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Patent US4510186 - Process for preparing a porous sheet material - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inPatentsA process for preparing a porous sheet material, which comprises impregnating and/or coating on a substrate a water-in-oil type polyurethane emulsion (d) comprising a hydrophobic polyurethane (a), a hydrophilic polyurethane (b), and organic solvent (c) and water, and drying it, characterized in that...http://www.google.com/patents/US4510186?utm_source=gb-gplus-sharePatent US4510186 - Process for preparing a porous sheet materialAdvanced Patent SearchPublication numberUS4510186 APublication typeGrantApplication numberUS 06/517,437Publication dateApr 9, 1985Filing dateJul 26, 1983Priority dateApr 3, 1982Fee statusPaidAlso published asDE3327862A1, DE3327862C2Publication number06517437, 517437, US 4510186 A, US 4510186A, US-A-4510186, US4510186 A, US4510186AInventorsKatsumi Kuriyama, Isao Kondo, Iwao MisaizuOriginal AssigneeDainichi Seika Color & Chemicals Mfg. Co., Ltd., Ukima Colour & Chemicals Mfg. Co., Ltd.Export CitationBiBTeX, EndNote, RefManPatent Citations (7), Referenced by (8), Classifications (31), Legal Events (4) External Links: USPTO, USPTO Assignment, EspacenetProcess for preparing a porous sheet material
US 4510186 AAbstract
1. A process for preparing a porous sheet material, which comprises:(1) impregnating and/or coating on a substrate a water-in-oil type polyurethane emulsion (d) comprising a hydrophobic polyurethane (a), a hydrophilic polyurethane (b), an organic solvent (c) and water; said process characterized in that said hydrophobic polyurethane (a) is a hydrophobic polyurethane dispersion (e) obtained by reacting a hydrophobic polyol, an organic diisocyanate and a chain extender in an organic solvent (c) which has a limited compatibility with water and in which the polyurethane thereby formed is substantially insoluble; said hydrophilic polyurethane (b) is a polyurethane containing about 20 to about 40% by weight, based on the total polymer, of polyoxyethylene groups; and the weight ratio of (a):(b) is about 90-99:about 10-1; and (2) drying at a temperature of 60� to 100� C. for about 1 to 3 minutes and 100� to 150� C. for about 1 to 3 minutes. 2. The process according to claim 1, wherein the hydrophobic polyol is selected from the group consisting of polyethylene adipate, polyethylenepropylene adipate, polyethylenebutylene adipate, polydiethylene adipate, polybutylene adipate, polyethylene succinate, polybutylene succinate, polyethylene sebacate, polybutylene sebacate, polytetramethylene ether glycol, poly-ε-caprolactonediol, polyhexamethylene adipate, carbonate polyol, and polypropylene glycol, which have terminal hydroxyl groups and a molecular weight of from 300 to 4000.
5. The process according to claim 1, wherein the hydrophobic polyurethane particles in the hydrophobic polyurethane dispersion (e) have a particle size of from about 0.1 to about 5 μm.
The hydrophobic polyurethane (a) to be used in the process of the present invention, is a material per se generally known. It is obtainable by reacting a hydrophobic polyol, an organic diisocyanate and a chain extender. As the hydrophobic polyol, there may be mentioned, for instance, polyethylene adipate, polyethylenepropylene adipate, polyethylenebutylene adipate, polydiethylene adipate, polybutylene adipate, polyethylene succinate, polybutylene succinate, polyethylene sebacate, polybutylene sebacate, polytetramethylene ether glycol, poly-ε-caprolactonediol, polyhexamethylene adipate, carbonate polyol, and polypropylene glycol which have terminal hydroxyl groups and a molecular weight of from 300 to 4000. As the organic diisocyanate, there may be mentioned 4,4'-diphenylmethanediisocyanate (MDI), hydrogenated MDI, isophorone diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,5-naphthaline diisocyanate, m-phenylene diisocyanate and p-phenylene diisocyanate As the chain extender, there may be mentioned ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, ethylenediamine, 1,2-propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, decamethylenediamine, isophoronediamine, m-xylylenediamine, hydrazin and water.
The characteristic feature of the polyurethane (a) to be used in the present invention is that it is dispersed in a certain specific organic solvent in a very fine state, for instance, with a particle size of from about 0.1 to about 5 μm to form a dispersion (e). With such a composition, it is possible to obtain a water-in-oil type emulsion having superior stability simply by adding a small amount of an emulsifier (i.e. a polyurethane (b)), and it is thereby possible to obtain the effect intended by the present invention. The dispersion (e) is prepared by reacting the above-mentioned three components in an organic solvent (c) which does not substantially dissolve the polyurethane (a) and has a limited compatibility with water and which preferably has a boiling point of at most 120� C. under atmospheric pressure. The reaction conditions, for instance, the temperature and reaction time, may be the same as the conditions commonly employed in the conventional processes.
As the substrate to be used in the present invention, any substrates such as various types of woven fabrics, knitted fabrics non-woven fabrics, release papers, plastic films, metal sheets or glass sheets. The application of the above-mentioned emulsion to the substrate may be conducted in any known methods such as a coating method, an impregnation method or a combination of these methods. The coating and/or impregnating amount thereof may be varied within a wide range of e.g. from about 5 to about 2000 gm (solid contents/m2 depending on the particular purpose.
The drying step in the process of the present invention can be completed in a very short period of time without requiring any cumbersome treatment. In a dry process like the process of the present invention, this drying step constitutes a decisive and controlling step for the productivity. Therefore, the drying operation which can be completed in a short period of time is extremely advantageous as compared with the conventional processes. Namely, the coated and/or impregnated substrate can simply be dried at a temperature of from about 60� to about 100� C. for about 1 to about 3 minutes and at a temperature of from about 100� to about 150� C. for about 1 to about 3 minutes without requiring a solidifying step as disclosed in Japanese Unexamined Patent Publication No. 41063/1976, whereby a porous sheet material of the present invention can readily be obtained. The reason why the drying operation can be completed in such a short period of time, is believed to be such that the hydrophobic polyurethane (a) used as a coating film-forming agent in the present invention constitutes at least 90% weight of the total polyurethane and it is present in the form of fine particles from the bigining to the end, whereby its particles are dispersed and emulsified with water in a stabilized condition by means of a small amount of a surfactant (i.e. the polyurethane (b), and when dried, they swiftly and readily contact water for gelation by the evaporation of the organic solvent.
(Preparation of hydrophobic and hydrophilic polyurethanes)
1. 1000 Parts of polytetramethylene glycol (average molecular weight: about 1000, hydroxyl group value: 112), 93 parts of ethylene-glycol and 625 g of diphenylmethane diisocyanate were added to 1500 parts of methylethyl ketone and reacted at 60� C. for 8 hours, and then 2500 parts methylethyl ketone was added. The mixture was cooled under stirring to a normal temperature, whereupon a milk-white polyurethane dispersion (1) having a solid content of 30% was obtained.
2. 1000 Parts of 1,4-butaneethylene adipate (average molecular weight: about 1000, hydroxyl group value: 112), 140 parts of 1,4-butanediol, 1140 parts of methylethyl ketone and 650 parts of diphenylmethane diisocyanate were reacted at 70� C. for 8 hours, and then 3042 parts of methylethyl ketone was added and homogeneously mixed. The mixture was cooled to a normal temperature under stirring, whereupon a milk-white polyurethane dispersion (2) having a solid content of 30% was obtained.
3. 1000 Parts of 1,6-hexamethylene adipate (average molecular weight: 2000, hydroxyl group value: 56), 125 parts of 1,4-butandiol and 472 parts of diphenylmethane diisocyanate were added to 1200 parts of methylethyl ketone and reacted at 70� C. for 8 hours, and then 2526 parts of methylethyl ketone was further added and homogeneously mixed. The mixture was cooled to normal temperature under stirring, whereupon a milk-white polyurethane dispersion (3) having a solid content of 30% was obtained. 4. 4000 Parts of polypropylene glycol (average molecular weight: about 2000, hydroxyl group value: 56) and 750 parts of diphenylmethane diisocyanate were reacted at 80� C. for 3 hours, and then 2000 parts of methylethyl ketone was added. The reaction system was adequately homogeneously mixed, and 2000 parts of polyethylene glycol (molecular weight: about 1000, hydroxyl group value: 112) was added thereto. The mixture was reacted at 75� C. for 5 hours, and then 2500 parts of methylethyl ketone was additionally added. The mixture was homogeneously stirred, whereupon a polyurethane solution (4) having a solid content of 60% and a polyethylene glycol content of about 29.6% was obtained.
5. 4000 Parts of 1,4-butaneethylene adipate (average molecular weight: 2000, hydroxyl group value: 56) and 786 parts of hydrogenated diphenylmethane diisocyanate were reacted at 110� C. for 4 hours, and then 1500 parts of methylethyl ketone was added thereto. The mixture was adequately homogeneously mixed. To this solution, 1400 parts of polyethylene glycol (average molecular weight: about 700, hydroxyl group value: 160) was added and reacted at 80� C. for 10 hours, and then 2624 parts of methylethyl ketone was added. The mixture was stirred until a homogeneous mixture was obtained, whereby a polyurethane solution (5) having a solid content of 60% and a polyethylene glycol content of 22.6% was obtained.
6. 6000 Parts of polytetramethylene glycol (average molecular weight: about 2000, hydroxyl group value: 56) and 750 parts of diphenylmethane diisocyanate were reacted at 80� C. for 3 hours, and then 2000 parts of methylethyl ketone was added. The mixture was adequately homogeneously mixed. To this solution, 3000 parts of polyethylene glycol (average molecular weight: about 1500, hydroxyl group value: 75) was added and reacted at 75� C. for 5 hours, and then 3167 parts of methylethyl ketone was further added. The mixture was homogeneously mixed, whereupon a polyurethane solution (6) having a solid content of 60% and a polyethylene glycol content of 38.7% was obtained.
(Preparation of polyurethane emulsions)
______________________________________7.  Polyurethane dispersion (1)                  100 parts    Polyurethane solution (4)                  4 parts    Methylethyl ketone 20 parts     Polyurethane    Toluene            20 parts     emulsion (7)    Water              80 parts8.  Polyurethane dispersion (1)                  100 parts    Polyurethane solution (5)                  5 parts    Dioxane            10 parts    Toluene            10 parts     Polyurethane    Xylene             20 parts     emulsion (8)    Water              60 parts9.  Polyurethane dispersion (2)                  100 parts    Polyurethane solution (5)                  3 parts    Methylethyl ketone 20 parts     Polyurethane    Xylol              20 parts     emulsion (9)    Water              75 parts10. Polyurethane dispersion (2)                  100 parts    Polyurethane solution (6)                  2 parts    Tetrahydrofuran    20 parts     Polyurethane    Xylene             20 parts     emulsion (10)    Water              80 parts11. Polyurethane dispersion (3)                  100 parts    Polyurethane solution (6)                  5 parts    Methylethyl ketone 20 parts     Polyurethane    Methylisobutyl ketone                  20 parts     emulsion (11)    Water              79 parts12. Polyurethane dispersion (3)                  100 parts    Polyurethane solution (4)                  4 parts    Ethylacetate       20 parts     Polyurethane    Methylethyl ketone 150 parts    emulsion (12)    Water              80 parts______________________________________
______________________________________1.  Polyurethane dispersion (1)                  100 parts    Polyurethane solution (4)                  0.3 parts    Methylethyl ketone 20 parts     Polyurethane    Toluene            20 parts     emulsion (13)    Water              80 parts2.  Polyurethane dispersion (1)                  100 parts    Polyurethane solution (4)                  10 parts    Methylethyl ketone 20 parts     Polyurethane    Toluene            20 parts     emulsion (14)    Water              80 parts______________________________________
TABLE 1______________________________________                          SolidEmulsions   Viscosity Stability    contents                                 b/a______________________________________7       20,000 (cps)             No change for                          14.5 (%)                                 92.6/7.4             one month or             more8       14,000    No change for                          16.0   90.9/9.1             one month or             more9       25,000.   No change for                          14.6   94.3/5.7             one month or             more10      23,000    No change for                          14.1   96.2/3.8             one month or             more11      31,000.   No change for                          15.3   90.9/9.1             one month or             more12        110     No change for                           9.2   92.6/7.4             one month or             more13      15,000    Phase separa-                          13.7   99.4/0.6             tion in 2 hours14      22,000    No change for                          15.7   83.3/16.7             one month or             more______________________________________ *In the above Table b/a is the hydrophobic polyurethane/hydrophilic polyurethane.
TABLE 2______________________________________(production conditions)                   Coated (or  Emul-   Sub-     impregnated)                             DryingExamples  sions   strates  amounts (g/m2)                             conditions______________________________________13     7       Release  200 (coated)                             80� C. for 2 min. +          paper              125� C. for 2 min.14     7       Nylon    600 (coated)                             80� C. for 2 min. +          taffeta            125� C. for 2 min.15     8       Cotton   400 (coated)                             80� C. for 2 min. +          fabric             125� C. for 2 min.16     9       T/R      800 (coated)                             80� C. for 3 min. +          Raised             140� C. for 3 min.          fabric17     10      Cotton   300 (coated)                             80� C. for 2 min. +          fabric             125� C. for 2 min.18     11      Tetlon   500 (coated)                             80� C. for 2 min. +          taffeta            125� C. for 2 min.19     12      Non-     1000 (impreg-                             90� C. for 3 min. +          woven    nated)    140� C. for 3 min.          fabric20     14      Release  200 (coated)                             80� C. for 2 min. +(Com-          paper              125� C. for 2 min.parativeexmp)______________________________________
TABLE 3______________________________________(characteristics of sheets)         Apparent       Moisture Outer   specific       permeability                                  InternalExam- appear- gravity  Thick-                        (g/m2 /24 hrs.)                                  porousples  ance    (g/cm3)                  ness  (JIS Z 0208 B)                                  Structure______________________________________13    White   0.452     64   3,750     Uniformly                                  fine14    "       0.515    169   3,450     Uniformly                                  fine15    "       0.594    108   3,210     Uniformly                                  fine16    "       0.538    217   3,160     Uniformly                                  fine17    "       0.623     67   2,870     Uniformly                                  fine18    "       0.506    151   3,560     Uniformly                                  fine19    "       --       --    2,650     Uniformly                                  fine20    Trans-  0.892     35     150     No porous lucent                           sheet was                                  obtainable______________________________________
Patent CitationsCited PatentFiling datePublication dateApplicantTitleUS3418198 *Nov 14, 1966Dec 24, 1968Du PontNon-roughening microporous laminate and process for producing the sameUS3546001 *Feb 11, 1969Dec 8, 1970Inmont CorpMethod of producing tough breathable coating of polyurethane on fabricsUS3582396 *Jul 31, 1968Jun 1, 1971Bayer AgPolyurethane microporous sheet structures and a process for the preparation thereofUS4233359 *Nov 8, 1978Nov 11, 1980Teijin LimitedLeathery sheet material and process for the preparation thereofGB1294711A * Title not availableGB1501244A * Title not availableGB2009192A * Title not available* Cited by examinerReferenced byCiting PatentFiling datePublication dateApplicantTitleUS4656057 *Jul 17, 1985Apr 7, 1987Rohm And Haas CompanyMicrobiocidal article for aqueous systemsUS4728542 *Jun 13, 1986Mar 1, 1988Bayer AktiengesellschaftIonically modified pur spreading pastes and their useUS5652278 *May 9, 1994Jul 29, 1997Imperial Chemical Industries PlcMicrovoid polyurethane materialsUS5763502 *Jun 7, 1995Jun 9, 1998Imperial Chemical Industries PlcMicrovoid polyurethane materialsUS9133299 *Jul 16, 2012Sep 15, 2015Lg Chem, Ltd.Poly-urethane resin and poly-urethane absorbing pad using the sameUS20130018118 *Jan 17, 2013Lg Chem, Ltd.Poly-urethane resin and poly-urethane absorbing pad using the sameCN1095899C *Jun 30, 1999Dec 11, 2002可乐丽股份有限公司Manufacturing process for leather-like sheetEP1270801A1 *Feb 8, 2001Jan 2, 2003Matsumoto Yushi-Seiyaku Co., Ltd.Process for producing porous object* Cited by examinerClassifications U.S. Classification427/381, 427/389.9, 428/904, 427/385.5, 427/245, 428/423.1International ClassificationC08J9/28, C08J9/00, D06M15/564, C08L75/04, C09D175/04, D06N3/14, C08J3/09, B32B5/18Cooperative ClassificationY10T428/31551, Y10S428/904, C08J2375/04, D06N3/14, D06N3/141, C09D175/04, C08J9/283, C08J3/091, D06M15/564, C08L75/04European ClassificationC08J3/09B, C08J9/28B, C08L75/04, C09D175/04, D06N3/14B, D06M15/564, D06N3/14Legal EventsDateCodeEventDescriptionDec 10, 1984ASAssignmentOwner name: DAINICHISEIKA COLOR & CHEMICALS MFG. CO., LTD., 7-Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:KURIYAMA, KATSUMI;KONDO, ISAO;MISAIZU, IWAO;REEL/FRAME:004339/0310Effective date: 19830715Owner name: UKIMA COLOUR & CHEMICALS MFG. CO., LTD., 7-6, BAKUFree format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:KURIYAMA, KATSUMI;KONDO, ISAO;MISAIZU, IWAO;REEL/FRAME:004339/0310Effective date: 19830715Owner name: DAINICHISEIKA COLOR & CHEMICALS MFG. CO., LTD.,JAPFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:KURIYAMA, KATSUMI;KONDO, ISAO;MISAIZU, IWAO;REEL/FRAME:004339/0310Effective date: 19830715Owner name: UKIMA COLOUR & CHEMICALS MFG. CO., LTD.,JAPANFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:KURIYAMA, KATSUMI;KONDO, ISAO;MISAIZU, IWAO;REEL/FRAME:004339/0310Effective date: 19830715Sep 7, 1988FPAYFee paymentYear of fee payment: 4Aug 11, 1992FPAYFee paymentYear of fee payment: 8Sep 9, 1996FPAYFee paymentYear of fee payment: 12RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services