WO2020107363A1 - Composition de production d'une mousse de polyuréthane - Google Patents

Composition de production d'une mousse de polyuréthane Download PDF

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Publication number
WO2020107363A1
WO2020107363A1 PCT/CN2018/118394 CN2018118394W WO2020107363A1 WO 2020107363 A1 WO2020107363 A1 WO 2020107363A1 CN 2018118394 W CN2018118394 W CN 2018118394W WO 2020107363 A1 WO2020107363 A1 WO 2020107363A1
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Prior art keywords
foam
component
composition
compound
polyol
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PCT/CN2018/118394
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English (en)
Inventor
Yoshiaki Miyazaki
Hiromi Onoda
Shaoguang Feng
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Dow Global Technologies Llc
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Priority to PCT/CN2018/118394 priority Critical patent/WO2020107363A1/fr
Publication of WO2020107363A1 publication Critical patent/WO2020107363A1/fr

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    • 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
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • C08G18/4841—Polyethers containing oxyethylene units and other oxyalkylene units containing oxyethylene end groups
    • 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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/4072—Mixtures of compounds of group C08G18/63 with other macromolecular compounds
    • 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
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4816—Two or more polyethers of different physical or chemical nature mixtures of two or more polyetherpolyols having at least three hydroxy groups
    • 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
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • C08G18/485—Polyethers containing oxyethylene units and other oxyalkylene units containing mixed oxyethylene-oxypropylene or oxyethylene-higher oxyalkylene end groups
    • 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
    • C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
    • C08G18/632—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polyethers
    • 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
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • 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
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent

Definitions

  • the present invention relates to a polyurethane foam-forming composition and a method for preparing a foam from the polyurethane foam-forming composition.
  • PU foam systems are known for producing PU foams for a wide variety of applications such as in cushioning, seating, bedding, furniture, transportation interiors, carpet underlay, and packaging applications.
  • a reaction mixture of polyols, polyisocyanates, catalysts and/or other additives is used to prepare foam-forming polyurethane reaction mixture compositions which, in turn, can be used to produce PU foams.
  • foam systems Even a slight change in concentration of the compounds used in the system can provide a foam system that performs poorly. In other foam systems, a change in a specific component in the foam system can also provide a foam system that performs poorly. Even in the same class of compounds, such as an autocatalytic polyol, it has been surprisingly found that not all autocatalytic polyols perform alike to provide a workable foam system or to provide a foam product with adequate properties for a particular application or enduse.
  • foam products made for automotive seats is an application where improvements can be made.
  • OEMs are continually looking for and requesting a swing-less foam product that can be used in automotive seats to improve the riding comfort of people riding on the seats.
  • One method for identifying a swing-less foam product is to measure the hardness distribution of the foam product.
  • a swing-less foam product tends to exhibit a substantially “linear” hardness distribution compared to a “U-shaped” hardness distribution which is exhibited by most known foam products.
  • JP2018048246A (equivalent to U.S. Patent Application Publication No. US2018/0079338 A1) discusses the hardness distribution of a flexible PU foam, but does not describe how the hardness distribution in the PU foam is created or the specific components of a formulation that specifically work to create the hardness distribution.
  • the above reference broadly discloses that from 0.05 parts to ⁇ 0.1 parts of silicone surfactant is used in the formulation; and that from 2 parts to ⁇ 7 parts of cell opener is used in the formulation.
  • the formulation disclosed in the above reference containing the above specified formulation compounds could not provide a swing-less foam product having a proper linear hardness distribution to pass specifications required by OEMs.
  • foam-forming compositions of the prior art do not exhibit advantageous processing properties such as fast reactivity, good flow, and stability while still maintaining the desired linear hardness distribution characteristics of a swing-less foam product. It is therefore desirable to provide an operable PU fast gelling foam-forming composition useful for producing a flexible foam product advantageously exhibiting a linear hardness distribution for use in the automotive industry.
  • the present invention is directed to a polyurethane foam-forming composition for producing a flexible PU foam that exhibit a certain set of required properties such as having a linear hardness distribution.
  • a particular selection, combination, and dosage of specific components are used to produce a PU foam having a linear hardness distribution useful for making automotive parts such as seat cushions.
  • a foam can be produced from PU foam-forming composition wherein the foam exhibits a linear hardness distribution; and thus, the foam can be useful in the automotive industry.
  • the PU foam-forming composition of the present invention includes a PU foam-forming reaction mixture composition including: (A) at least one isocyanate group-containing component; and (B) at least one polyol component; wherein component (B) can include (Bi) at least one polyol compound; (Bii) at least one catalyst compound for fast gelling in a time period of from 30 seconds (s) to 100 s without being dependent on temperature; (Biii) at least one cell opener; and (Biv) water and wherein the above composition provides a foam having a “linear-shaped” hardness distribution compared to a conventional foam having a U-shaped hardness distribution.
  • other optional additives may be added to component (A) and/or component (B) .
  • FIG. 1 is a graphical illustration showing the hardness distribution measurement results for four equal thickness layers of a foam article which has been cut into four sections to form the four equal thickness layers of foam.
  • “Swing” with reference to a foam material used in a seat cushion, in general herein means instability of a foam.
  • “swing” can be referred to the uncomfortable sensation a person feels when sitting on the cushion of a car seat while driving.
  • the uncomfortable sensation occurs when the person driving turns the car from left to right or right to left, the foam moves significantly in a lateral direction (the horizontal direction) , i.e., the foam “swings” from left to right or right to left; and the driver feels the movement action, i.e., the instability, of the foam structure.
  • Others in the art have referred to “swing” as a “sense of wobble” as disclosed in U.S. Patent Application Publication No. US2018/0079338 A1.
  • “Swing-less” with reference to a foam material, in general herein means the amount of swing is low or decreased in the foam material; or, the foam material has an increased stability.
  • Unstable or “instability” with reference to a foam material, herein means an increased swing level.
  • “Fry ability” with reference to foam material, hereinmeans the surface cure performance of a foam when PU rigid is sprayed; if the surface is well-cured, and not sticky, the ability to fry (fast gel) is good.
  • hard means a relative hardness as measured by the “50 percent (%) hardness” method.
  • the hardness of a top layer can be softer than that of the 2 nd ; and thus, in this case the top layer is “softer” than the 2 nd layer because the top layer shows a lower hardness than the 2 nd layer.
  • the present invention includes a PU foam-forming composition or formulation including: (A) at least one isocyanate group-containing component; and (B) at least one polyol component (or a hydroxyl group-containing component) .
  • the PU foam-forming composition is a two-component (2K) system but is not limited to such 2K system.
  • Other additives and compounds can be used to form the PU foam-forming composition or formulation of the present invention.
  • the isocyanate group-containing component, component (A) can be at least one isocyanate group-containing compound such as a polyisocyanate; or component (A) can be a mixture or blend of one or more different compounds.
  • component (A) can include an optional additive or compound as described herein.
  • the reaction between the isocyanate groups of the isocyanate group-containing compound, component (A) , and the polyol groups of the polyol component, component (B) beneficially provides urethane bonding which leads to toughness and enhanced mechanical properties, while the reaction between the isocyanate groups and water provides urea bonding and CO 2 ; urea bonding leads to foam hardness and CO 2 can function as a blowing agent.
  • the isocyanate group-containing compound, component (A) , useful in the PU foam-forming composition of the present invention can include, for example, a single aromatic isocyanate, or mixtures of two or more aromatic isocyanates.
  • a useful aromatic isocyanate includes, for example, a monomeric MDI (methylene diphenyl diisocyanate) , a polyisocyanate, an isocyanate prepolymer, and mixtures of two or more thereof.
  • An isocyanate prepolymer useful in the PU foam-forming composition of the present invention can include, for example, at least one prepolymer–polyol–chain extender compound structure such as MDI end-capped prepolymers based on EO (ethylene oxide) and/or PO (propylene oxide) based diols, triols, or compounds having higher functionality groups.
  • prepolymer–polyol–chain extender compound structure such as MDI end-capped prepolymers based on EO (ethylene oxide) and/or PO (propylene oxide) based diols, triols, or compounds having higher functionality groups.
  • the isocyanate compound, component (A) useful in the present invention can be a commercially available isocyanate compound such as Papi 27 and Papi 2940 (available from The Dow Chemical Company) .
  • the amount of the isocyanate compound (A) in the PU foam-forming composition can be generally in the range of from 30 weight percent (wt%) to 100 wt%in one embodiment; from 35 wt%to 80 wt%in another embodiment; and from 40 wt%to 65 wt%in still another embodiment based on the total weight of the components in the composition.
  • the polyol component, component (B) can be a solution, mixture or blend of one or more compounds including, for example: (Bi) at least one polyether polyol compound, (Bii) at least one catalyst compound, (Biii) at least one cell opener compound, and (Biv) water.
  • the polyether polyol compound, component (Bi) provides urethane bonding that leads to soft foam and enhanced mechanical properties.
  • the polyether polyol compound, component (Bi) , useful in the formulation of the present invention can include, for example, a polyether polyol; a co-polymer polyol; a polyester polyol; and mixtures thereof.
  • the polyol compound, component (Bi) , useful in the present invention can be, for example, one or more polyether polyols.
  • the polyol compound, component (Bi) , useful in the present invention can be a commercially available polyether polyol compound such as Specflex NC 138 or Specflex NC632 (both available from The Dow Chemical Company) ; or mixtures thereof.
  • the polyol compound, component (Bi) , useful in the present invention can be, for example, one or more co-polymer polyols.
  • the polyol compound, component (Bi) , useful in the present invention can be a commercially available co-polymer polyol compound such as Specflex NC701 or Specflex NC702 (both available from The Dow Chemical Company) ; or mixtures thereof.
  • the amount of the polyol compound, component (Bi) , in the polyol component, component (B) can be generally in the range of from 60 wt%to 99 wt%in one embodiment; from 70 wt%to 96 wt%in another embodiment; and from 80 wt%to 93 wt%in still another embodiment, based on the total weight of the components in the polyol component, component (B) , of the PU foam-forming composition.
  • component (Bi) When the amount of polyol compound, component (Bi) , is below 60 wt%, the amount of water, amine catalyst, and other additives remaining in component (B) may be too much such that the foam may tend to collapse, and a sufficient hardness distribution cannot be obtained; and when the amount of polyol compound, component (Bi) , is above 99 wt%, the amount of water, amine catalyst, and other additives remaining in component (B) may not be sufficient to produce a foam.
  • the catalyst compound, component (Bii) useful in the PU foam-forming composition, beneficially enhances reactivity for both the blowing and gelling reactions.
  • the catalyst compound, component (Bii) can include, for example, amine catalysts such as a tertiary amine, metal catalysts, and mixtures thereof.
  • the catalyst compound, component (Bii) can be any imidazole (e.g., 1, 3–diaza-2, 4-cyclopentadiene) type of amine including for example commercially available compounds such as Toyocat DM70 (available from Toso) .
  • An imidazole type catalyst can have the following general chemical structure:
  • Imidazole type of amines are not temperature dependent and can enhance gel reaction from the beginning of the foaming process.
  • Toyocat DM70 is a gelling catalyst that is not temperature dependent and that enhances gelling (the gelling reaction) to provide faster gelling of the composition of the present invention compared to conventional gelling catalysts such as Dabco 33LV or Dabco crystal, which are temperature dependent.
  • “Temperature dependent” with reference to a catalyst, herein means that the catalyst relies on temperature (heating source) for the catalyst to initiate or activate gelling.
  • TEDA tri ethylene diamine
  • TEDA is a strong gel catalyst once activated.
  • TEDA needs to be subjected to a high temperature (e.g., greater than [>] 60 degrees Celsius [ °C ] ) to be activated, i.e., heat must be applied to the catalyst to activate the catalyst; and thus, the catalyst to start the gelling process is said to be “temperature dependent” .
  • a catalyst such as 1, 2-dimethyl imidazole (e.g., Toyocat DM70) is not as strong a gel catalyst as Dabco 33LV.
  • a catalyst such as DM70 is activated as a gel catalyst without being subjected to a high temperature (e.g., >60 °C ) to be activated, i.e., application of heat to the catalyst is not required to activate the catalyst; and thus, the catalyst to start the gelling process is said to be “temperature independent” .
  • Temperature independence as opposed to temperature dependence is a desired property of the catalyst used in the present invention.
  • catalysts useful in the present invention may include, for example, (1) pyridine derivatives having the following general chemical structure:
  • R 1 , R 2 , R 3 , R 4 , and R 5 may be hydrogen (H) ; or C1 to C8 aliphatic-or aromatic-containing groups;
  • a Lewis acid metal catalyst such as a Sn- , Bi- , Hg- , or Zr-containing compound; and combinations thereof wherein, in one embodiment, the Lewis acid can be formed, for example, according to the following chemical scheme:
  • the high temperature is obtained from the reaction between polyol and isocyanate once the polyol side and isocyanate side are mixed together. And, once the polyol side and the isocyanate side are mixed together, a catalyst such as DM70 is activated immediately by the heat of reaction. In comparison, using a catalyst such as Dabco 33LV and once the polyol side and isocyanate side are mixed together, some period of time is required until heat is generated from the reaction between polyol and isocyanate for the activation of the catalyst and gelling begins.
  • the amount of the catalyst compound (Bii) present in the polyol component, component (B) can be generally in the range of from 0.01 wt%to 10 wt%in one embodiment; from 0.1 wt%to 5 wt%in another embodiment; and from 0.5 wt%to 3.0 wt%in still another embodiment, based on the total weight of the components in the polyol component, component (B) , of the PU foam-forming composition.
  • the cell opener compound, component (Biii) , useful in the formulation of the present invention can include, for example, polyethylene glycol, polyether polyol; and mixtures thereof.
  • the cell opener compound, component (Biii) can be, for example, a polyether polyol containing a high level (e.g., from 70 wt%to 85 wt%) of ethylene oxide (EO) groups.
  • EO ethylene oxide
  • the level of the EO groups in the polyether polyol can be up to 85 wt%EO groups.
  • a cell opener containing a high content EO groups is used in the composition of the present invention is because the cell opener having a high level of EO shows a high hydrophilicity leading to strong hydrogen bonding with water which is present as a blowing agent in the composition of the present invention.
  • a cell opener such as Voranol CP1421 (a glycerine-initiated, polyoxyethylene/polyoxypropylene-capped polyoxypropylene polyol available from The Dow Chemical Company) can delay the blowing reaction at the initial mixing stage of the components of the composition because of hydrogen bonding. This delay in the blowing reaction can lead to an enhancement of gel reaction (and better flow ability) of the composition of the present invention.
  • the concentration of the cell opener compound, component (Biii) , in the polyol component, component (B) can be generally in the range of from 0.5 wt%to 25 wt%in one embodiment; from 3 wt%to 20 wt%in another embodiment; and from 5 wt%to 15 wt%in still another embodiment, based on the total weight of the components in the polyol component, component (B) , of the PU foam-forming composition.
  • the amount of cell opener compound, component (Biii) is below 0.5 wt%, a sufficient hardness distribution cannot be obtained; and when the amount of cell opener compound is above 25 wt%, the foam hardness distribution can decrease and the curing of the foam can deteriorate.
  • the B-side material further comprises a blowing agent such as water, component (Biv) .
  • a blowing agent such as water, component (Biv) .
  • Water may perform both a blowing function and/or a chain extension function by reacting with isocyanate groups to generate carbon dioxide (CO 2 ) and form urea linkages (i.e., provides urea bonding via the reaction with the isocyanate component (A)) .
  • CO 2 carbon dioxide
  • Water also may determine the foam density; and provide a foam hardness by generating CO 2 (packing) .
  • Water is preferably the sole blowing agent in the foam formulation of the present invention, although it is possible to include an auxiliary blowing agent within the foam formulation in addition to the water.
  • the auxiliary blowing agent may be a chemical type such as a carbamate or a physical blowing agent such as, for example, carbon dioxide or a low-boiling hydrocarbon, hydrofluorocarbon or hydrochlorofluorocarbon.
  • a chemical type such as a carbamate
  • a physical blowing agent such as, for example, carbon dioxide or a low-boiling hydrocarbon, hydrofluorocarbon or hydrochlorofluorocarbon.
  • water is the sole blowing agent
  • the amount of water is an important contributing factor to the density of the resulting foam.
  • the concentration of water, component (Biv) , present in the polyol component, component (B) can be generally in the range of 1 wt%to 7 wt%in one embodiment, from 1.5 wt%to 5 wt%in another embodiment; and from 2.0 wt%to 4.0 wt%in still another embodiment, based on the total weight of the components in the polyol component, component (B) , of the PU foam-forming composition.
  • the PU foam-forming composition of the present invention may be formulated with a wide variety of optional additives, component (C) , to enable performance of specific functions while maintaining the excellent benefits/properties of the present PU foam-forming composition and the foam product made therefrom.
  • the optional components of the PU foam-forming composition may be added to the first isocyanate group-containing component (A) ; or the optional components of the PU foam-forming composition may be added to the second polyol component (B) .
  • the optional additives useful in the formulation may include surfactants such as silicone surfactants; adhesion promoters such as silane, epoxy and phenolic resin; chain extenders such as glycerin, trimethylol propane, diethylene glycol, propanediol, and 2-methyl-1, 3-propanediol; and other catalysts including a latent tin catalyst such as dioctyltinmercaptide; a non-tin based metal-organic catalyst such as bismuth (III) -neodecanaote; fillers, pigments, dyes, colorants; and mixtures thereof.
  • surfactants such as silicone surfactants
  • adhesion promoters such as silane, epoxy and phenolic resin
  • chain extenders such as glycerin, trimethylol propane, diethylene glycol, propanediol, and 2-methyl-1, 3-propanediol
  • other catalysts including a latent tin catalyst such as dioctylt
  • the amount of the optional additives, component (C) , useful in the PU foam-forming composition can be generally in the range of from 0 wt%to 10 wt%in one embodiment; from 0.01 wt%to 5 wt%in another embodiment; and from 0.05 wt%to 3 wt%in still another embodiment, based on the total weight of the components in the formulation.
  • the process for making the PU foam-forming composition of the present invention includes mixing, admixing orblending: (A) at least one isocyanate group-containing component; and (B) at least one polyol component.
  • One or more additional optional components, as component (C) may be added to the PU foam-forming composition as desired.
  • the components (A) and (B) can be mixed together in the desired concentrations discussed above and at a temperature of from 25 °C to 40 °C in one embodiment; and from 30 °C to 35 °C in another embodiment.
  • the order ofmixing of the components is not critical and two or more components can be mixed together followed by addition of the remaining components.
  • the PU foam-forming composition components may be mixed together by any known mixing process and equipment.
  • the two components (A) and (B) are prepared separately from one another; and the components are each stored in a separate container.
  • the other components and optional additives of the PU foam-forming composition may be present as part of the first component (A) or the second component (B) .
  • a suitable container for the storage of each component can be, for example, a drum, a hobbock, a bag, a bucket, a can, a cartridge or a tube.
  • the two components Prior to the application of the PU foam-forming composition, the two components are stored separately and mixed with one another only during or immediately prior to the application.
  • an example of the formulation for the PU foam-forming composition of the present invention can contain the following ingredients for the A-side: 87.7 wt%of a polyol plus a copolymer polyol blend; 3.0 wt%of water; 7.5 wt%of a cell opener; 1.1 wt%of an amine catalyst; and 0.8 wt%of a silicone surfactant.
  • the B-side of the above formulation can include a polyol compound at a concentration of 100.1 wt%.
  • the PU foam-forming composition of the present invention produced by the process of the present invention has several advantageous properties and benefits compared to conventional PU foam-forming compositions.
  • the PU foam-forming composition can exhibit an increased or faster gelling reaction (enhance gelling) .
  • the fast gelling exhibited by the PU foam-forming composition can be generally in the range of from 30 s to 100 s in one embodiment; from 50 s to 90 s in another embodiment; and from 60 s to 80 s in still another embodiment. If the gelling of the composition is below 30 s, the composition may gel too fast and may lead to poor flowability for the composition. In turn, the part or article made with the composition may incur defects due to air voids being formed in the composition when gelling occurs too fast.
  • a “welding line” may be formed in the gelling composition.
  • a “welding line” occurs because of the poor flow of the composition; and any urethane mixtures which already react (already gelling) meet together at the end of the flow and make what looks like a line similar to a line made from a welding operation.
  • the gelling of the PU foam-forming composition can be measured by techniques known in the art.
  • the method carried out to determine the gel time can be as follows: Firstly, using a needle, place the needle touching (slightly dipping into) the surface of the foam-forming mixture after the foam-forming mixture is poured from the mixing head into a mold. Secondly, pull the needle from the mixture, and when a string is generated from the needle to the foam surface as determined by visual observation, the time is recorded as the gel time.
  • the present invention includes a process for manufacturing a PU foam product from the reactive foam-forming composition of the present invention includes the steps of: (a) heating a mold to a temperature in the range of, for example, from 60 °C to 72 °C ; (b) heating the reactive foam-forming composition (polyol and prepolymer) to a temperature of, for example, from 25 °C to 40 °C ; (c) hand mixing the reactive foam-forming composition from step (b) ; (d) processing the mixed reactive foam-forming composition from step (c) through a low throughput high pressure machine at a rate of, for example, from 100 grams/second (g/s) to 200 g/s; and (e) processing the reactive foam-forming composition from step (d) through a high throughput high pressure machine at a rate of, for example, from 300 g/s to 500 g/s.
  • PU foam is the PU foam’s hardness distribution, in which the hardness of the PU foam increases from top to bottom (i.e., in a vertical direction) of the PU foam structure.
  • a PU foam produced by the process of the present invention can have a linear hardness distribution as measured by the “General Procedure for Measuring Foam Hardness” as described in the Examples herein below.
  • a foam article produced by the process of the present invention can be cut into four rectangular (e.g., square) equal thickness sections or parts (herein, each part can be referred to as a “layer” ) and the hardness of each layer is measured.
  • the foam article can be a rectangular block and the four layers are created by cutting the foam block horizontally, for example, in the following four equal thickness layers: (1) a top 1 st layer, (2) a 2 nd middle (or center) layer, (3) a 3 rd middle (or center) layer, and (4) a bottom 4 th layer.
  • the hardness of the first top layer of the foam can be generally in the range of, for example, from 0.7 to 0.8; the hardness of each of the 2 nd and 3 rd middle layers can be generally in the range of, for example, from 0.8 to 1.15, it being understood that the middle layers can include at least one or more middle layers of the foam; and the hardness of the bottom 4 th layer of the foam can be generally in the range of, for example, from 1.15 to 1.30.
  • the hardness distribution of the PU foam can be determined by known techniques in the art. For example, in the Examples herein below a general procedure for measuring foam hardness is provided. Also, OEMs can determine a foam’s hardness distribution and give the foam a rating of, for example, 0.5 to 1.50; and may designate the foam as a “Tier 1” or “Tier 2” foam product.
  • FIG. 1 there is shown the results of hardness distribution of a foam product which has been divided (cut) into 4 equal thickness rectangular or square plate parts.
  • the 4 layers include: (1) a top 1 st layer, (2) a 2 nd middle (or center) layer, (3) a 3 rd middle (or center) layer, and (4) a bottom 4 th layer.
  • a conventional foam e.g., Comparative Example A
  • Comparative Example A for an automotive seat has a high foam hardness at the top 1 st layer, a softer hardness for the 2 nd layer, and then an increasing foam hardness for the 3 rd layer and the bottom 4 th layer.
  • the conventional foam can also be referred to as a foam having a “U shaped hardness distribution” because as shown in FIG. 1, the hardness measurement data for the four layers of the conventional foam is “U-shaped” when the data is plotted and illustrated in graphical form.
  • an ideal swing-less foam for an automotive seat has a soft hardness at the top 1 st layer; and then an increasing foam hardness for the 2 nd , 3 rd and bottom 4th layers.
  • the hardness measurement data for the four layers of a foam of the present invention when the data is plotted and viewed in graphical form, has a “hockey stick” -like appearance and can be referred to as a “linear shaped hardness distribution” .
  • a conventional automotive seat with a conventional foam e.g., a seat foam having a “U shaped hardness distribution”
  • a swing-less foam of the present invention e.g., a seat foam having a “linear shaped hardness distribution”
  • the seat having a linear shaped hardness distribution provides an enhanced riding comfort/stability, in particular during long distance driving runs.
  • a higher mold temperature e.g., 60 °C ⁇ 72 °C
  • a higher material temperature e.g., 30 °C
  • a lower throughput e.g., going from hand mixing to a high pressure machine (e.g., 150 g/s) to an even higher pressure machine (e.g., 350 g/s) can be used.
  • the hand mixing procedure provides a more effective way to fasten gel; and then, after hand mixing the composition, the composition can be processed using a lower throughput in a high pressure machine.
  • the isocyanate side of the composition can include changing the isocyanate from toluene diisocyanate (TDI) to MDI because a faster gelling can be achieved with an isocyanate such as MDI having a higher functionality than that of TDI which has a functionality of 2.
  • the polyol side of the composition can include: (1) using Voranol cp1421/Voranol 4053/PEG (high EO content) –H 2 bonding (delay blowing to enhance gelling) ; and/or (2) using an amine catalyst that provides gelling and that is a type of catalyst that is not temperature dependent.
  • the PU foam product of the present invention can be used in any application where a swing-less foam is desired.
  • applications where the foam product can be useful include: molded sofa cushions, furniture, pillows, and the like.
  • the PU foam product of the present invention can be used for automotive seat cushions wherein the hardness distribution of the foam, from top to bottom, provides a comfortable ride for a user of the seat mounted on a vehicle.
  • the foam was prepared using the following process steps:
  • Step (1) A polyol side and an isocyanate side are prepared separately and each side is temperature controlled at a temperature of 30 °C .
  • Step (2) The polyol side and the isocyanate side of step (1) are then mixed together by using either (i) hand mixing or (ii) a high (or low) pressure machine.
  • Step (3) The resultant mixture from step (2) is poured into a mold which is temperature controlled at a temperature of from 60 °C to ⁇ 72 °C .
  • Step (4) The target ore density of a resultant PU foam is set at higher than 40 kg/m 3 so that the total weight of the mixture is calculated.
  • Step (5) The resultant PU foam from step (4) is demolded after 4 minutes of curing the mixture of step (4) ;
  • Step (6) After demolding, the foam is crashed by using either (i) a mechanical crasher or (ii) a vacuum crasher because after the demolding step (5) , the foam may contain hot CO 2 , and if the foam is left without crashing, the foam may shrink; and thus, crashing is carried out to ensure the break up the cells (i.e., the cells are opened to release CO 2 gas) ; and
  • Step (7) The PU foam from step (6) is then stored in a conditioning room (at 25 °C and 50%relative humidity [RH] ) for 24 hours.
  • a foam material, with skins on two sides, of 400 millimeters (mm) x 400 mm x 100 mm dimensions is cut into the following four equal (100 mm x 100 mm x 100 mm) thickness foam layer samples: a 1 st foam layer (top layer) , a 2 nd foam layer (middle layer) , a 3 rd foam layer (middle layer) , and a 4 th foam layer (bottom layer) such that the top layer has a skin on one side and the bottom layer has a skin on one side; but the two middle layers do not have a skin. Then; the 50%hardness of each of the foam layer samples is measured. Thereafter, the average hardness of the four foam layer samples is calculated. The relative hardness ratio for each of the foam layer samples is obtained from the 50%hardness of each of the foam layers divided by the average hardness.
  • the hardness target number (no units) for each of the foam layer samples can be as follows: the 1 st layer (top layer) can be from 0.7 to ⁇ 0.8; the 2 nd layer can be from 0.8 to ⁇ 0.9; the 3 rd layer can be from 1.0 to ⁇ 1.15; and the 4 th layer (bottom layer) can be from 1.15 to ⁇ 1.3.
  • Target value is obtained from a foam prepared by a high pressure machine that is operated with a throughput of 400 g/s.
  • the high water level leads to over packing (i.e., too much CO 2 is generated) and the top layer shows high hardness with a thick skin layer based on urea bonding.
  • the hardness distribution of the composition of Comp. Ex. A (without a cell opener or a catalyst) is better than that of the composition of Comp. Ex. C, but the required targeted hardness distribution for the composition of Comp. Ex. A cannot be achieved.

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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

La présente invention concerne une composition de mélange réactionnel formant mousse de polyuréthane comprenant : (A) au moins un composant contenant un groupe isocyanate étant au moins un composé contenant un groupe isocyanate; et (B) au moins un composant polyol comprenant : (Bi) au moins un composé polyol; (Bii) au moins un composé catalyseur; (Biii) au moins un ouvreur d'alvéoles; et (Biv) de l'eau; un procédé de fabrication d'une mousse de polyuréthane à partir de la composition ci-dessus de mélange réactionnel formant mousse de polyuréthane, la mousse de polyuréthane ayant une distribution de dureté linéaire telle que comparée à une mousse classique ayant une distribution de dureté en forme de U; et un article en mousse fabriqué à partir de la mousse de polyuréthane.
PCT/CN2018/118394 2018-11-30 2018-11-30 Composition de production d'une mousse de polyuréthane WO2020107363A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105682983A (zh) * 2013-10-29 2016-06-15 丰田纺织株式会社 车辆座椅用垫的制造方法
JP2016164248A (ja) * 2014-08-08 2016-09-08 三洋化成工業株式会社 軟質ポリウレタンフォームの製造方法
WO2017135289A1 (fr) * 2016-02-03 2017-08-10 東ソー株式会社 Composition de polyisocyanate pour mousse de polyuréthane souple
JP2017179359A (ja) * 2016-03-25 2017-10-05 三洋化成工業株式会社 軟質ポリウレタンフォームの製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105682983A (zh) * 2013-10-29 2016-06-15 丰田纺织株式会社 车辆座椅用垫的制造方法
JP2016164248A (ja) * 2014-08-08 2016-09-08 三洋化成工業株式会社 軟質ポリウレタンフォームの製造方法
WO2017135289A1 (fr) * 2016-02-03 2017-08-10 東ソー株式会社 Composition de polyisocyanate pour mousse de polyuréthane souple
JP2017179359A (ja) * 2016-03-25 2017-10-05 三洋化成工業株式会社 軟質ポリウレタンフォームの製造方法

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