WO2007142425A1 - Process for preparing non-yellowing flexible polyurethane foam with high resilience and durability - Google Patents

Process for preparing non-yellowing flexible polyurethane foam with high resilience and durability Download PDF

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Publication number
WO2007142425A1
WO2007142425A1 PCT/KR2007/002637 KR2007002637W WO2007142425A1 WO 2007142425 A1 WO2007142425 A1 WO 2007142425A1 KR 2007002637 W KR2007002637 W KR 2007002637W WO 2007142425 A1 WO2007142425 A1 WO 2007142425A1
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WO
WIPO (PCT)
Prior art keywords
weight
parts
glycol
polyol
polyurethane foam
Prior art date
Application number
PCT/KR2007/002637
Other languages
French (fr)
Inventor
Joung-Yun Ko
Chang-Ha Park
In-Ha Park
Sung-Ho Lee
Dong-Kwon Heo
Original Assignee
Skc Co., Ltd.
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Filing date
Publication date
Application filed by Skc Co., Ltd. filed Critical Skc Co., Ltd.
Publication of WO2007142425A1 publication Critical patent/WO2007142425A1/en

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    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
    • C08G18/722—Combination of two or more aliphatic and/or cycloaliphatic polyisocyanates
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
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    • C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
    • C08G18/163—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22
    • C08G18/165—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22 covered by C08G18/18 and C08G18/24
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    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C—CHEMISTRY; METALLURGY
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
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    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1833—Catalysts containing secondary or tertiary amines or salts thereof having ether, acetal, or orthoester groups
    • C—CHEMISTRY; METALLURGY
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    • C08G18/20—Heterocyclic amines; Salts thereof
    • C08G18/2045—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings
    • C08G18/2054—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings having one nitrogen atom in the condensed ring system
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    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
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    • C08G18/2045—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings
    • C08G18/2063—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings having two nitrogen atoms in the condensed ring system
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/242—Catalysts containing metal compounds of tin organometallic compounds containing tin-carbon bonds
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/409—Dispersions of polymers of C08G in organic compounds having active hydrogen
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C—CHEMISTRY; METALLURGY
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
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    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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    • C08G18/48—Polyethers
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    • C08G18/40—High-molecular-weight compounds
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    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/02—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by the reacting monomers or modifying agents during the preparation or modification of macromolecules
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
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    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a process for preparing a flexible polyurethane foam having yellowing resistance while securing a stable foam structure and high resilience and durability. More specifically, the present invention relates to a process for preparing a flexible polyurethane foam having high yellowing resistance via catalytic reaction of isocyanates with polyols, the process comprising reacting a resin premix composed of
  • a polyol including combined use of (A) a polyether polyol having an ethylene oxide content of 0 to 30% by weight, a propylene oxide content of 70 to 100% by weight and a molecular weight of 400 to 7,000, (B) a polyether polyol containing 20 to 60% by weight of solids of a polyvinyl compound and (C) a polyester polyol which is synthesized by polycondensation of an alcohol with an acid and has a functionality of 2 to 3 and a viscosity of 5,000 to 30,000 cps,
  • Flexible polyurethane can achieve numerous physical properties and have unique resilience/lightweightness, and therefore are widely used as cushioning materials of bedclothes, materials of apparel products, shoe materials and for medical applications.
  • Non-yellowing polyurethane techniques utilizing aliphatic or cycloaliphatic isocyanates are not widely known in flexible urethane fields and particularly there is very little known about techniques relating to foams having a low density of not more than 50 kg/m .
  • representative conventional arts of non-yellowing polyurethane foams including processes for preparing foams having a high density of not less than 50 kg/m are disclosed in Japanese Patent Examined Publication Nos. Sho 52-030437 and Sho 54-015599, Japanese Patent Unexamined Publication Nos. Sho 54-162795, Hei 4-239016, 2000-226429, 2000-273136, 2001-72738 and 2001-278942, US Patent Nos. 4,067,832, 6,031,013 and 6,191,179, and US Patent Application Publication No. 2002/0035165.
  • Japanese Patent Examined Publication No. Sho 52-030437 discloses a polyurethane foam having improved weatherability while maintaining physical properties thereof, using aliphatic or cycloaliphatic isocyanates in conjunction with a certain catalyst.
  • Japanese Patent Examined Publication No. Sho 54-015599 discloses a method of obtaining color stability of polyurethane, using polyisocyanate wherein no NCO group is directly bound to an aromatic ring, as an isocyanate compound and a certain catalyst.
  • Japanese Patent Unexamined Publication No. Sho 54-162795 discloses polyurethane having improved photostability, i.e., reduced light-induced yellowness, via combined use of aliphatic or cycloaliphatic polyisocyanates with at least one compound selected from hydroxides, alcoholates or phenolates of alkali metals, alkali metal salts of weak acids and hexahydrotriazine-S-derivatives, and at least one compound selected from organic compounds of lead, zinc and iron.
  • Japanese Patent Unexamined Publication No. 2001-72738 discloses a process for preparing a non-yellowing polyurethane foam having a swelling rate of not more than 15% in an aqueous solution containing 0.5% by weight of an alkaline detergent, which comprises reacting a polyol having an oxy ethylene content of not more than 18% by weight with aliphatic polyisocyanate in the presence of a certain catalyst, followed by curing the resulting product.
  • US Patent No. 4,025,466 discloses a process for the preparation of a low-density, flexible foam having a density of 27 to 37 kg/m 3 , using diethylene glycol/adipate polyester polyol or polyether polyol as a polyol component, isophorone diisocyanate or hydrogenated diphenylmethane diisocyanate as an isocyanate compound, and a catalyst combination comprising diazabicycloalkene and metal salts of carboxylic acids.
  • US Patent No. 6,031,013 discloses preparation of a foam for non-yellowing furniture having a density of 50 to 80 g/L, comprising reacting isocyanates having biuret or iso- cyanurate structures with a mixture of polyols having a molecular weight of from 400 to 8,000 and including a polyol containing at least 50% primary hydroxyl groups, blowing agents, catalysts consisting of a mixture of a metal salt and amine compound at a temperature of 40? or higher.
  • isocyanates having biuret or iso- cyanurate structures with a mixture of polyols having a molecular weight of from 400 to 8,000 and including a polyol containing at least 50% primary hydroxyl groups, blowing agents, catalysts consisting of a mixture of a metal salt and amine compound at a temperature of 40? or higher.
  • 6,191,179 discloses preparation of a foam having a density of 30 to 78 g/L, comprising reacting isocyanates having biuret or isocyanurate structures with a mixture of polyols having a molecular weight of from 400 to 8,000 and including at least one polyol containing at least 50% primary hydroxyl groups, compounds having primary amine groups, for example diethanol amine and N,N-dimethylpropylene diamine, blowing agents, tin and tertiary amine catalysts, at a temperature of 25 to 35?.
  • US Patent Application Publication No. 2002/0035165 describes addition of acrylate polyols in order to supplement inferior physical properties of aliphatic or cy- cloaliphatic isocyanate foams.
  • Korean Patent Registration No. 0525352 discloses a process for preparing a polyurethane foam, wherein a ratio of tin octoate:dibutyltin dilaurate is set to 1:0.5 to 10% by weight relative to the polyol weight, and 0.05 to 5% by weight of metal carboxylate catalysts.
  • Anti-yellowing urethane is produced via reaction of aliphatic or cycloaliphatic isocyanates, but low reactivity of such isocyanates usually involves the use of an excess amount of a catalyst which consequently excessively raises the reactivity, thereby resulting in unstable foam profiles. Further, the resulting urethane foams suffer from weak or unstable polymer chains, thus undergoing disintegration, due to in- completion of urethane resin reaction, or resilience and durability of the produced urethane foam tend to decrease as compared to conventional foams using aromatic isocyanates. Therefore, the present invention has been made in view of the above problems, and it is an object of the present invention to provide a non-yellowing foam having superior resilience and durability via optimization of polyol components and isocyanates.
  • a polyol including (A) 10 to 90% by weight of a polyether polyol having an ethylene oxide content of 0 to 30% by weight, a propylene oxide content of 70 to 100% by weight and a molecular weight of 400 to 7,000 and (B) 10 to 90% by weight of a polyether polyol containing 20 to 60% by weight of solids of a polyvinyl compound,
  • a polyol including (A) 5 to 90% by weight of a polyether polyol having an ethylene oxide content of 0 to 30% by weight, a propylene oxide content of 70 to 100% by weight and a molecular weight of 400 to 7,000, (B) 5 to 90% by weight of a polyether polyol containing 20 to 60% by weight of solids of a polyvinyl compound and (C) 1 to 80% by weight of a polyester polyol which is synthesized by polycondensation of an alcohol with an acid and has a functionality of 2 to 3 and a viscosity of 5,000 to 30,000 cps;
  • a polyol that can be used in the present invention is preferably a mixture of (A) a polyether polyol having a functionality of 2 to 5, an ethylene oxide content of 0 to 30% by weight and a propylene oxide content of 70 to 100% by weight and a molecular weight of 400 to 7,000, preferably a polyether polyol having a functionality of 2 to 3, an ethylene oxide content of 10 to 20% by weight and a molecular weight of 400 to 7,000 and (B) a polyether polyol containing 30 to 50% by weight of solids in the form of a copolymer of acrylonitrile and styrene monomer, which are vinyl compounds.
  • a mixing ratio of polyols (A):(B) is preferably in a range of 10 to 90% by weight : 90 to 10% by weight.
  • polyester polyol may also be employed as a polyol component that is utilizable in the present invention.
  • Polyester polyol is synthesized by alcohol-acid polycondensation.
  • examples of the alcohol may include trimethyl propanol, dipropyl glycol, tripropyl glycol, propyl glycol, diethyl glycol, ethyl glycol and the like
  • examples of the acid may include terephthalic acid, adipic acid, dimethyl acid and the like.
  • the polyester polyol, which is synthesized by polycondensation of an alcohol with an acid preferably has a functionality of 2 to 3 and a viscosity of 5,000 to 30,000 cps.
  • polyol of the present invention may employ a mixture of polyols
  • a mixing ratio of polyols (A):(B):(C) is preferably in a range of 5-90:5-90: 1-80.
  • aliphatic or cycloaliphatic isocyanates that can be used in the present invention may include 1,6-hexamethylene diisocyanate, isophorone di- isocyanate, methylene dicyclohexylisocyanate, hydrogenated 4,4'-diamino diphenylmethane, lysine diisocyanate, a monomer or oligomer of 2,5 (2,6)-bis(isocyanatomethyl)bicyclo(2.2.1)heptane, and the like.
  • 1,6-hexamethylene diisocyanate, isophorone diisocyanate or a monomer or oligomer of 2,5 (2,6)-bis(isocyanatomethyl)bicyclo(2.2.1)heptane is particularly preferably used.
  • Aliphatic isocyanates and cycloaliphatic isocyanates may be used in a ratio of 5-90:10-95 equivalent %, preferably 20-50:50-80 equivalent %. These ranges are preferred for stable production of foams due to achievement of the balance between proper blowing reaction and gelling reaction.
  • ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, diethyl toluene diamine, glycerin, diethanol amine and triethanol amine which is used singly or in any combination thereof, may be used in a range of 0.1 to 2.5% by weight. If a content of the cross-linking agent is higher than the above-specified range, the stable production range of foams is undesirably narrowed as occurrence of closed cells is significantly increased.
  • a catalyst for resinification of the present invention simultaneous use of a tin catalyst and an amine catalyst is preferred to exert synergistic effects of resinification.
  • the tin catalyst may include tin octoate and dibutyltin dilaurate, which are preferably used in a combination thereof.
  • tin octoate is preferably used in a range of 0.2 to 10.0 parts by weight and dibutyltin dilaurate is preferably used in a range of 0.2 to 10.0 parts by weight.
  • amine catalyst a strong blowing catalyst is used in admixture with a balance catalyst.
  • amine catalyst may include Methylene diamine, triethylamine, bis(dimethylaminoethyl)ether, N,N,N'-trimethylaminoethylethanolamine, bis(N,N- dimethylaminoethyl)ether, N,N'-dimethylpiperazine, pentamethyldipropyltriamine, l,8-diazabicyclo(5,4,0)undecane-7, N-(N',N'-2-dimethylaminoethyl)morpholine, tri(dimethylaminemethyl)phenol, 33% triethylene diamine dissolved in dipropylene glycol and the like.
  • the amine catalyst is preferably used in a range of 0.5 to 5.0 parts by weight. If the amine catalyst is used in an amount of less than 0.5 parts by weight, blowing reaction of the foam is retarded and therefore underrunning of processes or shrinkage of the foam tends to occur. Conversely, if the content of the amine catalyst is higher than 5.0 parts by weight, it is likely to result in disintegration or splitting of the foam.
  • the silicone surfactant that can be used in the present invention is commercially available and includes, for example L-580, L-600, L-603, L-3002, L-626 and L-627 (Crompton), DABOC DC-198, DC-5230 and DC-5388 (Air Products) and BF- 2370, B4900, B-8002 and B-8680 (Degussa) and any combination thereof.
  • L-626, DC-198, B-8002, or any combination thereof may be used in a range of 0.5 to 4.5% by weight. If the silicone surfactant is used in an excess amount outside the above range, large amounts of closed cells are produced, thereby adversely affecting elongation or durability of the resulting foams.
  • the amount of the silicone surfactant used is too low, this may result in disintegration or splitting of the foam.
  • blowing agent that can be used in the present invention, there may be mentioned water, methylene chloride, liquid carbon dioxide, n-pentane and hy- drogenated chloro fluoro carbon (HCFC), which are appropriately selected and used depending upon desired applications and density.
  • the blowing agent is preferably used in a range of 0.2 to 5.0 parts by weight.
  • UV stabilizers and antioxidants are not particularly limited as long as they are conventionally used in the art to which the present invention pertains.
  • a resin premix was prepared according to the composition formula for polyols, water, a cross-linking agent, catalysts, a surfactant and a stabilizer, which is given in Table 1 below.
  • the resin premix was mixed with diisocyanate having an isocyanate index of 110, and the resulting mixture was stirred at 5,000 rpm for 8 seconds, thereby preparing a flexible urethane foam.
  • Diisocyanate was a mixture of 1,6-hexamethylene diisocyanate and isophorone diisocyanate in an equivalence ratio of 5:5.
  • Diisocyanates used in Examples 2 through 4 were the same as in Example 1.
  • polyurethane foams were prepared in the same manner as in Example 1, except that Example 2 included changes in kinds of amine catalysts, and Examples 3 and 4 included changes in amounts of water in order to increase density of the foam, in conjunction with varied kinds of cross-linking agents and amounts of polyol B.
  • the composition formula of the respective polyurethane foams, which were used in Examples 2 through 4, is set forth in Table 1 below.
  • a polyurethane foam was prepared in the same manner as in Example 1.
  • the composition formula of the polyurethane foam used is set forth in Table 1 below.
  • a polyurethane foam was prepared in the same manner as in Example 1.
  • the composition formula of the polyurethane foam used is set forth in Table 1 below.
  • Comparative Examples 1 and 2 employed isophorone diisocyanate, whereas Comparative Example 3 employed tolune diisocyanate-80.
  • Comparative Example 1 employed only a polyether polyol containing no solids of a polyvinyl compound as a polyol component and isophorone diisocyanate as a diisocyanate component
  • Comparative Example 2 employed isophorone diisocyanate alone as an aliphatic isocyanate, for comparison of physical properties of the foams.
  • Comparative Example 3 a low-yellowing polyurethane foam was prepared in which tolune diisocyanate-80 was used as an isocyanate component and yellowing was delayed by addition of a light stabilizer.
  • Polyol A Polypropylene glycol having an average molecular weight of 3,500 (48 mg
  • Polyol B Polypropylene glycol containing 25% by weight of solids of a copolymer of acrylonitrile and styrene monomer (YUKOL 1564, SKC, Korea)
  • Polyol C Ester polyol having a functionality of 2.7 and a viscosity of 20,000 cps
  • Catalyst 1 Bis(dimethylaminoethyl)ether
  • Catalyst 2 Triethylene diamine
  • Catalyst 3 33% triethylene diamine dissolved in dipropylene glycol
  • Catalyst 4 Pentamethyldipropylenetriamine
  • Catalyst 5 l,8-diazabicyclo(5,4,0)undecane-7
  • Catalyst 6 Tin octoate
  • Catalyst 7 Dibutyltin dilaurate
  • Surfactant L-626 (GE)
  • Stabilizer Tinuvin B 75 (Ciba Specialty Chemicals)
  • Isocyanates Examples 1 through 5 employed a mixture of 1,6-hexamethylene di- isocyanate and isophorone diisocyanate in an equivalence ratio of 5:5. Comparative Examples 1 and 2 employed isophorone diiso
  • Aromatic isocyanate Comparative Example 3 employed tolune diisocyanate-80.
  • Test for Reactivity and Physical properties of foams [85] Upon foaming of urethane, reactivity of the resulting urethane foam was evaluated by measuring a cream time (sec) and a rise time (sec) using a stopwatch. Stability of the foam was determined by observing a degree of settling down of the foam by naked eyes, after reaching a maximum height upon foaming of urethane. In addition, resilience and durability of the foam were respectively measured according to ASTM D3574. The results thus obtained are shown in Table 2 below.
  • Example 1 Upon comparing Example 1 with Comparative Example 2, it can be seen that the flexible polyurethane foam of Example 1 exhibited sharp increases in resilience and durability thereof, as compared to Comparative Example 2. Further, it can also be seen that the resilience and durability of the foams are maintained even with increasing contents of poly ol B.
  • Example 1 and Comparative Example 3 Flexible polyurethane foams obtained in Example 1 and Comparative Example 3 were respectively placed in a light-fastness tester (available from KYUNG JIN INSTRUMENTS, Busan, KOREA), and a yellowness index of the foams was measured for 0 to 40 hours, at intervals of 10 hours, according to methods specified under ASTM E313-96 and ASTM D 1925.
  • a light source of the light-fastness tester was a 300W sunlight lamp (available from Osram). The test results thus obtained are shown in FTG. 1.
  • FTG. 1 is a graph showing Yellowness Index (YI) of flexible polyurethane foams obtained in Example 1 of the present invention and Comparative Example 3.
  • YI Yellowness Index
  • YI Yellowness Index
  • urethane prepared according to the process of the present invention have stable moldability, resilience and durability while exhibiting yellowing resistance even upon prolonged exposure to light, and therefore can substitute conventional urethane utilizing aromatic isocyanates, which has been used in clothes, hygienic articles, automobile utensils, as well as for packaging materials, medical materials, and the like.

Abstract

Provided is a process for preparing a flexible polyurethane foam via catalytic reaction of isocyanates with polyols. The process comprises reacting a resin premix, which simultaneously utilizes a polyol including combined use of (A) a polyether polyol having an ethylene oxide content of 0 to 30% by weight, a propylene oxide content of 70 to 100% by weight and a molecular weight of 400 to 7,000 and (B) a polyether polyol containing 20 to 60% by weight of solids of a polyvinyl compound, or (C) a polyester polyol which is synthesized by polycon-densation of an alcohol with an acid and has a functionality of 2 to 3 and a viscosity of 5,000 to 30,000 cps, or a mixture of polyols A, B and C, a mixed catalyst of tin octoate and dibutyltin dilaurate, and amine catalysts, with aliphatic isocyanates having modified reactivity, thereby preparing a flexible urethane foam having superior yellowing resistance.

Description

Description
PROCESS FOR PREPARING NON- YELLO WING FLEXIBLE POLYURETHANE FOAM WITH HIGH RESILIENCE AND
DURABILITY
Technical Field
[1] The present invention relates to a process for preparing a flexible polyurethane foam having yellowing resistance while securing a stable foam structure and high resilience and durability. More specifically, the present invention relates to a process for preparing a flexible polyurethane foam having high yellowing resistance via catalytic reaction of isocyanates with polyols, the process comprising reacting a resin premix composed of
[2] i) a polyol including combined use of (A) a polyether polyol having an ethylene oxide content of 0 to 30% by weight, a propylene oxide content of 70 to 100% by weight and a molecular weight of 400 to 7,000 and (B) a polyether polyol containing 20 to 60% by weight of solids of a polyvinyl compound,
[3] ii) (C) a polyester polyol which is synthesized by polycondensation of an alcohol with an acid and has a functionality of 2 to 3 and a viscosity of 5,000 to 30,000 cps, or
[4] iii) a polyol including combined use of (A) a polyether polyol having an ethylene oxide content of 0 to 30% by weight, a propylene oxide content of 70 to 100% by weight and a molecular weight of 400 to 7,000, (B) a polyether polyol containing 20 to 60% by weight of solids of a polyvinyl compound and (C) a polyester polyol which is synthesized by polycondensation of an alcohol with an acid and has a functionality of 2 to 3 and a viscosity of 5,000 to 30,000 cps,
[5] a mixed catalyst of tin octoate and dibutyltin dilaurate, and
[6] amine catalysts
[7] with aliphatic and cycloaliphatic isocyanates having modified reactivity.
[8]
Background Art
[9] Flexible polyurethane can achieve numerous physical properties and have unique resilience/lightweightness, and therefore are widely used as cushioning materials of bedclothes, materials of apparel products, shoe materials and for medical applications.
[10] However, conventional polyurethane foams primarily employ aromatic compounds such as toluene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI), which convert into a structure of an azo compound or quinone imide upon exposure thereof to light, thereby resulting in formation of yellow or brown appearance. Such changes do not directly lead to significant deterioration in physical properties but give rise to unpleasant impression in external appearance of products, thus resulting in decreased saleability of some products. Therefore, UV stabilizers and UV absorbers are usually added to delay such yellowing, upon synthesis of urethane, but it is impossible to fundamentally block occurrence of a yellowing phenomenon without excluding the use of aromatic isocyanates which are main causes of such yellowing. It is known that essential prevention of the yellowing phenomenon can be made via synthesis of urethane using aliphatic or cycloaliphatic isocyanates as an isocyanate compound.
[11] Non-yellowing polyurethane techniques utilizing aliphatic or cycloaliphatic isocyanates are not widely known in flexible urethane fields and particularly there is very little known about techniques relating to foams having a low density of not more than 50 kg/m . Meanwhile, representative conventional arts of non-yellowing polyurethane foams including processes for preparing foams having a high density of not less than 50 kg/m are disclosed in Japanese Patent Examined Publication Nos. Sho 52-030437 and Sho 54-015599, Japanese Patent Unexamined Publication Nos. Sho 54-162795, Hei 4-239016, 2000-226429, 2000-273136, 2001-72738 and 2001-278942, US Patent Nos. 4,067,832, 6,031,013 and 6,191,179, and US Patent Application Publication No. 2002/0035165.
[12] Japanese Patent Examined Publication No. Sho 52-030437 discloses a polyurethane foam having improved weatherability while maintaining physical properties thereof, using aliphatic or cycloaliphatic isocyanates in conjunction with a certain catalyst. Japanese Patent Examined Publication No. Sho 54-015599 discloses a method of obtaining color stability of polyurethane, using polyisocyanate wherein no NCO group is directly bound to an aromatic ring, as an isocyanate compound and a certain catalyst.
[13] Japanese Patent Unexamined Publication No. Sho 54-162795 discloses polyurethane having improved photostability, i.e., reduced light-induced yellowness, via combined use of aliphatic or cycloaliphatic polyisocyanates with at least one compound selected from hydroxides, alcoholates or phenolates of alkali metals, alkali metal salts of weak acids and hexahydrotriazine-S-derivatives, and at least one compound selected from organic compounds of lead, zinc and iron.
[14] Japanese Patent Unexamined Publication No. 2001-72738 discloses a process for preparing a non-yellowing polyurethane foam having a swelling rate of not more than 15% in an aqueous solution containing 0.5% by weight of an alkaline detergent, which comprises reacting a polyol having an oxy ethylene content of not more than 18% by weight with aliphatic polyisocyanate in the presence of a certain catalyst, followed by curing the resulting product.
[15] US Patent No. 4,025,466 discloses a process for the preparation of a low-density, flexible foam having a density of 27 to 37 kg/m3, using diethylene glycol/adipate polyester polyol or polyether polyol as a polyol component, isophorone diisocyanate or hydrogenated diphenylmethane diisocyanate as an isocyanate compound, and a catalyst combination comprising diazabicycloalkene and metal salts of carboxylic acids.
[16] US Patent No. 6,031,013 discloses preparation of a foam for non-yellowing furniture having a density of 50 to 80 g/L, comprising reacting isocyanates having biuret or iso- cyanurate structures with a mixture of polyols having a molecular weight of from 400 to 8,000 and including a polyol containing at least 50% primary hydroxyl groups, blowing agents, catalysts consisting of a mixture of a metal salt and amine compound at a temperature of 40? or higher. US Patent No. 6,191,179 discloses preparation of a foam having a density of 30 to 78 g/L, comprising reacting isocyanates having biuret or isocyanurate structures with a mixture of polyols having a molecular weight of from 400 to 8,000 and including at least one polyol containing at least 50% primary hydroxyl groups, compounds having primary amine groups, for example diethanol amine and N,N-dimethylpropylene diamine, blowing agents, tin and tertiary amine catalysts, at a temperature of 25 to 35?.
[17] US Patent Application Publication No. 2002/0035165 describes addition of acrylate polyols in order to supplement inferior physical properties of aliphatic or cy- cloaliphatic isocyanate foams.
[18] In addition, Korean Patent Registration No. 0525352 discloses a process for preparing a polyurethane foam, wherein a ratio of tin octoate:dibutyltin dilaurate is set to 1:0.5 to 10% by weight relative to the polyol weight, and 0.05 to 5% by weight of metal carboxylate catalysts.
[19]
Disclosure of Invention Technical Problem
[20] Anti-yellowing urethane is produced via reaction of aliphatic or cycloaliphatic isocyanates, but low reactivity of such isocyanates usually involves the use of an excess amount of a catalyst which consequently excessively raises the reactivity, thereby resulting in unstable foam profiles. Further, the resulting urethane foams suffer from weak or unstable polymer chains, thus undergoing disintegration, due to in- completion of urethane resin reaction, or resilience and durability of the produced urethane foam tend to decrease as compared to conventional foams using aromatic isocyanates. Therefore, the present invention has been made in view of the above problems, and it is an object of the present invention to provide a non-yellowing foam having superior resilience and durability via optimization of polyol components and isocyanates.
[21]
Technical Solution [22] In accordance with the present invention, the above and other objects can be accomplished by the provision of a process for preparing a flexible polyurethane foam having high yellowing resistance, comprising:
[23] reacting a resin premix composed of
[24] 100 parts by weight of a polyol including (A) 10 to 90% by weight of a polyether polyol having an ethylene oxide content of 0 to 30% by weight, a propylene oxide content of 70 to 100% by weight and a molecular weight of 400 to 7,000 and (B) 10 to 90% by weight of a polyether polyol containing 20 to 60% by weight of solids of a polyvinyl compound,
[25] (C) 100 parts by weight of a polyester polyol which is synthesized by polycon- densation of an alcohol with an acid and has a functionality of 2 to 3 and a viscosity of 5,000 to 30,000 cps, or
[26] 100 parts by weight of a polyol including (A) 5 to 90% by weight of a polyether polyol having an ethylene oxide content of 0 to 30% by weight, a propylene oxide content of 70 to 100% by weight and a molecular weight of 400 to 7,000, (B) 5 to 90% by weight of a polyether polyol containing 20 to 60% by weight of solids of a polyvinyl compound and (C) 1 to 80% by weight of a polyester polyol which is synthesized by polycondensation of an alcohol with an acid and has a functionality of 2 to 3 and a viscosity of 5,000 to 30,000 cps;
[27] 0.1 to 2.5 parts by weight of a cross-linking agent;
[28] 0.5 to 5.0 parts by weight of tin octoate;
[29] 1.0 to 10 parts by weight of dibutyltin dilaurate;
[30] 0.5 to 5.0 parts by weight of an amine catalyst;
[31] 0.2 to 3 parts by weight of a silicone surfactant; and
[32] 0.2 to 5 parts by weight of a blowing agent
[33] with aliphatic and cycloaliphatic isocyanates in an isocyanate index of 90 to 130.
[34]
Brief Description of the Drawings
[35] The above and other objects, features and other advantages of the present invention will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawing, in which: [36] FlG. 1 is a graph showing Yellowness Index (YI) of flexible polyurethane foams obtained in Example 1 of the present invention and Comparative Example 3. [37]
Mode for the Invention
[38] Hereinafter, the present invention will be described in more detail.
[39] A polyol that can be used in the present invention is preferably a mixture of (A) a polyether polyol having a functionality of 2 to 5, an ethylene oxide content of 0 to 30% by weight and a propylene oxide content of 70 to 100% by weight and a molecular weight of 400 to 7,000, preferably a polyether polyol having a functionality of 2 to 3, an ethylene oxide content of 10 to 20% by weight and a molecular weight of 400 to 7,000 and (B) a polyether polyol containing 30 to 50% by weight of solids in the form of a copolymer of acrylonitrile and styrene monomer, which are vinyl compounds. A mixing ratio of polyols (A):(B) is preferably in a range of 10 to 90% by weight : 90 to 10% by weight.
[40]
[41] In addition to the above-mentioned polyether polyols (A) and (B), (C) polyester polyol may also be employed as a polyol component that is utilizable in the present invention. Polyester polyol is synthesized by alcohol-acid polycondensation. Specifically, examples of the alcohol may include trimethyl propanol, dipropyl glycol, tripropyl glycol, propyl glycol, diethyl glycol, ethyl glycol and the like, and examples of the acid may include terephthalic acid, adipic acid, dimethyl acid and the like. The polyester polyol, which is synthesized by polycondensation of an alcohol with an acid, preferably has a functionality of 2 to 3 and a viscosity of 5,000 to 30,000 cps.
[42] Furthermore, the polyol of the present invention may employ a mixture of polyols
(A), (B) and (C). Herein, a mixing ratio of polyols (A):(B):(C) is preferably in a range of 5-90:5-90: 1-80.
[43] In preparation of the non-yellowing flexible polyurethane foam according to the present invention, it is possible to prepare such a foam by modifying an aliphatic or cy- cloaliphatic isocyanate to have an isocyanate index of 90 to 130, followed by reacting with a resin premix including the above polyols and other additives such as catalysts.
[44] Specific examples of aliphatic or cycloaliphatic isocyanates that can be used in the present invention may include 1,6-hexamethylene diisocyanate, isophorone di- isocyanate, methylene dicyclohexylisocyanate, hydrogenated 4,4'-diamino diphenylmethane, lysine diisocyanate, a monomer or oligomer of 2,5 (2,6)-bis(isocyanatomethyl)bicyclo(2.2.1)heptane, and the like. Of these compounds, 1,6-hexamethylene diisocyanate, isophorone diisocyanate or a monomer or oligomer of 2,5 (2,6)-bis(isocyanatomethyl)bicyclo(2.2.1)heptane is particularly preferably used. Aliphatic isocyanates and cycloaliphatic isocyanates may be used in a ratio of 5-90:10-95 equivalent %, preferably 20-50:50-80 equivalent %. These ranges are preferred for stable production of foams due to achievement of the balance between proper blowing reaction and gelling reaction.
[45] As the cross-linking agent that can be used in the present invention, mention may be made of ethylene glycol, diethylene glycol, Methylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, diethyl toluene diamine, glycerin, diethanol amine, Methanol amine, and diol, triol and tetraol having a molecular weight of not more than 2,000, which may be used alone or as a mixture of two or three. Preferably, ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, diethyl toluene diamine, glycerin, diethanol amine and triethanol amine, which is used singly or in any combination thereof, may be used in a range of 0.1 to 2.5% by weight. If a content of the cross-linking agent is higher than the above-specified range, the stable production range of foams is undesirably narrowed as occurrence of closed cells is significantly increased.
[46] As a catalyst for resinification of the present invention, simultaneous use of a tin catalyst and an amine catalyst is preferred to exert synergistic effects of resinification. Examples of the tin catalyst may include tin octoate and dibutyltin dilaurate, which are preferably used in a combination thereof. In order to ensure stable production of foams, tin octoate is preferably used in a range of 0.2 to 10.0 parts by weight and dibutyltin dilaurate is preferably used in a range of 0.2 to 10.0 parts by weight.
[47] Further, as the amine catalyst, a strong blowing catalyst is used in admixture with a balance catalyst. Specific examples of the amine catalyst that can be used in the present invention may include Methylene diamine, triethylamine, bis(dimethylaminoethyl)ether, N,N,N'-trimethylaminoethylethanolamine, bis(N,N- dimethylaminoethyl)ether, N,N'-dimethylpiperazine, pentamethyldipropyltriamine, l,8-diazabicyclo(5,4,0)undecane-7, N-(N',N'-2-dimethylaminoethyl)morpholine, tri(dimethylaminemethyl)phenol, 33% triethylene diamine dissolved in dipropylene glycol and the like. The amine catalyst is preferably used in a range of 0.5 to 5.0 parts by weight. If the amine catalyst is used in an amount of less than 0.5 parts by weight, blowing reaction of the foam is retarded and therefore underrunning of processes or shrinkage of the foam tends to occur. Conversely, if the content of the amine catalyst is higher than 5.0 parts by weight, it is likely to result in disintegration or splitting of the foam.
[48] In addition, the silicone surfactant that can be used in the present invention is commercially available and includes, for example L-580, L-600, L-603, L-3002, L-626 and L-627 (Crompton), DABOC DC-198, DC-5230 and DC-5388 (Air Products) and BF- 2370, B4900, B-8002 and B-8680 (Degussa) and any combination thereof. Preferably, L-626, DC-198, B-8002, or any combination thereof may be used in a range of 0.5 to 4.5% by weight. If the silicone surfactant is used in an excess amount outside the above range, large amounts of closed cells are produced, thereby adversely affecting elongation or durability of the resulting foams. Conversely, if the amount of the silicone surfactant used is too low, this may result in disintegration or splitting of the foam. However, if necessary, it may be possible to perform a foaming process with increasing amounts of silicone, for formation of pores or the composition formula for which large amounts of the blowing agent are required.
[49] Furthermore, as the blowing agent that can be used in the present invention, there may be mentioned water, methylene chloride, liquid carbon dioxide, n-pentane and hy- drogenated chloro fluoro carbon (HCFC), which are appropriately selected and used depending upon desired applications and density. The blowing agent is preferably used in a range of 0.2 to 5.0 parts by weight.
[50] Additionally, polyurethane foams utilizing aliphatic or cycloaliphatic isocyanates exhibit superior yellowing resistance, but may suffer from occurrence of yellowing due to additives being used. Therefore, it is preferred to select and use proper UV stabilizers and antioxidants. UV stabilizers and antioxidants are not particularly limited as long as they are conventionally used in the art to which the present invention pertains.
[51] EXAMPLES
[52] Now, the present invention will be described in more detail with reference to the following examples. These examples are provided only for illustrating the present invention and should not be construed as limiting the scope and spirit of the present invention.
[53] Example 1
[54] A resin premix was prepared according to the composition formula for polyols, water, a cross-linking agent, catalysts, a surfactant and a stabilizer, which is given in Table 1 below. The resin premix was mixed with diisocyanate having an isocyanate index of 110, and the resulting mixture was stirred at 5,000 rpm for 8 seconds, thereby preparing a flexible urethane foam. Diisocyanate was a mixture of 1,6-hexamethylene diisocyanate and isophorone diisocyanate in an equivalence ratio of 5:5.
[55] Examples 2 through 4
[56] Diisocyanates used in Examples 2 through 4 were the same as in Example 1. In addition, polyurethane foams were prepared in the same manner as in Example 1, except that Example 2 included changes in kinds of amine catalysts, and Examples 3 and 4 included changes in amounts of water in order to increase density of the foam, in conjunction with varied kinds of cross-linking agents and amounts of polyol B. The composition formula of the respective polyurethane foams, which were used in Examples 2 through 4, is set forth in Table 1 below.
[57] Example 5
[58] Using an ester polyol as a polyol component, a polyurethane foam was prepared in the same manner as in Example 1. The composition formula of the polyurethane foam used is set forth in Table 1 below.
[59] Example 6
[60] Using a mixture of polyols A, B and C as a polyol component, a polyurethane foam was prepared in the same manner as in Example 1. The composition formula of the polyurethane foam used is set forth in Table 1 below.
[61] Comparative Examples 1 through 3
[62] As a diisocyanate compound, Comparative Examples 1 and 2 employed isophorone diisocyanate, whereas Comparative Example 3 employed tolune diisocyanate-80. In addition, Comparative Example 1 employed only a polyether polyol containing no solids of a polyvinyl compound as a polyol component and isophorone diisocyanate as a diisocyanate component, whereas Comparative Example 2 employed isophorone diisocyanate alone as an aliphatic isocyanate, for comparison of physical properties of the foams. Meanwhile, in Comparative Example 3, a low-yellowing polyurethane foam was prepared in which tolune diisocyanate-80 was used as an isocyanate component and yellowing was delayed by addition of a light stabilizer.
[63] Flexible polyurethane foams were prepared in the same manner as in Example 1, with exception of requirements as described above. The composition formula of the polyurethane foams obtained in Comparative Examples 1 through 3 is set forth in Table 1 below. Each unit for components listed in Table 1 is part(s) by weight.
[64]
[65] Table 1
[Table 1] [Table ]
Figure imgf000011_0001
[66]
[67] Hereinafter, respective components including polyols, which were used in Examples
1 through 5 and Comparative Examples 1 through 3, will be specifically described. [68] Polyol A: Polypropylene glycol having an average molecular weight of 3,500 (48 mg
KOH/g) and an EO content of 11% by weight (YUKOL4813, SKC, Korea) [69] Polyol B: Polypropylene glycol containing 25% by weight of solids of a copolymer of acrylonitrile and styrene monomer (YUKOL 1564, SKC, Korea) [70] Polyol C: Ester polyol having a functionality of 2.7 and a viscosity of 20,000 cps
(Desmophen 2200, Bayer, Germany) [71] Cross-linking agent 1: 1,4-butadiene
[72] Cross-linking agent 2: Ethylene glycol
[73] Catalyst 1: Bis(dimethylaminoethyl)ether [74] Catalyst 2: Triethylene diamine [75] Catalyst 3: 33% triethylene diamine dissolved in dipropylene glycol [76] Catalyst 4: Pentamethyldipropylenetriamine [77] Catalyst 5: l,8-diazabicyclo(5,4,0)undecane-7 [78] Catalyst 6: Tin octoate [79] Catalyst 7: Dibutyltin dilaurate [80] Surfactant: L-626 (GE) [81] Stabilizer: Tinuvin B 75 (Ciba Specialty Chemicals) [82] Isocyanates: Examples 1 through 5 employed a mixture of 1,6-hexamethylene di- isocyanate and isophorone diisocyanate in an equivalence ratio of 5:5. Comparative Examples 1 and 2 employed isophorone diisocyanate alone as an isocyanate component.
[83] Aromatic isocyanate: Comparative Example 3 employed tolune diisocyanate-80. [84] Test for Reactivity and Physical properties of foams [85] Upon foaming of urethane, reactivity of the resulting urethane foam was evaluated by measuring a cream time (sec) and a rise time (sec) using a stopwatch. Stability of the foam was determined by observing a degree of settling down of the foam by naked eyes, after reaching a maximum height upon foaming of urethane. In addition, resilience and durability of the foam were respectively measured according to ASTM D3574. The results thus obtained are shown in Table 2 below.
[86] [87] Table 2 [Table 2] [Table ]
Figure imgf000012_0001
[88] [89] Upon comparing Example 1 with Comparative Example 2, it can be seen that the flexible polyurethane foam of Example 1 exhibited sharp increases in resilience and durability thereof, as compared to Comparative Example 2. Further, it can also be seen that the resilience and durability of the foams are maintained even with increasing contents of poly ol B.
[90]
[91] Test for yellowness
[92] Flexible polyurethane foams obtained in Example 1 and Comparative Example 3 were respectively placed in a light-fastness tester (available from KYUNG JIN INSTRUMENTS, Busan, KOREA), and a yellowness index of the foams was measured for 0 to 40 hours, at intervals of 10 hours, according to methods specified under ASTM E313-96 and ASTM D 1925. A light source of the light-fastness tester was a 300W sunlight lamp (available from Osram). The test results thus obtained are shown in FTG. 1.
[93] FTG. 1 is a graph showing Yellowness Index (YI) of flexible polyurethane foams obtained in Example 1 of the present invention and Comparative Example 3. In FTG. 1, Yl is Yellowness Index (YI) and the lower value represents lower yellowing. It can be seen that the flexible polyurethane foam prepared in Example 1 exhibited no changes in a yellowness value over time.
[94] Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims. Industrial Applicability
[95] As apparent from the above description, urethane prepared according to the process of the present invention have stable moldability, resilience and durability while exhibiting yellowing resistance even upon prolonged exposure to light, and therefore can substitute conventional urethane utilizing aromatic isocyanates, which has been used in clothes, hygienic articles, automobile utensils, as well as for packaging materials, medical materials, and the like.

Claims

Claims
[1] A process for preparing a non-yellowing flexible polyurethane foam, comprising reacting a resin premix composed of
100 parts by weight of a polyol including 10 to 90% by weight of a polyether polyol having an ethylene oxide content of 0 to 30% by weight, a propylene oxide content of 70 to 100% by weight and a molecular weight of 400 to 7,000 and 10 to 90% by weight of a polyether polyol containing 20 to 60% by weight of solids of a polyvinyl compound; 0.1 to 2.5 parts by weight of a cross-linking agent; 0.5 to 5.0 parts by weight of tin octoate; 1.0 to 10 parts by weight of dibutyltin dilaurate; 0.5 to 5.0 parts by weight of an amine catalyst; 0.2 to 3 parts by weight of a silicone surfactant; and 0.2 to 5 parts by weight of a blowing agent with aliphatic and cycloaliphatic isocyanates in an isocyanate index of 90 to 130.
[2] A process for preparing a non-yellowing flexible polyurethane foam, comprising reacting a resin premix composed of
100 parts by weight of a polyester polyol which is synthesized by poly condensation of an alcohol with an acid and has a functionality of 2 to 3 and a viscosity of 5,000 to 30,000 cps; 0.1 to 2.5 parts by weight of a cross-linking agent; 0.5 to 5.0 parts by weight of tin octoate; 1.0 to 10 parts by weight of dibutyltin dilaurate; 0.5 to 5.0 parts by weight of an amine catalyst; 0.2 to 3 parts by weight of a silicone surfactant; and 0.2 to 5 parts by weight of a blowing agent with aliphatic and cycloaliphatic isocyanates in an isocyanate index of 90 to 130.
[3] A process for preparing a non-yellowing flexible polyurethane foam, comprising reacting a resin premix composed of
100 parts by weight of a polyol including 5 to 90% by weight of a polyether polyol having an ethylene oxide content of 0 to 30% by weight, a propylene oxide content of 70 to 100% by weight and a molecular weight of 400 to 7,000, 5 to 90% by weight of a polyether polyol containing 20 to 60% by weight of solids of a polyvinyl compound, and 1 to 80% by weight of a polyester polyol which is synthesized by polycondensation of an alcohol with an acid and has a functionality of 2 to 3 and a viscosity of 5,000 to 30,000 cps; 0.1 to 2.5 parts by weight of a cross-linking agent;
0.5 to 5.0 parts by weight of tin octoate;
1.0 to 10 parts by weight of dibutyltin dilaurate;
0.5 to 5.0 parts by weight of an amine catalyst;
0.2 to 3 parts by weight of a silicone surfactant; and
0.2 to 5 parts by weight of a blowing agent with aliphatic and cycloaliphatic isocyanates in an isocyanate index of 90 to 130.
[4] The process according to claim 2 or 3, wherein the alcohol is at least one selected from the group consisting of trimethylpropanol, dipropyl glycol, tripropyl glycol, propyl glycol, diethyl glycol and ethyl glycol, and the acid is at least one selected from the group consisting of terephthalic acid, adipic acid and dimethyl acid.
[5] The process according to any one of claims 1 to 3, wherein an equivalence ratio of aliphatic isocyanate:cycloaliphatic isocyanate is in a range of 5-90: 10-95 equivalent %.
[6] The process according to any one of claims 1 to 3, wherein the aliphatic isocyanate is at least one selected from the group consisting of 1,6-hexamethylene diisocyanate, hydrogenated 4,4'-diamino diphenylmethane and lysine diisocyanate, and the cycloaliphatic isocyanate is at least one selected from the group consisting of isophorone diisocyanate, methylene dicyclo- hexylisocyanate and 2,5 (2,6)-bis(isocyanatomethyl)bicyclo(2.2.1)heptane.
[7] The process according to any one of claims 1 to 3, wherein the cross-linking agent is selected from ethylene glycol, diethylene glycol, Methylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, diethyl toluene diamine, glycerin, diethanol amine, Methanol amine, diol, triol and tetraol having a molecular weight of less than 2,000, and a mixture of two or three.
[8] The process according to any one of claims 1 to 3, wherein the amine catalyst is at least one selected from the group consisting of triethylene diamine, tri- ethylamine, bis(dimethylaminoethyl)ether,
N,N,N'-trimethylaminoethylethanolamine, bis(N,N- dimethylaminoethyl)ether, N,N'-dimethylpiperazine, pentamethyldipropyltriamine, l,8-diazabicyclo(5,4,0)undecane-7, N-(N',N'-2-dimethylaminoethyl)morpholine, tri(dimethylaminemethyl)phenol, and 33% triethylene diamine dissolved in dipropylene glycol.
[9] The process according to any one of claims 1 to 3, wherein the blowing agent is selected from the group consisting of water, methylene chloride, liquid carbon dioxide, n-pentane and hydrogenated chloro fluoro carbon (HCFC).
[10] A non-yellowing flexible polyurethane foam for use in a bra-cup or an outsole, which is prepared by a process of any one of claims 1 to 3.
PCT/KR2007/002637 2006-06-02 2007-05-31 Process for preparing non-yellowing flexible polyurethane foam with high resilience and durability WO2007142425A1 (en)

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WO2008108250A1 (en) * 2007-02-27 2008-09-12 Tosoh Corporation Catalyst composition for production of flexible polyurethane foam
JP2012167221A (en) * 2011-02-16 2012-09-06 Inoac Corp Soft polyurethane foam
DE102012102758A1 (en) 2012-03-30 2013-10-02 Chien-Chang Chen Premix composition useful for producing polyurethane foam, comprises polyether polyol, and foaming agent, where polyether polyol is e.g. and copolymer of propylene oxide, ethylene oxide and trimethylolpropane
US8906977B2 (en) 2012-03-29 2014-12-09 Chien-Chang Chen Polyether polyol based-premix composition and foaming composition containing the premix composition
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WO2008108250A1 (en) * 2007-02-27 2008-09-12 Tosoh Corporation Catalyst composition for production of flexible polyurethane foam
JP2012167221A (en) * 2011-02-16 2012-09-06 Inoac Corp Soft polyurethane foam
US8906977B2 (en) 2012-03-29 2014-12-09 Chien-Chang Chen Polyether polyol based-premix composition and foaming composition containing the premix composition
DE102012102758A1 (en) 2012-03-30 2013-10-02 Chien-Chang Chen Premix composition useful for producing polyurethane foam, comprises polyether polyol, and foaming agent, where polyether polyol is e.g. and copolymer of propylene oxide, ethylene oxide and trimethylolpropane
CN108587114A (en) * 2018-03-23 2018-09-28 苏州凌科特新材料有限公司 A kind of preparation method and applications of the medical composite material containing polyurethane
CN110483732A (en) * 2018-05-15 2019-11-22 科思创德国股份有限公司 Flexible foam
CN110423330A (en) * 2019-07-30 2019-11-08 广东康诚新材料科技股份有限公司 Integrally formed shoes outsole and preparation method thereof
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CN115093539A (en) * 2021-12-09 2022-09-23 上海联景高分子材料有限公司 Polyurethane elastomer easy to process and preparation method thereof
CN115093539B (en) * 2021-12-09 2024-03-01 上海联景高分子材料有限公司 Polyurethane elastomer easy to process and preparation method thereof
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