CN100390214C - Porous polyurethane object - Google Patents
Porous polyurethane object Download PDFInfo
- Publication number
- CN100390214C CN100390214C CNB2004800256258A CN200480025625A CN100390214C CN 100390214 C CN100390214 C CN 100390214C CN B2004800256258 A CNB2004800256258 A CN B2004800256258A CN 200480025625 A CN200480025625 A CN 200480025625A CN 100390214 C CN100390214 C CN 100390214C
- Authority
- CN
- China
- Prior art keywords
- chain propagation
- propagation agent
- carbamate prepolymer
- agent
- porous polyurethane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Classifications
-
- 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
-
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
-
- 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
-
- 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
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- 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
- C08G2101/00—Manufacture of cellular products
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
A porous polyurethane object having interconnected micropores which has been obtained with a polyamine compound as the only crosslinking agent. The porous polyurethane object is obtained by polymerizing a polyol, a chain extender, a hydrophilic chain extender, and an isocyanate, crossliking the resultant aqueous dispersion of an isocyanate-terminated urethane propolymer with a polyamine compound, and removing water from the resultant gel.
Description
Technical field
The present invention relates to have the porous polyurethane object of fine continuous pore.
Technical background
In the past, had the porous polyurethane object of fine continuous pore, and for example, made the reaction of carbamate emulsion make (with reference to patent documentation 1) by using as the water-soluble polyisocyanates of primary cross-linking agent with as the polyamine compound of secondary crosslinking agent.
Patent documentation 1: the spy opens the 2003-48940 communique
For the emulsion of carbamate prepolymer, if only use the polyamine compound to make porous polyurethane object, then owing to the number that can reduce used composition, so consider very useful from the viewpoint of manufacturing cost as linking agent.
Summary of the invention
The object of the present invention is to provide and only use the porous polyurethane object with fine continuous pore of polyamine compound as the linking agent preparation.
In order to solve above-mentioned problem, porous polyurethane object of the present invention is characterized in that: carry out removing moisture the gelation thing that crosslinking reaction obtains and make from making the end that polyvalent alcohol, chain propagation agent, wetting ability chain propagation agent and isocyanic ester polymerization are obtained have the carbamate prepolymer water dispersion of isocyanate group and polyamine compound.
Porous polyurethane object of the present invention, owing to contain the wetting ability chain propagation agent, and only use the polyamine compound as linking agent, be applicable to the fine continuous pore of various uses so form, but also can suppress manufacturing cost.
Description of drawings
Fig. 1 is the microphotograph (multiplying power: 600 times) of the resultant of reaction that makes of embodiment 1.
Fig. 2 is the microphotograph (multiplying power: 600 times) of the resultant of reaction that makes of comparative example 1.
Embodiment
Porous polyurethane object of the present invention is to make carbamate prepolymer water dispersion and polyamine compound that carbamate prepolymer is dispersed in the water carry out the porous insert that crosslinking reaction makes.Moreover so-called carbamate prepolymer of the present invention is meant the prepolymer that end that polyvalent alcohol, chain propagation agent, wetting ability chain propagation agent and isocyanic ester polymerization are obtained has isocyanate group.
As polyvalent alcohol, if the polyvalent alcohol that has more than or equal to 2 hydroxyls in the common molecule that uses in the urethane manufacturing does not then have particular determination, for example, can enumerate polyether glycol, polyester polyol, polycarbonate polyol, poly-lactone polyol, polyolefin polyhydric alcohol, acrylic acid series multiple alcohol, Viscotrol C is polyvalent alcohol, polysiloxane series polyvalent alcohol etc., and these can use separately or will mix more than or equal to 2 kinds and use.Wherein, consider, preferably use polycarbonate polyol from the viewpoint that suppresses gained porous polyurethane object deterioration.Aforementioned said deterioration comprises the deterioration of light generation, the deterioration of water generates.
As polyether glycol, epoxide (oxyethane, propylene oxide, butylene oxide ring etc.) and/or (tetrahydrofuran (THF) etc.) polymerization of hetero ring type ether or copolymerization are obtained, can enumerate polyoxyethylene glycol, polypropylene glycol, polyethylene glycol-propylene glycol (block or random), polyoxyethylene glycol-1 particularly, 4-butyleneglycol (block or random), poly-1,4-butyleneglycol, poly-2-methyl isophthalic acid, 4-butyleneglycol, poly-1,6-hexylene glycol etc.
As polyester polyol, be to make aliphatic dicarboxylic acid (succsinic acid, hexanodioic acid, sebacic acid, pentanedioic acid, nonane diacid etc.) and/or aromatic dicarboxylic acid (m-phthalic acid, terephthalic acid etc.) with low-molecular-weight diol (ethylene glycol, propylene glycol, 1, the 4-butyleneglycol, 1, the 6-hexylene glycol, the 3-methyl isophthalic acid, the 5-pentanediol, neopentyl glycol, 1,4-hydroxymethyl-cyclohexanes etc.) polycondensation obtains, and can enumerate polyethylene glycol adipate particularly, poly adipate succinic acid ester, poly-hexanodioic acid hexylene glycol ester, poly-hexanodioic acid 3-methyl pentanediol ester, polyneopentyl glycol adipate, poly-hexanodioic acid ethylidene/butylidene esterdiol, poly-hexanodioic acid neo-pentyl/polyhexamethylene glycol, poly-m-phthalic acid butanediol ester glycol etc.
As polycarbonate polyol, can enumerate organic carbonate (methylcarbonate, diethyl carbonate, ethylene carbonate, diphenyl carbonate, phosgene etc.) with low-molecular-weight diol (butyleneglycol, pentanediol, hexylene glycol, the 3-methyl pentanediol, nonanediol, 2-methyl ethohexadiol, cyclohexanedimethanol etc.) polycarbonate polyol that reaction obtains, can enumerate polytetramethylene carbonate diol particularly, poly-carbonic acid 3-methyl pentanediol ester, poly-carbonic acid hexylene glycol ester, poly-carbonic acid nonanediol ester, poly-carbonic acid butyleneglycol hexylene glycol ester, poly-neopentyl glycol carbonate ester, poly-neopentyl glycol carbonate hexylene glycol ester, poly-carbonic acid 3-methyl pentanediol hexylene glycol ester, poly-carbonic acid 2-methyl ethohexadiol ester, poly-carbonic acid 2-methyl ethohexadiol nonanediol ester, poly-carbonic acid 1, the 4-cyclohexanedimethanoester ester, poly-carbonic acid 1,4 cyclohexane dimethanol hexylene glycol ester etc.
As poly-lactone polyol, can enumerate polycaprolactone glycol, polycaprolactonetriol, the interior esterdiol of poly--3-methylpent etc.
As polyolefin polyhydric alcohol, can enumerate polybutadiene diol, polyisoprene glycol or its hydride etc.
So-called polysiloxane series polyvalent alcohol is a polyvalent alcohol of having introduced hydroxyl on polysiloxane backbone.In addition, the hydroxyl of introducing can be at two ends of polysiloxane backbone, perhaps at single end.
In addition, as the number-average molecular weight of aforementioned polyvalent alcohol, the viewpoint that forms fine continuous pore from the porous polyurethane object that makes gained considers, preferably 500～5000, be more preferably 500～4000, especially preferably 500～3000.
As chain propagation agent, so long as have short chain diatomic alcohol compounds in the molecule that usually in the urethane manufacturing, uses more than or equal to 2 hydroxyls, then there is not particular determination, for example, can enumerate ethylene glycol, glycol ether, propylene glycol, dipropylene glycol, 1,3 butylene glycol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, neopentyl glycol, 3-methyl pentanediol, nonanediol, ethohexadiol, dihydroxymethyl heptane etc., these can use separately or will mix more than or equal to 2 kinds and use.
Consider that from the viewpoint of the porous polyurethane object that obtains to have good article characteristic the use level of chain propagation agent is with respect to above-mentioned polyvalent alcohol 100 weight parts, preferably 0.1～10 weight part, more preferably 0.5～7 weight part, 1～5 weight part especially preferably.
In addition, as the wetting ability chain propagation agent, can enumerate intramolecularly and have cationic chain propagation agents such as nonionic chain propagation agent, N methyldiethanol amine such as anionic property chain propagation agent, oxirane compound such as polyol more than or equal to 1 anionic property hydrophilic group (carboxyl or sulfonic group), these can use separately or will mix more than or equal to 2 kinds and use.Wherein, the preferred anionic property chain propagation agent that uses, particularly, can enumerate 2,2-dihydroxymethyl lactic acid, 2,2-dimethylol propionic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylolpropionic acid, 2,2-dihydroxymethyl valeric acid, 1,4-butyleneglycol-2-sulfonic acid etc., these can use separately or will mix more than or equal to 2 kinds and use.
Though the use level of wetting ability chain propagation agent depends on the kind of used polyvalent alcohol and isocyanic ester described later, but consider from the water dispersible of raising gained carbamate prepolymer and the viewpoint of the viewpoint of gelling characteristics described later and the porous polyurethane object that acquisition has fine continuous pore, in the total overall reaction composition that constitutes carbamate prepolymer, be preferably 0.1～4 weight %, more preferably 1～4 weight %, especially preferably 1～3 weight %.That is, when the use level of wetting ability chain propagation agent was lower than 0.1 weight %, the water dispersible of gained carbamate prepolymer might reduce terrifically.And the use level of wetting ability chain propagation agent might be destroyed the gelling characteristics of gained carbamate prepolymer water dispersion during greater than 4 weight %.
As isocyanic ester, so long as in urethane is made, use usually, the compound that end has more than or equal to 2 isocyanate group does not then have particular determination, for example, can enumerate 2, the 4-tolylene diisocyanate, 2, the 6-tolylene diisocyanate, 4,4 '-diphenylmethanediisocyanate, 3,3 '-two chloro-4,4 '-diphenylmethanediisocyanate, 2,2 '-diphenylmethanediisocyanate, 2,4 '-diphenylmethanediisocyanate, xylylene diisocyanate, phenylene diisocyanate, 1, the 5-naphthalene diisocyanate, hydrogenated diphenyl methane diisocyanate, aromatic polyisocyanate and hydride thereof such as hydrogenation of benzene dimethylene diisocyanate; 1, alicyclic polyisocyanates such as 4-cyclohexyl diisocyanate, isophorone diisocyanate, norbornene alkyl diisocyanate; Tetramethylene diisocyanate, 1, aliphatic polyisocyantes such as 6-hexamethylene diisocyanate etc., these can use separately or will mix more than or equal to 2 kinds and use.
Use level as isocyanic ester, then do not have particular determination so long as the end of gained carbamate prepolymer has isocyanate group, can cooperate the active hydrogen base that itself and aforementioned polyvalent alcohol, chain propagation agent and wetting ability chain propagation agent are had separately to react quantitatively.
Carbamate prepolymer can adopt the known method manufacturing, there is not particular determination, for example, can enumerate and do not contain in the presence of the organic solvent of active hydrogen base or in the presence of non-, adopt a step foaming or multiple process to make polyvalent alcohol and chain propagation agent and wetting ability chain propagation agent and isocyanic ester preferably 20～150 ℃, more preferably 60～120 ℃ of methods of 2～10 hours of reaction down at intramolecularly.Here, the interpolation of each composition does not have particular determination in proper order.In addition, preferably monitor reaction end with viscosity.
The viewpoint of the viscosity when making carbamate prepolymer from reducing is used above-mentioned organic solvent, for example can enumerate acetone, methylethylketone, N-Methyl pyrrolidone, toluene, tetrahydrofuran (THF), diox, N, N '-dimethyl formamide etc.
Carbamate prepolymer water dispersion among the present invention is to make above-mentioned carbamate prepolymer be dispersed in dispersion in the water, carbamate prepolymer is with respect to the cooperation ratio of water, considers preferred 5～60 weight %, more preferably 10～50 weight %, preferred especially 15～40 weight % from the viewpoint of the apparent density of control gained porous polyurethane object.
Manufacture method as the carbamate prepolymer water dispersion does not have particular determination, for example, can enumerate use dispersing and mixing machine, homomixer, homogenizer five equilibrium in bulk put with carbamate prepolymer mix with water, dispersive method etc.
Here, when using the anionic property chain propagation agent, consider, can make the anionic property hydrophilic group neutralization of the wetting ability chain propagation agent that constitutes carbamate prepolymer in advance from the viewpoint of the water dispersible that improves carbamate prepolymer as the wetting ability chain propagation agent.As described neutralizing agent, for example, can enumerate low-grade alkylamines such as Trimethylamine 99, triethylamine, Tri-n-Propylamine, tri-n-butylamine; Inorganic neutralizing agent such as ammonia.Wherein, consider, preferably use the boiling point Trimethylamine 99 lower, triethylamine than water from the viewpoint that easy employing dehydration procedure described later is removed.
Use level as neutralizing agent does not have particular determination, usually preferably with the anionic property hydrophilic group of wetting ability chain propagation agent roughly equal parts cooperate.
In addition, consider, can suitably use tensio-active agent from the viewpoint of the water dispersible that improves carbamate prepolymer.As spendable tensio-active agent, for example, can enumerate higher alcohols ethylene oxide adduct (polyoxyethylene lauryl ether, polyoxyethylene cetyl base ether, polyoxyethylene stearyl base ether, polyoxyethylene oleyl ether etc.), the higher alcohols propylene oxide adduct, higher alcohols (epoxy ethane-epoxy propane) affixture, alkylphenol ethylene oxide adduct (polyoxyethylene nonylplenyl ether, polyoxyethylene octyl phenyl ether etc.), the aryl phenol ethylene oxide adduct, the lipid acid ethylene oxide adduct, fatty acid polyglycol ester, the fatty amide ethylene oxide adduct, chain alkyl amine ethylene oxide adduct, the polyhydric alcohol fatty acid ester ethylene oxide adduct, greasy ethylene oxide adduct, glycerol fatty acid ester, polyglycerol ester, pentaerythritol fatty ester, Sorbitol Powder fatty acid ester (sorbitan ester), the sorbitan ester ethylene oxide adduct, sucrose fatty ester, the alkyl oxide of polyvalent alcohol, nonionogenic tensides such as the fatty amide of alkanolamine; Anion surfactants such as alkyl ether sulphate salts, alkylbenzene sulfonate, dialkyl sulfosuccinate salt; Cats products such as alkyl quaternary ammonium salts etc., these can use separately or will mix more than or equal to 2 kinds and use.Wherein, consider that preferred HLB value is 6～20 nonionic surfactant from water dispersible viewpoint that improves carbamate prepolymer and the viewpoint of carrying out washing step described later expeditiously.
The use level of tensio-active agent is with respect to preferred 0.1～20 weight % of carbamate prepolymer, more preferably 1～10 weight %, 2～5 weight % especially preferably.
The manufacture method of the carbamate prepolymer water dispersion during as the matching surface promoting agent, for example, can enumerate 1) carry out dispersive method, 2 with above-mentioned homomixer five equilibrium carbamate prepolymer and the water that will be mixed with tensio-active agent put in bulk that similarly uses) similarly use in bulk the putting of homomixer five equilibrium that the carbamate prepolymer and the aqueous solution that contains tensio-active agent are carried out dispersive method etc. with above-mentioned.
The carbamate prepolymer water dispersion that makes like this, the viewpoint of the porous polyurethane object that has fine continuous pore from the viewpoint that improves gelling characteristics described later and acquisition consider, preferably through the time unsettled.Here, so-called " through the time unsettled " be meant that carbamate prepolymer is dispersed in the water after, when leaving standstill at normal temperatures and pressures, disperse the back 24 hours situations with part or all separate and subside of interior urethane resin composition.
As above-mentioned polyamine compound, can then there be particular determination with the polyamine compound of the hydrogen atom (containing in 1 molecule) of the isocyanic ester radical reaction of carbamate prepolymer water dispersion so long as have in the molecule more than or equal to 2 uncles and/or secondary amino group more than or equal to 2, for example, can enumerate quadrol, propylene diamine, 1,3-diamino pentane, 1,5-diamino pentane, 1, the 4-butanediamine, 1, the 6-hexanediamine, 1,7-diamino heptane, 1,5-diamino-2-methylpentane, 1,8-diamino octane, 1,12-diamino dodecane, 3,3 '-the diamino dipropyl amine, 3,3 '-the methyl-imino dipropyl amine, diethylenetriamine, Triethylenetetramine (TETA), tetren, penten, polyethyene diamine, N, N '-diamino propyl group-1, the 3-propylene diamine, N, N '-diamino propyl group-1, the 4-butanediamine, 1,2-two (2-amino ethoxy) ethane, 1,2-two (the amino propoxy-of 3-) ethane, 1,4-two (the amino propoxy-of 3-) butane, 2-hydroxylamino propylamine, two-(3-aminopropyl) ethers, 1,3-two-(the amino propoxy-of 3-)-2, aliphatic polyamines such as 2-dimethylpropane; 1, alicyclic polyamines such as 4-diamino-cyclohexane, 4, isophorone diamine, norbornane diamines; 4,4 '-aromatic polyamines such as diaminodiphenyl-methane; Hydrazine classes such as hydrazine hydrate; Piperazine, 2-methylpiperazine, 2,5-lupetazin, 2-amino methyl piperazine, high piperazine, 4-amino methyl piperidines, (3R)-(+)-3-amino-pyrrolidine, (3S)-(-)-heterocyclic such as 3-amino-pyrrolidine etc., these can use separately or will mix more than or equal to 2 kinds and use.
In addition, as the polyamine compound, also can use α, end has the terminal thing of amino polyamine etc. in the propylene oxide adduct of polyoxyalkylene amine, TriMethylolPropane(TMP) or glycerine such as ω-diamino poly(propylene oxide), the former preferably uses the polyamine compound of molecular weight 230～2000, and the latter preferably uses the polyamine compound of molecular weight 480～5000.
Use level as the polyamine compound, the viewpoint that has the porous polyurethane object of good article characteristic from acquisition is considered, as the equivalence ratio of the active isocyanate base of carbamate prepolymer water dispersion (theoretical value before the water-dispersion) with the active hydrogen base of polyamine compound, preferred 0.1～90%, more preferably 1～50%, especially preferably 5～30%.
Porous polyurethane object of the present invention can adopt the known method manufacturing, there is not particular determination, for example, can enumerate the above-mentioned carbamate prepolymer water dispersion that makes is mixed equably with the polyamine compound, the mixture that makes is flowed in the shaping mould, at room temperature, under leaving standstill, carry out crosslinking reaction, dewatered method etc. from gained gelation thing more than or equal to 10 hours state.
In porous polyurethane object of the present invention, in the scope of not destroying the object of the invention, can contain additives such as tinting material, antiseptic-germicide, oxidation inhibitor, UV light absorber, photostabilizer, defoamer, tackifier, pH regulator agent, these can be used individually or will mix add more than or equal to 2 kinds.
In addition, when in containing the carbamate prepolymer water dispersion that anionic property chain propagation agent as the wetting ability chain propagation agent is a constituent, adding neutralizing agent, consider from the viewpoint that suppresses gained porous polyurethane object deterioration, can add the compound that can react and make carbamate prepolymer crosslinked with the anionic property hydrophilic group of anionic property chain propagation agent.As such compound, for example, can enumerate carbodiimide based compound, oxazoline based compound, epoxy based compound, trimeric cyanamide based compound etc.In addition, when adding above-claimed cpd, owing to dissociate from the anionic property chain propagation agent with the salifiable neutralizing agent of anionic property hydrophilic group shape, so can carry out washing step described later expeditiously.
In the manufacturing of above-mentioned porous polyurethane object, the terminal isocyanate group of the carbamate prepolymer in the carbamate prepolymer water dispersion, because with the water reaction that exists on every side, so after carbamate prepolymer disperses in water, preferably reacted with the polyamine compound with interior making it usually at 48 hours.
Promptly, contain aforementioned wetting ability chain propagation agent, when also containing previous neutralizers, aforementioned surfactants, the dispersed of the carbamate prepolymer water dispersion of manufacturing improves really, but after carbamate prepolymer is dispersed in the water, when leaving standstill at normal temperatures and pressures, though the time long 48 hours with interior, with part or all of interior urethane resin composition separate and subside took place at 24 hours usually.Like this, since the carbamate prepolymer water dispersion be through the time unsettled, after so preferred carbamate prepolymer disperses in water, usually 48 hours with interior, preferably 24 hours with interior, more preferably reacted with interior and polyamine compound at 12 hours.
Remove method as above-mentioned moisture, seasoning at room temperature, but remove the time in order to shorten moisture, preferred usually use hot air dryer etc. carries out drying under more than or equal to 70 ℃.When containing neutralizing agent, tensio-active agent, defoamer, tackifier, pH regulator agent etc. in the gelation thing of gained, preferably before above-mentioned drying process, for example use washing machine etc. that these compositions are washed.
The porous polyurethane object that makes like this has fine continuous pore, and article characteristic such as apparent density, tensile strength, elongation also can satisfy practicality simultaneously.
Embodiment
Below enumerate embodiment and specifically describe the present invention, but the invention is not restricted to following embodiment.
(embodiment 1～7 and comparative example 1～3)
In the cooperation ratio shown in the table 1 in three mouthfuls of round-bottomed flasks, add polycarbonate diol [Asahi Kasei Corporation's system, trade(brand)name: T-4671, number-average molecular weight: 1000] as polyvalent alcohol, as the ethylene glycol of chain propagation agent, as 2 of wetting ability chain propagation agent, 2-dimethylol propionic acid and as 1 of isocyanic ester, the 6-hexamethylene diisocyanate, stirred 3 hours down at 90 ℃, make carbamate prepolymer.
Make the above-mentioned carbamate prepolymer that makes become 80 ℃, the triethylamine that adds as neutralizing agent carries out stirring in 2 minutes.Then, add Voranol EP 2001 type nonionogenic tenside [rising sun electrochemical industry system, trade(brand)name: ァ デ カ ト one Le TN-100, HLB:13.8, cloud point: 75 ℃], carry out again stirring in 2 minutes as tensio-active agent.
Then, the carbamate prepolymer that has added neutralizing agent and tensio-active agent is added in the distilled water, uses homomixer to carry out stirring in 5 minutes, make the carbamate prepolymer water dispersion.
The limit is stirred and to be contained quadrol and join in the above-mentioned carbamate prepolymer water dispersion that makes as the aqueous solution limit of polyamine compound, after at room temperature using stirrer to carry out mixing for 10 seconds, this mixture is flowed into have in the water-proof shaping mould, at room temperature leave standstill and reacted in 12 hours.Then the reactant that obtains is washed, under 80 ℃, carried out drying, make resultant of reaction.The proportioning of each composition is illustrated in table 1.
Table 1
According to apparent density, tensile strength and the elongation of following method evaluation as the resultant of reaction rerum natura.
[A. apparent density]
Cut out the test piece of 50mm * 50mm * 3mm size from above-mentioned resultant of reaction, measure the weight of test piece, according to formula: [apparent density (kg/m
3)]=[weight of test piece (g)] ÷ [volume (mm of test piece
3)] * 10
6Obtain apparent density.(according to JIS K6400)
[B. tensile strength]
Cut out the test piece of long 60mm * wide 10mm * thick 2mm size from above-mentioned resultant of reaction, use universal testing machine [strain formula can Shimadzu Seisakusho Ltd.'s system, model: ASG-D] to measure.Making draw direction is vertically measuring of test piece, and the intensity when using the test piece fracture is according to formula: [tensile strength (MPa)]=[breaking tenacity (N)] ÷ [sectional area (mm of test piece
2)] obtain tensile strength.(according to JIS K6301)
[C. elongation]
Cut out the test piece of long 60mm * wide 10mm * thick 2mm size from above-mentioned resultant of reaction, use universal testing machine [strain formula can Shimadzu Seisakusho Ltd.'s system, model: AGS-D] to measure.Make draw direction be test piece vertically, measure by graticule 20mm, elongation when using test piece to break, by formula: [elongation (%)]=([length when breaking between graticule (mm)]-[graticule distance (mm)]) ÷ [graticule is apart from (mm)] * 100 obtains elongation.(according to JIS K6301)
All rerum naturas of the resultant of reaction that embodiment 1～7 and comparative example 1～3 are made are shown in table 2.
Table 2
The resultant of reaction that embodiment 1～7 makes presents as water-absorbent roller, office machine roller, water-absorbent parts, the useful rerum natura of seal face component.
In addition, to embodiment 1～7 and the resultant of reaction that comparative example 1～3 makes, use digital microscope [キ of Zhu Shi commercial firm one ェ Application ス system, model: VH-6300], observe for 600 times with multiplying power.As concrete example, the observation photo of embodiment 1 is shown in Fig. 1, the observation photo of comparative example 1 is shown in Fig. 2.
As shown in Figure 1, the resultant of reaction that embodiment 1 makes is observed has fine continuous pore, and the resultant of reaction that embodiment 2～7 makes is also observed and had fine continuous pore similarly to Example 1.On the other hand, as shown in Figure 2, the resultant of reaction that comparative example 1 makes does not have vesicular structure, becomes filminess, and the resultant of reaction that comparative example 2～3 makes is also same with comparative example 1, and observing becomes filminess.
Porous polyurethane object of the present invention can be suitable for making in the various goods such as relevant supplies equipment, health benefit articles for use and using with roller, water-absorbent parts, seal face component, mattress, used for cosmetic powder puff, abrasive sheet, air purifier filter, leatheroid, agriculture materials, electronics at water-absorbent roller, office machine.
Claims (4)
1. porous polyurethane object, it carries out removing moisture the gelation thing that crosslinking reaction makes and makes from making the end that polyvalent alcohol, chain propagation agent, wetting ability chain propagation agent and isocyanic ester polymerization are obtained have the carbamate prepolymer water dispersion of isocyanate group and polyamine compound, aforementioned chain propagation agent is the short chain diatomic alcohol compounds that has in the molecule more than or equal to 2 hydroxyls, and aforementioned wetting ability chain propagation agent is anionic property chain propagation agent, nonionic chain propagation agent or cationic chain propagation agent.
2. the described porous polyurethane object of claim 1, wherein said wetting ability chain propagation agent occupies 0.1～4 weight % in the total overall reaction composition that constitutes described carbamate prepolymer.
3. claim 1 or 2 described porous polyurethane objects, wherein said carbamate prepolymer water dispersion be through the time unsettled.
4. the manufacture method of porous polyurethane object, it comprises:
The wetting ability chain propagation agent of polyvalent alcohol, chain propagation agent, isocyanic ester and 0.1～4 weight % is carried out the polymeric operation as reacted constituent,
The carbamate prepolymer that the end that makes is had isocyanate group mixes with water and carries out the dispersive operation,
Use the polyamine compound with the carbamate prepolymer water dispersion that makes carry out crosslinked operation and
Dewatered operation from gained gelation thing;
Aforementioned chain propagation agent is the short chain diatomic alcohol compounds that has in the molecule more than or equal to 2 hydroxyls, and aforementioned wetting ability chain propagation agent is anionic property chain propagation agent, nonionic chain propagation agent or cationic chain propagation agent.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003343619 | 2003-10-01 | ||
| JP343619/2003 | 2003-10-01 | ||
| JP2004104888A JP3641270B1 (en) | 2003-10-01 | 2004-03-31 | Polyurethane porous body |
| JP104888/2004 | 2004-03-31 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1845942A CN1845942A (en) | 2006-10-11 |
| CN100390214C true CN100390214C (en) | 2008-05-28 |
Family
ID=34425336
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800256258A Expired - Fee Related CN100390214C (en) | 2003-10-01 | 2004-09-24 | Porous polyurethane object |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP3641270B1 (en) |
| KR (1) | KR101105184B1 (en) |
| CN (1) | CN100390214C (en) |
| TW (1) | TWI332018B (en) |
| WO (1) | WO2005033163A1 (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7381331B2 (en) * | 2005-09-30 | 2008-06-03 | General Electric Company | Hydrophilic membrane and associated method |
| JP2009249470A (en) * | 2008-04-04 | 2009-10-29 | Daido Kasei Kogyo Kk | Polyurethane porous structure and method for producing the same |
| KR100872542B1 (en) * | 2008-04-24 | 2008-12-08 | (주)유창하이텍 | A high cell elastic body and manufacturing method thereof |
| JP2010024426A (en) | 2008-06-16 | 2010-02-04 | Toyo Polymer Co Ltd | Cast molded article made of polyurethane porous substance and method for producing the same |
| JP2011116951A (en) * | 2009-10-26 | 2011-06-16 | Sanyo Chem Ind Ltd | Method for producing porous resin |
| WO2015033732A1 (en) | 2013-09-06 | 2015-03-12 | Dic株式会社 | Urethane resin composition, leather-like sheet, and method for manufacturing leather-like sheet |
| CN103467970A (en) * | 2013-09-06 | 2013-12-25 | 惠州市远安新材料有限公司 | Powder puff based on application of polyurethane (PU) |
| JP6254020B2 (en) * | 2014-03-05 | 2017-12-27 | 第一工業製薬株式会社 | Aqueous urethane urea resin composition and production method, reactive emulsifier and emulsification method |
| KR101599236B1 (en) | 2014-12-11 | 2016-03-04 | 주식회사 덕성 | Method for Manufacturing Sponge Sheet for Cosmetic Puffs Continuously |
| CN107208363B (en) | 2015-03-03 | 2019-12-24 | Dic株式会社 | Method for producing leather-like sheet |
| JP2019034070A (en) * | 2017-08-21 | 2019-03-07 | 株式会社リブドゥコーポレーション | Solid-liquid separation sheet for absorbent article and absorbent article with the same |
| JP6596710B2 (en) * | 2018-02-23 | 2019-10-30 | トーヨーポリマー株式会社 | Polyurethane porous body and method for producing polyurethane porous body |
| KR101952323B1 (en) | 2018-07-27 | 2019-02-26 | 대원화성 주식회사 | Polyurethane foam sheet for a cosmetic puff and method of manufacturing the same |
| KR102293565B1 (en) | 2019-10-18 | 2021-08-26 | 대원화성 주식회사 | Functional polyurethane film excellent in durability and flexibility, and method for manufacturing the same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003048939A (en) * | 2001-08-08 | 2003-02-21 | Achilles Corp | Method for producing polyurethane porous |
| JP2003048940A (en) * | 2001-06-01 | 2003-02-21 | Achilles Corp | Polyurethane porous |
| CN1406298A (en) * | 2000-02-28 | 2003-03-26 | 松本油脂制药株式会社 | Process for producing porous object |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02189345A (en) * | 1989-01-18 | 1990-07-25 | Mitsubishi Kasei Corp | Production of porous sheet material |
| JPH06199974A (en) * | 1992-12-29 | 1994-07-19 | Nikka Chem Co Ltd | Polyurethane dispersion |
| ATE253090T1 (en) | 1998-12-07 | 2003-11-15 | Bayer Ag | COAGULATES OF AQUEOUS PURE DISPERSIONS AND THEIR USE |
| JP4916050B2 (en) * | 2000-08-30 | 2012-04-11 | 株式会社Ａｄｅｋａ | Method for producing cosmetic puff |
-
2004
- 2004-03-31 JP JP2004104888A patent/JP3641270B1/en not_active Expired - Fee Related
- 2004-09-08 TW TW093127151A patent/TWI332018B/en not_active IP Right Cessation
- 2004-09-24 CN CNB2004800256258A patent/CN100390214C/en not_active Expired - Fee Related
- 2004-09-24 KR KR1020067004992A patent/KR101105184B1/en active IP Right Grant
- 2004-09-24 WO PCT/JP2004/013970 patent/WO2005033163A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1406298A (en) * | 2000-02-28 | 2003-03-26 | 松本油脂制药株式会社 | Process for producing porous object |
| JP2003048940A (en) * | 2001-06-01 | 2003-02-21 | Achilles Corp | Polyurethane porous |
| JP2003048939A (en) * | 2001-08-08 | 2003-02-21 | Achilles Corp | Method for producing polyurethane porous |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200519146A (en) | 2005-06-16 |
| TWI332018B (en) | 2010-10-21 |
| JP3641270B1 (en) | 2005-04-20 |
| JP2005126670A (en) | 2005-05-19 |
| KR20060072144A (en) | 2006-06-27 |
| CN1845942A (en) | 2006-10-11 |
| KR101105184B1 (en) | 2012-01-12 |
| WO2005033163A1 (en) | 2005-04-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100390214C (en) | Porous polyurethane object | |
| CN101784593B (en) | EO/PO block copolymers as stabilizers for polyurethane foams | |
| CN104822877B (en) | The synthetic leather based on polyurethane dispersing liquid with improved embossed features | |
| CN101535359B (en) | Alkylpolyglycoside useful as stabilizer for PUR foams | |
| CN103649146A (en) | Process for the production of polyurethane polyureas containing side chains and of aqueous dispersions of these | |
| CN1854163B (en) | Polyurethane foams made with blowing catalyst compositions containing primary hydroxyl groups and high ethylenediamine backbones | |
| KR101602152B1 (en) | Aqueous polyurethane-polyurea dispersions | |
| CN102161743A (en) | Solvent free aqueous polyurethane dispersions and methods of making and using the same | |
| CN102918085A (en) | Stable aqueous wax dispersions | |
| KR20150084962A (en) | Polyurethane foam by reaction injection molding | |
| ES2527024T3 (en) | Aqueous polyurethane-polyurea dispersions | |
| CN1922231B (en) | Polyurethane dispersions and coatings made therefrom | |
| JP2009096998A (en) | Method for producing polyurethane resin aqueous dispersion | |
| CN100465205C (en) | Method for preparing Soft polyurethane foam with excellent ball elasticity | |
| KR102535128B1 (en) | Polyurethane porous body and method for producing polyurethane porous body | |
| JP2009249470A (en) | Polyurethane porous structure and method for producing the same | |
| CN100354329C (en) | Polyurethane resin,water polyurethane resin,hydrophilic modifier,moisture resin and process for producing polyurethaneresin | |
| JP2012158643A (en) | Method for producing aqueous polyurethane resin dispersion | |
| JP2010155879A (en) | Method for producing polyurethane resin aqueous dispersion | |
| JP2012153854A (en) | Method for producing polyurethane resin aqueous dispersion | |
| JP4613085B2 (en) | Absorber | |
| JP2010024426A (en) | Cast molded article made of polyurethane porous substance and method for producing the same | |
| JP2013209534A (en) | Aqueous polyurethane resin composition and leather-like sheet | |
| JP2012158642A (en) | Method for producing aqueous polyurethane resin dispersion | |
| CN101759842A (en) | Flame resistant aqueous polyurethane dispersion liquid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080528 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |