CN102753595A - Polyurethane resin composition and molded article thereof - Google Patents
Polyurethane resin composition and molded article thereof Download PDFInfo
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- CN102753595A CN102753595A CN2011800086914A CN201180008691A CN102753595A CN 102753595 A CN102753595 A CN 102753595A CN 2011800086914 A CN2011800086914 A CN 2011800086914A CN 201180008691 A CN201180008691 A CN 201180008691A CN 102753595 A CN102753595 A CN 102753595A
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- G—PHYSICS
- G02—OPTICS
- G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
- G02C7/00—Optical parts
- G02C7/02—Lenses; Lens systems ; Methods of designing lenses
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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
- C08G18/10—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
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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
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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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
- C08G18/61—Polysiloxanes
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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
- C08G18/72—Polyisocyanates or polyisothiocyanates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- Ophthalmology & Optometry (AREA)
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Abstract
Provided is a polyurethane resin composition which can be molded by a one-shot method or a prepolymer method using a silicone polyol highly miscible with a polyol to be used as a starting material of a polyurethane resin, and achieves excellent blooming resistance, Si atom aggregability, various physical properties, and low frictional properties when formed into a polyurethane molded article, and also provided is a molded article thereof. The polyurethane resin composition comprises (A) a polyisocyanate and (B) a polyol, and is characterized in that the polyol (B) comprises 0.01 to 5% by mass of a silicone polyol having one end modified with lactone (B1) obtained by the ring-opening addition polymerization of 5 to 10 moles of a lactone monomer at each primary hydroxyl group of an organopolysiloxane having two primary hydroxyl groups at one end and 95 to 99.99% by mass of another polyol (B2).
Description
Technical field
The present invention relates to obtain polyurethane resin composition and the forming composition of using it to obtain of the urethane cures thing of excellent frost-resistance, Si atom compendency, all rerum naturas and low frictional properties.
Background technology
In recent years; Organopolysiloxane compound is because interfacial characteristicses such as low frictional properties, thermostability, water-repellancy, defoaming, release property are excellent; So in order to improve the performance of synthetic resins such as coating, moulding article; For example, adding properties-correcting agent such as dimethyl polysiloxane, methyl phenyl silicone, the dimethyl polysiloxane that contains reactive group, polyether-modified organopolysiloxane uses.
Yet because the consistency of they and resin is insufficient, thermotolerance is insufficient, so use range is limited.Therefore be purpose to improve these shortcomings, addition lactone on the addition reaction of ZGK 5 and glycerin monoallyl ether is proposed and obtain in ester modified organopolysiloxane compound (for example with reference to patent documentation 1).
But; This compound has a plurality of polylactone chains owing to a plurality of hydroxyl reactions of lactone and glycerin monoallyl ether so crosslinking structure becomes many; Therefore reactivity is uneven because primary hydroxyl and secondary hydroxyl mix existence when urethane reacts; And then since poor with the consistency of polyvalent alcohol, therefore be difficult to use with raw material as urethane resin.
In addition, in the time of only will being used for moulding as polyurethane resin composition that must composition with polymeric polyisocyanate and polyvalent alcohol, resulting forming composition rub resistance is poor.In order to improve said problem, therefore, propose in urethane polymer, to import organopolysiloxane (for example with reference to patent documentation 2).
Yet; Though the technology of patent documentation 2 has some improvement really about rub resistance; But because the consistency of organopolysiloxane and polyvalent alcohol is poor, so cause frosting in the resulting forming composition easily, particularly such unfavorable condition is remarkable in the moulding that utilizes single stage method.
As stated; The consistency of expectation exploitation and polyvalent alcohol improves and no matter in single stage method still is arbitrary method of forming of prepolymer method, the polyvalent alcohol that contains polysiloxane chain that all can use well with raw material as urethane resin (below be called the silicone polyvalent alcohol).
The prior art document
Patent documentation
Patent documentation 1: japanese kokai publication hei 03-6230 communique
Patent documentation 2: TOHKEMY 2003-186366 communique
Summary of the invention
Invent problem to be solved
The object of the present invention is to provide a kind of polyurethane resin composition and forming composition thereof; Said polyurethane resin composition through use with excellent as the polyvalent alcohol consistency of urethane resin raw material and with the reactive excellent silicone polyvalent alcohol of NCO; Thereby the arbitrary method through in single stage method and the prepolymer method is all plastic, the frost-resistance when forming polyurethane moldings, Si atom compendency, all rerum naturas, low frictional properties excellence.
The method that is used to deal with problems
The inventor furthers investigate with the silicone polyvalent alcohol urethane resin; The result finds; On specific ZGK 5 addition the consistency of silicone polyvalent alcohol and polyvalent alcohol of specified quantitative internal ester monomer excellent; When using, can access frost-resistance, Si atom compendency, all rerum naturas and the excellent urethane cures thing of low frictional properties, thereby accomplish the present invention as the urethane resin raw material.
Promptly; The present invention provides a kind of polyurethane resin composition; It is characterized in that; It is to contain (A) polymeric polyisocyanate and (B) polyurethane resin composition of polyvalent alcohol; Wherein, ester modified single tip type silicone polyvalent alcohol (B1) 0.01～5 quality % and other polyvalent alcohol (B2) 95～99.99 quality % in polyvalent alcohol (B) contains, said in ester modified single tip type silicone polyvalent alcohol have at single end on the above-mentioned hydroxyl of organopolysiloxane of 2 primary hydroxyls respectively that 5～10 moles of internal ester monomers of ring opening polyaddition obtain.
The effect of invention
The present invention can provide a kind of polyurethane resin composition; Its through use specified quantitative with as the excellent addition on specific ZGK 5 of the consistency of the polyvalent alcohol of urethane resin raw material other polyvalent alcohol of the silicone polyvalent alcohol that obtains of specified quantitative internal ester monomer and specified quantitative; The ability one-step moulding; Frost-resistance when forming polyurethane moulded material, Si atom compendency, all rerum naturas, the excellent curable urethane resin thing of low frictional properties can form through the arbitrary method in the one-step moulding method and the prepolymer method of forming, so be useful as the urethane resin raw material.
Embodiment
Ester modified single tip type silicone polyvalent alcohol (B1) 0.01～5 quality % and other polyvalent alcohol (B2) 95～99.99 quality % in above-mentioned polyvalent alcohol (B) contains, said in ester modified single tip type silicone polyvalent alcohol (B1) have at single end on the above-mentioned hydroxyl of organopolysiloxane of 2 primary hydroxyls respectively that 5～10 moles of internal ester monomers of ring opening polyaddition obtain.If it is not can not give urethane resin at least with low frictional properties,, therefore preferred if occur isolating tendency at most than 5 quality % than 0.01 quality %.
The organopolysiloxane that uses among the present invention is to have the ZGK 5 that does not have reactive functional group having on single end on 2 primary hydroxyls and the other end.Above-mentioned organopolysiloxane is preferably the ZGK 5 of molecular weight 1000～4000, is preferably the ZGK 5 of molecular weight 2000～4000 especially.In addition, hydroxyl value is preferably 20～60mgKOH/g, and acid number is preferably below the 0.5mgKOH/g.
If the molecular weight of above-mentioned organopolysiloxane is more than 1000, then give polyurethane resin composition of the present invention easily with excellent effects such as low frictional properties, so be preferred.In addition, if molecular weight is below 4000, the reaction of then above-mentioned internal ester monomer and above-mentioned organopolysiloxane is carried out smoothly, and the unreacted primary hydroxyl reduces, so be preferred.
Yet the molecular weight of above-mentioned organopolysiloxane was greater than 4000 o'clock, and the reaction of above-mentioned internal ester monomer and above-mentioned organopolysiloxane can not be carried out well, formed 2 peaks, and the unreacted primary hydroxyl has the tendency that becomes many, so not preferred.In addition, molecular weight is less than 1000 o'clock, has that to be difficult to give urethane resin compositions be the tendency of effects such as low frictional properties with the effect of organopolysiloxane, so not preferred.
Wherein, so-called molecular weight is meant the value of obtaining according to following calculating formula among the present invention.
Molecular weight=(56100 * 2)/(hydroxyl value+acid number)
The internal ester monomer that uses among the present invention for example, can be enumerated out beta-propiolactone, gamma-butyrolactone, δ-Wu Neizhi, 6-caprolactone, γ-crotonoyl lactone etc., is preferably 6-caprolactone.When reacting with above-mentioned organo-siloxane, 5～10 moles of internal ester monomers of per 1 primary hydroxyl ring opening polyaddition in the preferred above-mentioned organo-siloxane.More preferably 8 moles of internal ester monomers of each addition polymerization on 2 one-sided primary hydroxyls of organopolysiloxane.When per 1 primary hydroxyl addition polymerization that organopolysiloxane had was less than 5 moles of internal ester monomers, it is many that the unreacted primary hydroxyl becomes, therefore not preferred in reaction as the carbamate raw material.On the other hand, than 10 moles for a long time, the viscosity of the urethane resin that obtains uprises, the property handled is poor.
Ester modified single tip type silicone polyvalent alcohol (B1) is made in the presence of catalyzer through under 80～140 ℃ of the temperature in system in above-mentioned.More preferably 80～120 ℃.When temperature was lower than 80 ℃ in the system, speed of response was slack-off, need synthesize in long hour.In addition, when the temperature in the system is higher than 140 ℃, has on single end and have the organopolysiloxane that does not have reactive functional group on 2 primary hydroxyls and the other end and decompose, can not get desired in ester modified single tip type silicone polyvalent alcohol.
Above-mentioned catalyzer is preferably the tin series catalysts, is preferably three (2 ethyl hexanoic acid) butyl tin especially.At this moment, catalyst concentration is 100～500ppm with respect to the total quality optimization of the synthesis material of ester modified single tip type silicone polyvalent alcohol (B1) in above-mentioned in the system.
In the manufacturing during ester modified single tip type silicone polyvalent alcohol (B1); In reaction vessel, drop into and have on single end that to have the molecular weight that does not have reactive functional group on 2 primary hydroxyls and the other end be 1000～4000 organopolysiloxane and catalyzer; Temperature in the system is set at 80～140 ℃; The mode that reaches 5～10 moles according to per 1 hydroxyl of organopolysiloxane drops into internal ester monomer under nitrogen atmosphere; Preferably carried out 6～24 hours, and more preferably carried out reaction in 8～15 hours, react in case nonvolatile component reaches above just end of 99.5 quality %.Taking out the silicone polyvalent alcohol afterwards gets final product.
The molecular weight that ester modified single tip type silicone polyvalent alcohol (B1) preferably uses hydroxyl value and acid number to obtain through the aforementioned calculation formula in above-mentioned is 2500～6000.If (molecular weight of (B1) is said scope to ester modified single tip type silicone polyvalent alcohol in above-mentioned, then can give excellent low frictional properties, and the property handled is not poor yet, so preferred.
As the concrete example of ester modified single tip type silicone polyvalent alcohol (B1) in above-mentioned, can enumerate out the compound shown in the following general formula (1).
In addition, the R in the formula (1)
1The alkyl of expression carbonatoms 1～4, R
2The expression methyl or phenyl, m representes 1～4, n representes 20～40 number of repeat unit.
[Chemical formula 1]
Above-mentioned polyvalent alcohol (B) is through processing polyvalent alcohol (B) with ester modified single tip type silicone polyvalent alcohol (B1) in above-mentioned and other polyvalent alcohol (B2) mixing, through processing the curable urethane resin thing with polymeric polyisocyanate (A) reaction.Method of manufacture as this moment; Can in advance polyvalent alcohol (B) and polymeric polyisocyanate (A) be processed carbamate prepolymer; The solidifying agent that contains active hydrogen compounds through interpolation solidifies and to carry out the prepolymer moulding, also can polymeric polyisocyanate (A), polyvalent alcohol (B), as required chain-lengthening agent mixed and carries out one-step moulding.
Above-mentioned polymeric polyisocyanate (A); For example can enumerate out 2; 4-toluene support vulcabond, 2,6-toluene support vulcabond or their mixture, m-benzene diisocyanate or PPDI, terephthalylidene vulcabond, ethylidene diisocyanate, tetramethylene-1,4-vulcabond, hexa-methylene-1; 6-vulcabond, 4; 4 '-ditan-vulcabond, 3,3 '-dimethyl--ditan-4,4-biphenyl diisocyanate, 3; 3-dichloro--4; 4-biphenyl diisocyanate, 4,4-biphenyl diisocyanate or 1,5-naphthalene diisocyanate, tolidine vulcabond, isophorone diisocyanate, cyclohexyl diisocyanate, Tolylamine vulcabond, rough diphenylmethanediisocyanate and diphenylmethanediisocyanate, triphenylmethane triisocyanate and their various verivates.In addition, also can enumerate the end of sening as an envoy to following polyvalent alcohol and the reaction of above-mentioned arbitrary polymeric polyisocyanate and obtaining is the carbamate prepolymer of NCO.
Above-mentioned other polyvalent alcohol (B2) also comprises various polyether glycols, polycarbonate polyol, polylactone polyester polyol or common polyester polyol; That is, make polyvalent alcohol and polycarboxylic acid in the presence of catalyzer, carry out condensation reaction and have the polyvalent alcohol of ester bond.It is 600～6000 polyvalent alcohol that above-mentioned other polyvalent alcohol is preferably the molecular weight of obtaining through hydroxyl value and acid number, is preferably 600～3000 especially.
If above-mentioned other the molecular weight of polyvalent alcohol (B2) is said scope, when then will ester modified single tip type silicone polyvalent alcohol (B1) in above-mentioned mixing, do not cause separation with above-mentioned other polyvalent alcohol (B2), obtain having the forming composition of the strength and elongation of excellence, so preferably.
Yet above-mentioned other the molecular weight of polyvalent alcohol (B2) is less than 600 o'clock, when ester modified single tip type silicone polyvalent alcohol (B1) in above-mentioned and above-mentioned other polyvalent alcohol (B2) are mixed, has to cause isolating tendency, so not preferred.In addition, above-mentioned other the molecular weight of polyvalent alcohol (B2) is greater than 6000 o'clock, the tendency that is difficult to obtain to embody the forming composition of excellent strength and elongation arranged, so not preferred.
Above-mentioned polyester polyol so long as with polyvalent alcohol and polycarboxylic acid in the presence of catalyzer, carry out polyvalent alcohol that condensation reaction has an ester bond then arbitrarily polyvalent alcohol all can, also comprise polyester ether polylol, polycarbonate polyester polyvalent alcohol etc.It is 600～6000 polyvalent alcohol that above-mentioned polyester polyol is preferably the molecular weight of obtaining through hydroxyl value and acid number, is preferably 600～3000 especially.
As above-mentioned polyvalent alcohol; Preferably with the straight diol of main chain carbon number 2～15, particularly be terepthaloyl moietie, 1; Ammediol, glycol ether, 1; 4-butyleneglycol, 1,5-pentamethyl-glycol, 1, the hydrocarbon of glycolss such as 6-hexamethylene glycol, two hydroxyl-oxethyl benzene or p-Xylol glycol is as the polyvalent alcohol of main chain.The total number of carbon atoms is preferably 3～34, and more preferably 3～17, for example can enumerate out 1,2-Ucar 35,2-methyl isophthalic acid, ammediol, two-1; 2-Ucar 35,1,2-butyleneglycol, 1,3 butylene glycol, 2,3-butyleneglycol, 2,2-dimethyl--1; Ammediol, 3-methyl isophthalic acid, 5-pentanediol, 3-methyl isophthalic acid, 3,5-penta triol, 2,2; 4-trimethylammonium-1,3-pentanediol, 2-ethyl-1,3-pinakon, 2,2-dimethyl--3-hydroxypropyl-2,2-dimethyl--3-hydroxy propionate, NSC 6366,2-normal-butyl-2-ethyl-1; Ammediol, 3-ethyl-1,5-pentanediol, 3-propyl group-1,5-pentanediol, 2,2-diethylammonium-1, ammediol, 3-octyl group-1; 5-pentanediol, 2-ethyl-1,3-pinakon, 3-myristyl-1,5-pentanediol, 3-stearyl-1,5-pentanediol, 3-phenyl-1; 5-pentanediol, 3-(4-nonyl phenyl)-1,5-pentanediol, 3, two (the 4-nonyl phenyl)-1 of 3-, 5-pentanediol, 1; Two (hydroxymethyl) Trimetylene, 1 of 2-, two (hydroxyethyl) tetramethylene, 1 of 3-, two (hydroxymethyl) pentamethylene, 1 of 3-, two (hydroxymethyl) hexanaphthenes, 1 of 4-; Two (hydroxyethyl) hexanaphthenes, 1 of 4-, two (hydroxypropyl) hexanaphthenes, 1 of 4-, two (hydroxyethyl) suberane, 1 of 4-, two (hydroxyl methoxyl group) hexanaphthenes, 1 of 4-; Two (hydroxyl-oxethyl) hexanaphthenes, 2 of 4-, two (the 4 '-hydroxyl methoxyl group cyclohexyl) propane, 2 of 2-, two (the 4 '-hydroxyl-oxethyl cyclohexyl) propane of 2-, TriMethylolPropane(TMP) etc., they can use separately or use more than 2 kinds.
As above-mentioned polyhydroxy reactant, can and using hydroxyl value is the compound more than 3.As can and the compound of usefulness, get final product so long as generally be used for the compound of polyester polyol, can enumerate out for example multifunctional polyols such as glycerine, hexanetriol, trolamine, tetramethylolmethane, Edamine.
Above-mentioned polycarboxylic acid can use for example succsinic acid, toxilic acid, hexanodioic acid, pentanedioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, 1 separately; 9-nine methylene radical dicarboxylicacid, 1; 10-decamethylene dicarboxylicacid, 1; 11-11 methylene radical dicarboxylicacid, 1,12-ten dimethylene dicarboxylicacid, dodecanedicarboxylic acid or as for example phthalic acid, m-phthalic acid, terephthalic acid, six hydrogen terephthalic acids, six hydrogen m-phthalic acids or the ester derivatives such as their acid anhydrides, methyl esters etc. of fragrant family dicarboxylicacid or with more than 2 kinds and use.From the viewpoint of industry, mainly use hexanodioic acid.Also can use dimeracid that the polymerization through ready denier oil acid obtains etc.As ready denier oil acid, be the mixture of unsaturated acid such as oleic acid, linolic acid and palmitinic acid, Triple Pressed Stearic Acid etc.
Above-mentioned polyether glycol is the polyvalent alcohol that obtains having that the for example above-mentioned polyvalent alcohol of the compound that more than 2, preferably has 2～6 reactive hydrogens, glycerine, TriMethylolPropane(TMP), tetramethylolmethane, Sorbitol Powder, mannitol, two (trishydroxymethyl) propane, Dipentaerythritol etc. are gone up oxirane hydro carbons such as independent addition polymerization or preferred 2～9 mol of alkylene oxide hydrocarbon more than 2 kinds, for example oxyethane, propylene oxide, butylene oxide ring.The molecular weight of obtaining through its hydroxyl value is preferably 300～6000, is preferably 600～3000 especially.In addition, hydroxyl value is preferably 20～750.
As above-mentioned polylactone polyester polyol, for example, also can use lactone ring-opening polymerizations such as 6-caprolactones and the lactone that obtains is the polyester glycol class.As this lactone is the polyester glycol class, a kind of of addition polymerization 6-caprolactone, δ-Wu Neizhi, Beta-methyl-δ-Wu Neizhi etc. on the above-mentioned polyvalent alcohol or more than two kinds and the glycols that obtains all can use.
As above-mentioned polycarbonate polyol for example is to make low molecular polylol and dialkyl carbonate ester condensation reaction and the polyvalent alcohol that obtains.As above-mentioned low molecular polylol, for example can enumerate out 1,6-pinakon, 1,5-pentanediol etc.In addition, as dialkyl carbonate, can enumerate out for example methylcarbonate, diethyl carbonate, ethylene carbonate etc.
In addition; As polycarbonate polyol, for example can enumerate out on polycarbonate polyol further ring opening polyaddition lactone and cocondensation polycarbonate polyol that the lactone modified polycarbonate polyvalent alcohol that obtains or polyester polyol that makes other or polyether glycol etc. obtain with the polycarbonate polyol cocondensation.
Low molecular weight linear glycol, the diamine compound of carbon number 2～10 preferably used in above-mentioned chain-lengthening agent.As its typical example, can enumerate out terepthaloyl moietie, 1,2-Ucar 35,1, ammediol, 2; 3-butyleneglycol, 1,4-butyleneglycol, 2,2 '-dimethyl--1; Ammediol, glycol ether, 1,5 pentamethylene glycol, 1,6-hexamethylene glycol, hexanaphthene 1; Independent or mixture such as 4-glycol, hexanaphthene-1,4 glycol, hexanaphthene-1,4 dimethanol; Edamine, 1,6-hexamethylene-diamine, piperazine, 2,5-lupetazin, isophorone diamine, 4; 4 '-dicyclohexyl methyl hydride diamines, 3,3 '-dimethyl--4,4 '-dicyclohexyl methyl hydride diamines, 1; 4-cyclohexane diamine, 1; 2-propanediamine, NSC 446, Triethylenetetramine (TETA), 3,3 '-dichloro--4, hydrazine class such as amine compound such as 4 '-diaminodiphenyl-methane and hydrazine, hydrazides.Preferred especially 1,4-butyleneglycol, TriMethylolPropane(TMP).
Polyurethane resin composition of the present invention not only can be processed urethane elastomers, can also process waterborne polyurethane resin, aqueous polyurethane resin.This polyurethane resin composition be import in order to carry out water-dispersion be selected from the group of forming by anionic property group, cationic group and nonionic group etc. more than a kind as the compsn of hydrophilic radical.At this moment; Can in the polyester polyol that adopts catalyzer to make, use the chain-lengthening agent of possess hydrophilic property group; The polyester polyol as the raw material of the polyester polyol that adopts the catalyzer manufacturing uses a part to comprise the glycol of hydrophilic radical and/or thereby the diprotic acid that comprises hydrophilic radical is made hydrophilization uses, and can adopt known method to process water system or aqueous urethane resin composition.
As its method of manufacture; For example; Can adopt following method: (i) use the polyester polyol that does not contain hydrophilic radical that adopts the catalyzer manufacturing; Use and to comprise in a part more than at least 1 and can and in a part, comprise the compound that is selected from an above hydrophilic radical in the group of forming by anionic property group, cationic group and nonionic group, manufacturing water system or waterborne polyurethane resin with hydroxyl, the amido of isocyanic ester radical reaction;
(ii) use to contain with anionic property group, cationic group and nonionic group or their neutralized salt as the polyvalent alcohol of the hydrophilic radical of representative and/or the poly carboxylic acid or its ester derivative that contain above-mentioned hydrophilic radical as polyvalent alcohol and dicarboxylicacid that must composition; Use the catalyzer manufacturing to contain the polyester polyol of hydrophilic radical, make the water system or the waterborne polyurethane resin that have used polyester polyol.
Anionic property group as above-mentioned hydrophilic radical; Preferably enumerate out carboxyl, carboxylate group, sulfonic group, sulphonate-base etc.; The cationic group preferably enumerates out uncle's amino, with one of which partly or entirely with acidic cpd neutralization or with the group of season agent seasonization; The nonionic group is the group with poly (oxyalkylene) based structures, preferably enumerates out for example polyoxyethylene glycol and multipolymer thereof.
Above-mentioned anionic property group, cationic group can be with their part or the group that all neutralizes and form through various basic cpds or acidic cpd, also can be the groups that the uncle's amino as the cationic group is formed with season agent seasonization.
As the polyester polyol that contains above-mentioned anionic property group, can enumerate out for example carboxylic polyester polyol or contain sulfonic polyester polyol.
Polyurethane resin composition of the present invention can be used the method for manufacture of various urethane, for example method such as single stage method, prepolymer method or quasi-prepolymer process and mass polymerization, solution polymerization, letex polymerization, emulsion polymerization etc.The mode of production also can be a known method in the past, can use slab mode, double conveyor mode, thermofixation mode, cold-curing mode, RIM mode, utilize the methods such as moulding, one-body molded, the site operation mode with matrix material, spray pattern, curtain coating mode, injection, coating, impregnation of open mode.During manufacturing, preferably with polymeric polyisocyanate and polyvalent alcohol with mol ratio (NCO/ (OH+NH
2)) meter 0.8～1.1 reacts, more preferably 1.0～1.05.In addition, can be when making urethane resin the general addition that adopts use known urethane catalyzer, tensio-active agent, other auxiliary agent etc.
And then polyurethane resin composition of the present invention can be added inhibitor, UV light absorber, anti hydrolysis agent, weighting agent, tinting material, reinforcer, releasing agent, fire retardant etc. as required.And then, can in the scope of the effect of not damaging polyurethane resin composition of the present invention, add other TPUE or interchangeable heat plastic resin in addition, for example ABS resin, AS resin, vinyl chloride resin, polymeric amide etc.Also can contain the various additives that are selected from tensio-active agent, catalyzer, stablizer and the pigment in the compsn of the present invention.
Polyurethane resin composition of the present invention can be used as thermoplastic elastomer (TPU), Thermocurable elastomerics (TSU), waterborne polyurethane resin, the use of radically curing based polyurethane resin, can be used for the polyurethane product of all areass such as formed material, caking agent, tackiness agent, coating, foam, sealing agent, light-cured resin.Concrete purposes can be used for many fields such as silk, film, sheet material, band, flexible pipe, cylinder, tire, packing, packing ring, sole etc. 3 dimension forming composition and artificial leather, synthetic leather, soft/hard foam, filamentary material, Industrial materials, motor electronic material, optical material, medical material, civil construction material.
Embodiment
Below, enumerate out embodiment and specify the present invention, but be not limited to these embodiment.In addition, " part " in the literary composition, " % " are quality criterias.
Synthetic example 1 (synthesizing of the single tip type silicone of the modification of addition mole lactone 16 polyvalent alcohol)
In the 1 liter of four-hole boiling flask that possesses nitrogen ingress pipe, TM, prolong, whipping appts, add to have on single end of following structural formula (2) (n=33 in the formula) and have the organopolysiloxane (hydroxyl value: 41.1mgKOH/g that does not have reactive functional group on 2 primary hydroxyls and the other end; Acid number: 0.05mgKOH/g) 500g, 6-caprolactone 335g, as three (2 ethyl hexanoic acid) butyl tin 0.250g of catalysts, the limit feeds the nitrogen limit 100 ℃ of reactions 13 hours down.(about reaction end, suitably measure nonvolatile component (NV), NV is reached moment more than 99.5% as terminal point.)
React after 13 hours, because NV reaches 99.7%, so ester modified single tip type silicone polyvalent alcohol (affixture of 8 moles of lactones of each primary hydroxyl addition is also referred to as the Lc/Si polyvalent alcohol) takes out from flask in inciting somebody to action.Obtaining hydroxyl value is that 24.4mgKOH/g, acid number are that 0.55mgKOH/g, normal temperature (25 ℃) descend to white solid, are the reactant of transparent liquid 100 ℃ times.The MWD of utilizing GPC to measure shows normal distribution, utilizes
13The ratio of the unreacted primary hydroxyl of the organopolysiloxane that C-NMR measures is 5% (that is, the primary hydroxyl with the 6-caprolactone reaction is 95%).
[Chemical formula 2]
Synthetic example 2,3 and relatively more synthetic example 1
With the prescription shown in the table 1, with the single tip type silicone of synthetic example 1 12 moles, 20 moles and 4 moles modifications of likewise synthetic lactone polyvalent alcohol.These silicone polyvalent alcohols are respectively 6 moles of affixtures of per 1 primary hydroxyl and 10 moles of affixtures and 2 moles of affixtures.The proterties of the Lc/Si polyvalent alcohol that obtains is shown in Table 1.
[table 1]
In addition, evaluation method is described below.
< nonvolatile component >
Get the 1g sample in the metal ware, add 5ml toluene, obtain the residual quantity after under 107.5 ℃ dry 1 hour.
Nonvolatile component (%)=((B-C)/(A-C)) * 100
Wherein, A: the quality (g) of the sample before metal ware+drying
B: the quality of metal ware+dried sample (g)
C: the quality of metal ware
< hydroxyl value >
After in sample, adding the acetylizing agent that constitutes by acetic anhydride and pyridine, acetylize 115 ℃ * 1 hour.Then add water excessive acetic anhydride is resolved into acetic acid, behind interpolation acetone, the toluene, use N/2 potassium hydroxide-ethanol solution neutralization titration acetic acid.
Hydroxyl value (mgKOH/g)=((B-T) * F * 28.05/S)+AN
Wherein, B: the dripping quantity (ml) of the N/2 potassium hydroxide-ethanol solution in the blank test
T: the dripping quantity (ml) of the N/2 potassium hydroxide-ethanol solution in this test
The titre of F:N/2 potassium hydroxide-ethanol solution
S: sample collection amount (g)
The N:mol/ liter
AN: the acid number of sample
< acid number >
After in sample, adding neutral solvent (toluene and methanol) dissolving, with 0.1N potassium hydroxide-ethanol solution neutralization titration.
Acid number (mgKOH/g)=V * F * 5.611/S
Wherein, the dripping quantity of V:0.1N potassium hydroxide-ethanol solution (ml)
The titre of F:0.1N potassium hydroxide-ethanol solution
S: sample collection amount (g)
The N:mol/ liter
< molecular weight BIAS >
Obtain BIAS according to the target molecular weight of obtaining through calculating by the mol ratio of hydroxyl value, acid number and the terminal diol type organopolysiloxane of 6-caprolactone/list of single terminal diol type organopolysiloxane with by the hydroxyl value of resulting resin, the experiment molecular weight that acid number is obtained through calculating.
Molecular weight BIAS (%)=((target molecular weight-experiment molecular weight)/target molecular weight) * 100
Wherein, molecular weight=(56100 * 2)/(hydroxyl value+acid number)
< ratio of unreacted primary hydroxyl the ratio of the primary hydroxyl of the organopolysiloxane of lactone reaction (not with) >
Sample dissolution in deuterochloroform, is measured through ordinary method
13C-NMR.By the peak of locating to occur at 65.5ppm (with the carbon of the unreacted primary hydroxyl primary hydroxyl of the organopolysiloxane of lactone reaction (not with) adjacency) and 620ppm (with the carbon of the primary hydroxyl adjacency of lactone reaction) peak locating to occur calculates.
The ratio of unreacted primary hydroxyl (%)=(65.5ppm peak area/(65.5ppm peak area+62.0ppm peak area)) * 100
< MWD of utilizing GPC to measure >
Sample dissolution in THF (THF) (0.4% solution), is carried out gel osmoticing chromatogram analysis.Estimate the shape of resulting collection of illustrative plates.
[condition determination] elutriant: THF, post: TSKgel, flow: 1.0ml/min
Post: TSKgelG5432, detector: RI
(compatibility test)
Ester modified single tip type silicone polyvalent alcohol and the unmodified organopolysiloxane that on single end, has 2 primary hydroxyls in synthetic example 1, the relatively more synthetic example 1 are added 3 quality % in various polyvalent alcohols, placed 70 ℃ * 4 days, observe evaluation through visual.
(evaluation)
* *: upper strata has more than the parting liquid 3mm
*: the upper strata has more than the parting liquid 1mm and is lower than 3mm
Zero: do not separate
[table 2]
| Table 2 | Synthetic example 1 | Relatively more synthetic example 1 | Unmodified |
| PTMG molecular weight 1000 | ○ | × | × |
| BG/AA polyester polyol molecular weight 2000 | ○ | × | × |
| BGHG/AA polyester polyol molecular weight 2000 | ○ | × | × |
| 3MPD/AA polyester polyol molecular weight 2000 | ○ | × | × |
| Polycaprolactone polyol molecular weight 2000 | ○ | × | × |
| Polycarbonate polyol (HG skeleton) molecular weight 2000 | ○ | × | × |
PTMG: polytetramethylene glycol polyether glycol
The BG/AA polyester polyol: 1, the polyester polyol of 4-butyleneglycol and hexanodioic acid
The BGHG/AA polyester polyol: 1,4-butyleneglycol and 1, the polyester polyol of 6-pinakon and hexanodioic acid
3MPD/AA polyester polyol: 3-methyl isophthalic acid; The polyester polyol polycaprolactone polyol of 5-pentanediol and hexanodioic acid: with the 6-caprolactone addition polyester polyol polycarbonate polyol of terepthaloyl moietie as initiator: by 1, the polycarbonate polyol that 6-pinakon and methylcarbonate form is unmodified: the organopolysiloxane that on single end, has 2 primary hydroxyls
Embodiment 1 (prepolymer method)
(synthesizing of carbamate prepolymer)
In 2 liters of flasks, add 4; 4 '-diphenylmethanediisocyanate 483.0g; To mix as ester modified single tip type silicone polyvalent alcohol 16.7g in 6-caprolactone addition polyester polyol (molecular weight 2000) 1000g and synthetic routine 1 of initiator with terepthaloyl moietie; Under nitrogen atmosphere, under 70 ℃, carry out reaction in about 5 hours.Reach 525 mode by the NCO equivalent and add 4 of (adjustment) trace, 4 '-diphenylmethanediisocyanate or 6-caprolactone addition polyester polyol obtain containing the carbamate prepolymer of silicone.
(processing of urethane elastomers)
With temperature regulation become 80 ℃ the carbamate prepolymer 400g that contains silicone become with temperature regulation 50 ℃ 1; 70/30 (mass ratio) mixture 32.6g of 4-butyleneglycol/TriMethylolPropane(TMP) mixes; Be cast in the centrifugal shaper after it is solidified; Under 110 ℃ * 16 hours condition, carry out regelate, obtain the thick urethane elastomers sheet material of 2mm.
Embodiment 2 (single stage method)
(modulation of polyol blends)
Modulation is with ester modified single tip type silicone polyvalent alcohol 16.7g, 1 in 6-caprolactone addition polyester polyol (molecular weight 2000) 1000g, the synthetic example 1, and 70/30 (mass ratio) mixture 122.1g of 4-butyleneglycol/TriMethylolPropane(TMP) mixes the polyol blends that (70 ℃ * 10 minutes) form in 2 liters of flasks.
(processing of urethane elastomers)
With temperature regulation become 70 ℃ polyol blends 300g become with temperature regulation 60 ℃ 4; 4 '-diphenylmethanediisocyanate 127.2g mixes; Be cast in the centrifugal shaper after it is solidified; Under 110 ℃ * 16 hours condition, carry out regelate, obtain the thick urethane elastomers sheet material of 2mm.
Embodiment 3,5,7,9,11 (prepolymer method)
(synthesizing of carbamate prepolymer)
Prepolymer through with embodiment 1 synthesizes same operation, obtains the carbamate prepolymer of the prescription shown in the table 3.
[table 3]
MDI:4,4 '-diphenylmethanediisocyanate
(processing of urethane elastomers)
Through the operation same, obtain the thick urethane elastomers sheet material of 2mm of the prescription shown in the table 4 with the urethane elastomers of embodiment 1.Evaluation result is shown among the table 7-8.
[table 4]
Embodiment 4,6,8,10,12 (single stage method)
(modulation of polyol blends)
Through with the same operation of modulation of the polyol blends of embodiment 2, obtain the polyol blends of the prescription shown in the table 5.
[table 5]
(processing of urethane elastomers)
Through the operation same, obtain the thick urethane elastomers sheet material of 2mm of the prescription shown in the table 6 with the urethane elastomers of embodiment 2.Evaluation result is shown among the table 7-8.
[table 6]
MDI:4,4 ' diphenylmethanediisocyanate
(evaluation result)
[table 7]
[table 8]
In addition, evaluation method is described below.
< sheet material outward appearance (frosting) >
Through visual and refer to touch the sheet material state after 1 month after the moulding that reaches soon after the moulding of estimating.
Zero: do not have frosting.
△:, arrive oily matter through tactile finger recognition though can not judge through visual.
*: through visual and refer to touch (oily matter) frosting obviously takes place for both.
< tension stress, M100, M300, elongation >
The centrifugal forming sheet material is carried out punching press with No. 3 dumbbells, measure according to JIS K 7312.
Bit speed: 500mm/min
< tear strength >
The centrifugal forming sheet material is carried out punching press with non-incision dihedral dumbbell, measure according to JIS K 7312.
Bit speed: 500mm/min
< static friction coefficient, kinetic friction coefficient >
The centrifugal forming sheet material is finishing to carry out 2 all indoor keepings after 2 curing.Afterwards, be cut into 10 * 20cm and measuring the day before yesterday with the acetone thorough washing for several times sheet surface.
In the mensuration, measure static friction coefficient, the kinetic friction coefficient of centrifugal forming sheet material with surperficial trier.
Plane pressure head (the fixing anchor clamps of using of strap shape test film): 30 * 30mm, 84g
Determination object thing: OA common paper (being installed on the anchor clamps)/centrifugal forming sheet material
Increase the weight of: the 84g of plane pressure head (do not have force increase the weight of) only
Surface trier: Type-HEIDON-14 type (new eastern science Co., Ltd.)
< aggegation of Si atom >
The centrifugal forming sheet material is finishing to carry out 2 all indoor keepings after 2 curing.Afterwards measure the day before yesterday with sheet surface with the acetone thorough washing a few days.In the mensuration, utilize the SEM of sheet surface (the air contact surface during moulding) to carry out atom and distribute and estimate.
The Si atom occurs with circle with the position that peripheral specific concentration mutually uprises.Diameter through the high density position is judged.
Zero: do not have or diameter is lower than 1 μ m
△: diameter 1 μ m is above and be lower than 5 μ m
*: more than the diameter 5 μ m
Comparative example 1,3,5,7,9 (prepolymer method)
(synthesizing of carbamate prepolymer)
Prepolymer through with embodiment 1 synthesizes same operation, obtains the carbamate prepolymer of the prescription shown in the table 9.
[table 9]
MDI:4,4 '-diphenylmethanediisocyanate
(processing of urethane elastomers)
Through the operation same, obtain the thick urethane elastomers sheet material of 2mm of the prescription shown in the table 10 with the urethane elastomers of embodiment 1.Evaluation result is shown among the table 13-14.
[table 10]
Comparative example 2,4,6,8,10 (single stage method)
(modulation of polyol blends)
Through with the same operation of modulation of the polyol blends of embodiment 2, obtain the polyol blends of the prescription shown in the table 11.
[table 11]
(processing of urethane elastomers)
Through the operation same, obtain the thick urethane elastomers sheet material of 2mm of the prescription shown in the table 12 with the urethane elastomers of embodiment 2.Evaluation result is shown among the table 13-14.
[table 12]
MDI:4,4 '-diphenylmethanediisocyanate
(evaluation result)
[table 13]
[table 14]
HEIDON: surperficial trier
Comparative example 1,2 so friction resistance is big, can not get low frictional properties owing to do not add the silicone composition.Comparative example 3,4 so on sheet material, see frosting, in addition, occurs high circular position owing to observe the Si atomic percent in sheet surface with peripheral comparing owing to be not the silicone polyvalent alcohol of proper range, and so heterogeneity is not preferred.During especially for the cylinder of stamping machine, cleaning balde etc., owing to photoreceptor or print are polluted in frosting, if Si atomic percent inequality first cylinder, cleaning balde cause and collapse cutter (breach phenomenon), so not preferred.
In the comparative example 5～10 owing to used unmodified silicone, so because of the same reason of above-mentioned comparative example 3-4 not preferred.Particularly not anti-practicality in one-step moulding.
Utilizability on the industry
Polyurethane resin composition of the present invention can form the urethane cures thing of excellent performances such as frost-resistance, Si atom compendency, all rerum naturas, low frictional properties through the one-step moulding method and the prepolymer method of forming; So for example can be used for 3 dimension forming composition such as silk, film, sheet material, band, flexible pipe, cylinder, tire, packing, packing ring, sole, and many fields such as artificial leather, synthetic leather, soft/hard foam, filamentary material, Industrial materials, motor electronic material, optical material, medical material, civil construction material.
Claims (7)
1. polyurethane resin composition; It is characterized in that; It is the polyurethane resin composition that contains (A) polymeric polyisocyanate, (B) polyvalent alcohol; Wherein, Ester modified single tip type silicone polyvalent alcohol (B1) 0.01～5 quality % and other polyvalent alcohol (B2) 95～99.99 quality % in polyvalent alcohol (B) contains, said in ester modified single tip type silicone polyvalent alcohol (B1) have at single end on the above-mentioned hydroxyl of organopolysiloxane of 2 primary hydroxyls respectively that 5～10 moles of internal ester monomers of ring opening polyaddition obtain.
2. polyurethane resin composition according to claim 1, wherein, said other polyvalent alcohol (B2) is the polyvalent alcohol more than a kind that is selected from polyether glycol, the polyester polyol.
3. polyurethane resin composition according to claim 1, wherein, the molecular weight of said (B2) is 600～3000.
4. polyurethane resin composition according to claim 1, wherein, the molecular weight of said (B1) is 2500～6000.
5. polyurethane resin composition according to claim 1, wherein, said internal ester monomer is a 6-caprolactone.
6. polyurethane resin composition according to claim 1, wherein, said in ester modified single tip type silicone polyvalent alcohol (B1) be 8 moles of internal ester monomers of per 1 primary hydroxyl addition of organopolysiloxane and the polyvalent alcohol that obtains.
7. a forming composition is characterized in that, it is obtained by each described polyurethane resin composition in the claim 1～6.
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| JP2010-181662 | 2010-08-16 | ||
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| PCT/JP2011/065768 WO2012023358A1 (en) | 2010-08-16 | 2011-07-11 | Polyurethane resin composition and molded article thereof |
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| CN104945588A (en) * | 2015-06-25 | 2015-09-30 | 安徽志诚机电零部件有限公司 | Foaming technology for soft polyurethane film |
| CN110194827A (en) * | 2018-02-26 | 2019-09-03 | 信越化学工业株式会社 | Silicon-containing compound, carbamate resins, retractility film and forming method thereof |
| CN112513126A (en) * | 2018-07-25 | 2021-03-16 | 东曹株式会社 | Allophanate group-containing polyisocyanate composition, urethane resin-forming composition, sealing material, and film assembly |
| CN112533992A (en) * | 2018-08-03 | 2021-03-19 | 艾维恩股份有限公司 | Bloomless thermoplastic polyurethane compounds and thermoplastic articles molded therefrom |
| CN114206968A (en) * | 2019-08-05 | 2022-03-18 | 路博润先进材料公司 | Thermoplastic polyurethanes and process for preparing thermoplastic polyurethanes and components thereof |
| CN114206970A (en) * | 2019-08-05 | 2022-03-18 | 路博润先进材料公司 | Thermoplastic polyurethanes containing polysiloxane caprolactone polyols |
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| CN111108244B (en) * | 2017-09-19 | 2023-03-07 | Dic株式会社 | Synthetic leather |
| KR102027574B1 (en) * | 2018-03-09 | 2019-10-01 | 에스케이씨 주식회사 | Composition for potting material |
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| KR102651984B1 (en) * | 2021-12-14 | 2024-03-29 | 주식회사 비엔엘테크 | Multifunctional silicone-modified urethane adhesive having minimal carbide with minimal change in optical properties and high-functional protective film for OLED and optical materials using the same |
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| CN104945588A (en) * | 2015-06-25 | 2015-09-30 | 安徽志诚机电零部件有限公司 | Foaming technology for soft polyurethane film |
| CN110194827A (en) * | 2018-02-26 | 2019-09-03 | 信越化学工业株式会社 | Silicon-containing compound, carbamate resins, retractility film and forming method thereof |
| CN110194827B (en) * | 2018-02-26 | 2021-09-10 | 信越化学工业株式会社 | Silicon-containing compound, urethane resin, stretchable film, and method for forming same |
| CN112513126A (en) * | 2018-07-25 | 2021-03-16 | 东曹株式会社 | Allophanate group-containing polyisocyanate composition, urethane resin-forming composition, sealing material, and film assembly |
| CN112513126B (en) * | 2018-07-25 | 2023-08-08 | 东曹株式会社 | Allophanate group-containing polyisocyanate composition, polyurethane resin-forming composition, sealing material, and film module |
| CN112533992A (en) * | 2018-08-03 | 2021-03-19 | 艾维恩股份有限公司 | Bloomless thermoplastic polyurethane compounds and thermoplastic articles molded therefrom |
| CN114206968A (en) * | 2019-08-05 | 2022-03-18 | 路博润先进材料公司 | Thermoplastic polyurethanes and process for preparing thermoplastic polyurethanes and components thereof |
| CN114206970A (en) * | 2019-08-05 | 2022-03-18 | 路博润先进材料公司 | Thermoplastic polyurethanes containing polysiloxane caprolactone polyols |
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| TWI454527B (en) | 2014-10-01 |
| JPWO2012023358A1 (en) | 2013-10-28 |
| JP5019011B2 (en) | 2012-09-05 |
| TW201211155A (en) | 2012-03-16 |
| KR101694237B1 (en) | 2017-01-09 |
| WO2012023358A1 (en) | 2012-02-23 |
| KR20130098849A (en) | 2013-09-05 |
| CN102753595B (en) | 2014-04-30 |
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