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WO2010119494A1 - Composé de polyol et composition thermodurcissable le contenant - Google Patents

Composé de polyol et composition thermodurcissable le contenant Download PDF

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Publication number
WO2010119494A1
WO2010119494A1 PCT/JP2009/006978 JP2009006978W WO2010119494A1 WO 2010119494 A1 WO2010119494 A1 WO 2010119494A1 JP 2009006978 W JP2009006978 W JP 2009006978W WO 2010119494 A1 WO2010119494 A1 WO 2010119494A1
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Prior art keywords
polyol
pet
polyester
polyol compound
compound
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English (en)
Japanese (ja)
Inventor
岡本大地
有馬聖夫
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Taiyo Holdings Co Ltd
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Taiyo Ink Mfg Co Ltd
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Priority to CN200980158534.4A priority Critical patent/CN102395616B/zh
Publication of WO2010119494A1 publication Critical patent/WO2010119494A1/fr
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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
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C08G18/4219—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from aromatic dicarboxylic acids and dialcohols in combination with polycarboxylic acids and/or polyhydroxy compounds which are at least trifunctional
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters

Definitions

  • the present invention relates to paints, inks, coating agents, adhesives for various substrates such as paper, wood, metal, plastic, glass and ceramic, polyol compounds useful as raw materials for urethane foam, and thermosetting compositions containing the same. About.
  • polyurethane has been used as an adhesive component and a paint component, but its heat resistance and adhesiveness are inferior to those of epoxy resins, and its use is limited.
  • Polyurethane is composed of a polyol component and an isocyanate component. Since the polyol component is alcohol-terminated, the density of the aromatic ring cannot be increased compared to an epoxy resin starting from a phenol resin. This is considered to be a low cause.
  • PET bottles made from polyester has been rapidly increasing in recent years due to its light weight, transparency, excellent gas barrier properties, and high strength, and the disposal method has become a social problem. For this reason, PET bottles are generally collected separately and recycled.
  • the molecular weight of PET decreases due to hydrolysis of ester bonds, and the melt viscosity and mechanical strength of PET decrease. Such a decrease in quality is a factor in inhibiting the recycling of PET bottles. Therefore, at present, recycled PET resin is mainly used only in the field of fibers and industrial materials.
  • a new effective method of using recycled PET resin is sought. ing.
  • Examples of the new method include the production of alkyd resins for paints using a depolymerization reaction with glycols (see Patent Document 1), the production of polyester resins for paints using recycled polyester (see Patent Documents 2 and 3), Furthermore, utilization of recycled polyester as a raw material for photocurable urethane resin (see Patent Document 4) has been studied.
  • the present invention has been made in view of the prior art as described above, and its purpose is useful as a raw material for polyurethane having excellent flexibility, chemical resistance, heat resistance, and fast curability of a cured coating film. It is an object of the present invention to provide a novel polyol that can be regenerated from waste plastic and a thermosetting composition containing the same.
  • thermosetting composition characterized by containing the said polyol compound and an isocyanate compound or a block isocyanate compound, or an amino resin is provided.
  • the polyol compound is obtained by heating and dissolving the polyester without using a solvent, and adding the polyol to depolymerize the polyester.
  • the polyester is preferably recycled PET, and the polyol component having a plurality of hydroxyl groups in one molecule preferably contains at least trimethylolpropane or polycarbonate diol.
  • the obtained polyol compound is an amorphous semi-solid or fluid liquid with a nonvolatile content of 100%, and is preferably solvent-soluble.
  • the novel polyol compound of the present invention and the thermosetting composition containing the same are polyol compounds obtained by depolymerizing a polyester with a polyol having a plurality of hydroxyl groups in one molecule, and have heat resistance, chemical resistance, It can be used as a raw material for polyurethane having excellent moisture resistance and flexibility. Moreover, it can be used also as a thermosetting composition which mix
  • the polyol compound when it is 100% non-volatile and semi-solid, it can be suitably used for adhesives and sealants, and can also be used for various coating agents and paints by adding solvents and reactive diluents.
  • the polyester when the polyester is a polyester recovered from a waste product, a highly concentrated recycled resin can be used, and it can be synthesized by depolymerization without using a solvent, so that the product can contribute to CO 2 reduction from the viewpoint of environmental protection. Can be applied.
  • the characteristic of the polyol compound of the present invention is that polyester is depolymerized with a polyol having a plurality of hydroxyl groups in one molecule without solvent. Furthermore, recycled PET or the like can be used as the polyester, and can be contained at a high concentration, and an amorphous semi-solid polyol compound can be produced with a nonvolatile content of 100%.
  • a novel polyol compound obtained by depolymerizing a polyester with a polyol having a plurality of hydroxyl groups in one molecule has at least a polycarbonate diol as a component of the polyol having a plurality of hydroxyl groups in one molecule.
  • the characteristic is exhibited most when a trifunctional polyol, especially trimethylolpropane are used.
  • bifunctional alcohols such as ethylene glycol, propylene glycol, and neopentyl glycol, and tetrafunctional or higher alcohols such as pentaerythritol and dipentaerythritol, are used alone to solve the polyester.
  • the depolymerized product does not become turbid immediately after the depolymerization, but becomes crystallized when left for several days. The crystals did not dissolve in the solvent and had to be dissolved at a temperature close to 200 ° C. for further dissolution.
  • a trifunctional polyol such as polycarbonate diol or trimethylolpropane
  • equimolar trimethylolpropane is used as a repeating unit of PET
  • a resinous (amorphous) substance having a nonvolatile content of 100% is obtained.
  • This material is transparent even after 3 months, is transparent, and has extremely high solubility in a solvent. It can be used in a 100% solid state or diluted with a solvent and a reactive diluent. Found that you can. Such a phenomenon was surprising and unexpected.
  • the reaction in which the polyester is depolymerized with a polyol having a plurality of hydroxyl groups in one molecule is a liquid (in the case of a solid, heated and dissolved to be liquid without using a solvent) in a state where the polyester is heated and dissolved. Is added at a temperature of about 200 to 300 ° C., preferably in the presence of a catalyst.
  • Polyesters used for the synthesis of the polyol compound can be all known and known polyesters. Among them, polyethylene terephthalate (PET) polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), PET bottles, PET films, and other PET products produced by pulverizing the remaining products, and recycled PET recovered from waste and washed. Preferred is recycled PET, but these can be obtained from the market as washed and pelletized.
  • PET polyethylene terephthalate
  • PBT polytrimethylene terephthalate
  • PBT polybutylene terephthalate
  • PEN polyethylene naphthalate
  • PBN polybutylene naphthalate
  • PET bottles PET films, and other PET products produced by pulverizing the remaining products, and recycled PET recovered from waste and washed.
  • PET films, and other PET products produced by pulverizing the remaining products, and recycled PET recovered
  • the polyol having a plurality of hydroxyl groups in one molecule may be any bifunctional or higher polyol, and is not limited to a specific one.
  • Bifunctional polyols include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, spiroglycol, dioxane glycol, adamantane Diol, 3-methyl-1,5-pentanediol, methyloctanediol, 1,6-hexanediol, 1,1,4-cyclohexanedimethanol, 2-methylpropanediol, 1,3,3-methylpentanediol, Ethylene oxide of bifunctional phenols such as 1,5-hexamethylene glycol, octylene glycol, 9-nonanedio
  • Epaul manufactured by Idemitsu Petrochemical Co., Ltd., hydrogenated polyisoprene diol, molecular weight 1,860, average polymerization degree 26
  • PIP Idemitsu Petrochemical Co., Ltd., polyisoprene diol, molecular weight 2,200, average polymerization degree 34
  • polytail HA Mitsubishi Chemical Corporation, hydrogenated polybutadiene diol, molecular weight 2,200, average polymerization degree 39
  • R-45HT Idemitsu
  • petrochemicals polybutanediol, molecular weight 2,270, average polymerization degree 42
  • Examples of the tri- or higher functional polyol include glycerin, diglycerin, triglycerin, trimethylolethane, trimethylolpropane, sorbitol, pentaerythritol, ditrimethylolpropane, dipentaerythritol, tripentaerythritol, adamantanetriol, and more. Ethylene oxide or propylene oxide modified products are also included.
  • Examples of the polyol having an aromatic ring include ethylene oxide or propylene oxide modified products of trifunctional or higher functional phenol compounds, and examples having a heterocyclic ring include Sake manufactured by Shikoku Kasei Kogyo Co., Ltd.
  • polyols can be used alone or in combination of two or more.
  • a long-chain diol such as carbonate diol or a trifunctional polyol typified by trimethylolpropane
  • the depolymerized product obtained by depolymerization with trimethylolpropane has a high carbon ratio derived from polyester, and when recycled polyester is used, the recycled resin utilization rate increases, and polyester, polyurethane and thermosetting resin It becomes an advantageous raw material.
  • polycarbonate diol trimethylol propane and / or their derivatives or polyols containing them
  • polycarbonate diol, trimethylol propane and / or their derivatives are polyols.
  • Those containing 50 mol% or more are particularly preferred.
  • a depolymerization catalyst can be used.
  • the depolymerization catalyst include monobutyltin hydroxide, dibutyltin oxide, monobutyltin-2-ethylhexanoate, dibutyltin dilaurate, stannous oxide, tin acetate, zinc acetate, manganese acetate, cobalt acetate, and calcium acetate.
  • Lead acetate antimony trioxide, tetrabutyl titanate, tetraisopropyl titanate and the like.
  • the amount of these depolymerization catalysts used is usually in the range of 0.005 to 5 parts by mass, preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the total amount of polyester and polyol.
  • water is a compound that promotes depolymerization. This is present as an impurity in, for example, recycled PET, and causes a decrease in molecular weight when PET is recycled. Therefore, it is usually necessary to remove it by a very energy-consuming process such as drying. is there. However, in the application of the present invention, it is not necessary.
  • the use of recycled PET pellets once melted and kneaded in a pellet manufacturing machine such as an extruder with water added has a lower molecular weight of the recycled PET. Since the reaction temperature at the time of superposition
  • the ratio is less than 0.5, the polyol is excessively contained, the ratio of the aromatic ring derived from the polyester is decreased, and the effect of improving heat resistance and chemical resistance is decreased, which is not preferable.
  • the ratio is greater than 3, the depolymerized product is crystallized in most cases and is insoluble in the solvent, which is not preferable.
  • thermosetting composition of the present invention can be obtained by blending the polyol compound obtained as described above together with an isocyanate compound, a blocked isocyanate compound or an amino resin. These components can be used alone or in combination of two or more, and the blending ratio thereof is suitably in the range of 20 to 300 parts by mass with respect to 100 parts by mass of the polyol compound.
  • isocyanate compound for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is used.
  • aromatic polyisocyanate include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m- Examples include xylylene diisocyanate and 2,4-tolylene dimer.
  • aliphatic polyisocyanate examples include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), and isophorone diisocyanate.
  • Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate.
  • the adduct body, burette body, and isocyanurate body of the isocyanate compound enumerated above are mentioned.
  • Isocyanate compounds may be commercially available, such as Duranate (registered trademark) 24A-100, Duranate 22A-75PX, Duranate TPA-100, Duranate THA-100, Duranate P-301-75E, Duranate 21S-75E, Duranate 18H-70B, Duranate MFA-90X (trade name, manufactured by Asahi Kasei Chemicals), Basonat HB-175, Basonat HI-100, Basonat HI-190B, Basonat HI-290, Basonat HB-275B, Basonat HI-168, Basonat HI-268, Basonat HW-180PC, Basonat HW-100, Laromer LR9000 (above, trade name, manufactured by BASF) and the like.
  • the blocked isocyanate group contained in the blocked isocyanate compound is a group in which the isocyanate group is protected by reaction with a blocking agent and temporarily deactivated. When heated to a predetermined temperature, the blocking agent is dissociated to produce isocyanate groups.
  • a blocking agent When heated to a predetermined temperature, the blocking agent is dissociated to produce isocyanate groups.
  • the blocked isocyanate compound an addition reaction product of an isocyanate compound and an isocyanate blocking agent is used.
  • the isocyanate compound that can react with the blocking agent include isocyanurate type, biuret type, and adduct type.
  • aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic polyisocyanate is used, for example. Specific examples of the aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate include the compounds exemplified above.
  • isocyanate blocking agent examples include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam blocking agents such as ⁇ -caprolactam, ⁇ -palerolactam, ⁇ -butyrolactam and ⁇ -propiolactam; Active methylene blocking agents such as ethyl acetoacetate and acetylacetone; methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl Ether, methyl glycolate, butyl glycolate, diacetone alcohol, lactic acid Alcohol-based blocking agents such as chill and ethyl lactate; oxime-based blocking agents such as formaldehyde oxime, acetoaldoxime, acetoxi
  • the blocked isocyanate compound may be commercially available, for example, Sumidur BL-3175, BL-4165, BL-1100, BL-1265, Death Module TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117.
  • amino resins examples include methylol melamine compounds, methylol benzoguanamine compounds, methylol glycoluril compounds, and methylol urea compounds.
  • the alkoxymethylated melamine compound, alkoxymethylated benzoguanamine compound, alkoxymethylated glycoluril compound and alkoxymethylated urea compound are the methylol groups of the respective methylolmelamine compound, methylolbenzoguanamine compound, methylolglycoluril compound and methylolurea compound. Obtained by conversion to an alkoxymethyl group.
  • the type of the alkoxymethyl group is not particularly limited and can be, for example, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, or the like.
  • a melamine derivative having a formalin concentration which is friendly to the human body and the environment is preferably 0.2% or less.
  • Examples of commercially available amino resins include Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156. 1158, 1123, 1170, 1174, UFR65, 300 (above, manufactured by Mitsui Cyanamid Co., Ltd.), Nicalak Mx-750, Mx-032, Mx-270, Mx-280, Mx-290, Mx-706, Mx-708, Mx-40, Mx-31, Ms-11, Mw-30, Mw-30HM, Mw-390, Mw-100LM, Mx-100 Mw-750LM (manufactured by Sanwa Chemical Co., Ltd.).
  • the said amino resin can be used individually by 1 type or in combination of 2 or more types.
  • thermosetting composition of the present invention may further include, if necessary, colorants such as catalysts, pigments and dyes necessary for thermosetting, antioxidants, stabilizers, UV absorbers, flame retardants, mechanical agents.
  • colorants such as catalysts, pigments and dyes necessary for thermosetting, antioxidants, stabilizers, UV absorbers, flame retardants, mechanical agents.
  • An inorganic filler for increasing the strength, an organic solvent used for decreasing the viscosity, an adhesion imparting agent such as a silane coupling agent, an antifoaming agent, and a leveling agent, and other additives can be added.
  • a conductive composition such as a metal such as silver or copper, or a conductive material such as carbon can be added to form a conductive composition.
  • Synthesis example 1 Charged 192 parts of recycled PET flakes with an IV value of 0.6 to 0.7 to a 500 ml four-necked round bottom separable lasco equipped with a stirrer, a nitrogen inlet tube, and a cooling tube. It was immersed in a heated salt bath. When PET was dissolved, stirring was started and 0.65 part of dibutyltin oxide was added. Next, 134 parts of trimethylolpropane previously heated and dissolved at 130 ° C. was added little by little while being careful not to solidify the PET. During this time, the stirring speed was increased to 150 rpm when the viscosity decreased.
  • Synthesis example 2 Charged 192 parts of recycled PET flakes with an IV value of 0.6 to 0.7 to a 500 ml four-necked round bottom separable lasco equipped with a stirrer, a nitrogen inlet tube, and a cooling tube. It was immersed in a heated salt bath. When PET was dissolved, stirring was started and 0.65 part of dibutyltin oxide was added. Next, 94 parts of trimethylolpropane previously heated and dissolved at 130 ° C. was added little by little while taking care not to solidify the PET. During this time, the stirring speed was increased to 150 rpm when the viscosity decreased.
  • Synthesis example 3 Charged 192 parts of recycled PET flakes with an IV value of 0.6 to 0.7 to a 500 ml four-necked round bottom separable lasco equipped with a stirrer, a nitrogen inlet tube, and a cooling tube. It was immersed in a heated salt bath. When PET was dissolved, stirring was started and 0.65 part of dibutyltin oxide was added. Subsequently, 67 parts of trimethylolpropane previously heated and dissolved at 130 ° C. were added little by little while being careful not to solidify the PET. During this time, the stirring speed was increased to 150 rpm when the viscosity decreased.
  • Synthesis example 4 A 500 ml four-necked round bottom separable lasco equipped with a stirrer, nitrogen inlet tube, and cooling tube was charged with 39 parts of recycled PET flakes having an IV value of 0.6 to 0.7, and the atmosphere in the flask was changed to 300 ° C. It was immersed in a heated salt bath. When PET was dissolved, stirring was started and 0.65 part of dibutyltin oxide was added. Next, 161 parts of DURANOL T5650J (manufactured by Asahi Kasei Chemicals Corporation) preheated at 130 ° C. was added little by little while taking care not to solidify the PET. During this time, the stirring speed was increased to 150 rpm when the viscosity decreased.
  • DURANOL T5650J manufactured by Asahi Kasei Chemicals Corporation
  • Synthesis example 5 A 500 ml four-necked round bottom separable lasco equipped with a stirrer, nitrogen inlet tube, and cooling tube was charged with 39 parts of recycled PET flakes having an IV value of 0.6 to 0.7, and the atmosphere in the flask was changed to 300 ° C. It was immersed in a heated salt bath. When PET was dissolved, stirring was started and 0.65 part of dibutyltin oxide was added. Next, 80.5 parts of DURANOL T5650J (manufactured by Asahi Kasei Chemicals Corporation) preheated at 130 ° C. was added little by little while taking care not to solidify the PET. During this time, the stirring speed was increased to 150 rpm when the viscosity decreased.
  • DURANOL T5650J manufactured by Asahi Kasei Chemicals Corporation
  • Synthesis Example 6 Charged 192 parts of recycled PET flakes with an IV value of 0.6 to 0.7 to a 500 ml four-necked round bottom separable lasco equipped with a stirrer, a nitrogen inlet tube, and a cooling tube. It was immersed in a heated salt bath. When PET was dissolved, stirring was started and 0.65 part of dibutyltin oxide was added. Next, 104 parts of neopentyl glycol, which was heated and dissolved in advance at 130 ° C., was added little by little while being careful not to solidify the PET. During this time, the stirring speed was increased to 150 rpm when the viscosity decreased. Then, the salt bath was replaced with an oil bath that had been heated to 240 ° C.
  • Synthesis example 7 Charged 192 parts of recycled PET flakes with an IV value of 0.6 to 0.7 to a 500 ml four-necked round bottom separable lasco equipped with a stirrer, a nitrogen inlet tube, and a cooling tube. It was immersed in a heated salt bath. When PET was dissolved, stirring was started and 0.65 part of dibutyltin oxide was added. Next, 90 parts of 1,3-butanediol preheated at 130 ° C. was added little by little while taking care not to solidify the PET. During this time, the stirring speed was increased to 150 rpm when the viscosity decreased. Then, the salt bath was replaced with an oil bath that had been heated to 240 ° C.
  • ab-7 resin An IR chart of the ab-7 resin is shown in FIG.
  • Synthesis example 8 Charged 192 parts of recycled PET flakes with an IV value of 0.6 to 0.7 to a 500 ml four-necked round bottom separable lasco equipped with a stirrer, a nitrogen inlet tube, and a cooling tube. It was immersed in a heated salt bath. When PET was dissolved, stirring was started and 0.65 part of dibutyltin oxide was added. Next, 92 parts of glycerin previously heated and dissolved at 130 ° C. were added little by little while being careful not to solidify the PET. During this time, the stirring speed was increased to 150 rpm when the viscosity decreased.
  • Synthesis Example 9 Charged 192 parts of recycled PET flakes with an IV value of 0.6 to 0.7 to a 500 ml four-necked round bottom separable lasco equipped with a stirrer, a nitrogen inlet tube, and a cooling tube. It was immersed in a heated salt bath. When PET was dissolved, stirring was started and 0.65 part of dibutyltin oxide was added. Subsequently, 136 parts of pentaerythritol was added little by little while taking care not to solidify the PET. During this time, the stirring speed was increased to 150 rpm when the viscosity decreased.
  • the reaction product was a yellow transparent semi-solid at room temperature. This is referred to as ab-9 resin.
  • Synthesis Example 10 Charged 192 parts of recycled PET flakes with an IV value of 0.6 to 0.7 to a 500 ml four-necked round bottom separable lasco equipped with a stirrer, a nitrogen inlet tube, and a cooling tube. It was immersed in a heated salt bath. When PET was dissolved, stirring was started and 0.65 part of dibutyltin oxide was added. Next, 254 parts of dipentaerythritol was added in small portions, taking care not to solidify the PET. During this time, the stirring speed was increased to 150 rpm when the viscosity decreased. Next, the salt bath was replaced with an oil bath that had been heated to 240 ° C. in advance, and the temperature inside the flask was kept at 220 ° C. ⁇ 10 ° C. and reacted for 5 hours. The reaction product was a yellow transparent solid at room temperature. This is referred to as ab-10 resin.
  • Synthesis Example 11 Charged 192 parts of recycled PET flakes with an IV value of 0.6 to 0.7 to a 500 ml four-necked round bottom separable lasco equipped with a stirrer, a nitrogen inlet tube, and a cooling tube. It was immersed in a heated salt bath. When PET was dissolved, stirring was started and 0.65 part of dibutyltin oxide was added. Subsequently, 127 g of dipentaerythritol and 67 parts of trimethylolpropane were added little by little while being careful not to solidify the PET. During this time, the stirring speed was increased to 150 rpm when the viscosity decreased. Next, the oil bath was heated up to 240 ° C. from the salt bath in advance, and the temperature inside the flask was kept at 220 ° C. ⁇ 10 ° C. for 2 hours. The reaction product was a yellow transparent solid at room temperature. This is referred to as ab-11 resin.
  • Synthesis Example 12 A 500 milliliter four-necked round bottom separable lasco equipped with a stirrer, nitrogen introduction tube, and cooling tube was charged with 250 parts of recycled PET flakes having an IV value of 0.6 to 0.7, and the atmosphere in the flask was changed to a nitrogen atmosphere. It was immersed in a heated salt bath. When PET was dissolved, stirring was started and 0.65 part of dibutyltin oxide was added. Next, 104 parts of DURANOL T5650J (manufactured by Asahi Kasei Chemicals Corporation) and 157 parts of trimethylolpropane previously heated at 130 ° C. were added little by little while taking care not to solidify the PET.
  • DURANOL T5650J manufactured by Asahi Kasei Chemicals Corporation
  • the stirring speed was increased to 150 rpm when the viscosity decreased.
  • the salt bath was replaced with an oil bath that was previously heated to 240 ° C., and the temperature in the flask was kept at 220 ° C. ⁇ 10 ° C. for 5 hours.
  • the reaction product was a yellow transparent liquid at room temperature. This is referred to as ab-12 resin.
  • Synthesis Example 13 Charged 192 parts of recycled PET flakes with an IV value of 0.6 to 0.7 to a 500 ml four-necked round bottom separable lasco equipped with a stirrer, a nitrogen inlet tube, and a cooling tube. It was immersed in a heated salt bath. When PET was dissolved, stirring was started and 0.65 part of dibutyltin oxide was added. Next, 45 parts of 1,3-butanediol and 68 parts of pentaerythritol, which had been preheated at 130 ° C., were added little by little while taking care not to solidify the PET. During this time, the stirring speed was increased to 150 rpm when the viscosity decreased.
  • the reaction product was a yellow transparent liquid at room temperature. This is referred to as ab-13 resin.
  • Example of polyester resin varnish preparation Using a heating and melting pot, 100 parts of PMA as a solvent was added to 100 parts of Byron (registered trademark) 560 (manufactured by Toyobo Co., Ltd.), heated to 60 ° C., and stirred until completely dissolved. This is called varnish A.
  • Byron registered trademark 560
  • Tables 1 and 2 show the evaluation results of the recycled resin usage rate, appearance, hydroxyl value, molecular weight, and solvent solubility of the polyols obtained in Synthesis Examples 1-13.
  • the solubility evaluation method is as follows. ⁇ : Dissolved. (Triangle
  • Formulation Examples 1-8 The polyols obtained in Synthesis Examples 1, 2, and 4 were mixed with isocyanates and methylol melamine, and performance as adhesives and coating agents were evaluated. Table 3 shows the mixing ratio.
  • compositions of Formulation Examples 1 to 6 were applied to a glass plate with a film thickness of 30 ⁇ m using an applicator. This was dried at 50 ° C. for 10 minutes in a hot-air circulating drying oven and cured at 120 ° C. for 30 minutes. The following test was done about the obtained hardened
  • Rubbing test In order to test the curability of the cured product obtained as described above, a rubbing test was performed as follows. The obtained cured product was rubbed 50 times with a waste cloth containing acetone, and it was judged that the one having no surface dissolution was sufficiently cured. evaluated. The evaluation results are shown in Table 4.
  • Adhesion test with glass 0.1 cc of each composition (adhesive) of Formulation Examples 1 to 3 was dropped onto a glass plate having a thickness of 0.1 mm using a syringe.
  • a similar glass plate was laminated with a glass plate to which an adhesive was dropped, and this was put into a hot air circulation drying furnace and cured at 120 ° C. for 30 minutes. The adhesion of the glass plate thus bonded was confirmed.
  • the case where the glass plate could not be peeled was evaluated as ⁇ , and the case where the glass plate was peeled off was evaluated as x.
  • the evaluation results are shown in Table 4.
  • Adhesion test with PET film Test piece preparation conditions for Formulation Examples 1 to 3: It apply
  • Test piece preparation conditions of Formulation Examples 4 to 6 It apply
  • Example 7 After coating the composition of Formulation Example 7 on a bonderite steel sheet with a film thickness of 500 ⁇ m, it was cured under three curing conditions (100 ° C. ⁇ 30 minutes, 140 ° C. ⁇ 30 minutes, 160 ° C. ⁇ 30 minutes). . Under any of the curing conditions, no peeling was confirmed in the obtained coating film by a pencil hardness of 3H, a gobang eye adhesion test 100/100, and a 2 mm bending test.
  • Example 8 The composition of Formulation Example 8 was applied to a PET film having a thickness of 125 ⁇ m with a film thickness of 30 ⁇ m using an applicator. After application, the same PET film was laminated on the adhesive-coated PET film and laminated in two stages (60 ° C. ⁇ 10 minutes ⁇ 3 kgf / cm 2 , 120 ° C. ⁇ 20 minutes ⁇ 10 kgf / cm 2 ). After curing, a peel test of the test piece was performed, and it was confirmed that the PET films were firmly adhered to each other. Next, after irradiating this test piece with an exposure amount of 1 J / cm 2 using a conveyor type exposure apparatus equipped with a high-pressure mercury lamp, the same peel test was performed. The PET films were firmly adhered to each other. Was confirmed.
  • the novel polyol compound of the present invention does not use any solvent in the process of synthesis, and further uses a recycled resin with high efficiency. It can be said that it is useful as a polyol component in the field.
  • the polyol compound of the present invention can be used as a thermosetting resin by mixing with an isocyanate compound, an amino resin, etc., and particularly an adhesive for film lamination such as an IC card, a touch panel, an organic EL display, etc. It can be suitably used as a coating agent and a sealing agent.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

La présente invention concerne un nouveau polyol utile comme matière de départ pour former un polyuréthane, qui permet d'obtenir un revêtement durci présentant d'excellentes flexibilité, résistance chimique, résistance thermique, et capacité de durcissement rapide, et qui est apte à être régénéré à partir de déchets plastiques. L'invention concerne également une composition thermodurcissable contenant ledit polyol. Selon l'invention, un composé de polyol est obtenu par dépolymérisation d'un polyester à l'aide d'un polyol possédant une pluralité de groupes hydroxy par molécule. L'invention concerne également une composition thermodurcissable contenant le composé de polyol et un composé d'isocyanate ou un composé d'isocyanate bloqué ou une résine aminique. De préférence, le composé de polyol est obtenu par chauffage et fusion du polyester sans utilisation de solvant, et dépolymérisation du polyester par ajout du polyol à celui-ci, et consiste en un liquide semi-solide ou coulant. Le polyester est de préférence du PET régénéré.
PCT/JP2009/006978 2009-04-14 2009-12-17 Composé de polyol et composition thermodurcissable le contenant Ceased WO2010119494A1 (fr)

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WO2012014480A1 (fr) * 2010-07-28 2012-02-02 太陽ホールディングス株式会社 Résine phénolique et résine époxy et leur procédé de préparation
WO2012029468A1 (fr) * 2010-08-30 2012-03-08 太陽ホールディングス株式会社 Composition de résine durcissable, film sec de celle-ci, produit durci de ladite composition de résine durcissable et carte de circuit imprimé utilisant ladite composition
WO2012067690A1 (fr) * 2010-11-19 2012-05-24 E. I. Du Pont De Nemours And Company Poly(triméthylène éther)polyols ramifiés
EP3183286A4 (fr) * 2014-08-20 2018-08-22 Resinate Materials Group, Inc. Polyols de polyester issus de polymères recyclés et de flux de déchets

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US8916322B2 (en) * 2012-11-15 2014-12-23 Xerox Corporation Sustainable toner
WO2014112165A1 (fr) * 2013-01-21 2014-07-24 太陽インキ製造株式会社 Composition de type thermodurcissable, et structure stratifiée
CN110352222A (zh) * 2017-03-14 2019-10-18 陶氏环球技术有限责任公司 膨胀型涂料体系
CN110218515A (zh) * 2019-05-31 2019-09-10 广东合胜实业股份有限公司 一种建筑外墙用的聚氨酯防水涂料及其制备方法
CN115710343A (zh) * 2022-10-31 2023-02-24 浙江明士达股份有限公司 耐折防腐蚀软体水囊材料及其制备方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012014480A1 (fr) * 2010-07-28 2012-02-02 太陽ホールディングス株式会社 Résine phénolique et résine époxy et leur procédé de préparation
WO2012029468A1 (fr) * 2010-08-30 2012-03-08 太陽ホールディングス株式会社 Composition de résine durcissable, film sec de celle-ci, produit durci de ladite composition de résine durcissable et carte de circuit imprimé utilisant ladite composition
WO2012067690A1 (fr) * 2010-11-19 2012-05-24 E. I. Du Pont De Nemours And Company Poly(triméthylène éther)polyols ramifiés
US8618184B2 (en) 2010-11-19 2013-12-31 E I Du Pont De Nemours And Company Polyurethane foams containing branched poly(trimethylene ether) polyols
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EP3183286A4 (fr) * 2014-08-20 2018-08-22 Resinate Materials Group, Inc. Polyols de polyester issus de polymères recyclés et de flux de déchets

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CN102395616B (zh) 2015-04-08
TW201037015A (en) 2010-10-16
JP2010248345A (ja) 2010-11-04
CN102395616A (zh) 2012-03-28
JP5662650B2 (ja) 2015-02-04

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