CN1683427A - Method for producing polyurethane foam with high air permeability and low resilience - Google Patents

Method for producing polyurethane foam with high air permeability and low resilience Download PDF

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Publication number
CN1683427A
CN1683427A CNA2005100717354A CN200510071735A CN1683427A CN 1683427 A CN1683427 A CN 1683427A CN A2005100717354 A CNA2005100717354 A CN A2005100717354A CN 200510071735 A CN200510071735 A CN 200510071735A CN 1683427 A CN1683427 A CN 1683427A
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CN
China
Prior art keywords
polyol
polyurethane foam
flexible polyurethane
resilience
low
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Granted
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CNA2005100717354A
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Chinese (zh)
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CN100460438C (en
Inventor
吉井直哉
平山智子
矢口仁史
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Nippon Polyurethane Industry Co Ltd
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Nippon Polyurethane Industry Co Ltd
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Classifications

    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
    • E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
    • E04B1/38—Connections for building structures in general
    • E04B1/61—Connections for building structures in general of slab-shaped building elements with each other
    • E04B1/6108—Connections for building structures in general of slab-shaped building elements with each other the frontal surfaces of the slabs connected together
    • E04B1/612—Connections for building structures in general of slab-shaped building elements with each other the frontal surfaces of the slabs connected together by means between frontal surfaces
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
    • E04B2/00—Walls, e.g. partitions, for buildings; Wall construction with regard to insulation; Connections specially adapted to walls
    • E04B2/74—Removable non-load-bearing partitions; Partitions with a free upper edge
    • E04B2/7401—Removable non-load-bearing partitions; Partitions with a free upper edge assembled using panels without a frame or supporting posts, with or without upper or lower edge locating rails
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
    • E04B2/00—Walls, e.g. partitions, for buildings; Wall construction with regard to insulation; Connections specially adapted to walls
    • E04B2/72—Non-load-bearing walls of elements of relatively thin form with respect to the thickness of the wall
    • E04B2/721—Non-load-bearing walls of elements of relatively thin form with respect to the thickness of the wall connections specially adapted therefor
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
    • E04B2/00—Walls, e.g. partitions, for buildings; Wall construction with regard to insulation; Connections specially adapted to walls
    • E04B2/74—Removable non-load-bearing partitions; Partitions with a free upper edge
    • E04B2/7407—Removable non-load-bearing partitions; Partitions with a free upper edge assembled using frames with infill panels or coverings only; made-up of panels and a support structure incorporating posts
    • E04B2/7448—Removable non-load-bearing partitions; Partitions with a free upper edge assembled using frames with infill panels or coverings only; made-up of panels and a support structure incorporating posts with separate framed panels without intermediary posts, extending from floor to ceiling

Abstract

The invention provides a viscoelastically flexible polyurethane foam having excellent viscoelastic performance useful as a vibration, sound or impact absorber or as a mattress, pillow, cushion, or the like, capable of more uniformly dispersing human body pressure than conventional flexible polyurethane foam, thus effective in reducing sense of fatigue and bedsore, therefore excellent in terms of human engineering. The flexible polyurethane foam is provided, comprising carrying out a reaction between a polyisocyanate(A), a polyol(B), a foaming agent(C), a catalyst(D) and a foam stabilizer(E),wherein, the polyol(B) comprises (b1) a polyester polyol with an average functional group number of 2.5-4.5 and a hydroxy equivalent of 300-500 and (b2) a polyalkylene polyol with an average functional group number of 2.5 and a hydroxy equivalent of 500-3,000 in a specific proportion. The isocyanate index of this flexible polyurethane foam is 50-100.

Description

The manufacture method of highly air-permeable, low-resilience, flexible polyurethane foam
Technical field
The present invention relates to a kind of manufacture method with flexible polyurethane foam of low-resilience, highly air-permeable.
Background technology
Up to now, as the various laminated products processing of impact absorbing material, absorption of vibrations material with or liner, mattress, cushion plate, back cushion, clothing with institute in the liner etc. generally the low resilience flexible polyurethane foam body of use be known.The urethane foam that uses in these goods is according to forming by the resin of selecting ammonia ester foams aptly, promptly, the kind of polyhydroxy reactant and polyisocyanate compound is prepared in the mode of the urethane foam of the rebound resilience rate that obtains having expectation.
But, though the urethane foam of disclosed low-resilience has the low-resilience rate of expectation up to now, but almost do not have ventilation property, can not fully discharge the heat, the water vapour that produce by human body when for example using, easily heating at aspects such as liner, mattress, cushion plate or back cushions.
And low-repulsion polyurethane foam is strong to temperature sensitivity, and the words of temperature step-down must be hardened.For example the tactility that has so-called foams such as liner, cushion plate, mattress with the variation of envrionment temperature change, the problem of the bigger variation of usability.
As the method that addresses this problem, for example having put down in writing polyhydroxy reactant in patent documentation 1, to use by molecular weight be the polyol blend that high molecular weight polyols more than 500 and low molecular polylol make, low molecular weight diol is dipropylene glycol and/or 1,3-butyleneglycol, lower molecular weight trivalent alcohol are the example of glycerine and/or TriMethylolPropane(TMP).But the prescription of document record can not substantially improve the high rigidityization of foams under the low temperature, exists in winter etc. can not get the softish usability under the low temperature condition problem.
[patent documentation 1] spy opens the 2004-2591 communique
Summary of the invention
The present invention provides a kind of urethane foam that interdependence is little and weather resistance is high that has good low-resilience, highly air-permeable, hardness to temperature simultaneously in view of above-mentioned present situation.
In order to address this problem, the inventor concentrates on studies, discovery is in polyhydroxy reactant and polyisocyanate compound as the mixed preparing of the resinous principle of the urethane foam of existing low-resilience, the pure and mild high-molecular weight polyoxyalkylene polyol of polyester polyols with specific blend ratio mixing specified molecular weight forms polyhydroxy reactant, by being at isocyanate index under the condition below 100 with the reaction of this polyol blend composition and polyisocyanate compound, can access and have low-resilience, fabulous ventilation property, the temperature dependency of soft, and the unusual flexible polyurethane foam of good compression residual strain, thereby finish the present invention.
Be that content of the present invention is as shown in following (1)～(5).
(1) a kind of density that with polyisocyanates (A), polyvalent alcohol (B), whipping agent (C), catalyzer (D) and suds-stabilizing agent (E) at isocyanate index is reaction obtains under 50～100 the condition is 40～80kg/m 3, hardness is 8～150N/100cm 2Highly air-permeable, low-resilience, the manufacture method of flexible polyurethane foam, the polyol blend that wherein polyvalent alcohol (B) is that average functionality is 2.5～4.5, hydroxyl equivalent is 300～500 polyester polyol (b1) and average functionality is 2.5～4.5, hydroxyl equivalent is 300～5000 polyoxyalkylene polyol (b2), and blending ratio is (b1): (b2)=70～90: 30～10 (weight ratios).
(2) a kind of xeothermic compressed residual strain value of measuring according to JIS K6400 (1997) that with polyisocyanates (A), polyvalent alcohol (B), whipping agent (C), catalyzer (D) and suds-stabilizing agent (E) at isocyanate index is that reaction obtains under 50～100 the condition is below 5% and density 40～80kg/m 3, hardness 8～150N/100cm 2Highly air-permeable, low-resilience, the manufacture method of flexible polyurethane foam, the polyol blend that wherein polyvalent alcohol (B) is that average functionality is 2.5～4.5, hydroxyl equivalent is 300～500 polyester polyol (b1) and average functionality is 2.5～4.5, hydroxyl equivalent is 300～5000 polyoxyalkylene polyol (b2), and blending ratio is (b1): (b2)=70～90: 30～10 (weight ratios).
(3) manufacture method of aforementioned (1) or (2) described highly air-permeable, low-resilience, flexible polyurethane foam, wherein the average functionality that obtains for addition propylene oxide and oxyethane in the polyol that has the hydroxyl more than 2 at per molecule of polyoxyalkylene polyol (b2) is 2.5～4.5, hydroxyl equivalent is 300～5000 polyoxyalkylene polyol.
(4) manufacture method of any one the described highly air-permeable in aforementioned (1)～(3), low-resilience, flexible polyurethane foam, wherein catalyzer (D) is for containing the catalyzer of glyoxaline compound.
(5) manufacture method of any one the described highly air-permeable in aforementioned (1)～(4), low-resilience, flexible polyurethane foam, wherein polyvalent alcohol (B) further contains the polyoxyalkylene monohydroxy-alcohol.
According to the present invention, may make and have the flexible polyurethane foam that sufficient low-resilience and highly air-permeable, hardness are improved significantly to the interdependence of temperature simultaneously.And flexible polyurethane foam of the present invention has unexistent, the unusual good compression residual strain rate of existing foams.Thereby impact absorbing material, absorption of vibrations material or liner, mattress, cushion plate, back cushion, the clothing that can provide the variation of the use feeling that produces with variation of ambient temperature little, to be difficult for heating, high-durability is with liner etc.
Embodiment
As mentioned above, basis of the present invention is highly air-permeable, the manufacture method of the flexible polyurethane foam of low-resilience, it is characterized in that average functional group several 2.5～4.5, polyester polyol of hydroxyl equivalent 300～500 (b1) and average functional group several 2.5～4.5, the polyoxyalkylene polyol of hydroxyl equivalent 300～5000 (b2) is with weight ratio (b1): (b2)=70～90: 30～10 mixed is as the polyol blend composition, this polyhydroxy reactant and polyisocyanate compound reacted under the condition of isocyanate index 50～100 to make density be 40～80kg/m 3, hardness 8～150N/100cm 2Foams.
For the consideration of manufacturing cost, in general the density of flexible polyurethane foam is preferably lower, but the foams of extreme low densityization can not satisfy low resilient rate, the high-durability that the present invention will deal with problems.And, owing to can produce the problems such as tactility variation that low densityization causes hardness deficiency and foams product surface, be lower than 40kg/m 3Density to set be not preferred.And for the consideration of cost, production efficiency etc., upper density limit is 80kg/m 3The hardness of foams need be in the certain limit according to such use, the hardness 8N/100cm that represents with 25%CLD 2Be lower limit, the 150N/100cm of same expression 2Be the upper limit.Under this softish occasion, the hardness of the face that the low-resilience foams that stress relaxation rate is big contact with the foams bottom, the sensation variation of shape, can not demonstrate the effect of sufficient pressure dispersion, shock absorption, and, in the situation harder than this, have that flexibility is impaired, the sensation variation, can not get the problem of shock absorbing capability.
The present invention is topmost to be characterised in that: use that average functional group is several 2.5～4.5, the polyester polyol (b1) of hydroxyl equivalent 300～500 and average functional group are several 2.5～4.5, the polyoxyalkylene polyol (b2) of hydroxyl equivalent 300～5000 is with weight ratio (b1): (b2)=70～90: 30～10 mixed is as the polyol blend composition.
The average functional group of polyvalent alcohol of the present invention number is that functional group's number of the raw material that uses when being prepared by polyvalent alcohol and mole number calculate and get, and the average functional group number of polyester polyol (b1) is to be calculated by functional group's number of functional group's number of carboxylic acid composition and mole number, pure composition and mole number to get.And then the hydroxyl equivalent of polyester polyol is got by hydroxyl value and the number calculating of above-mentioned average functional group.
The average functional group number of polyoxyalkylene polyol of the present invention is meant the average functional group number of polymerization starter.When making multifunctional initiator addition oxyalkylene, because side reaction takes place, the reaction of addition end stops, confirm to have generated the alcohol lower than functional group's number of polymerization starter, but because can not establish the method for the terminal concentration that this reaction of correct calculating stops, in the present invention, with generally as the average functional group number of the polymerization starter of functional group's number of polyoxyalkylene polyol functional group's number as polyvalent alcohol.The hydroxyl equivalent of polyoxyalkylene polyol is the value of being calculated by hydroxyl value and above-mentioned average functional group number.
Polyester polyol (b1) is to be obtained by polycarboxylic acid composition more than a kind or 2 kinds and the polyhydroxy reactant polycondensation more than a kind or 2 kinds.As the polycarboxylic acid composition, except that polycarboxylic acid, also can be the acid anhydrides of its derivative, the form of carboxylicesters.And, also can add cyclic ester ring-opening polymerization polymer class, lactic acid etc. such as polycaprolactone and have compound of hydroxyl and carboxyl etc. simultaneously.
As what polycarboxylic acid can be enumerated aliphatic carboxylic acid and aromatic carboxylic acid arranged.Be specially propanedioic acid, toxilic acid, succsinic acid, hexanodioic acid, tartrate, sebacic acid, oxalic acid, phthalic acid, terephthalic acid, trimellitic acid.
As the polyhydroxy reactant of (b1) raw material, that can enumerate has glycol, a triol etc.Be specially ethylene glycol, Diethylene Glycol, propylene glycol, dipropylene glycol, triethylene glycol, 1,3-and 1,4-butyleneglycol, tetramethylene glycol, neopentyl glycol, 1,6-hexylene glycol, decamethylene-glycol, glycerine, TriMethylolPropane(TMP), tetramethylolmethane, Sorbitol Powder etc.The resulting polyester polyvalent alcohol preferably is liquid at normal temperatures, therefore, preferably contains Diethylene Glycol as diol component, preferably contains TriMethylolPropane(TMP) as the polyhydroxy reactant of trifunctional.
(b1) average functional group number is 2.5～4.5, but for the consideration of viscosity aspect more preferably 2.5～3.5.
(b1) hydroxyl equivalent is 300～500, less than 300 and surpass the effect that 500 words all can not be given full play to low-resilience of the present invention.For the consideration of low-resilience more preferably 300～400.
As what polyoxyalkylene polyol (b2) can be enumerated ethylene glycol, propylene glycol, Diethylene Glycol, triethylene glycol, dipropylene glycol, 1 arranged, polyvalent alcohols such as ammediol, glycerine, tetramethylolmethane, TriMethylolPropane(TMP), Sorbitol Powder, sucrose are as the oxyalkylene affixture of initiator; Oxyalkylene affixture as the polyatomic phenol of dihydroxyphenyl propane and so on; The polyol of phosphoric acid, Tripyrophosphoric acid (for example triphosphoric acid and four phosphoric acid) etc.; Contract and product at phenol-aniline-formaldehyde, quadrol, Diethylenetriaminee (DETA), triethylenetetramine, methylene bis Ortho-Chloro aniline, 4,4 '-and 2,4 '-ditan diamines, 2,4-tolylene diamine, 2, the polynary amine of 6-tolylene diamine etc., the polyoxyalkylene polyol that obtains more than a kind or 2 kinds of addition of ethylene oxide, propylene oxide, butylene oxide ring, tetrahydrofuran (THF), Styrene oxide 98min. etc. in the alkanol amine of trolamine, diethanolamine etc.
Also can add the polyoxyalkylene polyol that contains ethylenic copolymer in the polyhydroxy reactant (B).The example can be enumerated: in the presence of free radical, and the material that vinyl polymer such as polypropylene nitrile, vinylbenzene and stable dispersion obtain in the above-mentioned polyoxyalkylene polyol that illustrates for example.In addition, the content of the vinyl polymer in the polyoxyalkylene polyol is usually about 10～45 weight %.
The average functional group number of (b2) of the present invention is 2.5～4.5, and hydroxyl equivalent (b2) is 300～5000.Hydroxyl equivalent increases excessively the tactility variation less than 500 words hardness.Hydroxyl equivalent when obtaining very good tactility is preferably 1000～3000.
And then, the polyester polyol (b1) of polyhydroxy reactant (B) and the blending ratio (mass ratio) of polyoxyalkylene polyol (b2) are (b1): (b2)=70～90: 30～10, (b1) surpass the words of 90 weight %, hardness significantly uprises with respect to the interdependence of temperature, words less than 70 weight %, use general silicon class tensio-active agent can't keep the shape of foam, can not get flexible polyurethane foam.
Among the present invention, preferably in polyhydroxy reactant (B) except that polyester polyol (b1) and polyoxyalkylene polyol (b2), further add polyoxyalkylene monohydroxy-alcohol (b3).By adding the Gas permeability that (b3) can further improve foams.The polyoxyalkylene monohydroxy-alcohol can be with to as the monohydroxy-alcohol of the initiator material that obtains of methyl alcohol, ethanol, propyl alcohol, butanols, 2-Ethylhexyl Alcohol addition oxyalkylene for example.
As the oxyalkylene of addition, optimization ethylene oxide, propylene oxide, oxyethane preferably account for 30～80 moles of %.
Hydroxyl equivalent (=molecular weight) is preferably 76～1000.Take all factors into consideration addition and additive effect more preferably 76～500.Addition is preferably 0.5～10 weight part for (b1)+(b2) of 100 mass parts.If below lower limit, then be difficult to show the effect that Gas permeability improves, if more than the upper limit, the viscosity sense grow of foam surface then causes problems such as bonding mutually between the goods, rubber adhesion.
In the present invention, preferably in polyhydroxy reactant (B) except that polyester polyol (b1) and polyoxyalkylene polyol (b2), add further that average functional group is several 2.5～4.5, hydroxyl equivalent is less than 300 polyoxyalkylene polyol (b4).By adding (b4), can when keeping advantage of the present invention, freely adjust hardness corresponding to the amount of desired foams hardness.Addition is preferably 0.5～10 weight part with respect to (b1)+(b2) of 100 mass parts.(b4) addition is adjusted according to desired foams hardness, but below 0.5 part, can't see hardness and rise, and it is above to add 10 weight parts, can produce foam bubble hole and become problem big, the tactility variation.
On the other hand, be not particularly limited, can use normally used known polyisocyanate compound in the urethane foam manufacturing as polyisocyanate compound.Can suitably select to use the polyisocyanates of the fragrant same clan, the alicyclic ring same clan, aliphatic category and more than a kind or 2 kinds of modified polyisocyanate that their modifications are obtained particularly.
Have 2 as what fragrant family polyisocyanates can be enumerated, 4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate and 2, the mixture of 6-tolylene diisocyanate, diphenylmethanediisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, xylylene vulcabond, polymethylene polyphenyl group diisocyanate etc.
As what alicyclic ring family polyisocyanates can be enumerated cyclohexyl-methane vulcabond, cyclohexyl diisocyanate, hydrogenation MDI etc. are arranged.And, as what fatty family polyisocyanates can be enumerated HDI etc. arranged.
These polyisocyanate compounds are the polyisocyanates 2,4 toluene diisocyanate or 2 of the fragrant same clan particularly in the present invention, and 6-tolylene diisocyanate and its mixture (TDI-80, TDI-65) can obtain good result.
Of the present invention one is characterized as the specific amine catalyst of use greatly.In the whipping agent main body is in the foaming of flexible foam body of water, must keep the balance between resinifying and the generation carbonic acid gas,, will produce in the foaming process and bounce back if this balance is destroyed, abscess connective insufficient, the problem of plasticities such as foaming post shrinkage.And amine catalyst uses particularly preferably in the occasion of the less stinks of needs such as bedding purposes because have less stink.
As the amine catalyst that improves above-mentioned foams plasticity, the reaction that preferably makes alcohols and isocyanates and the reacting phase of water and isocyanic ester are than more being activated.Further study multiple catalyzer, found that, use or all use the imidazoles catalyzer, can realize the low-down compressed residual strain of the problem of the present patent application by part in catalyzer.The imidazoles catalyzer is preferably the ratio that accounts for more than 5% with respect to whole amounts of the catalyzer that uses when foaming.Preferably add more than 15% in order to obtain more fully effect.
As what the imidazoles catalyzer can be enumerated alkyl imidazole being arranged, is 1,2 dimethylimidazole, 1-ethyl-glyoxal ethyline, 1-butyl-glyoxal ethyline etc. specifically.Can buy TOYOCAT DMI, TOYOCAT DM70, TOYOCAT F2, TOYOCAT F10, TOYOCAT F94 of Tosoh company limited etc. as the commodity that contain them, NC-IM, the IMICURE EMI-24 etc. of エ ア プ ロ ダ Network Star company, U-CAT 2026, U-CAT 2030, U-CAT 2034X, the U-CAT 2503 etc. of サ Application ア プ ロ company limited.
The catalyzer that uses as the present invention can and foam with the known urethane foam of the amines catalyst outside the above-mentioned imidazoles, organo-metallic catalyst etc. and uses catalyzer.As this catalyzer, that can enumerate has for example as 1 of amine series catalysts, 8-diazabicyclo (5.4.0) undecylene-7, two (2-dimethylaminoethyl) ether, N, N, N ', N '-4-methyl hexamethylene diamine, triethylenediamine, triethylamine, tripropyl amine, tri-isopropyl amine, Tributylamine, trioctylamine, N-methylmorpholine, N-ethylmorpholine, lupetazin, N, the N-dimethylaminoethanol, N, N-dimethylamino ethoxy ethanol, N, N, N '-trimethylammonium amino ethyl ethanolamine, N, N, N '; N ", N "-dilution of pentamethyl-dipropylenetriamine etc. and its solvent etc.; two or more these mixture of catalysts; utilize organic acid part corrective etc., but because above-mentioned reason; and in the catalyzer of usefulness more preferably 1,8-diazabicyclo (5.4.0) undecylene-7; triethylenediamine; N-ethylmorpholine, N-methylmorpholine, lupetazin, dimethylaminoethanol amine, its organic acid salt etc.
And, as what metal catalyst can be enumerated stannous octoate, tin laurate, dibutyl tin laurate etc. are arranged.
In the urethane foam of the present invention, except these polyhydroxy reactants and polyisocyanate compound, can also add softening agent.As softening agent, can use with dioctyl phthalate (DOP) (DOP), diisononyl phthalate (DINP), butyl benzyl phthalate (BBP), Di Iso Decyl Phthalate (DIDP), phthalic acid two (undecane) ester (DUP) etc. is the common phthalic ester plasticizer of representative, with Octyl adipate (DOA), dioctyl sebacate (DOS), dioctyl azelate (DOZ) is the common fats esters of gallic acid softening agent of representative, with trioctyl trimellitate (TOTM) is the trimellitic acid ester plasticizer of representative, with polypropylene glycol adipic acid ester etc. is the polymer class softening agent such as polyester softening agent of representative, sebacic acid is a softening agent, the general softening agent of clorafin etc., Tritolyl Phosphate (TCP), tricresyl phosphate (dimethylbenzene) ester (TXP), tricresyl phosphate (isopropyl phenyl) ester, tributyl phosphate, triethyl phosphate, triphenylphosphate, phosphate plasticizer such as tricresyl phosphate ethyl phenyl ester, the epoxide of vegetables oil, Resins, epoxy, as what the epoxide of vegetables oil can be enumerated epoxidised soybean oil arranged, epoxidized linseed etc., as what Resins, epoxy can be enumerated epoxidized polybutadiene arranged, methyl epoxy stearate, butyl epoxy stearate, the epoxystearic acid ethylhexyl, three (epoxypropyl) isocyanuric acid ester, 3-(2-biphenylyloxy)-1, the 2-propylene oxide, bisphenol A diglycidyl ether, vinyl two tetrahydrobenzene diepoxides, 2, the epoxies such as polycondensate of two (4-hydroxyphenyl) propane of 2-and epoxy chloropropane are softening agent.These softening agent can use separately or mix more than 2 kinds and use.
The addition of these softening agent can add 2～15 mass parts with respect to the above-mentioned polyhydroxy reactant of 100 mass parts (B).If the softening agent addition is too much, the binding property of foam surface will be too high sometimes.
And, can use other various additives in the urethane foam of the present invention, for example fire retardant, antioxidant, UV light absorber, tinting material, pigment, antiseptic-germicide, deodorizing composition, reodorant, perfume compound etc.
As fire retardant, can use phosphoric acid ester such as Tritolyl Phosphate (TCP), tricresyl phosphate (β-chloroethyl) ester, tricresyl phosphate (two chloropropyls) ester, tricresyl phosphate (dibromopropyl) ester, bromo phosphoric acid ester; Halon such as clorafin, ethylene tetrabromide; Inorganic combustion inhibitors such as zinc borate, magnesium hydroxide, aluminium hydroxide, weisspiessglanz, molybdenum oxide, zinc molybdate etc.These fire retardants can use separately or multiple mixing is used.
As what antioxidant can be enumerated alkylphenol, alkylene bis-phenol, alkylphenol thioether, β, β '-thiopropionate, organophosphite etc. are arranged.These antioxidants can separately or mix more than 2 kinds and use.
As what UV light absorber can be enumerated salicylate, benzotriazole, dihydroxy benaophenonel, vinyl cyanide substituent etc. are arranged.These UV light absorber can separately or be mixed more than 2 kinds and use.Can enumerate 2 specifically, 4-dihydroxy benaophenonel, 2-hydroxyl-4-methoxy benzophenone, 2-hydroxyl-4-oxethyl-diphenyl-ketone, 2-hydroxyl-4-octyloxy benzophenone, 5,5 '-methylene bis 2-hydroxy benzophenone ketones such as (2-hydroxyls-4-methoxy benzophenone); 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-5-chlorinated benzotriazole, 2-(2 '-hydroxyl-the 3 '-tertiary butyl-5 '-aminomethyl phenyl)-5-chlorinated benzotriazole, 2-(2 '-hydroxyl-5 '-uncle's octyl phenyl) benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-dicumylphenyl) benzotriazole, 2,2-(2 '-hydroxy phenyl) benzotriazole categorys such as 2 '-methylene bis (uncle's 4-octyl group-6-benzotriazole) phenol; Salol, resorcinol monobenzoate, 2,4-di-tert-butyl-phenyl-3 ', 5 '-di-t-butyl-4 '-hydroxybenzoate, six decyls-3, benzoates such as 5-di-tert-butyl-4-hydroxybenzoic acid ester; The oxanilide class of 2-oxyethyl group-4 '-dodecyl oxanilide etc.; Alpha-cyano-β, β-diphenyl-ethyl acrylate, 2-cyano group-cyanoacrylates such as 3-methyl-3-(p-methoxyphenyl) methyl acrylate.These UV light absorber may be used alone, can also be two or more kinds in combination.
Can use normally used those pigment as organic system pigment, specifically, that can enumerate has an insoluble azo lake, the solubility azo lake, insoluble azo inner complex, condensation azo inner complex, azo pigments such as other azo inner complexs, phthalocyanine blue, phthualocyanine pigments such as phthalocyanine green, anthraquinone, naphthalene embedding benzoquinones (ベ リ ノ Application), perylene, anthracene series pigments such as thioindigo, antimony (anti) series pigments, nitro pigment, isoindoline ketone series pigments, building dyestuff series pigments, nitrose pigment, the matching stain series pigments, the basic dyestuff series pigments, quinoline a word used for translation ketone series pigments dioxazine series pigments, isoindoline ketone series pigments etc.
As inorganic series pigments, selenide, yellow prussiate and carbon black etc. vulcanize in have titanium oxide, ferric oxide (rhombohedral iron ore etc.), chromic acid (chrome yellow etc.), molybdic acid, cadmium system sulfuration selenide, the mercury system that can enumerate.These pigment may be used alone, can also be two or more kinds in combination.
As antiseptic-germicide, can use natural antibacterial agent, quaternary ammonium, above-mentioned substances such as organic class antiseptic-germicide such as metal-powders such as silver, zinc, copper, these metal-powders, alcohols antiseptic-germicide, phenolic antiseptic, natural extract and natural crystal to load on inorganic particulate antiseptic-germicide on the carriers such as zeolite, silicon-dioxide, aluminum oxide etc.These antiseptic-germicides may be used alone, can also be two or more kinds in combination.
As deodorizing composition, can use carbon dusts such as charcoal and bamboo charcoal, high-quality charcoal, hard charcoal, black wood charcoal, gac and silicon-dioxide, aluminum oxide, zeolite etc.These carbon dusts can not only be used as deodorizing composition, and can also be as humextant or moisture adsorbent, far infrared irradiation agent.
As reodorant, can compatibly use from each kind of plant of for example Theaceae plant, purple perilla section plant, fragrant canella, endeavor river pear section plant, campanulaceae plant, kurrajong plant etc. by isolating deodorizing compositions of means such as extractions.Particularly preferably in the material that reduces pressure destructive distillation tealeaves, Flower of Japanese Camellia, camellia, Yang Tong, Ternstroemia gymnanthera etc., vacuum fractionation to obtain.And, also can use by the suitable composition of the deodorizing composition with being derived from above-mentioned natural goods of synthesis method manufacturing (polyphenol and flavonoid, Flavonol, catechuic acid etc.).And then above-mentioned reodorant can use on carriers such as silicon-dioxide, aluminum oxide, zeolite, different light body, pottery in load.
Be not particularly limited as perfume compound, the natural aromatic agent can be enumerated animality perfume compound such as Moschus, civet (mourning hall perfume (or spice)), カ ス ト Le (castoreum), grane ambra; Vegetalitas perfume compound such as oleum lavendulae, spearmint oil, lemon oil, mandarin oil, rose oil, white oil of camphor, santal oil, hinokitiol.And, as what artificial perfume compound can be enumerated synthetic aromatising agents such as acetyl syringic acid, the different syringic acid of acetyl, olibanol, phellandrene, fatty aldehyde, thymol, isothymol, bornyl methoxyl group hexalin, oxymethoxyallylbenzene, phenylacrolein, phenyl aldehyde, clovene, tonka bean camphor, big ring-type Moschus, vanillal, Yi Bilin acid, TRANSCINNAMIC ACID, Vanillin, guaiol, furfural, phenyl methyl ketone, γ-11 carbon lactone, γ-decalactone are arranged; Go out the separation perfume compound of the main component of essential oil by fractionation separates; Mix the natural aromatic agent or/and the mediation perfume compound of artificial perfume compound preparation etc.The concrete commodity of artificial perfume compound comprise the ALDEHYDEC-10 that KAO. Corp. SA makes, ALDEHYDE C-11, UNDECYL, ALDEHYDE C-111 LEN, ALDEHYDE C-12 LAURYL, ALDEHYDE C-12 MNA, ALDEHYDE C-6, ALDEHYDE C-8, ALDEHYDE C-9, AMBERCORE, AMYL CINNAMICALDEHYDE, FRUITATE, GAMMA DECALACTION, GAMMA NONALACTONE, GAMMA UNDECALACTONE, HEXYL CINNAMIC ASDEHYDE, IONONE 100%, MAGNOL, o-t-BCHA, p-t-BCHA, PEARLIDEB.B., PEARLIDE DEP, PEARLIDE IPM, PEARLIDEPURE, POIRENATE, POLLENAL 2, SAGETONEV, SANDALMYSORE CORE etc.
Main composition is made in having with water that the whipping agent that uses when making urethane foam can be enumerated, with mixtures more than two kinds such as carbonic acid gas, methylene dichloride, HFC-245fa, HFC-365mfc.
And can use present known organopolysiloxane as suds-stabilizing agent is tensio-active agent.L-520, the L-532, L-540, L-544, L-3550, L-5740S, L-5740M, the L-6202 etc. that make as the Japanese ユ ニ カ of having of can enumerating of such organopolysiloxane tensio-active agent one company; SH-190, the SH-192 that east beautiful DOW CORNING siloxanes company makes, SH-193, SH-194, SRX-290, SRX-294A, SRX-298 etc.; F-114, F-121, F-122, F-230, F-258, F-260B, F-317, F-341, F-601, F-606 that シ リ コ one Application company of SHIN-ETSU HANTOTAI makes; TEGOSTABB8002, the B4900 of go one Le De シ ュ ミ ッ ト company, B8040, B8233, B8229, B8110, B8300, B8317, B8324 etc.These suds-stabilizing agents may be used alone, can also be two or more kinds in combination.
In the urethane foam composition of the present invention that contains above-mentioned polyhydroxy reactant, polyisocyanate compound, softening agent, catalyzer and whipping agent etc., the blending ratio of each composition, so long as can be by the foaming of this urethane foam composition, obtain the urethane foam with highly air-permeable, low-resilience as purpose of the present invention, this blending ratio just is not particularly limited.
For example, polyhydroxy reactant (B) with respect to 100 mass parts, catalyzer is 0.01～5 mass parts, preferred 0.2～3 mass parts, water are 0.5～5 mass parts, preferred 0.8～3.5 mass parts, when mixing suds-stabilizing agent is 0.1～4 mass parts, preferred 0.4～2.0 mass parts is 0.001～2.0 mass parts during hybrid pigment, about preferred 0.01～1.5 mass parts.
In the present invention, the blending ratio of polyisocyanate compound, being expressed as isocyanate index is 50～100, preferred 60～100.Here so-called isocyanate index is for on duty with 100 divided by the total mole number of aqueous isocyanate-reactive active hydrogen of isocyanate group mole number.If isocyanate index is low excessively, the physical strength of foams reduces sometimes, the compressed residual strain becomes big.If isocyanate index is too high, exist foams that the problem such as trend, tactility variation, shock absorbing capability reduction of hardening is arranged.
The manufacture method of urethane foam of the present invention can be carried out based on the manufacture method of the urethane foam of existing continuous air bubbles, for example can be suitable for pre-polymerization method, single stage method, part pre-polymerization method etc. and carry out.
The Gas permeability of the urethane foam of highly air-permeable of the present invention, low-resilience, low compression residual strain is at 50cm 3/ cm 2More than/the s, rebound resilience is below 20%, and the compressed residual strain is below 5%.
In addition, compressed residual strain (being the xeothermic compressed residual strain of measuring according to JIS K6400 (1997) specifically), consideration for obtaining the urethane foam that tactility and shock absorbing capability aspect be more suitable for is preferably below 2.5%, more preferably below 1.5%.Wherein, for the very good consideration of tactility and shock absorbing capability aspect, be preferably below 1.0% especially.
Flexible polyurethane foam rebound degree of the present invention is below 10%, and good especially prescription embodies the good low-resilience of 1% front and back, and ventilation property is at least at 80cm 3/ cm 2More than/the s, has 200cm according to prescription 3/ cm 2The highly air-permeable that/s is above.In addition, compressed residual is answered step-down, good especially formula table reveals xeothermic, damp and hot compressed residual strain all at the high-durability below 1%, thereby can compatibly be used as absorption of vibrations material, various laminated product factorial lumber or liner, mattress, cushion plate, back cushion, clothing with liner etc.
Embodiment 1
Below, specify the present invention by embodiment, reference example, comparative example, but the invention is not restricted to these embodiment.
Embodiment 1～3, reference example 1, comparative example 1
Each mixing element according to following table 1 record prepares urethane foam.That is, polyhydroxy reactant and water, catalyzer, whipping agent are mixed, add polyisocyanate compound therein, make its mixing, this mixture prepares flexible polyurethane foam by foaming.As amine catalyst, use reference example 1 stink of piperazines catalyzer strong, preferably avoid using at aspects such as beddings.
Embodiment 4～6, comparative example 2 and 3
According to the blending ratio of the pure and mild polyether glycol of putting down in writing in the table 2 of each mixing element change polyester polyols, mode same as the previously described embodiments prepares urethane foam.Polyether glycol is in the comparative example 3 of 40 mass parts, can not get the normal appearance foams.Can obviously find out by this table, must mix in the specific blend ratio.
Embodiment 7～9, comparative example 4 and 5
Change isocyanate index as shown in table 3.This table shows that the isocyanate index of specified range is necessary.
The urethane foam that obtains according to each embodiment, reference example and comparative example is to its density (kg/m 3), hardness (25%CLD:N/100cm 2), tensile strength (kPa), compressed residual strain (%), ball rebound degree (%), recovery of shape time, Gas permeability (cm 3/ cm 2/ s) and to the degree of breaking, the being clamminess property each side of the foam bubble hole that obtains estimate.The result is shown in the table in the lump.
Table 1
Embodiment 1 Embodiment 2 Embodiment 3 Reference example 1 Comparative example 1
Polyisocyanate compound polyalcohol 1 polyalcohol 2 polyalcohols 3 polyalcohols 4 catalyst 1 catalyst 2 catalyst 3 catalyst 4 foam stabilizer water TDI 80 20 ? ? 0.2 0.2 ? ? 1 2 TDI 85 15 ? ? ? 0.2 ? 0.2 1 2 TDI 85 15 ? 6 ? 0.2 ? 0.2 1 2 TDI 80 20 6 ? ? ? 1.3 ? 1 2 TDI ? 20 80 6 0.2 0.2 ? ? 1 2
Isocyanate index 80 80 80 80 80
Density [kg/m 3] hardness [N/100cm 2] 25 ℃ of 10 ℃ of hot strengths [kPa] compressed residual strain values [%] ball rebound degrees [%] recovery time air permeability [cm3/cm 2/ second] the preceding crushing of crushing back being clamminess property of abscess state 53.0 17 31 153 0.5 2 7.8 ? 98 100 ○ ○ ? 54.4 20 39 129 0.8 2 8.1 ? 88 88 ○ ○ ? 60.6 34 67 145 0.1 1 8.9 ? 158 158 ○ ○ ? 48.0 15 27 106 1.4 3 3.2 166 173 00 stinks are stronger 40.5 6.8 25 101 2.8 26 0.5 ? 68 68 ○ ○ ?
Table 2
Comparative example 2 Embodiment 4 Embodiment 5 Embodiment 6 Comparative example 3
Polyisocyanate compound polyalcohol 1 polyalcohol 2 polyalcohols 3 polyalcohols 4 catalyst 1 catalyst 2 catalyst 3 foam stabilizer water TDI 100 ? ? 6 0.2 0.2 ? 1 2 TDI 85 15 ? 6 0.2 0.2 ? 1 2 TDI 80 20 ? 6 0.2 0.2 ? 1 2 TDI 70 30 ? 6 0.2 0.2 ? 1 2 TDI 60 40 ? 6 0.2 0.2 ? 1 2
Isocyanate index 80 80 80 80 80
Density [kg/m 3] hardness [N/100cm 2] 25 ℃ of 10 ℃ of hot strengths [kPa] compressed residual strain values [%] ball rebound degrees [%] recovery time air permeability [cm3/cm 2/ second] the preceding crushing of crushing back being clamminess property of abscess state 63.4 35 110 88 6.6 8 8.6 161 163 break zero 57.6 28 50 124 0.2 1 8.9 ? 203 203 ○ ○ 55.0 19 32 147 0.5 2 8.8 ? 198 196 ○ ○ 53.7 11 23 88 1.3 5 8.2 ? 178 177 ○ ○ Can not get the foam (retraction) that to measure
Table 3
Comparative example 4 Embodiment 7 Embodiment 8 Embodiment 9 Comparative example 5
Polyisocyanate compound polyalcohol 1 polyalcohol 2 polyalcohols 3 polyalcohols 4 catalyst 1 catalyst 2 catalyst 3 foam stabilizer water TDI 80 20 ? 6 0.2 0.2 ? 1 2 TDI 80 20 ? 6 0.2 0.2 ? 1 2 TDI 80 20 ? 6 0.2 0.2 ? 1 2 TDI 80 20 ? 6 0.2 0.2 ? 1 2 TDI 80 20 ? 6 0.2 0.2 ? 1 2
Isocyanate index 105 100 90 70 40
Density [kg/m 3] hardness [N/100cm 2] 25 ℃ of 10 ℃ of hot strengths [kPa] compressed residual strain values [%] ball rebound degrees [%] recovery time air permeability [cm3/cm 2/ second] the preceding crushing of crushing back being clamminess property of abscess state 52.2 195 372 160 1.5 18 56.2 ? 121 121 ○ ○ 53.4 84 185 160 1.5 9 34.3 ? 185 183 ○ ○ 54.1 35 71 106 2.1 5 8.6 ? 161 163 ○ ○ 60.8 15 29 89 2.2 6 7.8 ? 143 143 ○ ○ 68.0 5.3 11 37 5.8 0 100 ? 89 - ○ ○
The raw material that uses is as follows.
" the コ ロ ネ one ト T-80 (2,4 toluene diisocyanate and 2, the 6-tolylene diisocyanate is with 80: 20 mixture of mass ratio) that polyisocyanates uses Japanese polyurethane industrial to make.Use following polyvalent alcohol as polyvalent alcohol.
Polyvalent alcohol 1: hexanodioic acid kind polyester polyvalent alcohol, Japanese polyurethane industrial makes; ニ Star Port ラ Application 131, average functional group is several 3, hydroxyl value: 150 (hydroxyl equivalents: 374)
Polyvalent alcohol 2: poly-(propylene oxide ethylene oxide) triol, Sanyo changes into industrial and makes; サ Application ニ Star Network ス FA703, glycerine, hydroxyl value: 33 (hydroxyl equivalents: 1700)
Polyvalent alcohol 3: hexanodioic acid kind polyester polyvalent alcohol, Japanese polyurethane industrial makes ニ Star Port ラ Application 2200, and average functional group is several 3, hydroxyl value: 60 (hydroxyl equivalents: 933)
Polyvalent alcohol 4: poly-(ethylene oxide propylene oxide) monohydroxy-alcohol.Sanyo changes into industrial and makes 50HB55, hydroxyl value 234 (hydroxyl equivalent: 240)
Catalyzer 1: non-imidazoles amine series catalysts, Tosoh company makes HX63
Catalyzer 2:1,2-methylimidazole class catalyzer, Tosoh company makes TOYOCAT DMI
Catalyzer 3: the piperazines catalyzer, go one Le De シ ュ ミ Star ト company makes EPS
Catalyzer 4: the imidazoles catalyzer, サ Application ア プ ロ company makes U-2030
Suds-stabilizing agent: SH190 (eastern beautiful DOW CORNING siloxanes company make)
The measuring method of various physical propertiess
(a) density, compressed residual strain, rebound resilience: measure according to JIS K6400 (1997).
(b) hardness: on compression more than the sample load area sample strip of 100mm * 100mm * 50mm being prepared compression, be returned to compression once again behind the abundant height, is 75% o'clock of the original thickness stress value when measuring compression at thickness of sample.
(c) tensile strength:, measure with No. 1 dumbbell shape according to JIS K6400 (1997).
(d) by step measurements recovery time as follows.
1, measures environment: 23 ± 2 ℃ of temperature, relative humidity 50 ± 5%
2, sample size: the foams center of vertical 100mm * horizontal 100mm * thick 40mm is pressed into 20mm with pressurization of diameter 30mm.
3, keep this state 10s.
4, measure from removing the sub moment of pressurizeing to the time that resets into original-shape (not having depression).
(e) Gas permeability: the A method according to JIS K6400 (1997) is measured.
(f) the coarse evaluation of abscess is whether the abscess-size of estimating urethane foam has deviation.Deviously think that abscess is coarse.
(g) according to following being clamminess property of metewand evaluation.
Zero: do not have fully or being clamminess property not almost, also do not have the problem of processing, storage.
*: if contact has the sensation that finger is stained with tackiness agent.
The urethane foam with highly air-permeable, low-resilience that method constructed in accordance obtains can not prepare with the known urethane foam of prior art, has the temperature dependency of low-resilience, fabulous ventilation property, low hardness and unusual good compression residual strain.Therefore, this polyurethane foam physical efficiency is in the field of various requirement, for example can be suitable for as the various laminated products processing uses of impact absorbing material, absorption of vibrations material or liner, mattress, cushion plate, back cushion, clothing being especially suitable for use as the nursing bedding with in the liner etc.

Claims (5)

1, a kind of density that with polyisocyanates (A), polyvalent alcohol (B), whipping agent (C), catalyzer (D) and suds-stabilizing agent (E) at isocyanate index is reaction obtains under 50～100 the condition is 40～80kg/m 3, hardness is 8～150N/100cm 2Highly air-permeable, low-resilience, the manufacture method of flexible polyurethane foam, it is characterized in that: the polyol blend that polyvalent alcohol (B) is that average functionality is 2.5～4.5, hydroxyl equivalent is 300～500 polyester polyol (b1) and average functionality is 2.5～4.5, hydroxyl equivalent is 300～5000 polyoxyalkylene polyol (b2), and its blending ratio is (b1): (b2)=70～90: 30～10 (mass ratioes).
2, a kind of xeothermic compressed residual strain value of measuring according to JIS K6400 (1997) that with polyisocyanates (A), polyvalent alcohol (B), whipping agent (C), catalyzer (D) and suds-stabilizing agent (E) at isocyanate index is that reaction obtains under 50～100 the condition is below 5% and density 40～80kg/m 3, hardness 8～150N/100cm 2Highly air-permeable, low-resilience, the manufacture method of flexible polyurethane foam, it is characterized in that: the polyol blend that polyvalent alcohol (B) is that average functionality is 2.5～4.5, hydroxyl equivalent is 300～500 polyester polyol (b1) and average functionality is 2.5～4.5, hydroxyl equivalent is 300～5000 polyoxyalkylene polyol (b2), and its blending ratio is (b1): (b2)=70～90: 30～10 (mass ratioes).
3, the manufacture method of highly air-permeable as claimed in claim 1 or 2, low-resilience, flexible polyurethane foam, wherein the average sense that obtains for addition propylene oxide and oxyethane on the polyol that has the hydroxyl more than 2 at per molecule of polyoxyalkylene polyol (b2) becomes 2.5～4.5, hydroxyl equivalent is 300～5000 polyoxyalkylene polyol.
4, as the manufacture method of any one the described highly air-permeable in the claim 1～3, low-resilience, flexible polyurethane foam, wherein catalyzer (D) is for containing the catalyzer of glyoxaline compound.
5, as the manufacture method of any one the described highly air-permeable in the claim 1～4, low-resilience, flexible polyurethane foam, wherein polyvalent alcohol (B) further contains the polyoxyalkylene monohydroxy-alcohol.
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