WO2005052057A1 - Procede de production d'une mousse de polyurethane flexible - Google Patents

Procede de production d'une mousse de polyurethane flexible Download PDF

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Publication number
WO2005052057A1
WO2005052057A1 PCT/JP2004/016987 JP2004016987W WO2005052057A1 WO 2005052057 A1 WO2005052057 A1 WO 2005052057A1 JP 2004016987 W JP2004016987 W JP 2004016987W WO 2005052057 A1 WO2005052057 A1 WO 2005052057A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyol
polyurethane foam
mdi
flexible polyurethane
foam
Prior art date
Application number
PCT/JP2004/016987
Other languages
English (en)
Japanese (ja)
Other versions
WO2005052057A8 (fr
Inventor
Naoyuki Ohmori
Hitoshi Yaguchi
Yoshiaki Maeda
Original Assignee
Nippon Polyurethane Industry Co., Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Polyurethane Industry Co., Ltd filed Critical Nippon Polyurethane Industry Co., Ltd
Publication of WO2005052057A1 publication Critical patent/WO2005052057A1/fr
Publication of WO2005052057A8 publication Critical patent/WO2005052057A8/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0008—Foam properties flexible
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/06—Flexible foams

Definitions

  • the present invention relates to a method for producing a flexible polyurethane foam, and more particularly, to a method for producing a flexible polyurethane foam having excellent antifungal and antibacterial properties by a mechanical floss method.
  • flexible polyurethane foam has been used for relatively directly in contact with the human body, such as kitchen cleaners, body sponges, cosmetic applicators (figure puffs), filter elements, mattresses, pillows, and seat cushions. Often done. In such applications, antifungal and antibacterial properties are often required.
  • flexible polyurethane foams for cosmetic applicators include (1) open-cell dry polyurethane foam (Patent Document 1 and the like), and (2) open-cell wet polyurethane foam (Patent Document 2). And (3) composite materials (Patent Document 3 and the like) in which these foamed elastic bodies are combined with cloth, flocking, and the like are known.
  • Patent Document 1 JP-A-9-1188777
  • Patent Document 2 JP-A-58-189242
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2002-262929
  • Patent Document 4 JP-A-11-56741
  • an easy and simple manufacturing method which has a soft skin contact and a mildew-proof property
  • the present invention relates to a method for producing a flexible polyurethane foam for cosmetic puffs by a mechanical floss method, which is an easy and simple method for producing a soft polyurethane foam having a soft skin contact.
  • an isocyanate liquid (A) comprising an organic polyisocyanate (a), a polyol (bl)
  • the catalyst (b2), the foam stabilizer (b3), and the colemanite (b4) are previously mixed, and the inert gas (C) are mixed and dispersed by mechanical stirring, and then the mixed liquid is mixed.
  • the organic polyisocyanate (a) used in the present invention includes diphenylmethane diisocyanate (hereinafter abbreviated as “MDI”), polyphenylenepolymethylene polyisocyanate (hereinafter “MDI”). Abbreviated as "MDI polynuclear condensate”), tolylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, naphthalenediene Isocyanate, hydrogenated diphenylmethane diisocyanate , Hydrogenated xylylene diisocyanate, etc., and part of these isocyanate groups of compounds having an isocyanate group into urethane, biuret, arophanate, carbodiimide, uretonimine, oxazolidone, amide, imide, isocyanurate, uretdi
  • MDI polymeric MDI
  • 4, —MDI 4, A'—diphenylmethane diisocyanate
  • 2, 4′—diphenylmethane diisocyanate hereinafter, abbreviated as 2, —MDI
  • 2,2'-MDI 2,2'-Diphenylmethane diisocyanate in the form of a mixture (in some cases, single or miscellaneous) of any three types of isomers Exists in.
  • the MDI-based polynuclear mixture has three or more benzene rings having an isocyanate group bonded in one molecule, and exists in the form of a mixture of compounds having different degrees of condensation. Usually, it is not supplied in the form of an MDI-based polynuclear mixture alone, but in the form of a mixture with MDI (a mixture of MDI and an MDI-based polynuclear mixture is abbreviated as "polymeric MDI").
  • Polymeric MDI is obtained by converting a condensed mixture (polyamine) obtained by a condensation reaction between aniline and formalin from an amino group to an isocyanate group by phosgenation or the like. MDI polynuclear mixture with different degrees of condensation.
  • the composition of MDI and polymeric MDI can be changed by changing the raw material composition ratio and reaction conditions during condensation, and by partially removing MDI by distillation.
  • the MDI content of polymeric MDI and the isomer composition ratio of MDI can be determined from a calibration curve based on the area percentage of each peak obtained by gel permeation chromatography / gas chromatography.
  • the MDI having an MDI content of 50 to 100% by mass '—Polymeric MDIs containing MDI with an MDI content of 50-100% by weight, and urethane prepolymers terminated with isocyanate groups, are preferred.
  • the polyol (bl) used in the present invention comprises a polymer polyol and a chain extender.
  • High molecular polyols include polyether polyols, polyester polyols, polycarbonates Bonate polyol, hydrophobic polyol and the like can be mentioned.
  • the polyether polyol for example, those obtained by addition-polymerizing an alkylene oxide starting from propylene glycol, ethylene glycol, glycerin, trimethylolpropane, hexanetriol, or the like are preferable.
  • ethylene oxide or ethylene oxide is added to glycerin. Those obtained by addition polymerization of propylene oxide and propylene oxide are preferred.
  • polyester polyol examples include a condensed polyester polyol obtained by condensation of a dicarboxylic acid with a diol or a triol, a rataton-based polyester polyol obtained by ring-opening polymerization of a diol or a triol, and a polyether polyol.
  • a polyol such as an ester-modified polyol obtained by ester-modifying the above with rataton is preferably used.
  • polycarbonate carbonate polyol examples include those obtained by a transesterification reaction between a low molecular weight polyol such as butanediol and hexanediol and a low molecular weight carbonate such as propylene carbonate and getyl carbonate.
  • a low molecular weight polyol such as butanediol and hexanediol
  • a low molecular weight carbonate such as propylene carbonate and getyl carbonate.
  • hydrophobic polyol polyisoprene polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, or the like is used. These polymer polyol components may be used alone or in combination of two or more.
  • the above-mentioned polymer polyol has a substantial average number of functional groups of 2 to 4 and a number average molecular weight of 1,000 to 10,000 (particularly preferably 2 to 4) in consideration of the softness and the like of the obtained flexible polyurethane foam. , 000- 8, 000 Okishiechiren group content) of Ru Ah at 50 mass 0/0 following poly (O key dipropylene) polio one Norre or poly (Okishiechiren O carboxymethyl propylene) polyol.
  • the poly (oxyethylene oxypropylene) polyol includes, for example, a block copolymer type or a random copolymer type, or a product obtained by adding an ethylene oxide to the terminal of a poly (oxypropylene) polyol. If the substantial average number of functional groups is too small or if the number average molecular weight is too large, the physical properties of the foam tend to be too small. If the substantial average number of functional groups is too large or if the number average molecular weight is too small, the foam becomes hard and the feel is poor.
  • Examples of the chain extender include ethylene glycol, propylene glycol, 1,4-butanediol, trimethylolpropane, tetramethylene ether glycol, polyethylene glycol and the like. These chain extenders may be used alone or in combination of two or more. They may be used together. In the present invention, 1,4-butanediol is preferred. This is because 1,4-butanediol has a primary hydroxyl group and therefore has good reactivity.It is a liquid at room temperature, so it has excellent workability, and it has a moderate molecular weight, so it has excellent mechanical strength. Is obtained.
  • Examples of the catalyst (b2) used in the present invention include monoamines such as triethylamine and dimethylcyclohexylamine; diamines such as tetramethylethylenediamine, tetramethylpropanediamine and tetramethylhexanediamine; and pentane.
  • Triamines such as methylethylenetriamine, pentamethyldipropylenetriamine and tetramethyldanidine, triethylenediamine, dimethylbiperazine, methylethylbiperazine, methinolemonorephorin, dimethylaminoethylmorpholine, dimethyl Cyclic amines such as imidazole, alcohol amides such as dimethinoleaminoethanol, dimethylaminoethoxyethanol, trimethylaminoethylethanolamine, methylhydroxyethylpiperazine and hydroxyethylmorpholine , Ether amines such as bis (dimethylaminoethyl) ether, ethylene glycol bis (dimethyl) aminopropyl ether, stannasoctoate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin marker peptide, dibutyltin thiocarboxylate
  • the foam stabilizer (b3) used in the present invention is an organic silicon-based surfactant known in the art, for example, L-520, L-540, L_5309, L_5366, and L_5366 manufactured by Nippon Tunicer. SZ-1306, SH-193 and SRX-274C manufactured by Toray Dow Corning, and B-4113 manufactured by Goldschmidt.
  • the present invention is most characterized by using colemanite (b4).
  • Cholemanite is a calcium-boron based natural mineral represented by the general formula: Ca [B O (OH)] ⁇ ⁇ . Also
  • Koremanai HCa ⁇ '2B O) obtained by calcining this is also preferably used.
  • calcined colemanite having a high boron content is preferred.
  • the use amount of colemanite (b4) is preferably 0.110% by mass relative to the polyol (bl), and particularly preferably 0.55% by mass.
  • other conventionally known additives can also be used, if necessary. For example, antioxidants, ultraviolet absorbers, flame retardants, coloring agents, conductive agents, insulating agents, luminescent agents, antibacterial agents Agents, fragrances and the like.
  • the polyisocyanate component, the polyol component, the catalyst, and other additives stored or prepared in separate containers.
  • Into a single mixing head while mixing the inert gas mix the mixture to make it homogeneous, pour the mixture over a conveyor lined with a formwork and base paper, and heat and harden it.
  • a method in which the composition is cast into a predetermined mold and cured by heating is used.
  • the foam obtained by such a method is a polyurethane foam having uniform fine cells and moderate hardness.
  • the isocyanate index (isocyanate group Z active hydrogen group X 100) is preferably from 60 to 120, particularly preferably from 80 to 110. If the index is too low, the foam surface tends to stick to the surface. If the index is too high, the foam may not be foamed or may collapse to obtain a flexible foam.
  • the flexible polyurethane foam thus obtained has a density of 0.1-0.9 g / cm 3 , a Asker hardness F of 30-90 °, and is a uniform foam having fine cells. .
  • the flexible polyurethane foam obtained by the present invention has open cells, is fine in cells, and has excellent antifungal and antibacterial properties, and has a cosmetic puff, bedding (pillow, mat), cushion, and microphone. 'Easy for headphone covers and clothing.
  • ratios are mass ratios and “%” is “mass%” unless otherwise specified.
  • a reactor equipped with a stirrer, a cooling pipe, a nitrogen inlet pipe, and a thermometer A 1,000-ml reactor was charged with 308 g of MDI-1, 1 lg of reactive silicon, and 581 g of polyol-11, and stirred for 80 minutes. Reaction at 4 ° C for 4 hours to obtain NCO-1 It was. The isocyanate content of NCO-1 was 7.9%.
  • MDI Diphenylmethane diisocyanate
  • Polio one _1 Polio one _1:
  • a polyol premix OH-1-4 was prepared by charging as shown in Table 1 into a 2,000 ml reactor.
  • Nominal average number of functional groups 3
  • number average molecular weight 6,000
  • oxyethylene group content 17%
  • a 5 mm-thick foam sample was placed in a Petri dish, planted with mold spores, placed in an atmosphere of 25 ° C x 90% RH for 5 days, and the degree of mold growth was visually evaluated.
  • ⁇ : Mold growth area is less than 1Z3 or less of surface area
  • the area of the mold growing part is 1Z3 or less of the surface area
  • a 5 mm-thick foam sample was placed in a Petri dish, and one drop of cultured E. coli was added thereto. Thereafter, the cells were placed in an atmosphere of 35 ° C. ⁇ 90% RH for 24 hours, and the viable cell count was measured.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne un procédé de production d'une mousse de polyuréthane flexible présentant une excellente résistance aux moisissures et d'excellentes propriétés anti-bactériennes, le procédé consistant à utilliser un processus de moussage mécanique. Le procédé de production d'une mousse de polyuréthane flexible se caractérise par le mélange d'un isocyanate liquide (A) composé d'un polyisocyanate organique (a), d'un polyol liquide (B) dans lequel un polyol (b1), un catalyseur (b2), un agent stabilisant (b3) de mousse et une colemanite (b4) sont mélangés à l'avance, et d'un gaz inerte (C), ledit mélange étant ensuite dispersé par brassage mécanique, et le mélange obtenu soumis à des processus de moussage et de durcissement.
PCT/JP2004/016987 2003-11-25 2004-11-16 Procede de production d'une mousse de polyurethane flexible WO2005052057A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2003-393447 2003-11-25
JP2003393447A JP2005154533A (ja) 2003-11-25 2003-11-25 軟質ポリウレタンフォームの製造方法

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WO2005052057A1 true WO2005052057A1 (fr) 2005-06-09
WO2005052057A8 WO2005052057A8 (fr) 2006-01-12

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108778533A (zh) * 2016-03-04 2018-11-09 沙特阿拉伯石油公司 硅酮橡胶泡沫刷子
WO2021201792A1 (fr) * 2020-04-02 2021-10-07 Safaş Saf Plasti̇k Sanayi̇ Ve Ti̇caret Anoni̇m Şi̇rketi̇ Matériau composite formé à l'aide de bore au cours de la production d'un matériau de base en polyuréthane

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008274051A (ja) * 2007-04-26 2008-11-13 Nippon Polyurethane Ind Co Ltd 軟質ポリウレタンフォーム用ポリイソシアネート組成物及び該組成物を用いた軟質ポリウレタンフォームの製造方法
JP5629538B2 (ja) * 2010-09-14 2014-11-19 株式会社ブリヂストン 不織布用生分解性ポリウレタン
JP6106523B2 (ja) * 2013-05-17 2017-04-05 株式会社東洋クオリティワン 化粧塗布用ポリウレタンフォームの製造方法
EP3850029A1 (fr) * 2019-08-09 2021-07-21 Safas Saf Plastik Sanayi Ve Ticaret Anonim Sirketi Mousse de polyuréthane souple modifiée au bore pour l'hygiène et son procédé de production

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0335088A (ja) * 1989-05-30 1991-02-15 Bayer Ag 耐燃性要素
JPH03231964A (ja) * 1990-02-07 1991-10-15 Inoue Mtp Co Ltd 抗菌性ポリウレタンフォーム、抗菌性ポリウレタンエラストマー及び抗菌性ポリウレタン塗料組成物
JPH06122746A (ja) * 1992-10-13 1994-05-06 Daiyu Shoji:Kk 抗菌・抗カビ・防臭・消臭機能をもった発泡ウレタンの製造方法
JPH10114812A (ja) * 1997-08-22 1998-05-06 Bridgestone Corp 抗菌性軟質ポリウレタンフォームの製造方法
JP2002020210A (ja) * 2000-05-01 2002-01-23 Shoichi Okochi 抗菌および抗かび剤並びにその製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0335088A (ja) * 1989-05-30 1991-02-15 Bayer Ag 耐燃性要素
JPH03231964A (ja) * 1990-02-07 1991-10-15 Inoue Mtp Co Ltd 抗菌性ポリウレタンフォーム、抗菌性ポリウレタンエラストマー及び抗菌性ポリウレタン塗料組成物
JPH06122746A (ja) * 1992-10-13 1994-05-06 Daiyu Shoji:Kk 抗菌・抗カビ・防臭・消臭機能をもった発泡ウレタンの製造方法
JPH10114812A (ja) * 1997-08-22 1998-05-06 Bridgestone Corp 抗菌性軟質ポリウレタンフォームの製造方法
JP2002020210A (ja) * 2000-05-01 2002-01-23 Shoichi Okochi 抗菌および抗かび剤並びにその製造方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108778533A (zh) * 2016-03-04 2018-11-09 沙特阿拉伯石油公司 硅酮橡胶泡沫刷子
CN108778533B (zh) * 2016-03-04 2022-01-11 沙特阿拉伯石油公司 硅酮橡胶泡沫刷子
WO2021201792A1 (fr) * 2020-04-02 2021-10-07 Safaş Saf Plasti̇k Sanayi̇ Ve Ti̇caret Anoni̇m Şi̇rketi̇ Matériau composite formé à l'aide de bore au cours de la production d'un matériau de base en polyuréthane

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JP2005154533A (ja) 2005-06-16
WO2005052057A8 (fr) 2006-01-12

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