CN103459462A - Method for producing polyester polyol, method for producing modified polyester, polyester polyol and modified polyester - Google Patents
Method for producing polyester polyol, method for producing modified polyester, polyester polyol and modified polyester Download PDFInfo
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- CN103459462A CN103459462A CN2012800166542A CN201280016654A CN103459462A CN 103459462 A CN103459462 A CN 103459462A CN 2012800166542 A CN2012800166542 A CN 2012800166542A CN 201280016654 A CN201280016654 A CN 201280016654A CN 103459462 A CN103459462 A CN 103459462A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
- C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
- C08J11/24—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds containing hydroxyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/16—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with inorganic material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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Abstract
Provided is a method by which a polyester polyol can be produced by depolymerizing a starting material polyester within a short time without using a tin-based metal catalyst. The method for producing the polyester polyol is characterized by comprising a step wherein a starting material polyester is depolymerized by heating a mixture that contains, as essential ingredients, the starting material polyester, a polyol component, and a non-tin-based metal catalyst or a non-metal basic catalyst. It is preferable that the non-tin-based metal catalyst is a compound that is selected from the group consisting of zinc compounds, manganese compounds, lithium compounds and calcium compounds.
Description
Technical field
The polyester polyol that to the present invention relates to take polyester be raw material and manufacture method, polyester polyol and the polyester modification thing of polyester modification thing, the manufacture method of the polyester modification thing of the polyester polyol modification that is specifically related to not use the manufacture method and making of the polyester polyol of tin metalloid catalyzer to be obtained by this manufacture method.
Background technology
The polyester that the polyethylene terephthalate (PET) of take is representative is used in the various uses such as products formed, film, fiber.Wherein, in recent years, because PET bottle amount is light and transparent, gas barrier property is excellent, intensity is also high, so consumption just sharply increases.
On the other hand, carried out following technology: utilize polyvalent alcohol depolymerization polyester to manufacture polyester polyol or to make this polyester polyol modification and derive various resins.
For example, disclose the coating that utilizes the depolymerization reaction based on the glycols manufacture of Synolac in patent documentation 1, disclose the coating that the uses recycled polyester manufacture method of vibrin in patent documentation 2 and 3, disclose in patent documentation 4 and utilize the raw material of recycled polyester as the light solidified urethane resin.The resin of above-mentioned patent documentation record all take that to use in coating composition be purpose.
All the time, the depolymerization reaction of polyester is by reactor that raw material polyester and polyvalent alcohol, depolymerization catalyzer are packed into, and heating is carried out.Now, as the depolymerization catalyzer, use metal catalyst, especially tin class catalyzer.
the prior art document
patent documentation
Patent documentation 1: No. 3310661st, Japan's special permission
Patent documentation 2: No. 3443409th, Japan's special permission
Patent documentation 3: No. 3256537th, Japan's special permission
Patent documentation 4: TOHKEMY 2004-307779 communique
Summary of the invention
the problem that invention will solve
Yet, there is report to point out the particularly toxicity of organic tin compound to organism of tin compound, also pointed out the impact on environment.Therefore, seeking can to replace the exploitation of the catalyzer of tin metalloid catalyzer in the depolymerization reaction of polyester.
Therefore, the object of the present invention is to provide a kind of do not use tin metalloid catalyzer and at short notice depolymerization raw material polyester to manufacture the method for polyester polyol.
for the scheme of dealing with problems
For addressing the above problem, the inventor etc. conduct in-depth research, and found that, by using non-tin metalloid catalyzer or non-metal kind basic catalyst, can address the above problem, and have so far completed the present invention.
; the manufacture method of polyester polyol of the present invention; it is characterized in that possessing and heated the operation with depolymerization raw material polyester to containing raw material polyester, polyhydroxy reactant and non-tin metalloid catalyzer or non-metal kind basic catalyst as the mixture of neccessary composition.
In the manufacture method of polyester polyol of the present invention, preferably above-mentioned non-tin metalloid catalyzer is the compound in the group of selecting free zn cpds, manganic compound, lithium compound and calcium cpd to form, is more preferably the compound in the group of selecting free naphthenic acid metal complex, acetylacetone metal complex and sad metallic soap to form.
And, in the manufacture method of polyester polyol of the present invention, preferably above-mentioned non-tin metalloid catalyzer is the compound in the group of selecting free zinc naphthenate, zinc acetylacetonate, zinc octoate, calcium naphthenate, calcium acetylacetonate, calcium octoate, naphthenic acid lithium, methyl ethyl diketone lithium, sad lithium, Lithium Acetate, manganese naphthenate, manganese acetylacetonate and manganese octoate to form.
In the manufacture method of polyester polyol of the present invention, preferred above-mentioned non-metal kind basic catalyst is the hetero ring type compound with amidine structure.
In the manufacture method of polyester polyol of the present invention, preferred above-mentioned non-metal kind basic catalyst is more than one in the group of selecting free diazabicycloundecene, diazabicyclo-nonene and their derivative to form.
In addition, in the manufacture method of polyester polyol of the present invention, preferred above-mentioned polyhydroxy reactant comprises the above polyvalent alcohol of trifunctional.
In addition, in the manufacture method of polyester polyol of the present invention, preferably the above-mentioned raw materials polyester is recycled polyester.
In addition, in the manufacture method of polyester polyol of the present invention, preferably to containing in raw material polyester, polyhydroxy reactant and the mixture of non-tin metalloid catalyzer as neccessary composition, add water, to carry out the depolymerization of raw material polyester.
In addition, in the manufacture method of polyester polyol of the present invention, preferred above-mentioned depolymerization is carried out under 200 ℃～300 ℃.
In addition, in the manufacture method of polyester polyol of the present invention, preferably obtain the mixture of compound shown in following general formula (1).
(in formula, R
1the group of OH base, R are removed in expression from the polyvalent alcohol of (1+m) valency
2mean the alkylidene group of carbonatoms 1～10 or the arylidene of replacement or unsubstituted carbonatoms 6～20, R
3mean to replace or the arylidene of unsubstituted carbonatoms 6～20, l is that 0～10 integer, m are 1～10 integers, and n is 1～10 integer.）
Polyester polyol of the present invention is characterised in that, described polyester polyol obtains by the manufacture method of above-mentioned any polyester polyol.
The manufacture method of polyester modification thing of the present invention is characterised in that, makes to have to react with the polyester polyol that the compound of the group of hydroxyl reaction and ethylenically unsaturated group obtains with manufacture method by above-mentioned polyester polyol.
Polyester modification thing of the present invention is characterised in that, described polyester modification thing obtains by the manufacture method of above-mentioned polyester modification thing.
the effect of invention
According to the manufacture method of polyester polyol of the present invention, do not use tin metalloid catalyzer and the raw material polyester can be dissolved in easily in organic solvent to convert the polyester polyol that can carry out various chemical modifications to.Based on this, with the polyester polyol that uses the existing method of utilizing tin class catalyzer to make, compare, can access the polyester polyol that tin content reduces.In addition, in the situation that used nonmetal basic catalyst, the electrical insulating property that can avoid the impact because of kish catalyzer in products obtained therefrom to cause deteriorated.
And, according to the present invention, high efficiency ground is manufactured and has been given photosensitive polyester modification thing at lower cost.
Embodiment
The essential characteristic of the manufacture method of polyester polyol of the present invention is, uses non-tin metalloid catalyzer or non-metal kind basic catalyst when utilizing polyhydroxy reactant depolymerization raw material polyester.
［ non-tin metalloid catalyzer ］
As the non-tin metalloid catalyzer used in method of the present invention, preferred zn cpds, manganic compound, lithium compound, calcium cpd, more preferably naphthenic acid metal complex, acetylacetone metal complex, sad metallic soap.Wherein, particularly preferably zinc naphthenate, zinc acetylacetonate, zinc octoate, calcium naphthenate, calcium acetylacetonate, calcium octoate, naphthenic acid lithium, methyl ethyl diketone lithium, sad lithium, Lithium Acetate, manganese naphthenate, manganese acetylacetonate and manganese octoate.
With respect to total amount 100 mass parts of raw material polyester and polyhydroxy reactant, consumption part of above-mentioned non-tin metalloid catalyzer is preferably 0.005～5 mass parts, more preferably 0.05～3 mass parts.
［ non-metal kind basic catalyst ］
As the non-metal kind basic catalyst used in method of the present invention, preferred cyclic nitrogen compound, the hetero ring type compound that more preferably there is the amidine structure.Wherein, particularly preferably diazabicycloundecene (1,8-diazabicylo [5.4.0], 11 carbon-7-alkene, below also referred to as " DBU "), diazabicyclo-nonene (1,5-diazabicylo [4.3.0] nonene-5, below also referred to as " DBN ") and derivative.DBU and DBN are the organic alkali groups, and structural similitude is the compound that the catalyzer of the identical reaction such as ammonia esterification, Wittig reaction is used.
As diazabicycloundecene (DBU), diazabicyclo-nonene (DBN) and their derivative, for example, can list: DBU, DBN, DBU carbonate, DBU carboxylate salt, DBU phenolate, DBU thiolate, DBN carbonate, DBN carboxylate salt, DBN phenolate, DBN thiolate.
Commercially available product as DBU, DBN and their derivative, for example, can list: U-CAT SA1, U-CAT SA102, U-CAT SA506, U-CAT SA603, U-CAT SA810, U-CAT SA831, U-CAT SA841, U-CAT SA851, U-CAT881, the above trade(brand)name of U-CAT5002(are San-Apro Ltd. system).
With respect to total amount 100 mass parts of raw material polyester and polyhydroxy reactant, the consumption of above-mentioned non-metal kind basic catalyst is 0.005～5 mass parts preferably, more preferably 0.05～3 mass parts.
［ raw material polyester ］
The raw material polyester used in method of the present invention so long as known polyester be not particularly limited.As long as can carry out melting by heating, any polyester all is applicable to method of the present invention.
In addition, as the raw material polyester, preferably there is the polyester of repeating unit shown in following general formula (2).
(in formula, R
4mean the alkylidene group of carbonatoms 1～10 or the arylidene of replacement or unsubstituted carbonatoms 6～20, R
5the arylidene, the O that mean replacement or unsubstituted carbonatoms 6～20 mean the integer more than 1.）
As R in above-mentioned general formula (2)
4the alkylidene group of represented carbon number 1～10, can list methylene radical, ethylene, trimethylene, tetramethylene, 1,2-butylidene, pentamethylene etc.
As R in above-mentioned general formula (2)
4the arylidene of represented carbon number 6～20, can list Isosorbide-5-Nitrae-phenylene, 2,6-naphthylidene etc.These arylidene can be by replacements such as alkyl, alkoxyl group, halogen atoms.
As R in above-mentioned general formula (2)
5the arylidene of represented carbon number 6～20, can list and above-mentioned R
4the group that the group of example is identical.
Object lesson as preferred raw material polyester, can list the polycondensate, 4 of polyethylene terephthalate (PET), Poly(Trimethylene Terephthalate), polybutylene terephthalate, PEN, PBN, ethylene glycol terephthalate and P-hydroxybenzoic acid, the polycondensate of 4-dihydroxybiphenyl phenol and terephthalic acid and P-hydroxybenzoic acid, 2, the liquid crystalline polymerss such as the polycondensate of 6-hydroxynaphthoic acid and P-hydroxybenzoic acid etc.In the middle of above-mentioned, polyethylene terephthalate particularly preferably.
In addition, from the angle of environment protection, consider, the recirculation PET that more preferably will be reclaimed by Plastic Bottle rejected material the like waste and regenerative PET are as the raw material polyester.The PET be recovered is pulverized and washing, regenerative PET are washed and the material of particle (pellet) after changing can obtain from the market.
［ polyhydroxy reactant ］
As above-mentioned polyhydroxy reactant, be not particularly limited, can use two sense polyvalent alcohols, the above polyvalent alcohol of trifunctional etc.Above-mentioned polyhydroxy reactant can be used separately a kind of, also can be used in combination.
As two sense polyvalent alcohols, can list: ethylene glycol, 1,3-PD, 1,2-PD, BDO, Diethylene Glycol, triethylene glycol, polyoxyethylene glycol, dipropylene glycol, 1,3 butylene glycol, neopentyl glycol, the spiroglycol, the diox glycol, the diamantane glycol, the 3-methyl isophthalic acid, the 5-pentanediol, the methyl ethohexadiol, 1,6-hexylene glycol, 1,4 cyclohexane dimethanol, 2-methyl propanediol 1,3, 3-methyl pentanediol 1,5, hexamethylene glycol, ethohexadiol, the 9-nonanediol, 2,4-diethyl-1,5-PD, the oxyethane modified compound of the two sense phenol that dihydroxyphenyl propane is such, the epoxy pronane modification compound of the two sense phenol that dihydroxyphenyl propane is such, the oxyethane of dihydroxyphenyl propane, propylene oxide modification by copolymerization compound, the Copolymer polyether glycol of oxyethane and propylene oxide, polycarbonate diol, polyether glycol, polyester glycol, polycaprolactone glycol, Isosorbide-5-Nitrae-polyisoprene glycol, the 1，4-polybutadiene glycol, 1,2-polybutadiene diol, Isosorbide-5-Nitrae-or so poly-alkane two enediols (polyalkanedienediol) class of C-terminal of the hydrogenation products of 1,2-polybutadiene diol.
Example as the commercially available product of above-mentioned polycaprolactone glycol, for example, can list: Placcel205, Placcel L205AL, Placcel205U, Placcel208, Placcel L208AL, Placcel210, Placcel210N, Placcel212, Placcel L212AL, Placcel220, Placcel220N, Placcel220NP1, Placcel L220AL, Placcel230, Placcel240, Placcel220EB, be Daicel chemical industry (strain) system more than Placcel220EC().
Gather the example of the commercially available product of alkane two enediols as above-mentioned C-terminal, for example, can list エ Port ー Le (registered trademark; Hydrogenated polyisoprene glycol, molecular weight 1860, mean polymerisation degree 26, the emerging product of bright dipping (strain) system), PIP(polyisoprene glycol, molecular weight 2200, mean polymerisation degree 34, the emerging product of bright dipping (strain) system), Port リ テ ー Le H(hydrogenated butadiene polymer glycol, molecular weight 2200, mean polymerisation degree 39, Mitsubishi Chemical's (strain) system), R-45HT(polytetramethylene glycol, molecular weight 2270, mean polymerisation degree 42, the emerging product of bright dipping (strain) system).
As the polyvalent alcohol more than trifunctional, can list: glycerine, trimethylolethane, TriMethylolPropane(TMP), Sorbitol Powder, tetramethylolmethane, two TriMethylolPropane(TMP)s, Dipentaerythritol, tripentaerythritol, diamantane triol, polycaprolactonetriol etc.In addition, as the polyvalent alcohol more than the trifunctional with aromatic nucleus, can list the oxyethane, epoxy pronane modification thing of the above phenolic compound of trifunctional etc., as the polyvalent alcohol more than the trifunctional that contains heterocycle, can list four countries and change into industry (strain) THEIC processed etc.
Example as the commercially available product of above-mentioned polycaprolactonetriol, for example, can list: Placcel303, Placcel305, Placcel308, Placcel312, Placcel L312AL, Placcel320ML, PlaccelL320AL (more than be Daicel chemical industry (strain) system, trade(brand)name).
As polyhydroxy reactant, can use the pure composition (from the polyvalent alcohol of plant) from plant.As the pure composition from plant, preferred castor seeds oils alcohol composition.As commercially available product, for example, can list: URIC H-30, URIC H-31, URIC H-52, URIC H-56, URIC H-57, URIC H-62, URIC H-73X, URIC H-92, URIC H-420, URIC H-854, URIC Y-202, URIC Y-403, URIC Y-406, URIC Y-563, URIC AC-005, URIC AC-006, URIC PH-5001, URIC PH-5002, URIC PH-6000, URIC F-15, URIC F-25, URIC F-29, URIC F-40, URIC SE-2010, URIC SE-3510, URIC SE-2606, URIC SE-3506, URIC SE-2003, POLYCASTOR#10, POLYCASTOR#30, URIC SE-2003(is her rattan liquefaction company system).
The polyhydroxy reactant used in the present invention preferably contains the above polyvalent alcohol of trifunctional, particularly preferably contains TriMethylolPropane(TMP).
The consumption of above-mentioned polyhydroxy reactant is with respect to 1 mole of the ester bond of raw material polyester, and the hydroxyl of preferred polyol composition is 0.5 mole～7.0 moles, more preferably 1.0 moles～5.0 moles.
［ reaction conditions ］
In the method for the invention, the mixture that will contain above-mentioned each composition reactor of packing into, and heating, thus carry out the depolymerization of raw material polyester.Heating means can be used existing known method.Can mix above-mentioned each composition, reheat after being modulated into mixture, also can the limit heating edge successively each composition be imported to reactor.Preferably 150～350 ℃ of Heating temperatures, more preferably 200～300 ℃.In addition, in the time of with an organic solvent, although can use existing known solvent, from the angle of the impact on environment, consider, preferably in the situation that with an organic solvent do not reacted.
In method of the present invention, preferably in containing raw material polyester, polyhydroxy reactant and the mixture of non-tin metalloid catalyzer as neccessary composition, add water, to carry out the depolymerization of raw material polyester.By adding water, can make polyester, polyvalent alcohol as raw material become pulp-like, stirring efficiency improves, therefore preferably.
In the manufacture method of polyester polyol of the present invention, preferably obtain the mixture of compound shown in following general formula (1).
(in formula, R
1the group of OH base, R are removed in expression from the polyvalent alcohol of (1+m) valency
2mean the alkylidene group of carbonatoms 1～10 or the arylidene of replacement or unsubstituted carbonatoms 6～20, R
3mean to replace or the arylidene of unsubstituted carbonatoms 6～20, l is that 0～10 integer, m are 1～10 integers, and n is 1～10 integer.）
Although the R in above-mentioned general formula (1)
1the group of OH base is removed in expression from the polyvalent alcohol of (1+m) valency, but, as this polyvalent alcohol, can list above-mentioned two sense polyvalent alcohols, the above illustrated group of polyvalent alcohol of trifunctional.In addition, R
2represented alkylidene group, arylidene, R
3represented arylidene can list the group identical with above-mentioned group.
Compound shown in above-mentioned general formula (1) is the starting material that are applicable to the manufacture method of polyester modification thing of the present invention.
［ manufacture method of polyester modification thing ］
The manufacture method of polyester modification thing of the present invention is characterised in that, makes to have to react with the polyester polyol that the compound of the group of hydroxyl reaction and ethylenically unsaturated group obtains with manufacture method by above-mentioned polyester polyol.By this modification, can give polyester photosensitivity.The modified-reaction of polyester polyol is identical with existing known esterification, exists or does not exist under the condition of organic solvent, usually, adds acid catalyst, stopper, preferably in the temperature range of 80 ℃～130 ℃, carries out 2 hours to 10 hours.At normal pressure or add depress synthetic can, in the situation that pressurization can reduce temperature of reaction.And, even there is the unreacted hydroxyl from depolymerizing substance in the polyester modification thing obtained, also no problem on characteristic.
［ have can with the group of hydroxyl reaction and the compound of ethylenically unsaturated group ］
The compound that the modification of the polyester polyol obtained in above-mentioned manufacture method is used be in a part, have can with the group of hydroxyl reaction and the compound of ethylenically unsaturated group.Preferably can have 1 with the group of hydroxyl reaction in molecule, ethylenically unsaturated group has more than 1 in molecule.As above-mentioned can with the group of hydroxyl reaction, can list ring-type ether, the hydroxyls etc. such as carboxyl, isocyanate group, epoxy group(ing).
So long as in a part, have can with the group of hydroxyl reaction and the compound of ethylenically unsaturated group; just can be used in the modification of the polyester polyol that above-mentioned manufacture method obtains; therefore; be not particularly limited; but consider particularly preferably there is the compound of acryl or methacryloyl from the viewpoints such as reactivity with above-mentioned polyester polyol.
Compound as having 1 carboxyl and 1 above ethylenically unsaturated group can list: half ester (half ester) compound etc. that has (methyl) esters of acrylic acid of 1 hydroxyl in vinylformic acid, acrylic acid dimer, methacrylic acid, β-styrene acrylic, β-furfuryl group vinylformic acid, β-crotonic acid, alpha-cyano styracin, styracin, (methyl) vinylformic acid caprolactone affixture and saturated or unsaturated dicarboxylic acid anhydride and a part.As (methyl) esters of acrylic acid with hydroxyl for the manufacture of half ester cpds, for example, can list: (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) vinylformic acid hydroxy butyl ester, TriMethylolPropane(TMP) two (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, (methyl) vinylformic acid phenyl glycidyl ester etc.As the dibasic acid anhydride for the manufacture of half ester cpds, for example, can list: succinyl oxide, maleic anhydride, Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl carbic anhydride (methyl endo methylene tetrahydrophthalic anhydride) etc.These compounds can be used separately a kind of, also can be used in combination.
In addition, in this manual, (methyl) acrylate refers to the term of having summed up acrylate, methacrylic ester and their mixture, and other are similarly explained too.
As in a part with the compound of 1 isocyanate group and 1 above ethylenically unsaturated group; for example, can list: (methyl) acryl oxygen base ethyl isocyanate, (methyl) acryl oxygen base oxethyl ethyl isocyanate, two (acryloyl-oxy ylmethyl) ethyl isocyanates or their modifier etc.In addition, also can use half urethane compound of the vulcabond such as the compound that there is 1 hydroxyl and 1 above ethylenically unsaturated group in a part and isophorone diisocyanate, tolylene diisocyanate, tetramethylxylene diisocyanate, hexamethylene diisocyanate.These compounds can be used separately a kind of, also can be used in combination.
As the above-mentioned commercially available product that has the compound of 1 isocyanate group and 1 above ethylenically unsaturated group in a part concurrently, commercially available have " Karenz MOI " (methacryloyl oxygen base ethyl isocyanate) clear and that electrician's (strain) provides, " Karenz AOI " (acryl oxygen base oxethyl ethyl isocyanate), " Karenz MOI-EG " (methacryloyl oxygen base oxethyl ethyl isocyanate), " Karenz MOI-BM " (isocyanate-terminated body of Karenz MOI), " Karenz MOI-BP " (isocyanate-terminated body of Karenz MOI), " Karenz BEI " (1, two (acryloyl-oxy ylmethyl) ethyl isocyanates of 1-).In addition, these trade(brand)names are registered trademark.
As the compound that has 1 ring-type ether and 1 above ethylenically unsaturated group in a part concurrently, can list: (methyl) vinylformic acid 2-hydroxyl ethyl ester glycidyl ether, (methyl) vinylformic acid 2-hydroxypropyl acrylate glycidyl ether, (methyl) vinylformic acid 3-hydroxypropyl acrylate glycidyl ether, (methyl) vinylformic acid 2-hydroxy butyl ester glycidyl ether, (methyl) vinylformic acid 4-hydroxy butyl ester glycidyl ether, (methyl) vinylformic acid 2-hydroxyl peopentyl ester glycidyl ether, the own ester glycidyl ether of (methyl) vinylformic acid 6-hydroxyl or (methyl) glycidyl acrylate, 3, 4-epoxycyclohexyl methacrylic ester etc.These compounds can be used separately a kind of, also can be used in combination.
As the above-mentioned compound with hydroxyl and ethylenically unsaturated group, so long as there is the compound of 1 hydroxyl and 1 above ethylenically unsaturated group in a part, be not particularly limited.As object lesson, can list hydroxyalkyl (methyl) acrylate such as (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) vinylformic acid hydroxy butyl ester, TriMethylolPropane(TMP) two (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, Dipentaerythritol five (methyl) acrylate.These compounds can be used separately a kind of, also can be used in combination.
The polyester modification thing of manufacture method manufacture of the present invention is can react to carry out chemical modification with above-mentioned polyester polyol with the group of hydroxyl reaction and the compound of 1 above ethylenically unsaturated group by making to have, thereby given photosensitive photosensitive compounds, therefore, the photosensitivity composition as Photocurable resin composition or light solidifying/heat solidifying resin composition is useful.For example; by compounding oxime ester class Photoepolymerizationinitiater initiater, alpha-aminoacetophenone class Photoepolymerizationinitiater initiater, acylphosphine oxide class Photoepolymerizationinitiater initiater, bitter almond oil camphor compound, acetophenone compound, anthraquinone compounds, thioxanthone compound, ketal compound, benzophenone cpd, xanthone compound, tertiary amine compound etc. in the polyester modification thing above-mentioned existing known Photoepolymerizationinitiater initiater commonly used, light-initiated auxiliary agent and sensitizing agent, thereby can access Photocurable resin composition.
Embodiment
Embodiment and comparative example below are shown so that the present invention is specifically described, but the invention is not restricted to following embodiment.In addition, " part " of putting down in writing below reaches " % " and is unless otherwise noted quality criteria.
［ embodiment 1 ］
To pack in the removable flask of four-hole round bottom of the 500ml that agitator, nitrogen ingress pipe, prolong are installed PET sheet 192 parts of (Mitsubishi Chemical Ind's system: the Novapex(trade(brand)name)), 67 parts of TriMethylolPropane(TMP)s, 0.52 part of zinc octoate, after being nitrogen atmosphere in flask, immerse the oil bath that has been warming up to 220 ℃, sustained reaction until be transparent in flask, has obtained polyester oligomer.
［ embodiment 2 ］
Replace the zinc octoate of embodiment 1 with the zinc acetylacetonate of same amount, obtain polyester oligomer.
［ embodiment 3 ］
Replace the zinc octoate of embodiment 1 with the calcium acetylacetonate of same amount, obtain polyester oligomer.
［ embodiment 4 ］
Replace the zinc octoate of embodiment 1 with the methyl ethyl diketone lithium of same amount, obtain polyester oligomer.
［ embodiment 5 ］
Replace the zinc octoate of embodiment 1 with the zinc naphthenate of same amount, obtain polyester oligomer.
［ embodiment 6 ］
Replace the zinc octoate of embodiment 1 with the calcium naphthenate of same amount, obtain polyester oligomer.
［ embodiment 7 ］
Replace the zinc octoate of embodiment 1 with the calcium octoate of same amount, obtain polyester oligomer.
［ embodiment 8 ］
Replace the zinc octoate of embodiment 1 with the naphthenic acid lithium of same amount, obtain polyester oligomer.
［ embodiment 9 ］
Replace the zinc octoate of embodiment 1 with the sad lithium of same amount, obtain polyester oligomer.
［ embodiment 10 ］
Replace the zinc octoate of embodiment 1 with the manganese naphthenate of same amount, obtain polyester oligomer.
［ embodiment 11 ］
Replace the zinc octoate of embodiment 1 with the manganese acetylacetonate of same amount, obtain polyester oligomer.
［ embodiment 12 ］
Replace the zinc octoate of embodiment 1 with the manganese octoate of same amount, obtain polyester oligomer.
［ embodiment 13 ］
Replace the zinc octoate of embodiment 1 with the Lithium Acetate of same amount, obtain polyester oligomer.
［ embodiment 14 ］
1.87 parts of 187 parts, 225 parts of polyester oligomers, vinylformic acid, tosic acid, 1.50 parts of p methoxy phenols that the embodiment 2 that packs in the removable flask of four-hole round bottom of the 500ml that agitator, nitrogen ingress pipe, prolong are installed obtains, and stirred, after it is dissolved equably, immerse the oil bath be warming up to 118 ℃, and sustained reaction 16.5 hours.After reaction finishes, the acid number of assaying reaction liquid, to add the alkaline aqueous solution of acid equivalent in flask, neutralized.Then, add salt solution (20wt%), stirred.Then, solution is moved to separating funnel, and add the methyl iso-butyl ketone (MIBK) of 1.4 times of reaction solutions, give up water.Again clean oil phase with salt solution (5wt%), give up water.Then, in hexane, after the redeposition oil phase, make it be dissolved in methyl ethyl ketone, by suction filtration, remove impurity.After again precipitating filtrate with tap water, give up supernatant liquor, with tap water, further stir, wash the redeposition thing, finally with carbitol acetate, be diluted to solids component 70%, obtain acrylate resin varnish.
［ comparative example 1 ］
Replace the zinc octoate of embodiment 1 with the Dibutyltin oxide of same amount, obtain polyester oligomer.
［ comparative example 2 ］
Replace the zinc octoate of embodiment 1 with the dibutyl tin laurate of same amount, obtain polyester oligomer.
<depolymerization time>
The needed time of depolymerization of embodiment 1～13 and comparative example 1,2 as described in Table 1.Even carry out more than 10 hours reaction, raw material also residual situation is designated as " * ".
<Wuxi (tin free)>
Measured the concentration (ppm) of the tin that the depolymerizing substance of embodiment 1～13 and comparative example 1,2 comprises.The record method of estimating is as follows.
Zero: the not enough 10ppm of the concentration of tin
△: the concentration of tin is 10ppm～500ppm
*: the concentration of tin surpasses 500ppm
<molecular weight>
Use the GPC(gel permeation chromatography) measure the molecular weight of the depolymerizing substance of embodiment 1～13 and comparative example 1.Condition determination is: use the Shodex GPC KF-806L of clear and electrician's (strain) system * 3 as post, and use under 40 ℃ of column temperatures.The Application standard polystyrene is as primary standard, and elutriant is used tetrahydrofuran (THF) for the flow velocity divided with 1ml/.Measurement result is shown in following table 1.
The test of<solvent solubility>
Confirmed the solvent solubility of the depolymerizing substance of embodiment 1～13 and comparative example 1,2.
Confirmation method is, with respect to 50 parts of depolymerizing substances, adds 50 parts of all kinds of SOLVENTS, stirs, and makes the 50wt% solution of depolymerizing substance, estimates the transparency of its solution.The record method of estimating is as follows.
Fully transparent: zero
Muddiness: △ is slightly arranged
Muddy: *
[table 1]
Can be confirmed, for solvent solubility, with 2 pairs of each solvents of comparative example, have muddiness to compare by above, embodiment is all identical with stanniferous comparative example 1, fully transparent to each solvent.
［ reference example 1 ］
Make 100 parts, the acrylate resin varnish and the 5 parts of Photoepolymerizationinitiater initiater (Irgacure184 that obtain in above-described embodiment 14; BASF Japanese firm system), after mixing, use applicator to be coated with in the mode of thickness 20 μ m on sheet glass.After coating, in the hot-blast circulation dry furnace of 80 ℃, drying is 20 minutes, uses the exposure apparatus that is equipped with high voltage mercury lamp, with 1J/cm
2exposure exposed, obtain estimating and film.
<rub(bing)test>
The rag that contains acetone in use is filmed friction 50 times the time to above-mentioned evaluation, and surface, without dissolving, can be confirmed fully to solidify.
<pencil hardness test>
The pencil from B to 9H polished with the front end of pencil-lead, the angle that is 45 degree to film with respect to above-mentioned evaluation applies 1kg and loads and press to filming.Under the state that has applied this load, to the about 1cm of the delineation of filming left and right, measure tack-free pencil hardness of filming, result is 6H.
<thermal test>
Above-mentioned evaluation is filmed in the hot-blast circulation dry furnace that drops into 200 ℃, heat 3 minutes.Take out after heating, by the sign of visual observation melting, to carry out thermal test, now confirm to there is the thermotolerance of 3 minutes under 200 ℃.
As mentioned above, the method according to this invention, by using non-tin metalloid catalyzer, polyester can be dissolved in to organic solvent easily, convert to can various chemical modifications polyester polyol.
［ embodiment 15 ］
67 parts of 192 parts of recirculation PET sheets, TriMethylolPropane(TMP)s, DBU0.52 part that the IV value of packing in the removable flask of four-hole round bottom of the 500ml that agitator, nitrogen ingress pipe, prolong are installed is (inherent viscosity) 0.6～0.7, be nitrogen atmosphere in flask after, immerse in the oil bath that has been warming up to 220 ℃, sustained reaction, until be transparent in flask, obtain polyester oligomer.
［ embodiment 16 ］
In the removable flask of four-hole round bottom of the 500ml that agitator, nitrogen ingress pipe, prolong are installed, pack into 192 parts of PET sheets (company of Mitsubishi system: the Novapex(trade(brand)name)), 67 parts of TriMethylolPropane(TMP)s, DBU0.52 part, be nitrogen atmosphere in flask after, immerse in the oil bath that has been warming up to 220 ℃, sustained reaction, until be transparent in flask, obtain polyester oligomer.
［ embodiment 17 ］
30 parts, 67 parts of 192 parts of recirculation PET sheets, TriMethylolPropane(TMP)s, DBU0.52 part, water that the IV value of packing in the removable flask of four-hole round bottom of agitator, nitrogen ingress pipe, prolong 500ml is installed is 0.6～0.7, be nitrogen atmosphere in flask after, immerse in the oil bath that has been warming up to 180 ℃, on one side slowly except anhydrating, oil bath is warming up to 220 ℃ on one side, sustained reaction, until be transparent in flask, obtain polyester oligomer.
［ embodiment 18 ］
30 parts, 68 parts of 67 parts of 192 parts of recirculation PET sheets, TriMethylolPropane(TMP)s, tetramethylolmethanes, DBU0.52 part, water that the IV value of packing in the removable flask of four-hole round bottom of the 500ml that agitator, nitrogen ingress pipe, prolong are installed is 0.6～0.7, be nitrogen atmosphere in flask after, immerse in the oil bath that has been warming up to 180 ℃, on one side slowly except anhydrating, oil bath is warming up to 220 ℃ on one side, sustained reaction, until be transparent in flask, obtain polyester oligomer.
［ embodiment 19 ］
Use the DBN of same amount to replace the DBU of embodiment 17, obtain polyester oligomer.
［ embodiment 20 ］
1.87 parts of 187 parts, 225 parts of polyester oligomers, vinylformic acid, tosic acid, 1.50 parts of the p methoxy phenols of packing in the removable flask of four-hole round bottom of the 500ml that agitator, nitrogen ingress pipe, prolong are housed in embodiment 15 and obtaining, stir, after making its uniform dissolution, immerse in the oil bath that has been warming up to 118 ℃ sustained reaction 16.5 hours.After reaction finishes, the acid number of assaying reaction liquid, to add the alkaline aqueous solution of acid equivalent in flask, neutralized.Then, add salt solution (20wt%), stirred.Then, solution is moved to separating funnel, add the methyl iso-butyl ketone (MIBK) of 1.4 times of reaction solution, give up water.Again wash oil phase with salt solution (5wt%), give up water.Then, in hexane, after redeposition, make it be dissolved in methyl ethyl ketone oil phase, by suction filtration, remove impurity.After making the filtrate redeposition with tap water, give up supernatant liquor, with tap water, again stir, wash the redeposition thing, finally with carbitol acetate, being diluted to solids component is 70%, obtains acrylate resin varnish.
［ comparative example 3 ］
Replace the DBU of embodiment 17 with the Dibutyltin oxide of same amount, obtain polyester oligomer.
［ comparative example 4 ］
Replace the DBU of embodiment 17 with the dibutyl tin laurate of same amount, obtain polyester oligomer.
［ comparative example 5 ］
67 parts of 192 parts of recirculation PET sheets, the TriMethylolPropane(TMP)s of the IV value 0.6～0.7 of packing in the removable flask of four-hole round bottom of the 500ml that agitator, nitrogen ingress pipe, prolong are installed, 30 parts, water, be nitrogen atmosphere in flask after, immerse in the oil bath that has been warming up to 180 ℃, on one side slowly except anhydrating, oil bath is warming up to 220 ℃ on one side, is reacted.
<depolymerization time>
The needed time of the depolymerization of embodiment 15～19 and comparative example 3～5 is shown in following table 2.Even carry out more than 10 hours reaction, raw material also residual situation is designated as " * ".
<without metal>
Measured the concentration (ppm) of the contained metal of the depolymerizing substance of embodiment 15～19 and comparative example 3～5.The record method of estimating is as follows.
Zero: the not enough 10ppm of the concentration of metal
△: the concentration of metal is 10ppm～500ppm
*: the concentration of metal surpasses 500ppm
<molecular weight>
Use the GPC(gel permeation chromatography) measure the molecular weight of the depolymerizing substance of embodiment 15～19 and comparative example 3～5.Condition determination is: use the Shodex GPC KF-806L of clear and electrician's (strain) system * 3 as post, and use under 40 ℃ of column temperatures.The Application standard polystyrene is as primary standard, and elutriant is used tetrahydrofuran (THF) for the flow velocity divided with 1ml/.Measurement result is shown in following table 2.
The test of<solvent solubility>
Confirmed the solvent solubility of the depolymerizing substance of embodiment 15～19 and comparative example 3～5.Confirmation method is, with respect to 50 parts of depolymerizing substances, adds 50 parts of all kinds of SOLVENTS, stirs, and makes the 50wt% solution of depolymerizing substance, estimates the transparency of its solution.The record method of estimating is as follows.
Fully transparent: zero
Muddiness: △ is slightly arranged
Muddy: *
[table 2]
Can be confirmed, for solvent solubility, with 4,5 pairs of each solvents of comparative example, have muddiness to compare by above, embodiment is all identical with metallic comparative example 3, fully transparent to each solvent.
［ reference example 2 ］
Make 100 parts, the acrylate resin varnish and the 5 parts of Photoepolymerizationinitiater initiater (Irgacure184 that obtain in above-described embodiment 20; BASF Japanese firm system), after mixing, use applicator to be coated with in the mode of thickness 20 μ m on sheet glass.After coating, in the hot-blast circulation dry furnace of 80 ℃, drying is 20 minutes, uses the exposure apparatus that is equipped with high voltage mercury lamp, with 1J/cm
2exposure exposed, obtain estimating and film.
<rub(bing)test>
The rag that contains acetone in use is filmed friction 50 times the time to above-mentioned evaluation, and surface, without dissolving, can be confirmed fully to solidify.
<pencil hardness test>
The pencil from B to 9H polished with the front end of pencil-lead, the angle that is 45 degree to film with respect to above-mentioned evaluation applies 1kg and loads and press to filming.Under the state that has applied this load, to the about 1cm of the delineation of filming left and right, measure tack-free pencil hardness of filming, result is 6H.
<thermal test>
Above-mentioned evaluation is filmed in the hot-blast circulation dry furnace that drops into 200 ℃, heat 3 minutes.Take out after heating, by the sign of visual observation melting, to carry out thermal test, now confirm to there is the thermotolerance of 3 minutes under 200 ℃.
As mentioned above, the method according to this invention, by using nonmetal basic catalyst, polyester can be dissolved in to organic solvent easily, convert to can various chemical modifications polyester polyol.
Claims (14)
1. the manufacture method of a polyester polyol, is characterized in that, possesses and heated the operation with depolymerization raw material polyester to containing raw material polyester, polyhydroxy reactant and non-tin metalloid catalyzer or non-metal kind basic catalyst as the mixture of neccessary composition.
2. the manufacture method of polyester polyol according to claim 1, wherein, described non-tin metalloid catalyzer is the compound in the group of selecting free zn cpds, manganic compound, lithium compound and calcium cpd to form.
3. the manufacture method of polyester polyol according to claim 1 and 2, wherein, described non-tin metalloid catalyzer is the compound in the group of selecting free naphthenic acid metal complex, acetylacetone metal complex and sad metallic soap to form.
4. according to the manufacture method of the described polyester polyol of any one in claims 1 to 3, wherein, described non-tin metalloid catalyzer is the compound in the group of selecting free zinc naphthenate, zinc acetylacetonate, zinc octoate, calcium naphthenate, calcium acetylacetonate, calcium octoate, naphthenic acid lithium, methyl ethyl diketone lithium, sad lithium, Lithium Acetate, manganese naphthenate, manganese acetylacetonate and manganese octoate to form.
5. the manufacture method of polyester polyol according to claim 1, wherein, described non-metal kind basic catalyst is the hetero ring type compound with amidine structure.
6. the manufacture method of polyester polyol according to claim 5, wherein, described non-metal kind basic catalyst is more than one in the group of selecting free diazabicycloundecene, diazabicyclo-nonene and their derivative to form.
7. according to the manufacture method of the described polyester polyol of any one in claim 1 to 6, wherein, described polyhydroxy reactant comprises the above polyvalent alcohol of trifunctional.
8. according to the manufacture method of the described polyester polyol of any one in claim 1 to 7, wherein, described raw material polyester is recycled polyester.
9. according to the manufacture method of the described polyester polyol of any one in claim 1 to 8, wherein, add water to containing in raw material polyester, polyhydroxy reactant and the mixture of non-tin metalloid catalyzer as neccessary composition, to carry out the depolymerization of raw material polyester.
10. according to the manufacture method of the described polyester polyol of any one in claim 1 to 9, wherein, described depolymerization is carried out under 150～350 ℃.
11. according to the manufacture method of the described polyester polyol of any one in claim 1 to 10, wherein, obtain the mixture of compound shown in following general formula (1),
In formula (1), R
1the group of OH base, R are removed in expression from the polyvalent alcohol of (1+m) valency
2mean the alkylidene group of carbonatoms 1～10 or the arylidene of replacement or unsubstituted carbonatoms 6～20, R
3mean to replace or the arylidene of unsubstituted carbonatoms 6～20, l is that 0～10 integer, m are 1～10 integers, and n is 1～10 integer.
12. a polyester polyol, is characterized in that, described polyester polyol obtains by the manufacture method of the described polyester polyol of any one in claim 1 to 11.
13. the manufacture method of a polyester modification thing, is characterized in that, makes to have to react with the described polyester polyol of claim 12 with the group of hydroxyl reaction and the compound of ethylenically unsaturated group.
14. a polyester modification thing, is characterized in that, described polyester modification thing obtains by the manufacture method of the described polyester modification thing of claim 13.
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| JP2011-081293 | 2011-03-31 | ||
| JP2011081292 | 2011-03-31 | ||
| JP2011081293 | 2011-03-31 | ||
| JP2011-081292 | 2011-03-31 | ||
| PCT/JP2012/056019 WO2012132824A1 (en) | 2011-03-31 | 2012-03-08 | Method for producing polyester polyol, method for producing modified polyester, polyester polyol and modified polyester |
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| CN103459462A true CN103459462A (en) | 2013-12-18 |
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| KR (1) | KR101545071B1 (en) |
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| CN115594811A (en) * | 2022-09-07 | 2023-01-13 | 广东大盈新材料科技有限公司（Cn） | Polyurethane fabric resin for weather-resistant synthetic leather and preparation method thereof |
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| CN103265708B (en) * | 2013-04-24 | 2015-07-29 | 高松文 | A kind of modified poly ester polyvalent alcohol and its preparation method and application |
| US20230312451A1 (en) * | 2020-06-26 | 2023-10-05 | Korea Research Institute Of Chemical Technology | Efficient depolymerization method of polymers comprising ester functional group, and purification method thereof |
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| JP2000191766A (en) * | 1998-12-25 | 2000-07-11 | Nippon Polyurethane Ind Co Ltd | Production of terephthalic acid-based polyester polyol |
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| US4539341A (en) * | 1984-02-22 | 1985-09-03 | Jim Walter Resources, Inc. | Digestion products of polyalkylene terephthalate polymers and polycarboxylic acid-containing polyols and polymeric foams obtained therefrom |
| CN87101849A (en) * | 1987-03-10 | 1988-09-21 | 陕西省化学研究所 | The method and the catalyzer that are used for depolymerizing waste and old polyester plastics |
| JPH10251491A (en) * | 1997-03-12 | 1998-09-22 | Daiabondo Kogyo Kk | Thermosetting polyester resin composition |
| JP2000229916A (en) * | 1999-02-05 | 2000-08-22 | Mitsui Chemicals Inc | Ester group-containing dicarboxylic acid compound and its production |
| JP2002128880A (en) * | 2000-10-30 | 2002-05-09 | Kansai Paint Co Ltd | Method for producing alkyd resin |
| KR100765744B1 (en) * | 2001-12-15 | 2007-10-15 | 김도균 | Method for producing polymer for toner, ink and coating agent by recycling waste polyester |
| TW200906873A (en) * | 2007-05-30 | 2009-02-16 | Toagosei Co Ltd | Active energy ray curable composition, coating composition, coating member, and optical material |
| JP5748941B2 (en) * | 2009-04-14 | 2015-07-15 | 太陽ホールディングス株式会社 | Photosensitive compound and photocurable resin composition containing the same |
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| JPH03269016A (en) * | 1990-03-16 | 1991-11-29 | Unitika Ltd | Production of polyester |
| JP2000191766A (en) * | 1998-12-25 | 2000-07-11 | Nippon Polyurethane Ind Co Ltd | Production of terephthalic acid-based polyester polyol |
| JP2011043564A (en) * | 2009-08-19 | 2011-03-03 | Taiyo Holdings Co Ltd | Photocurable resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115594811A (en) * | 2022-09-07 | 2023-01-13 | 广东大盈新材料科技有限公司（Cn） | Polyurethane fabric resin for weather-resistant synthetic leather and preparation method thereof |
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| KR20130117877A (en) | 2013-10-28 |
| KR101545071B1 (en) | 2015-08-17 |
| JP5670552B2 (en) | 2015-02-18 |
| TWI455957B (en) | 2014-10-11 |
| CN103459462B (en) | 2016-04-27 |
| JPWO2012132824A1 (en) | 2014-07-28 |
| WO2012132824A1 (en) | 2012-10-04 |
| TWI496812B (en) | 2015-08-21 |
| TW201307435A (en) | 2013-02-16 |
| TW201422668A (en) | 2014-06-16 |
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