CN101608013A - The method for making of urethane formation property composition, polyhydric alcohol composition, urethane resin - Google Patents
The method for making of urethane formation property composition, polyhydric alcohol composition, urethane resin Download PDFInfo
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- CN101608013A CN101608013A CNA2009101472795A CN200910147279A CN101608013A CN 101608013 A CN101608013 A CN 101608013A CN A2009101472795 A CNA2009101472795 A CN A2009101472795A CN 200910147279 A CN200910147279 A CN 200910147279A CN 101608013 A CN101608013 A CN 101608013A
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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
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
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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
- C08G18/08—Processes
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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
- C08G18/08—Processes
- C08G18/089—Reaction retarding agents
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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
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/24—Catalysts containing metal compounds of tin
- C08G18/242—Catalysts containing metal compounds of tin organometallic compounds containing tin-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
Abstract
The urethane that the invention provides serviceable time that can prolong under the normal temperature and solidified nature excellence forms the manufacture method of property composition, polyhydric alcohol composition and urethane resin.Urethane of the present invention forms the property composition and cooperates and also modulates following composition: isocyanate prepolymer composition, and it comprises at least a kind or their mixture that is selected from the group that aliphatics and alicyclic isocyanate and their derivative and modification body formed; The polyhydroxy reactant of normal temperature liquid state; Reaction suppressor; The normal temperature solid organo-metallic series catalysts that in said composition, exists with solid form.
Description
Technical field
The present invention relates to urethane resin, in more detail, the urethane that relates to serviceable time that can prolong under the normal temperature and solidified nature excellence forms the manufacture method of property composition, polyhydric alcohol composition and urethane resin.
Background technology
Urethane resin is tough and physical properties excellent such as antifriction consumption, oil-proofness, solvent resistance, by various forms such as foam, film, elastomerics, powder, solution, emulsions, be used for various uses such as flexible foam, rigid foam, elastomerics, caking agent, coating, tackiness agent.By being reacted, polyvalent alcohol and polyisocyanates form this urethane resin under the coexistence of additives such as catalyzer and suitable whipping agent, tensio-active agent, linking agent.
When forming urethane resin, when whole raw materials mixing back is directly placed, then exist the blend compositions in being detained to proceed to react situation about can't use.Particularly thick weave cotton cloth or the manufacturing of air bag (air bug) etc. in use urethane to form the property composition as being to produce the situation that the mixed solution of raw material is detained what become problem especially aspect the processing to the situation of the tackiness agent of the encapsulant of base cloth or functional filler etc.For such background, in order to improve operability, expectation prolongs the so-called serviceable time.In the prior art, in order to prolong this serviceable time, known have active low catalyzer, a method of perhaps adding the refractory metal series catalysts of solid form used.
For example, Japanese kokai publication hei 2-242875 communique (patent documentation 1) discloses a kind of Thermocurable bonding composition, it is made up of the prepolymer that contains isocyanate group and polyether block, a kind of polyol and catalyzer at least, it is characterized in that it uses by carbon atom greater than a kind of catalyzer of forming and having the solid form of the melt temperature that is higher than 100 ℃ in the salt of bismuth, cadmium, lead or the zinc of 12 carboxylic acid at least.
In addition, TOHKEMY 2004-269733 communique (patent documentation 2) discloses a kind of two liquid type polyurethane system: compositions, it is by cooperating curing catalysts to form in as the polyhydroxy reactant of host and two liquid as the isocyanate prepolymer composition of solidifying agent, it is characterized in that, as this curing catalysts, be that the thermo-sensitivity curing catalysts directly is coupled in the host with powder to solid state at normal temperatures with the metal of 110～500 ℃ of fusing points.
Patent documentation 1: Japanese kokai publication hei 2-242875 communique
Patent documentation 2: TOHKEMY 2004-269733 communique
Summary of the invention
Invent problem to be solved
Yet, in the above-mentioned patent documentation 1 disclosed technology, in order to reach the polyurethane-reinforcement reaction of expectation, the fusion of the polyol of solid powdery becomes prerequisite, therefore, the partial ununiformity of the cooperation R ratio of OH base (the NCO base with) that can cause isocyanate prepolymer composition and polyhydroxy reactant, from the viewpoint of the plasticity of urethane resin and the characteristic that obtained, it is also insufficient.In addition, in the above-mentioned patent documentation 2 disclosed technology, be about several minutes set time in the condition of cure, even but the serviceable time is extended, also the degree more than 20～30 minutes near normal temperature～40 ℃, from prolongation and the following viewpoint that shortens set time of condition of cure of taking into account the serviceable time, it is also insufficient.
Therefore, the manufacture method that expectation provides a kind of urethane to form property composition, polyhydric alcohol composition and urethane resin, described urethane form the property composition not only about at least 24 hours the length of blend compositions realization of the excellent in uniformity of blend compositions but also polyvalent alcohol and polyisocyanates serviceable time and be implemented under the condition of cure set time from about several minutes to 25 minutes weak point.
The present invention finishes in view of above-mentioned the problems of the prior art, the object of the present invention is to provide the manufacture method of urethane formation property composition, polyhydric alcohol composition and urethane resin of the set time of serviceable time of realizing taking into account the length normal temperature under and the weak point under the condition of cure.
The method that is used to deal with problems
In the urethane that the inventor etc. constitute for comprising polyhydroxy reactant and isocyanate prepolymer composition formation property composition, calculating from cooperate the back under serviceable time that flowability disappears and the solidification value condition by the state of liquid state set time to elastomeric state, to forming serviceable time of obtaining and the result of set time furthers investigate by various, the result is by the polyhydroxy reactant of use normal temperature liquid state and the polyisocyanates composition of fatty family or alicyclic ring family, with the catalyzer of normal temperature solid organo-metallic series catalysts as curing reaction, it is disperseed with solid form, and then interpolation suppresses the reaction suppressor of curing reaction, surprised discovery, do not use plugging agent, also can make the difficult xanthochromia of urethane formation property composition, and the serviceable time of having realized at least 24 hours length under the normal temperature, and the set time under the condition of cure, thereby finished the present invention from about several minutes to 25 minutes weak point.
That is, among the present invention, modulation cooperates the urethane that following composition is arranged to form the property composition: isocyanate prepolymer composition, and it comprises at least a kind that is selected from the group that aliphatics and alicyclic isocyanate and their derivative and modification body formed; The polyhydroxy reactant of normal temperature liquid state; Reaction suppressor; The normal temperature solid organo-metallic series catalysts that in said composition, exists with solid form.And, said composition can by for example as condition of cure in 100～250 ℃ of heating of temperature, and be cured.
As isocyanate prepolymer composition, use the isocyanic ester of fatty family or alicyclic ring family and do not use the isocyanic ester of fragrant family, as polyhydroxy reactant, use the normal temperature liquid state but not normal temperature solid polyvalent alcohol, in the presence of the reaction suppressor that suppresses curing reaction, cooperate the normal temperature solid but not the organo-metallic series catalysts of normal temperature liquid, by it is existed with solid form, thereby can obtain to be difficult to xanthochromia in composition, reach the serviceable time of the length more than 24 hours under the normal temperature, and the urethane of the set time of the weak point about several minutes to 25 minutes under condition of cure formation property composition.Thus, can improve operability and plasticity in the manufacturing processed of urethane resin.In addition, owing to do not need plugging agent, alleviated plugging agent and remained in pollution that dispersing of plugging agent on the final molding, when being shaped cause etc. in the manufacturing processed of urethane resin aspect the environment and the load of security aspect.
Promptly according to the present invention, a kind of urethane formation property composition is provided, it is combined with following composition: isocyanate prepolymer composition, and it comprises at least a kind or their mixture that is selected from the group that aliphatics and alicyclic isocyanate and their derivative and modification body formed; The polyhydroxy reactant of normal temperature liquid state; Reaction suppressor; The normal temperature solid organo-metallic series catalysts that in said composition, exists with solid form.In addition, according to the present invention, be provided for obtaining the polyhydric alcohol composition of above-mentioned urethane formation property composition, the manufacture method that the above-mentioned urethane of use forms the urethane resin of property composition.
Among the present invention, above-mentioned polyhydroxy reactant can preferably comprise at least a kind or their mixture in polyester polyol and the polycarbonate polyol.In addition, among the present invention, above-mentioned organo-metallic series catalysts is preferably organo-tin compound.And then among the present invention, above-mentioned reaction suppressor is preferably phosphate ester acid.And then among the present invention, it is at least a kind or their mixture in the group formed of 2～5 hexamethylene diisocyanate and their derivative and modification body that above-mentioned isocyanate prepolymer composition preferably can comprise average functional group number.
In addition, among the present invention, mix above-mentioned polyhydroxy reactant, reaction suppressor and organo-metallic series catalysts down for 20～40 ℃ in temperature, modulation is dispersed with the polyhydric alcohol composition of organo-metallic series catalysts.In addition, among the present invention, can also mix synthetic polyhydric alcohol composition of institute and isocyanate prepolymer composition, modulate urethane formation property composition.And then among the present invention, can be heated to 100～250 ℃ of temperature by the synthetic urethane of institute being formed the property composition, and make its curing.
The invention effect
As mentioned above, according to the present invention, can access a kind of urethane formation property composition, it can reach the set time from about several minutes to 25 minutes weak point under serviceable time of the length more than 24 hours under the normal temperature and the condition of cure, therefore, can in the manufacturing processed of urethane resin, improve operability and plasticity.
Embodiment
Below, enumerate concrete embodiment explanation the present invention, but the present invention is not limited to embodiment described later.
Below, be described for urethane formation property composition of the present invention, the polyhydric alcohol composition that is used to obtain this urethane formation property composition, the manufacture method of using this urethane to form the urethane resin of property composition.
Urethane of the present invention formation property composition mainly cooperates following composition modulation to form: isocyanate prepolymer composition, polyhydroxy reactant, reaction suppressor, organo-metallic series catalysts.
As above-mentioned isocyanate prepolymer composition, can comprise at least a kind or their mixture of aliphatic isocyanates and alicyclic isocyanate and their derivative and modification body.As such isocyanic ester, for example can list, hexamethylene diisocyanate (HDI), 2,2, ester ring type polyisocyanates such as aliphatic polyisocyante class, hydrogenated diphenyl methane diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate such as 4-trimethyl hexamethylene diisocyanate, lysine methyl ester vulcabond.
From taking into account the viewpoint of long serviceable time and short set time, more preferably can to comprise average functional group number be 2～5 HDI and their derivative and modification body to isocyanate prepolymer composition.Derivative or modification body as such HDI, can list by HDI and 1, the urethane modified polyisocyanate that the 3-butyleneglycol obtains, the allophanate-modified polyisocyanates that obtains by HDI and Virahol, by HDI and 3-methyl isophthalic acid, the allophanate-modified polyisocyanates that 5-pentanediol (MPD) obtains, polyisocyanates that contains the isocyanuric acid ester group of obtaining by the isocyanuric acid esterification by HDI and 1,3 butylene glycol etc.The NCO content of above-mentioned isocyanate prepolymer composition preferably can be in the scope of 10～30 quality %, more preferably can be in the scope of 15～25 quality %.
As above-mentioned polyhydroxy reactant, can comprise at least a kind or their mixture of the polyvalent alcohol of normal temperature liquid state, more particularly, can list polyether glycol, polyester polyol, polycarbonate polyol and the polycaprolactone polyol of normal temperature liquid state.In addition, among the present invention, normal temperature be meant the regulation with JIS (JI S Z8703) identical, be the scope of 15 ℃ of the temperature tolerances of standard state, i.e. 5 ℃ to 35 ℃ the state of temperature of scope with 20 ℃.In addition, among the present invention, liquid state is meant that 2 " liquid definition " with the 69th of the rule relevant with the regulation of hazardous material are the state that benchmark is estimated, and test sample is put into vertical developmental tube (internal diameter 30mm; High 120mm; The glass of flat round tube type) in until the high 55mm in the end of distance developmental tube, during with this developmental tube horizontal positioned, with the front end of the all-moving surface of this test sample distance by the end of distance developmental tube be time till the part of 85mm be 90 seconds with interior, then be defined as liquid state.
As above-mentioned polyvalent alcohol,, preferably can adopt polyester polyol, the polycarbonate polyol of normal temperature liquid state from taking into account the viewpoint of long serviceable time and short set time.As above-mentioned polyester polyol, can list methyl isophthalic acid, the normal temperature liquid polyesters polyvalent alcohol that 5-pentanediol (MPD) and hexanodioic acid obtain, normal temperature liquid polyesters polyvalent alcohol of obtaining by TriMethylolPropane(TMP) (TMP), MPD and hexanodioic acid etc. by 3-.In addition,, can list the liquid polycarbonate diol of the normal temperature that 6-hexylene glycol, MPD and diethyl carbonate (DEC) obtain etc. by 1 as above-mentioned polycarbonate polyol.
In other examples, can be from by polycarboxylic acids such as hexanodioic acid, Tetra hydro Phthalic anhydride, m-phthalic acid, terephthalic acid, trihemellitic acid, pyromellitic acid acid anhydride, hexanodioic acid, sebacic acid, fumaric acid, maleic anhydride, dodecanedioic acid, nonane diacid and ethylene glycol, propylene glycol, 1,4-butyleneglycol, 1,6-hexylene glycol, Diethylene Glycol, triethylene glycol, neopentyl glycol, 3-methyl isophthalic acid adopt the liquid down material of normal temperature in the polyester polyol that polyvalent alcohols such as 5-pentanediol obtain.
From with above-mentioned same viewpoint, the number-average molecular weight of above-mentioned polyvalent alcohol can be preferably in 1000～5000 scope, more preferably in 1500～3500 scope.In addition, from above-mentioned same viewpoint, the average functional group number of above-mentioned polyvalent alcohol can be preferably about 2～4.
The proportioning of above-mentioned isocyanate prepolymer composition and polyhydroxy reactant is that the proportioning that forms urethane resin smoothly gets final product, usually, can be 0.2～1.5 scope according to mol ratio (NCO/OH, R value) with respect to the isocyanate group (NC O yl) of hydroxyl (OH yl), be preferably 0.3～1.3 scope, more preferably the proportioning of 0.9～1.1 scope is mixed.
As above-mentioned reaction suppressor, at least a kind or their mixture that can comprise phosphoric acid, phosphorous acid, phosphate ester acid, acid phosphorous acid ester, from taking into account the viewpoint of long serviceable time and short set time, preferably can adopt phosphate ester acid and these mixtures of carbon number 1～18.As above-mentioned phosphate ester acid, can list etherophosphoric acid, diethyl phosphoric acid, acidic isopropyl phosphate, acid butyl phosphate, acid phosphoric acid 2-ethylhexyl, acid phosphoric acid two (the 2-ethyl is own) ester, acid phosphoric acid isodecyl ester, acid lauryl phosphate, acid phosphoric acid tridecane ester, acid phosphoric acid stearyl ester, the different stearyl ester of acid phosphoric acid, acid phosphoric acid oil alkene ester, acid phosphoric acid stearyl ester etc.
From taking into account the viewpoint of long serviceable time and short set time, the addition of reaction suppressor can be preferably with respect to polyhydroxy reactant 50～1200 quality ppm (below, abbreviate ppm as) scope, more preferably in the scope of 80～700ppm, and then can be preferably in the scope of 80～300ppm.
Above-mentioned organo-metallic series catalysts is the organometallic compound that plays the catalyst action of curing reaction in the solidification value condition of regulation, as such organometallic compound, can be from for example comprising Sn, Pb, Cd, Zn, Al, Zr, Bi, Mg, Fe, Ti, Cu, Co, Ni, In, Ca, Y, Ce, Sr, in the malate compound of metal such as Mo, La, oxide compound, ester cpds, mercaptan compound and the inner complex compound, adopt normal temperature solid material or their mixture.
As above-mentioned organo-metallic series catalysts, the preferred normal temperature solid organo-tin compound that uses, as such organo-tin compound, can list distearyl acid dibutyl tin, dibutyltin maleate polymer, two (toxilic acid alkyl ester) dibutyl tin, two (toxilic acid alkyl ester dibutyl tin) maleate, s, o-mercaptan carboxylic acid dibutyl tin polymkeric substance, distearyl acid dioctyl tin, the dioctyl tin maleate polymkeric substance, two (toxilic acid alkyl ester) dioctyl tin, two (toxilic acid alkyl ester dioctyl tin) maleate, s, o-mercaptan carboxylic acid dioctyl tin polymkeric substance, two sad dioctyl tins, di-n-octyltin oxides etc. can adopt normal temperature solid material from these.
From the condition of cure of taking into account long serviceable time and 100 ℃～250 ℃ viewpoint of short set time down, more preferably can adopt dialkyl tin compounds such as oxidation dialkyl tin compound with carbon number 2～30 and oxysuccinic acid dialkyl tin compound.As above-mentioned normal temperature solid organo-tin compound, more preferably can use oxysuccinic acid di-n-octyl tin compound, di-n-octyltin oxide compound.
In addition, above-mentioned organo-metallic series catalysts preferably adds in the composition with Powdered.From improving dispersed viewpoint, above-mentioned organo-metallic series catalysts is more preferably pulverized with mixing by three roller roller mills etc. with softening agent etc., preferably makes the catalyst masterbatch that organo-metallic series catalysts differential is dispersed in the paste-like in the softening agent and adds.At this moment, the particle diameter of organo-metallic series catalysts is preferably below the 70 μ m, more preferably below the 50 μ m.From taking into account the viewpoint of long serviceable time and short set time, the addition of organo-metallic series catalysts is preferably the scope of 250～2000ppm, the scope of 400～1500ppm more preferably with respect to polyhydroxy reactant.In addition, in order to modulate the reactivity of expectation, except above-mentioned organo-metallic series catalysts, can also add the tertiary amine series catalysts.
In addition, urethane of the present invention forms the additive that the property composition can also contain tensio-active agent, surfactant, deaerating agent, fire retardant, softening agent, pigment, dyestuff, stablizer, fungistat, weighting agent etc. according to the specific purposes or the form of target, be used to improve the rerum natura of urethane resin.
Urethane of the present invention formation property composition preferably at first cooperates polyhydroxy reactant, reaction suppressor, organo-metallic series catalysts and other additives, the modulation polyhydric alcohol composition (below, abbreviate Preblend as), by synthetic this Preblend of institute is mixed with isocyanate prepolymer composition, can modulate above-mentioned urethane formation property composition.In the modulation of above-mentioned Preblend, be dispersed in for normal temperature solid organo-metallic series catalysts does not dissolve and exist in the composition, be no more than under 40 ℃ the temperature condition, mixing raw material stirs and modulates, and more preferably carries out at normal temperatures.Temperature condition when Preblend is mixed with isocyanate prepolymer composition is not particularly limited, and from the viewpoints such as plasticity of urethane resin, is preferably the temperature below 60 ℃.
In addition, the modulator approach of urethane formation property composition can also adopt mixed once to comprise the method for whole raw materials of isocyanate prepolymer composition, polyhydroxy reactant, reaction suppressor, organo-metallic series catalysts and other additives except with at first synthetic above-mentioned Preblend and the isocyanate prepolymer composition blended modulator approach.
Urethane of the present invention forms in the property composition, is defined as cooperating the serviceable time of back from the state of liquid state to flowability disappearance required time to reach at normal temperatures more than at least 24 hours, according to composition, can reach more than 70 hours.Therefore, after the mixing,, also suitable flowability be can keep, operability and plasticity in the manufacturing processed improved even produce long-term situation of being detained.
Urethane of the present invention forms the property composition can be by heating under the solidification value condition of regulation, 0.7～25 minute with interior, more preferably made its curing with interior in 3 minutes.Therefore, produce long-term situation of being detained, also can when keeping suitable flowability, when being shaped, under condition of cure, make its rapid curing, can improve operability and plasticity in the manufacturing processed even mix the back.In addition, as above-mentioned condition of cure, can be following condition: the organo-metallic series catalysts be dissolved in the composition, play the temperature condition of catalyst action of the curing reaction of expectation.More particularly, can be following 100 ℃～250 ℃ temperature condition of normal pressure.
In addition, in the present invention, be defined as set time by heating by liquid state to becoming the needed time of elastomeric state.The mensuration of above-mentioned set time can be implemented by the following method: use for example sweep type vibration pin type solidity test machine (Scanning Vibrating Needle Curemeter; SVNC), vibration probe put into measure sample composition, probe is forced to apply vibration, the METHOD FOR CONTINUOUS DETERMINATION amplitude, by resulting SVNC (frequency or amplitude) curve, the state by liquid state of calculating is up to the time of elastomeric state, thereby implements to measure.
Urethane of the present invention formation property composition forms urethane resin by the curing reaction of isocyanate prepolymer composition under condition of cure and polyhydroxy reactant.Urethane of the present invention form that the property composition does not use the isocyanic ester of fragrant family and the isocyanic ester that uses fatty family or alicyclic ring family as isocyanate prepolymer composition, use the normal temperature liquid state but not normal temperature solid polyvalent alcohol as polyhydroxy reactant, in the presence of the reaction suppressor that suppresses curing reaction, cooperate the normal temperature solid but not the organo-metallic series catalysts of normal temperature liquid, and be modulated into the organo-metallic series catalysts and in composition, exist with solid form.Thus, the xanthochromic urethane that is difficult to from set time of about several minutes to 25 minutes under serviceable time more than at least 24 hours under the accomplished normal temperature and the condition of cure forms the property composition.In addition, according to the composition condition, can obtain to realize that serviceable time more than 70 hours under the normal temperature and 3 minutes urethane with interior set time under the condition of cure form the property compositions.
Urethane of the present invention forms the property composition can keep the flowability of back time more than 1 day of modulation, and can promptly make its curing by heating when being shaped, and therefore, can improve operability and plasticity in the manufacturing processed of urethane resin.This urethane formation property composition can be as urethane formation property material of doubtful single-component thermosetting type.
The urethane resin that utilizes urethane of the present invention to form the manufacturing of property composition can form additive in the property composition or manufacturing process etc. according to adding urethane to, provide by various forms such as foam, film, elastomerics, powder, solution, emulsions, can be used in various uses such as flexible foam, rigid foam, elastomerics, caking agent, coating, tackiness agent.
Below, form the property composition, be used to obtain polyhydric alcohol composition that this urethane forms the property composition, use this urethane to form the manufacture method of the urethane resin of property composition for urethane of the present invention, use embodiment to carry out more specific description, the present invention is not limited to certain embodiments.
Embodiment
(experimental example 1)
(1) modulation blend compositions
Mix 636 mass parts by the 3-methyl isophthalic acid, that 5-pentanediol (MPD) and hexanodioic acid obtain, number-average molecular weight 2000, the average functional group of nominal number be 2 normal temperature liquid polyesters polyvalent alcohol (be called polyester polyol A in table 1 and the table 2, below, abbreviate polyvalent alcohol A as.), 159 mass parts are by TriMethylolPropane(TMP) (TMP), 3-methyl 1, that 5-pentanediol (MPD) and hexanodioic acid obtain, number-average molecular weight 3000, the average functional group of nominal number are that 3 normal temperature liquid polyesters polyvalent alcohol (is called polyester polyol B in table 1 and the table 2, below, abbreviate polyvalent alcohol B as.), Johoku Chemical Co., Ltd.'s system), with respect to the NW-96 of polyhydroxy reactant 1000ppm with respect to the JP-508 of polyhydroxy reactant 100ppm (phosphate ester acid: the mixture of single (acid phosphoric acid 2-ethylhexyl) and two (acid phosphoric acid 2-ethylhexyls):, obtain the Preblend blend compositions as reaction suppressor.Here, Common medicine Co., Ltd's system), be that the PN-250 (Asahi Denka Co., Ltd.'s corporate system) of softening agent cooperates according to 50: 50 mass ratio as adipic acid ester NW-96 is meant: will be as the KS-1010A-1 of organo-tin compound series catalysts (oxysuccinic acid dioctyltin polymkeric substance:, by three roller roller mills, mixing particle diameter up to KS-1010A-1 reaches the dispersion treatment product that 30 μ m obtain for maximum.
With 205 mass parts by hexamethylene diisocyanate (HDI) and 1, the 3-butyleneglycol obtains, NCO content is that 17.5 quality %, average functional group number are that 2 urethane modified polyisocyanate (is called isocyanic ester A in table 1 and the table 2, below, abbreviate isocyanic ester A as.) mix with the above-mentioned Preblend blend compositions of all measuring, obtain urethane and form the property blend compositions.The R value is 1.05.In addition, the temperature during cooperation is that the urethane modified polyisocyanate is that 45 ℃, Preblend blend compositions are 25 ℃.In addition, the Preblend composition is no more than 40 ℃ temperature up to cooperating all to maintain.
(2) mensuration of serviceable time
The resulting urethane of 50g is formed the vial that the property blend compositions is put into 100ml, mobile disappearance of 25 ℃ of following Visual Confirmations of temperature.The modulation that calculating forms the property blend compositions from the urethane of experimental example 1 is up to the time that flowability disappears, and the result is 48 hours.In addition, by not causing at once after vial is inverted that the time point that composition flows is judged to be mobile the disappearance.
(3) mensuration of set time
Inject the resulting urethane of 0.3ml on 150 ℃ the sample bench to being heated in advance of sweep type oscillatory type solidity test machine (Scanning Vibrating NeedleCuremeter:SVNC:RAPRA TECHNOLOGY LTD. system) and form the property blend compositions, with the frequency exciting immersion needle (carbon system) of 60Hz, the amplitude of measuring vibrations over time.By resulting SVNC curve, obtain amplitude by initial liquid state 9000 up to the 2000 needed times that are reduced to rubbery state, the result is 2 minutes.
(4) comprehensive evaluation
Table 1 illustrates that the mixing of summing up each experimental example comprise experimental example 1 is formed and resulting urethane forms the result of set time, serviceable time and the comprehensive evaluation of property blend compositions.In addition, in the comprehensive evaluation, be set time under 150 ℃ temperature condition, serviceable time is under 25 ℃ the atmosphere, will reach 3 minutes situations with interior set time and the serviceable time more than 24 hours and be designated as ◎, will reach 12 minutes situations with interior set time and the serviceable time more than 24 hours and be designated as zero, will reach 25 minutes situations with interior set time and the serviceable time more than 24 hours and be designated as △.In addition, under identical conditions,, set time irrelevant with the serviceable time surpass under 25 minutes the situation and situation irrelevant with set time, that only reach 24 hours serviceable time of less than all be comprehensive evaluation be *.In the above-mentioned experimental example 1, owing to reach 2 minutes set time and 48 hours serviceable time, thereby comprehensive evaluation is judged to be ◎.In addition, experimental example 1 is embodiments of the invention.
(experimental example 2)
(1) blend compositions modulation
Be 200ppm except making JP-508 as reaction suppressor, be the 2000ppm, obtain having and the experimental example 1 same Preblend blend compositions of forming as the NW-96 of organo-tin compound series catalysts.With experimental example 1 similarly, 205 mass parts isocyanic ester A are mixed with whole above-mentioned Preblend compositions of amount, obtain urethane formation property blend compositions.
(2) mensuration of serviceable time
According to the order same with experimental example 1, the resulting urethane of 50g is formed the vial that the property blend compositions is put into 100ml, under 25 ℃ of temperature, to the mobile time that disappears, the result is 48 hours up to Visual Confirmation in timing.
(3) mensuration of set time
According to the order same with experimental example 1, obtain amplitude and be reduced to 2000 needed times of rubbery state by 9000 of liquid state, the result is 1.2 minutes.
(4) comprehensive evaluation
In the experimental example 2, owing to reach 1.2 minutes set time and 48 hours serviceable time, comprehensive evaluation is judged to be ◎.Similarly, experimental example 2 the results are shown in table 1.In addition, experimental example 2 is embodiments of the invention.
(experimental example 3～5)
(1) modulation blend compositions
Except making JP-508 as reaction suppressor is 200ppm (experimental example 3), 500ppm (experimental example 4) or the 1000ppm (experimental example 5), obtains having and the experimental example 1 same Preblend blend compositions of forming.With experimental example 1 similarly, 205 mass parts isocyanic ester A are mixed with whole above-mentioned each Preblend compositions of amount, obtain urethane formation property blend compositions based on each experimental example.
(2) mensuration of serviceable time
According to the order same with experimental example 1, urethane formation property blend compositions of each experimental example of 50g is put into the vial of 100ml respectively, under 25 ℃ of temperature, to the mobile time that disappears, the result is respectively 56 hours (experimental example 3), 72 hours (experimental example 4), 48 hours (experimental example 5) up to Visual Confirmation in timing.
(3) mensuration of set time
For each experimental example, according to the order same with experimental example 1, obtain amplitude by liquid state 9000 up to the 2000 required times that are reduced to rubbery state, the result is respectively 5 minutes (experimental example 3), 11 minutes (experimental example 4), 20 minutes (experimental example 5).
(4) comprehensive evaluation
In the experimental example 3, owing to reach 5 minutes set time and 56 hours serviceable time, comprehensive evaluation is judged to be zero.In the experimental example 4, owing to reach 11 minutes set time and 72 hours serviceable time, comprehensive evaluation is judged to be zero.In the experimental example 5, owing to reach 20 minutes set time and 48 hours serviceable time, comprehensive evaluation is judged to be △.Similarly, experimental example 3～5 the results are shown in table 1.In addition, experimental example 3～5th, embodiments of the invention.
Observation experiment example 1 and experimental example 3～5 o'clock see having set time along with the increase of the addition of reaction suppressor and elongated tendency.On the other hand, see that the addition up to reaction suppressor is all to be extended the tendency that the serviceable time shortens on the contrary during 1000ppm the 500ppm serviceable time.In addition, when comparative experiments example 2 and experimental example 3, then under the situation identical with the condition of reaction suppressor, if the addition of organo-metallic series catalysts increases, though then have the tendency that there are some shortenings the serviceable time, but suitably be shortened set time, finds to have obtained preferred result's tendency.
(experimental example 6)
(1) modulation blend compositions
Use by 1 except replacing polyvalent alcohol A and polyvalent alcohol B as polyhydroxy reactant, 6-hexylene glycol and 3-methyl isophthalic acid, the mass ratio of 5-pentanediol (MPD) is that 1: 9 mixture and diethyl carbonate (DEC) take off that ethanol synthesis obtains, number-average molecular weight 2000, the average functional group of nominal number are that 2 the liquid polycarbonate diol of normal temperature (is called polycarbonate polyol C in table 1 and the table 2, below, abbreviate polyvalent alcohol C as.) in addition, obtain having and the experimental example 2 same Preblend blend compositions of forming.With experimental example 2 similarly, mix 205 mass parts isocyanic ester A, whole above-mentioned Preblend compositions of amount, obtain urethane and form the property blend compositions.
(2) result
According to the order same with experimental example 1, the resulting urethane of 50g is formed the vial that the property blend compositions is put into 100ml, timing under 25 ℃ of temperature, Visual Confirmation is to the mobile time that disappears, the result is 36 hours.According to the order same with experimental example 1, obtain amplitude by liquid state to the needed time of rubbery state, the result is 0.9 minute.
(3) comprehensive evaluation
In the experimental example 6, owing to reach 0.9 minute set time and 36 hours serviceable time, comprehensive evaluation is judged to be ◎.Experimental example 6 the results are shown in table 1.In addition, experimental example 6 is embodiments of the invention.When comparative experiments example 2 and experimental example 6, use the situation of polycarbonate polyol to compare,, the tendency that further is shortened is arranged set time though find to have shortened some serviceable times with the situation of using polyester polyol.
(experimental example 7)
(1) modulation blend compositions
Except change polyvalent alcohol A into as polyhydroxy reactant is that 649 mass parts, polyvalent alcohol B are 162 mass parts, obtains having and the experimental example 2 same Preblend blend compositions of forming.To obtain by hexamethylene diisocyanate (HDI) and Virahol as 189 mass parts of isocyanate prepolymer composition, NCO content 19.3 quality %, average functional group number are that 2 allophanate-modified polyisocyanates (is called isocyanic ester B in table 1 and the table 2, below, abbreviate isocyanic ester B as.) mix with the above-mentioned Preblend blend compositions of all measuring, obtain urethane and form the property blend compositions.The R value is 1.05.Temperature when in addition, allophanate-modified polyisocyanates and Preblend blend compositions cooperate is 25 ℃.
(2) result
According to the order same with experimental example 1, the resulting urethane of 50g is formed the vial that the property blend compositions is put into 100ml, under 25 ℃ of the timing temperature, the mobile time that disappears of Visual Confirmation, the result is 36 hours.According to the order same with experimental example 1, obtain amplitude by liquid state to the needed time of rubbery state, the result is 1.3 minutes.
(3) comprehensive evaluation
In the experimental example 7, owing to reach 1.3 minutes set time and 36 hours serviceable time, thereby comprehensive evaluation is judged to be ◎.Experimental example 7 the results are shown in table 1.In addition, experimental example 7 is embodiments of the invention.When comparative experiments example 2 and experimental example 7, the situation of using isocyanic ester B has some to shorten than the situation of using isocyanic ester A though can confirm the serviceable time, can reach the set time of equal extent.
(experimental example 8)
(1) modulation blend compositions
Except using 809 mass parts polyvalent alcohol A as polyhydroxy reactant, not using the polyvalent alcohol B, obtain having and the experimental example 2 same Preblend blend compositions of forming.Will be as 191 mass parts of isocyanate prepolymer composition by hexamethylene diisocyanate (HDI) and 3-methyl 1,5-pentanediol (MPD) obtains, NCO content is that 19.2 quality %, average functional group number are that 4.8 allophanate-modified polyisocyanates (is called isocyanic ester C in table 1 and the table 2, below, abbreviate isocyanic ester C as.) mix with the above-mentioned Preblend blend compositions of all measuring, obtain urethane and form the property blend compositions.The R value is 1.05.Temperature when in addition, allophanate-modified polyisocyanates and Preblend blend compositions cooperate is 25 ℃.
(2) result
According to the order same with experimental example 1, the resulting urethane of 50g is formed the vial that the property blend compositions is put into 100ml respectively, timing is under 25 ℃ of temperature, up to the mobile time that disappears of Visual Confirmation, and the result is 40 hours.According to the order same with experimental example 1, obtain amplitude by liquid state up to the needed time of rubbery state, the result is 0.8 minute.
(3) comprehensive evaluation
In the experimental example 8, owing to reach 0.8 minute set time and 40 hours serviceable time, comprehensive evaluation is judged to be ◎.Experimental example 8 the results are shown in table 1.In addition, experimental example 8 is embodiments of the invention.When comparative experiments example 2 and experimental example 8, confirm the situation of using isocyanic ester C and compare with the situation of using isocyanic ester A, though there are some shortenings the serviceable time, further be shortened set time.When comparative experiments example 7 and experimental example 8, confirm the situation of using isocyanic ester C and compare with the situation of using isocyanic ester B, the serviceable time is extended, and further be shortened set time.
(experimental example 9)
(1) modulation blend compositions
Except using 829 mass parts polyvalent alcohol A as polyhydroxy reactant, not using the polyvalent alcohol B, obtain having and the experimental example 2 same Preblend blend compositions of forming.Will as isocyanate prepolymer composition, 171 mass parts use 1, the 3-butyleneglycol with a part of urethaneization of hexamethylene diisocyanate (HDI), obtain by the isocyanuric acid esterification then, NCO content is that 21.8 quality %, average functional group number are that 3.5 polyisocyanates (is called isocyanic ester D in table 1 and the table 2, below, abbreviate isocyanic ester D as.) mix with the above-mentioned Preblend blend compositions of all measuring, obtain urethane and form the property blend compositions.The R value is 1.05.Temperature when in addition, polyisocyanates and Preblend blend compositions cooperate is 25 ℃.
(2) result
According to the order same with experimental example 1, the resulting urethane of 50g is formed the vial that the property blend compositions is put into 100ml respectively, under 25 ℃ of the timing temperature, up to the mobile time that disappears of Visual Confirmation, the result is 40 hours.According to the order same with experimental example 1, obtain amplitude by liquid state to the needed time of rubbery state, the result is 0.7 minute.
(3) comprehensive evaluation
In the experimental example 9, owing to reach 0.7 minute set time and 40 hours serviceable time, comprehensive evaluation is judged to be ◎.Experimental example 9 the results are shown in table 1.In addition, experimental example 9 is embodiments of the invention.When comparative experiments example 2 and experimental example 9, confirm the situation of using isocyanic ester D and compare with the situation of using isocyanic ester A, though there are some shortenings the serviceable time, further be shortened set time.When comparative experiments example 7 and experimental example 9, confirm the situation of using isocyanic ester D and compare with the situation of using isocyanic ester B, the serviceable time is extended, and also further be shortened set time.When comparative experiments example 8 and experimental example 9, the situation that confirms use isocyanic ester D has some shortenings set time than the situation of using isocyanic ester C.
(experimental example 10)
(1) modulation blend compositions
Except as reaction suppressor, replace JP-508 to use 50ppm phosphoric acid (85%) in addition, obtain having Preblend blend compositions with the same composition of experimental example 1.With experimental example 1 similarly, mix 205 mass parts isocyanic ester A and whole above-mentioned Preblend compositions of amount, obtain urethane and form the property blend compositions.
(2) result
According to the order same with experimental example 1, the resulting urethane of 50g is formed the vial that the property blend compositions is put into 100ml, under 25 ℃ of the timing temperature, up to the mobile time that disappears of Visual Confirmation, the result is 48 hours.According to the order same with experimental example 1, obtain amplitude by liquid state to the needed time of rubbery state, the result is 18 minutes.
(3) comprehensive evaluation
In the experimental example 10, owing to be 18 minutes set time and 48 hours serviceable time, comprehensive evaluation is judged to be △.Experimental example 10 the results are shown in table 1.In addition, experimental example 10 is embodiments of the invention.When comparative experiments example 1 and experimental example 10, when replacing phosphate ester acid to use phosphoric acid, observe elongated tendency set time as reaction suppressor.
(experimental example 11)
(1) blend compositions modulation
Except use DBTO (dibutyltin oxide) 500ppm as the organo-metallic series catalysts, obtain having Preblend blend compositions with the same composition of experimental example 1.With experimental example 1 similarly, mix 205 mass parts isocyanic ester A, all measure above-mentioned Preblend composition, obtain urethane and form the property blend compositions.
(2) result
According to the order same with experimental example 1, the resulting urethane of 50g is formed the vial that the property blend compositions is put into 100ml, timing is calculated under 25 ℃ of the temperature, up to the mobile time that disappears of Visual Confirmation, and the result is 48 hours.According to the order same with experimental example 1, obtain amplitude by liquid state to the needed time of rubbery state, the result is 6 minutes.
(3) comprehensive evaluation
In the experimental example 11, owing to be 6 minutes set time and 48 hours serviceable time, comprehensive evaluation is judged to be zero.Experimental example 11 the results are shown in table 2.In addition, experimental example 11 is embodiments of the invention.When comparative experiments example 1 and experimental example 11,, use a side of oxysuccinic acid dioctyltin polymkeric substance to have the tendency that shorten set time even find to use the situation of same normal temperature solid organo-tin compound.
(experimental example 12)
(1) modulation blend compositions
Except use 100ppm phosphoric acid (85%) as reaction suppressor, obtain having Preblend blend compositions with the same composition of experimental example 10.With experimental example 10 similarly, mix 205 mass parts isocyanic ester A and whole above-mentioned Preblend compositions of amount, obtain urethane and form the property blend compositions.
(2) result
According to the order same with experimental example 1, the resulting urethane of 50g is formed the vial that the property blend compositions is put into 100ml, under 25 ℃ of the timing temperature, up to the mobile time that disappears of Visual Confirmation, the result is 48 hours.According to the order same with experimental example 1, obtain amplitude by liquid state to the needed time of rubbery state, the result is 23 minutes.
(3) comprehensive evaluation
In the experimental example 12, owing to be 23 minutes set time and 48 hours serviceable time, so comprehensive evaluation is judged to be △.Experimental example 12 the results are shown in table 2.In addition, experimental example 12 is embodiments of the invention.Comparative experiments example 10 is during with experimental example 12, observe when the interpolation quantitative change of phosphoric acid for a long time, set time is elongated tendency further.
(experimental example 13～20)
(1) modulation blend compositions
For each experimental example,, obtain the above-mentioned Preblend composition of experimental example 13～20 according to composition condition polyol blend composition, reaction suppressor and the catalyzer shown in the table 2.For each experimental example, the isocyanate prepolymer composition of the composition condition shown in the mixture table 2 and the total amount of each Preblend composition, the urethane that obtains each experimental example forms the property blend compositions.In addition, in the table, isocyanic ester E represents that a part of carbon imideization with diphenylmethanediisocyanate obtains, NCO content 28.8 quality %, average functional group number are 2.1 modified polyisocyanate (below, abbreviate isocyanic ester E as.)。In addition, DB60 represents TOYOCAT-DB60 (TOSOH CORPORATION system) as the amine series catalysts in the table.In the table, DOTDL represents two lauric acid dioctyl tins as the organo-tin compound of normal temperature liquid.In addition, after catalyzer is added in (A) expression in the table Preblend composition temporarily is heated to 80 ℃, and after making the solid catalyst dissolving, is cooled to 25 ℃.
(2) result
According to the order same with experimental example 1, the urethane of each experimental example of 50g is formed the vial that the property blend compositions is put into 100ml respectively, under 25 ℃ of the timing temperature, up to the mobile time that disappears of Visual Confirmation, obtain the serviceable time shown in the table 2.In addition, for each experimental example, according to the order same with experimental example 1, obtain amplitude by liquid state to the needed time of rubbery state, obtain the set time shown in the table 2.
(3) comprehensive evaluation
By set time that obtains in the experimental example 13～20 and serviceable time, for whole experimental examples, comprehensive evaluation is judged to be *.In addition, experimental example 13～20th, comparative example.
Experimental example 13 is not except using jointly reaction suppressor and the catalyzer, with experimental example 1 identical conditions under, but under the situation of not adding reaction suppressor and organo-metallic series catalysts, obtain 72 hours long like this serviceable times, but need 60 minutes set time, can not take into account the serviceable time and fully short set time of abundant length.
Experimental example 14 is not except using catalyzer, with experimental example 1 identical conditions under, under the situation of not adding the organo-metallic series catalysts, though obtain the serviceable time of 72 hours such length, but because the effect of reaction suppressor, need the set time more than 60 minutes, can not take into account the serviceable time and fully short set time of abundant length.
Experimental example 15 is except the two lauric acid dioctyl tins that do not use reaction suppressor, replacement normal temperature solid organo-tin compound use normal temperature liquid, with experimental example 1 identical conditions under, under the situation of the catalyzer of the organo-tin compound that uses normal temperature liquid, obtain the set time of 1.8 minutes such weak points, but be dissolved in Preblend composition portion and homogenized at the heating procatalyst, obtain 0.5 hour so extremely short serviceable time, can not take into account the serviceable time and fully short set time of abundant length.
Experimental example 16 is except the two lauric acid dioctyl tins that replace normal temperature solid organo-tin compound use normal temperature liquid, with experimental example 1 identical conditions under, under the situation of the catalyzer of the organo-tin compound that uses normal temperature liquid, obtain the set time of 2.4 minutes such weak points, it is homogenized but the heating procatalyst is dissolved in Preblend composition portion, obtain 1 hour so extremely short serviceable time, can not take into account the serviceable time and fully short set time of abundant length.In addition, when comparative experiments example 15 and experimental example 16, owing to use reaction suppressor, thereby the serviceable time of experimental example 16 and set time, the both was elongated.
Experimental example 17 is not except using reaction suppressor with under external and experimental example 1 identical conditions, under the situation of not adding reaction suppressor, obtain 1.5 minutes short like this set times, but obtain 2 hours short like this serviceable times, can not take into account the serviceable time and fully short set time of abundant length.
Experimental example 18 is except after adding catalyzer, the Preblend composition temporarily is heated to 80 ℃, then, be cooled to beyond 25 ℃, with experimental example 1 identical conditions under, when in a single day the Preblend composition is heated to more than 40 ℃, the solid catalyst dissolving, even cooling is not separated out yet, therefore, demonstrate the serviceable time that can not reach abundant length.Experimental example 18 obtains the set time of 1.4 minutes such weak points, and the serviceable time is 0.5 hour, extremely short, can not take into account the serviceable time and fully short set time of abundant length.
Experimental example 19 is except replacing isocyanic ester A, using the isocyanic ester E as fragrant family isocyanic ester, beyond the composition and matching requirements of some change polyhydroxy reactants, with experimental example 1 identical conditions under, under the situation of using the fragrant family isocyanic ester higher than the reactivity of fatty family and alicyclic ring family, obtain 1 minute such ratio experimental example 1 shorter set time, on the other hand, obtain 4 hours short like this serviceable times, can not take into account the serviceable time and fully short set time of abundant length.
Experimental example 20 is except replacing normal temperature solid organo-tin compound, the amine series catalysts TOYOCAT-DB60 of use as normal temperature liquid, with experimental example 1 identical conditions under, do not use under the situation of amine series catalysts not using organo-tin compound, obtain 36 hours long like this serviceable times, but because catalyst activity is low, thereby need set time more than 60 minutes, can not take into account the serviceable time and fully short set time of abundant length.
Utilizability on the industry
As described above like that, according to the present invention, provide the manufacture method of urethane formation property composition, polyhydric alcohol composition and urethane resin of the set time of serviceable time of realizing taking into account the length normal temperature under and the weak point under the condition of cure.Urethane of the present invention forms the property composition in the flowability that can keep the time more than 1 day after the modulation, and can make its curing rapidly by heating when being shaped, thereby, can improve operability and plasticity in the manufacturing processed of urethane resin.
Above-mentioned urethane formation property composition can be as urethane formation property material of doubtful single-component thermosetting type, the urethane resin that forms the manufacturing of property composition by this urethane can form additive in the property composition or manufacturing process etc. according to adding urethane to, pass through foam, film, elastomerics, powder, solution, various forms such as emulsion provide, can be used in flexible foam, rigid foam, elastomerics, caking agent, coating, various uses such as tackiness agent can expect to improve the plasticity and the operability of the manufacturing process of the urethane resin that is used for the purposes on the various industries.
So far, be illustrated for embodiments of the present invention and embodiment, but embodiments of the present invention and embodiment are not limited to above-mentioned embodiment and embodiment, other embodiments and embodiment, append, conversion, deletion etc. can change in the scope that those skilled in the art can expect, as long as any mode plays effect of the present invention and effect, then within the scope of the present invention.
Claims (13)
1. a urethane forms the property composition, and it is combined with following composition: isocyanate prepolymer composition, and it comprises at least a kind or their mixture that is selected from the group that aliphatics and alicyclic isocyanate and their derivative and modification body formed;
The polyhydroxy reactant of normal temperature liquid state;
Reaction suppressor;
The normal temperature solid organo-metallic series catalysts that in said composition, exists with solid form.
2. urethane according to claim 1 formation property composition, aforementioned polyhydroxy reactant comprises at least a kind or their mixture in the pure and mild polycarbonate polyol of polyester polyols.
3. urethane according to claim 1 and 2 formation property composition, aforementioned organo-metallic series catalysts is an organo-tin compound.
4. according to each described urethane formation property composition of claim 1～3, the previous reaction inhibitor is a phosphate ester acid.
5. form property composition according to each described urethane of claim 1～4, aforementioned isocyanate prepolymer composition comprises that to be selected from average functional group number be at least a kind or their mixture in the group formed of 2～5 hexamethylene diisocyanate and their derivative and modification body.
6. polyhydric alcohol composition, it is the polyhydric alcohol composition that forms urethane resin with the isocyanate prepolymer composition reaction, it comprises and is combined with following composition:
The polyhydroxy reactant of normal temperature liquid state;
Reaction suppressor;
The normal temperature solid organo-metallic series catalysts that in said composition, exists with solid form;
Aforementioned isocyanate prepolymer composition comprises at least a kind or their mixture that is selected from the group that aliphatics and alicyclic isocyanate and their derivative and modification body formed.
7. polyhydric alcohol composition according to claim 6, aforementioned polyhydroxy reactant comprise at least a kind or their mixture in the pure and mild polycarbonate polyol of polyester polyols,
Aforementioned organo-metallic series catalysts is an organo-tin compound,
The previous reaction inhibitor is a phosphate ester acid,
Aforementioned isocyanate prepolymer composition comprises that to be selected from average functional group number be at least a kind or their mixture in the group formed of 2～5 hexamethylene diisocyanate and their derivative and modification body.
8. the manufacture method of a urethane resin, it comprises following operation:
The operation of modulation urethane formation property composition, described urethane forms the property composition and is combined with isocyanate prepolymer composition, and it comprises at least a kind or their mixture that is selected from the group that aliphatics and alicyclic isocyanate and their derivative and modification body formed; The polyhydroxy reactant of normal temperature liquid state; Reaction suppressor; And the normal temperature solid organo-metallic series catalysts that in said composition, exists with solid form;
Heat aforementioned urethane formation property composition and make its solidified operation.
9. manufacture method according to claim 8, aforementioned modulating process comprises following operation: under 20～40 ℃ of temperature aforementioned polyhydroxy reactant, previous reaction inhibitor and aforementioned organo-metallic series catalysts are mixed, modulate the operation that aforementioned organo-metallic series catalysts is dispersed in the polyhydric alcohol composition in the composition; The synthetic aforementioned polyhydric alcohol composition of institute is mixed with aforementioned isocyanate prepolymer composition, modulate the operation of aforementioned urethane formation property composition;
Aforementioned curing process comprises the operation that is heated to 100～250 ℃ of temperature.
10. according to Claim 8 or 9 described manufacture method, aforementioned polyhydroxy reactant comprises at least a kind or their mixture of polyester polyol and polycarbonate polyol.
11. each described manufacture method according to Claim 8～10, aforementioned organo-metallic series catalysts is an organo-tin compound.
12. each described manufacture method according to Claim 8～11, the previous reaction inhibitor is a phosphate ester acid.
13. each described urethane forms the manufacture method of property composition according to Claim 8～12, aforementioned isocyanate prepolymer composition comprises that to be selected from average functional group number be at least a kind or their mixture in the group formed of 2～5 hexamethylene diisocyanate and their derivative and modification body.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008160300A JP2010001349A (en) | 2008-06-19 | 2008-06-19 | Urethane forming composition, polyol composition, and method for producing urethane resin |
| JP2008160300 | 2008-06-19 |
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| CN101608013A true CN101608013A (en) | 2009-12-23 |
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| CNA2009101472795A Pending CN101608013A (en) | 2008-06-19 | 2009-06-19 | The method for making of urethane formation property composition, polyhydric alcohol composition, urethane resin |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP2010001349A (en) |
| KR (1) | KR20090132495A (en) |
| CN (1) | CN101608013A (en) |
| TW (1) | TW201000507A (en) |
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| CN101942267B (en) * | 2009-07-08 | 2012-11-21 | 东莞嘉卓成化工科技有限公司 | Single track elastic coating and manufacturing method thereof |
| CN107636033A (en) * | 2015-06-12 | 2018-01-26 | 三井化学株式会社 | Polyisocyantates composition, polyurethane resin and two-solution curing type urethane composition |
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| US10865269B2 (en) | 2015-06-12 | 2020-12-15 | Mitsui Chemicals, Inc. | Polyisocyanate composition, polyurethane resin, two-component curable polyurethane composition, coating material, and adhesive material |
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| TW201843203A (en) * | 2017-04-21 | 2018-12-16 | 日商迪愛生股份有限公司 | Urethane-modified polyisocyanate compound, curing agent for two-part curable urethane adhesive agent, adhesive agent, and back sheet for solar cell |
| CN113272351B (en) * | 2019-09-09 | 2023-03-17 | 株式会社Lg化学 | Curable composition |
| KR102519128B1 (en) * | 2019-09-09 | 2023-04-07 | 주식회사 엘지화학 | Curable Composition |
| CN113939572A (en) * | 2019-09-09 | 2022-01-14 | 株式会社Lg化学 | Curable composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2003226839A (en) * | 2002-02-04 | 2003-08-15 | Kansai Paint Co Ltd | Coating material composition |
| JP2004269733A (en) * | 2003-03-10 | 2004-09-30 | Sunstar Eng Inc | Two pack-type urethane-based composition |
-
2008
- 2008-06-19 JP JP2008160300A patent/JP2010001349A/en active Pending
-
2009
- 2009-04-22 KR KR1020090035189A patent/KR20090132495A/en not_active Application Discontinuation
- 2009-05-08 TW TW098115386A patent/TW201000507A/en unknown
- 2009-06-19 CN CNA2009101472795A patent/CN101608013A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112778888A (en) * | 2019-11-06 | 2021-05-11 | 旭化成株式会社 | Process for producing polyurethane coating film and coating composition |
| CN112778888B (en) * | 2019-11-06 | 2022-10-14 | 旭化成株式会社 | Process for producing polyurethane coating film and coating composition |
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| CN112625213B (en) * | 2020-12-04 | 2022-05-17 | 上海华峰新材料研发科技有限公司 | Solvent-free blocked polyurethane resin composition, polyurethane material and leather product |
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Also Published As
| Publication number | Publication date |
|---|---|
| KR20090132495A (en) | 2009-12-30 |
| JP2010001349A (en) | 2010-01-07 |
| TW201000507A (en) | 2010-01-01 |
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