ether diol of the raw material of the polyurethane elastic fiber which comprises the gather member of this invention. The NMR spectrum figure (example) of the polyurethane elastic fiber which comprises the gather member of this invention. The schematic of the apparatus which measures the running stress of an elastic fiber. Schematic of a thread breakage evaluation apparatus.

Hereinafter, the present invention will be described in detail.
In the gather member of the present embodiment, an elastic fiber is used as at least a part of the constituent material. The elastic fiber in the present embodiment includes a polyurethane elastic fiber, a polyester elastic fiber, a polyamide elastic fiber, a polyolefin elastic fiber, a natural rubber, a rubber thread made of a synthetic rubber, and a composite or mixture with other organic synthetic resins mainly composed of these. The one obtained by is used.

The polyurethane elastic fiber is composed of a soft segment portion made of polyether diol and organic diisocyanate and a hard segment portion made of organic diisocyanate and diamine or diol. FIG. 1 shows an example of a structural formula of a soft segment portion and a hard segment portion of polyurethane urea of a polyurethane elastic fiber used in the present embodiment. In FIG. 1, R ₁ represents a residue of a polyalkylene ether diol, R ₂ represents a residue of an organic diisocyanate, and R ₃ represents a residue of a diamine. In the present embodiment, it is preferable to use polyurethane elastic fibers from the viewpoint of developing specific elongation stress, recovery force, and residual strain.

  Examples of the polyalkylene ether diol in the polyurethane elastic fiber used in the present embodiment include straight chain C 2-6 alkylene groups such as polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol and the like. May be used in the form of an ether bond, or a straight chain having 2 to 6 carbon atoms such as ethylene, propylene, tetramethylene or hexamethylene, 1,2-propylene, 3-methyltetramethylene, 3 A copolymer polyalkylene ether diol having a methyl group in the side chain, in which two or more of branched alkylene groups having 2 to 10 carbon atoms such as methylpentamethylene and 2,2-dimethylpropylene are ether-bonded It may be used.

  From the viewpoint of stretch performance, water resistance, light resistance, and abrasion resistance of the obtained gather member, one of the alkylene groups is a tetramethylene group, and the other alkylene group is 3-methyltetramethylene or 2,2-dimethylpropylene. A copolymerized polyalkylene ether diol in which the groups are ether-bonded is preferred.

  As the organic diisocyanate compound in the polyurethane elastic fiber used in the present embodiment, for example, all of aliphatic, alicyclic and aromatic diisocyanates which are dissolved or liquid under reaction conditions can be applied. . For example, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, methylene-bis (3-methyl-4-phenylisocyanate), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m- And p-xylylene diisocyanate, α, α, α ′, α′-tetramethyl-p-xylylene diisocyanate, m- and p-phenylene diisocyanate, 4,4′-dimethyl-1,3-xylylene diisocyanate, 1 -Alkylphenylene-2,4 and 2,6-diisocyanate, 3- (α-isocyanatoethyl) phenyl isocyanate, 2,6-diethylphenylene-1,4-diisocyanate, diphenyl-dimethylmethane-4,4-diisocyanate, diphenyl ether -4 , 4'-diisocyanate, naphthylene-1,5-diisocyanate, 1,6-hexamethylene diisocyanate, methylene-bis (4-cyclohexylisocyanate), 1,3- and 1,4-cyclohexylene diisocyanate, trimethylene diisocyanate, tetra Examples include methylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. These diisocyanates may be used alone or in combination of two or more. From the viewpoint of reactivity and elongation stress, 4,4′-diphenylmethane diisocyanate is preferable.

  Examples of the polyfunctional active hydrogen atom-containing compound that is a chain extender that reacts with an isocyanate group in the polyurethane elastic fiber used in the present embodiment include hydrazine, polyhydrazine, a straight chain or branched chain having 2 to 10 carbon atoms. Compounds having an amino group or hydroxyl group having an aliphatic, alicyclic or aromatic active hydrogen such as ethylenediamine, 1,3-propylenediamine, 1,5-diaminopentane, 1,6-diaminohexane, N- Methylethylenediamine, N, N′-dimethylethylenediamine, N-ethylethylenediamine, N, N′-diethylethylenediamine, N-isopropylethylenediamine, 1,2-diaminopropane, 2-methyl-1,3-propanediamine, 3-methyl -1,5-pentanediamine, 1,3-bis ( Minomethyl) cyclohexane, phenylenediamine, xylylenediamine, 4,4′-diaminodiphenylmethane, piperazine, diamines having urea groups described in JP-A-5-155841, hydroxylamine, water, low molecular weight Glycols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, hexa Methylene glycol, diethylene glycol, 1,10-decanediol, 1,3-dimethylolcyclohexane, 1,4-dimethylolcyclohexane and the like can be used. Ethylenediamine or 1,2-propylenediamine is preferred.

  Examples of the monofunctional active hydrogen atom that is a terminal terminator that reacts with an isocyanate group in the polyurethane elastic fiber used in the present embodiment include dialkylamines such as diethylamine and alkyl alcohols such as ethanol. These chain extenders and end terminators may be used alone or in combination of two or more.

With respect to the reaction operation for the polyurethane formation of the polyurethane elastic fiber, a solventless solvent or a solvent such as dimethylformamide, dimethyl sulfoxide, dimethylacetamide may be used.
The polyurethane polymer of the polyurethane elastic fiber used in this embodiment is prepared by reacting polyalkylene ether diol with a molar excess of organic diisocyanate to synthesize a urethane intermediate polymer that becomes a soft segment, and then polymerizing the hard segment with a chain extender. However, it can be produced using a known technique such as end-capping with a terminal terminator.

In order to control the average number of side chain methyl groups of the polyalkylene ether diol contained in the soft segment portion of the polyurethane elastic fiber used in this embodiment, the type of polyalkylene ether diol, the number average molecular weight of the polyalkylene ether diol It is necessary to adjust Mdo, the copolymerization ratio of the polyalkylene ether diol, and the soft segment number average molecular weight Ms. FIG. 2 shows an example of a polyalkylene ether diol. o and p represent the average number of repetitions of the ether unit part A having no side chain methyl group and the ether unit part B having a side chain methyl group, respectively, q, r, and s represent the number of repetitions of each methylene group, R ₄ , R ₅ represents H or CH ₃ . The molecular weight of one unit of the ether unit part A having no side chain methyl group is Mnm, the molecular weight of one unit of the ether unit part B having the side chain methyl group is Mm, the copolymerization ratio of A and B is Ar: Br, side When the number of side chain methyl groups in one unit of the ether unit part B having a chain methyl group is NM, the average number Nmd of side chain methyl groups contained in one molecule of the polyalkylene ether diol is represented by the following formula (2 ):
Nmd = Mdo / [Mnm × {Ar / (Ar + Br)} + Mm × {Br / (Ar + Br)}] × Ar / (Ar + Br) × NM (2)
{In the formula, Nmd: average number of side chain methyl groups contained in one molecule of polyalkylene ether diol, Mdo: number average molecular weight of polyalkylene ether diol, Mnm: one unit of ether unit part A having no side chain methyl group Mm: molecular weight of one unit of ether unit part B having a side chain methyl group, Ar: copolymerization ratio of ether unit part A having no side chain methyl group, Br: ether unit part having a side chain methyl group B copolymerization ratio, NM: the number of side chain methyl groups in one unit of the ether unit part B having side chain methyl groups. }.

In order to control the average molecular weight Ms number soft segment, a number average molecular weight Mdo polyalkylene ether diol, is necessary to adjust the molar ratio N ₁ of the organic diisocyanate to polyalkylene ether diol. Here, the soft segment number average molecular weight Ms is represented by the following formula (3):
_{Ms = {Mdo + Mdi (N} 1 -N 0)} / (N 1 -N 0 -1) -2Mdi ... Equation (3)
{In the formula, Ms: number average molecular weight of soft segment portion, Mdo: number average molecular weight of polyalkylene ether diol, Mdi: molecular weight of organic diisocyanate, N ₁ : molar ratio of organic diisocyanate to polyalkylene ether diol, N ₀ : Formula (4):
N ₀ = aN ₁ ⁴ + bN ₁ ³ + cN ₁ ² + dN ₁ + e Formula (4)
(Wherein, constant a = 0.03806, constant b = −0.3997, constant c = 1.617, constant d = −2.144, constant e = 0.8795). It is the molar ratio of unreacted organic diisocyanate present after reaction to polyalkylene ether diol. }.

That is, in order to control the number average molecular weight Ms of the soft segment part, after determining the molecular weight Mdo of the polyalkylene ether diol to be used, the polyalkylene is adjusted so that Ms in the above formula (3) becomes a predetermined value. it may be designed molar ratio N ₁ of the organic diisocyanate to polyether diol. Further, since the average number of polyalkylene ether diols contained in the soft segment number average molecular weight Ms can be calculated from (Ms-Mdo) / (Mdo + Mdi) +1, the side chain methyl group of the polyalkylene ether diol contained in the soft segment part The average number Nmms of the following formula (5):
Nmms = Nmd × {(Ms−Mdo) / (Mdo + Mdi) +1} (5)
{In the formula, Nmd: average number of side chain methyl groups contained in one molecule of polyalkylene ether diol, Ms: number average molecular weight of soft segment portion, Mdo: number average molecular weight of polyalkylene ether diol, Mdi: molecular weight of organic diisocyanate It is. }.

  The average number Nmms of side chain methyl groups of the polyalkylene ether diol contained in this soft segment portion is the physical properties of the elastic fiber constituting the gather member, stress, recoverability, residual strain, and yarn breakage in the diaper manufacturing process In view of the above, the range is preferably 3 or more and 35 or less, more preferably 3 or more and 18 or less.

  The number average molecular weight Ms of the soft segment portion in the polyurethane elastic fiber is preferably 4800 or more and 11000 or less. If it is less than 4800, the proportion of the hard segment portion in the whole polyurethane increases, causing a decrease in the viscosity stability of the polyurethane polymer, and further causing yarn breakage in the spinning process. When it exceeds 11000, the proportion of the hard segment portion in the whole polyurethane is lowered, the heat resistance of the polyurethane elastic fiber is lowered, and the elastic performance of the polyurethane elastic fiber is greatly lowered.

  The polyurethane polymer composition may contain various stabilizers, pigments and the like. For example, light-proofing agents, hindered phenolic agents, benzotriazole-based, benzophenone-based, phosphorus-based and various hindered amine-based antioxidants, inorganic substances such as iron oxide, titanium oxide, zinc oxide, cerium oxide, magnesium oxide, carbon black and Various pigments, antibacterial agents and deodorants containing silver, zinc, and these compounds, antistatic agents, nitric oxide scavengers, thermal oxidation stabilizers, light stabilizers and the like may be added in combination.

  The polyurethane polymer thus obtained can be formed into a fiber by a known dry spinning, melt spinning or wet spinning method to obtain a polyurethane elastic fiber. Alternatively, a polyurethane polymer polymerized using different raw materials may be mixed and spun before spinning.

  The number of single yarns of the polyurethane elastic fiber is not limited and may be either a monofilament or a multifilament. From the viewpoint of adhesion, a multifilament having a single yarn fineness of 5 to 25 dt (decitex) is preferable. The total fineness of the elastic fiber is preferably 10 to 3000 dt. The obtained polyurethane elastic fiber is usually treated by a known method such as roll oiling, guide oiling, spray oiling or the like before or after being wound around the paper tube package. May be.

  The treatment agent used in this embodiment is not particularly limited, but polydimethylsiloxane, polyester-modified silicon, polyether-modified silicon, amino-modified silicon, mineral oil, mineral fine particles such as silica, colloidal alumina, talc and the like, higher fatty acids. Metal salt powder, for example, magnesium stearate, calcium stearate, etc., higher aliphatic carboxylic acid, higher aliphatic alcohol, paraffin, polyethylene and other oils such as solid wax at room temperature alone or in combination as needed It may be given. In addition, for the purpose of improving the adhesiveness to the nonwoven fabric via hot melt, the unwinding property from the wound yarn, and the frictional property during the diaper manufacturing process, carbon having a homo- or copolymerized polyalkylene ether diol and an OH group at the end. You may use the processing agent which added the mixture of mineral oil, dimethyl silicon, or a mineral oil and dimethyl silicon to the mixture of the higher alcohol of a number 8-25.

  The running stress of the elastic fiber used for the gather member is preferably 0.060 g / dt or more. When the running stress is less than 0.060 g / dt, the elastic fibers loosen or flutter between the guides and the rollers during gather production, and the elastic fibers are likely to break.

  Usually, the elastic fiber used for the gather member is drawn in a draft ratio of 2.0 to 4.0 through a guide or a roller after being unwound from the wound body when arranged in the gather portion, In this state, the hot melt is directly applied to the elastic fiber and bonded to the nonwoven fabric, or the elastic fiber is bonded to the nonwoven fabric coated with the hot melt. By passing through the process, the elastic fiber is lightly set, and an elastic fiber that expresses desired physical properties can be obtained.

The elastic fiber constituting the gather member of the present embodiment has a stress (cN / dT) at the time of 300% elongation of the third repetition in the 300% elongation recovery repeated test of 0.050 or more and 0.150 or less, and 300% elongation. The 200% stress retention (%) at the third repetition in the recovery repetition test is 65 or more and 95 or less, and the residual strain (%) after the third repetition in the 300% extension recovery repetition test is 42 or less. The stress (cN / dT) at the time of 300% elongation in the third repetition in the 300% elongation recovery repeated test is 0.050 or more and 0.150 or less. If it is less than 0.050, the stress is too low to exhibit the function as the original elastic body, and if it exceeds 0.150, it can be worn smoothly because the stretching force is large when wearing a paper diaper. Can not.
The stress (cN / dT) at 300% elongation in the third repetition in the 300% elongation recovery repeated test is preferably 0.060 or more and 0.145 or less. Further, the 200% stress retention (%) at the third repetition in the 300% stretch recovery repeated test is 65 or more and 95 or less. If it is less than 65, the fastening force at the time of wearing becomes weak and causes problems such as slippage, and elastic fibers exceeding 95 are physically difficult to produce.
Further, the residual strain (%) after the third repetition in the 300% stretch recovery repeated test is 42 or less. If it exceeds 42, the elastic fiber is distorted when worn, and the fastening force becomes weak, causing problems such as slippage.

The elastic fiber in the gather member used in the present embodiment may be a bare yarn or may be covered and covered with another elastic fiber or non-elastic fiber.
The gather member of this embodiment is suitably used as a base material for absorbent materials such as sanitary products and disposable paper diapers, and medical materials such as masks and bandages. In the paper diaper, there are portions where elastic fibers are bonded to the nonwoven fabric via hot melt at the waist and leg portions, but the gather member of this embodiment is particularly preferably used for such portions. The gather member can be produced by a usual method in the manufacturing process of disposable diapers, sanitary products, masks, and bandages, including a method in which elastic yarn is stretched and bonded to a nonwoven fabric or the like via hot melt or the like.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In the examples, the following methods were used.
(1) Viscosity stability evaluation method The polyurethane solution obtained by the polymerization was put in a sealed container so that the solvent would not scatter, and left in a safety oven at 50 ° C. (SPH-200 type, manufactured by Tabai Espec) for 15 days. The viscosity of the polyurethane solution before and after being allowed to stand at 50 ° C. for 15 days was measured using a rotational viscometer (BH type, manufactured by Tokyo Keiki Co., Ltd.), and the viscosity increase width Δη (poise) was used as an index of viscosity stability. The smaller Δη, the less the yarn breakage in the spinning process and the more stable the polyurethane solution that can be produced.

(2) Measuring method of running stress of elastic fiber The wound body 1 of elastic fiber obtained by spinning is applied to the apparatus shown in FIG. 4, the elastic fiber feed roll 2 is set at a speed of 10 m / min, and the winding roll 3 is set at a speed of 30 m / min. The yarn was run at a draw ratio of 3 times, and the stress (g) during yarn running was measured with a tension meter 4. A value obtained by dividing the obtained stress value by the fineness of the elastic fiber was defined as running stress (g / dt).

(3) Method for evaluating yarn breakage in diaper manufacturing process The wound body 1 of elastic fiber obtained by spinning is applied to the apparatus shown in FIG. 5, and the elastic fiber feed roll 5 is wound at a speed of 50 m / min and the elastic fiber is wound three times. The pre-draft roll 6 was run at a speed of 80 m / min and the take-up roll 7 was run at a speed of 85 m / min. The behavior of the elastic fiber at the observation site 8 is visually observed for 3 minutes, and the following evaluation criteria:
A: Yarn width of 0 mm to less than 2 mm O: Yarn width of 2 mm to less than 5 mm Δ: Yarn width of 5 mm or more x: Evaluation was made using thread breakage.

(4) Gather member manufacturing method Three elastic fibers are arranged in parallel at an interval of 5 mm, stretched to be three times the original length of the elastic fibers, and melted at 160 ° C. ) Asahi Kasei fiber coated with Discommelt 5434 made by Sun Tool Co., Ltd. with a comb gun of 0.03 g / m per fiber and stretched 5 cm in width and 17 g / m ² in weight. A gathered member was produced by sandwiching between two non-woven fabrics manufactured by (Co) and Eltus Guard (registered trademark) and pressing with a roller from above.

(5) Gather member attachment / detachment and fit evaluation method The gather member produced by the method (4) was allowed to stand for 1 day in an unstretched state to sufficiently relax the stress of the elastic fiber. Thereafter, the gather length of 42 cm was measured in a relaxed state, and the ends were heat-bonded with a heat sealer to produce a ring having a circumference of 42 cm made of a gather member. Ten subjects with a waist length of 75 cm to 80 cm wear this ring on the waist, and sensory evaluation of the feeling of wearing at that time was performed according to the following evaluation criteria.
Detachability ◎: When there are 8 to 10 people judged that the detachability is good ○: When 6 to 7 people judged that the detachability is good △: 4 to 4 people judged that the detachability is good In the case of 5 people ×: In the case where there are 3 or less people judged that the detachability is good and fit ◎: In the case of 8-10 people judged that the tightening is moderate ○: 6 people judged that the tightening is moderate ~ When 7 people △: When 4-5 people are judged to be tightened properly ×: When 3 or less people are judged to be tightened properly

(6) Measuring method of stress (cN / dT), 200% retention rate (%), and residual strain (%) at the third repetition of 300% elongation in the 300% elongation recovery repeated test Prepared by the method of (4) above. The gathered member was immersed in cyclohexane as an organic solvent for 10 minutes and stirred. After stirring, the elastic fiber peeled from the nonwoven fabric was taken out and air-dried for 1 day. After air drying, the fineness (dt) is calculated from the length (m) and weight (g) of the elastic fiber by the following formula (6):
Fineness (dt) = 10000 / length of elastic fiber (m) × weight of elastic fiber (g) Formula (6)
Determined by
Using a tensile tester (Orientec Co., Ltd. RTG-1210 type Tensilon), the elastic fiber after air drying with a sample length of 10 mm was stretched at a rate of 100 mm / min at 20 ° C. and a relative humidity of 65%. The elongation recovery repetition test of 0% to 300% was performed three times. At that time, the stress (cN) at the time of 300% elongation at the third repetition was measured. A value obtained by dividing the obtained stress value by the fineness (dt) of the elastic fiber obtained by the formula (6) was defined as a stress at 300% elongation (cN / dt).

Further, SM (cN) and RM (cN) at the time of the third 200% elongation were measured with SM as the stress at the time of elongation in the 300% elongation and recovery repeated test and RM as the stress at the time of recovery. The ratio of RM to SM at the time of 200% elongation is called 200% stress retention (%), and the following formula (7):
200% stress retention (%) = 200% RM / 200% SM × 100 (7)
{In the formula, RM (cN) at the time of 200% elongation at the third repetition in the 200% RM: 300% elongation recovery repetition test, 200% SM: 200% elongation at the third repetition in the 300% elongation recovery repetition test SM (cN) at the time of }.

Furthermore, the strain amount RS (mm) at which the RM after the 300% elongation recovery repeated test was performed three times was measured. The residual strain (%) at this time is expressed by the following formula (8):
Residual strain (%) = RS / 10 × 100 (8)
{In the formula, RS is the strain amount (mm) at which RM becomes 0 after the 300% elongation recovery repeated test is performed three times. }.

(7) Measuring method of number average molecular weight Ms of soft segment part by NMR The gathered member produced by the method of said (4) was immersed in cyclohexane of an organic solvent for 10 minutes, and was stirred. After stirring, the elastic fiber peeled from the nonwoven fabric was taken out and air-dried for 1 day. Thereafter, Soxhlet extraction was performed using chloroform as a solvent to remove organic additives. Chloroform was removed by drying, and measurement was performed with the following apparatus and conditions.
Measuring device: ECS400 manufactured by JEOL
Measurement nucleus: 1H
Resonance frequency: 400 MHz
Total number of times: 256 Measurement temperature: Room temperature Solvent: Deuterated dimethylformamide Measurement concentration: 1.5% by weight
Chemical shift criteria: dimethylformamide (8.023 ppm)

  FIG. 3 shows an example of an NMR spectrum of a polyurethane elastic fiber composed of a polyalkylene ether diol and 4,4′-diphenylmethane diisocyanate measured under these measurement conditions. A line P in FIG. 3 is an NMR spectrum, and I is an integral curve thereof. The peak of methylene group (f1) of 4,4′-diphenylmethane diisocyanate with urethane bonds at both ends is 3.87 ppm, the methylene group of 4,4′-diphenylmethane diisocyanate with one urethane bond and the other is urea bond. A peak (f2) was observed at 3.84 ppm. The heights of the integral curves of the peaks f1 and f2 were F1 and F2, respectively.

The average repeat number m of the soft segment portion in the structural formula of FIG. 1 is the following formula (9):
m = 2 × (F1 / F2) Equation (9)
Determined by

Furthermore, the number average molecular weight Ms of the soft segment portion is represented by the following formula (10):
Ms = (Mdo + Mdi) × m + Mdo Equation (10)
{In the formula, Mdo: number average molecular weight of polyalkylene ether diol, Mdi: molecular weight of organic diisocyanate, m: average number of repetitions m of the soft segment portion in the structural formula of FIG. . }.

The structure of the polyalkylene ether diol and the number average molecular weight Mdo of the polyalkylene ether diol can also be confirmed by NMR spectrum.
The average number Nmms of the side chain methyl groups of the polyalkylene ether diol contained in the soft segment portion was determined from the formula (5) using the number average molecular weight Ms value of the soft segment portion determined by the formula (10).

[Example 1]
1800 g (1.00 mol) of a copolymerized polyalkylene ether diol consisting of a tetramethylene group and a 2,2-dimethylpropylene group and having a number average molecular weight of 1800 and a copolymerization rate of 2,2 dimethylpropylene group of 10 mol%; 335 g (1.34 mol) of 4,4′-diphenylmethane diisocyanate was reacted under stirring in a dry nitrogen atmosphere at 60 ° C. for 3 hours to obtain a urethane prepolymer having a terminal isocyanate. After cooling this to room temperature, 2610 g of dimethylacetamide was added and stirred at room temperature to obtain a uniform prepolymer solution.
On the other hand, a solution prepared by dissolving 20.1 g (0.335 mol) of ethylenediamine as a diamine, 3.29 g (0.0450 mol) of diethylamine as a terminal terminator and 2545 g of dimethylacetamide was added to the above prepolymer solution under high-speed stirring. In addition to the reaction, the mixture was further reacted at room temperature for 1 hour to obtain a polyurethane solution. When the stock solution stability of this polyurethane solution was evaluated, Δη was 210 poise.

Furthermore, 1% by weight of a condensate of p-cresol, dicyclopentadiene and isobutylene as an additive to the polyurethane polymer solid content, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole was added in an amount of 0.2% by weight based on the polyurethane polymer solid content, and hydrotalcite was added in an amount of 0.3% by weight based on the polyurethane polymer solid content. did. The polyurethane solution to which the additive was added was defoamed under reduced pressure at room temperature to obtain a spinning dope.
This spinning dope is discharged into a heated nitrogen gas temperature of 270 ° C. directly below the spinning nozzle using a spinning nozzle, and the winding speed is set under a draft of 1.15 between the goded roller and the winding bobbin. After applying an oil agent containing dimethyl silicon as a main component at 400 m / min, it was wound around a bobbin to obtain a polyurethane elastic fiber of 620 dtex (72 filaments).

When the running stress of the polyurethane elastic fiber obtained by spinning was measured, it was 0.055 g / dt, and the yarn breakage evaluation in the diaper manufacturing process was ◯.
When a gather member made of this polyurethane elastic fiber was prepared and the wearing feeling of the gather member was evaluated, the detachability was ◎ and the fit property was ○. Moreover, when the physical properties of the polyurethane elastic fiber extracted from the gather member were measured, the stress at the time of 300% elongation in the third repetition of the 300% elongation recovery repeated test was 0.059 cN / dt, the 200% stress retention was 89%, The residual strain was 31%.

  Further, since this polyurethane elastic fiber has Mdo of 1800, Mnm of 72, Mm of 86, Ar: Br of 90:10, and NM of 2, Nmd is 4.9 from the above formula (2). Further, as a result of NMR measurement of the polyurethane elastic fiber extracted from the gather member, the spectrum of FIG. 3 was obtained. The heights F1 and F2 of the integral curves corresponding to f1 and f2 in FIG. 1 were 7.99 and 5.73, respectively. The average repeating number m of the soft segment portion determined from these was 2.79 from the above formula (9). That is, the number average molecular weight Ms of the soft segment portion of this polyurethane urea was 7520 from the above formula (10). This is because Ms obtained from the formula (3) and formula (4) from the raw material charge amount is 7550, and the value obtained by the NMR measurement is in good agreement with the value calculated from the raw material charge amount. . Furthermore, the average number Nmms of side chain methyl groups of the polyalkylene ether diol contained in the soft segment portion was 18.6 from the above formula (5).

[Examples 2 to 4, Reference Example 5, Comparative Examples 1 to 3]
A polyurethane solution produced in the same manner as in Example 1 with the raw materials and preparation ratios shown in Table 1 below was spun in the same manner as in Example 1 to obtain 620 dtex (72 filaments) of polyurethane elastic fiber. . Further, as in Example 1, a gather member was prepared, and the detachability and fit of the gather member, physical property evaluation of elastic fibers constituting the gather, and analysis by NMR were performed. The results are shown in Tables 1 and 2 below.

  The gather member of the present invention is used as a base material for medical materials such as absorbent articles typified by sanitary products and disposable paper diapers, masks, bandages, etc. It is possible to obtain products that are hard to fall off.

DESCRIPTION OF SYMBOLS 1 Winding body of elastic fiber 2 Sending roll 3 Winding roll 4 Tension meter 5 Sending roll 6 Predraft roll 7 Winding roll 8 Observation site 9 Ceramic hook guide 10 Ceramic hook guide 11 Ceramic hook guide 12 Bearing free roller 13 Bearing free Roller 14 Bearing free roller 15 Angle formed by the thread on the ceramic hook guide = 120 °
16 Angle formed by the thread on the ceramic hook guide = 120 °

Claims (3)

A gathering member containing a polyurethane elastic fiber obtained from a polyalkylene ether diol, an organic diisocyanate compound, and an active hydrogen atom-containing compound that reacts with an isocyanate group, the soft segment portion of the elastic fiber taken out from the gathering member The number average molecular weight Ms is 4800 or more and 11000 or less, and the stress (cN / dT) at the time of 300% elongation in the third repetition in the 300% elongation recovery repeated test of the elastic fiber is 0.050 or more and 0.150 or less, repeating third 200% stress retention of at 300% elongation recovery repetition test (%) is 65 or more 95 or less, 3 100% elongation recovery repetition residual strain of repeated after the third in the test (%) 42 der below And the soft segment of the polymer constituting the elastic fiber The average number Nmms of side chain methyl groups of the polyalkylene ether diol contained in the moiety is represented by the following formula (1):
3.8 ≦ Nmms ≦ 35 (1)
Meeting said gathering member. However, the number average molecular weight Ms of the soft segment portion of the elastic fiber is the peak of the methylene group of the organic diisocyanate whose both ends are urethane bonds in the NMR spectrum of the polyurethane elastic fiber composed of the polyalkylene ether diol and the organic diisocyanate ( f1) and the integral curve height of the methylene group peak (f2) of the organic diisocyanate, one of which is a urethane bond and the other is a urea bond, are F1 and F2, respectively.

{Wherein R _{1 to} R ₃ are organic groups. } The average number of repetitions m of the soft segment portion in the following formula (9):
m = 2 × (F1 / F2) Equation (9)
And the following formula (10) as the number average molecular weight Ms of the soft segment portion:
Ms = (Mdo + Mdi) × m + Mdo Equation (10)
{In the formula, Mdo: number average molecular weight of polyalkylene ether diol, Mdi: molecular weight of organic diisocyanate, m: average repeat number m of the soft segment portion in the structural formula determined by the above formula (9). } And the average number Nmms of side chain methyl groups of the polyalkylene ether diol contained in the soft segment portion of the polymer constituting the elastic fiber is the soft segment portion determined by the formula (10). The number average molecular weight Ms of the following formula (5):
Nmms = Nmd × {(Ms−Mdo) / (Mdo + Mdi) +1} (5)
{In the formula, Nmd: average number of side chain methyl groups contained in one molecule of polyalkylene ether diol, Ms: number average molecular weight of soft segment portion, Mdo: number average molecular weight of polyalkylene ether diol, Mdi: molecular weight of organic diisocyanate It is. } Is obtained by substituting for. An absorbent article comprising the gather member according to claim 1 . A medical material comprising the gather member according to claim 1 .

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