Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
  • C07C31/18—Polyhydroxylic acyclic alcohols
  • C07C31/20—Dihydroxylic alcohols
• • 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
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
• • 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
  • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
• • 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
  • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
  • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
  • C12P7/00—Preparation of oxygen-containing organic compounds
  • C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
  • C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
  • C12P7/18—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic polyhydric

Definitions

• the present invention relates to a 1,6-hexanediol composition, a polymer, a curable resin composition, and a coating material.
• 1,6-hexanediol (1,6-HD) compositions are useful intermediates for the production of polymers such as polyesters and polyurethanes.
• 1,6-hexanediol compositions are generally prepared by (1) hydrogenation of adipic acid or an adipic acid-containing feed stream, (2) hydrogenation of hydroxycaproic acid or an ester thereof, or (3) hydrogenation of caprolactone. It can be manufactured by
• An object of the present invention is to provide a 1,6-hexanediol composition, a polymer, a curable resin composition, and a paint that can extend the pot life without causing curing failure when made into a thermosetting resin composition.
• the present invention provides an oxidative polymerization type curable resin composition that can maintain curing (drying) time without delaying it even without adding a curing accelerator or reducing the amount of curing accelerator.
• 6-hexanediol composition, polymer, curable resin composition, and coating material in this specification, pot life means the pot life of the mixture, and refers to, for example, the time until gelation of the thermosetting resin composition under 50° C. conditions.
• thermosetting resin compositions containing polymers such as polyesters using 1,6-hexanediol compositions containing a specific amount of alkali metal elements as reaction raw materials have poor curing. They discovered that the pot life could be extended without causing any problems, and completed the present invention.
• the oxidation polymerization type curable resin composition containing the above polymer it is possible to maintain the curing (drying) time without delaying the curing (drying) time even if the curing accelerator is not added or the amount added is reduced. The present invention has been completed.
• the present inventors have discovered that the trivalent or tetravalent alcohol in the 1,6-hexanediol composition of the present invention affects the pot life of the thermosetting resin composition, and that in some cases polyester etc. It was also found that this effect affects the synthesis of polymers.
• a 1,6-hexanediol composition containing one or both of 1,6-hexanediol and 1,6-hexanediol derivatives, and an alkali metal element the composition comprising: A 1,6-hexanediol composition having a total content of alkali metal elements in the range of 1 to 5,000 ppm by mass.
• the 1,6-hexanediol composition of the present invention has a total content of alkali metal elements of 1 to 5,000 mass ppm, polyester etc. obtained by reacting the 1,6-hexanediol composition In a thermosetting resin composition containing a polymer, the pot life can be extended without causing curing failure, and in an oxidative polymerization type curable resin composition containing the polymer, it is possible to extend the pot life without curing failure. Alternatively, even if the amount is reduced, the curing (drying) time can be maintained without being delayed.
• the 1,6-hexanediol composition (hereinafter sometimes simply referred to as a composition) of the present invention contains either or both of 1,6-hexanediol and 1,6-hexanediol derivatives, and an alkali metal element.
• the total content of the alkali metal elements is in the range of 1 to 5,000 ppm by mass based on the total amount of the composition.
• the 1,6-hexanediol contained in the composition of the present invention is preferably unmodified 1,6-hexanediol, but may be a 1,6-hexanediol derivative. That is, the composition of the present invention contains at least one of 1,6-hexanediol and 1,6-hexanediol derivatives.
• the 1,6-hexanediol derivative contained in the composition of the present invention modifies one or both of the two hydroxyl groups possessed by the 1,6-hexanediol contained in the 1,6-hexanediol composition of the present invention.
• This is a compound that has
• as a method for modifying the hydroxyl group of 1,6-hexanediol known methods for modifying hydroxyl groups can be used, such as etherification reaction, esterification reaction, modification with (meth)acrylic acid, etc. .
• 1,6-hexanediol derivatives examples include epoxy group-containing 1,6-hexanediol derivatives such as 1,6-hexanediol diglycidyl ether and 6-hydroxyhexylglycidyl ether; (meth)acryloyl group-containing 1,6-hexanediol derivatives such as meth)acrylate, 6-hydroxyhexyl acrylate, 1,6-hexanediol monoacrylate monomethacrylate; 1,6-hexanediol divinyl ether, 1,6- Vinyl ether group-containing 1,6-hexanediol derivatives such as hexanediol monovinyl ether; 6-propyloxy-1-hexanol, 1,6-dipropoxy-hexane, 1,6-hexanediol methyl ether, 1,6-dimethoxyhexane, etc.
• aliphatic alkyl ether group-containing 1,6-hexanediol derivatives fatty acid ester group-containing 1,6- such as propyl 6-hydroxyhexanoate, di-n-propyl adipate, methyl 6-hydroxycaproate, dimethyl adipate, etc.
• fatty acid ester group-containing 1,6- such as propyl 6-hydroxyhexanoate, di-n-propyl adipate, methyl 6-hydroxycaproate, dimethyl adipate, etc.
• Examples include hexanediol derivatives; and the like. These may be used alone or in combination of two or more.
• a (meth)acryloyl group means one or both of an acryloyl group and a methacryloyl group
• (meth)acrylate means one or both of an acrylate and a methacrylate
• the total content of either or both of 1,6-hexanediol and 1,6-hexanediol derivatives is preferably 95.00 to 99.99% by mass, more preferably 96.0% by mass. 00 to 99.99% by mass, more preferably 99.00 to 99.99% by mass.
• the present invention can be achieved by keeping the total content of alkali metal elements and, if necessary, the content of trivalent or tetravalent alcohol within the above range, and keeping the purity of the 1,6-hexanediol composition within the above range. There is a tendency for the effect of the above to be obtained more preferably.
• the total content of either or both of 1,6-hexanediol and 1,6-hexanediol derivatives is a value measured by gas chromatography-mass spectrometry (GC-MS).
• alkali metal element contained in the composition of the present invention is not particularly limited, and examples include lithium, sodium, potassium, rubidium, and cesium. These may be used alone or in combination of two or more. Among these, sodium and potassium are preferred.
• the state of the alkali metal element contained in the composition of the present invention is not particularly limited, and may be an alkali metal alone, an alkali metal compound, an alkali metal ion, or the like.
• Specific examples of the alkali metal compound include metal salts of the above-mentioned alkali metal elements and acids such as acetic acid, phosphoric acid, and nitric acid.
• the upper limit of the total content of alkali metal elements is preferably 5,000.
• the mass is less than ppm.
• the lower limit of the total content is not particularly limited, and is preferably 1 mass ppm or more, more preferably 100 mass ppm or more, still more preferably 500 mass ppm or more, particularly preferably 800 mass ppm or more. Any combination of these upper and lower limits can be used.
• the total content of alkali metal elements is 1 to 5,000 ppm by mass, but preferably The amount is 100 to 5,000 ppm by mass, more preferably 500 to 5,000 ppm by mass, and even more preferably 800 to 5,000 ppm by mass. If the total content of alkali metals is within the above range, the above effects will be exhibited, and in a curable resin composition using a polymer such as polyester obtained by reacting a 1,6-hexanediol composition. , good curing (drying) properties.
• the total content of alkali metals is a value measured by inductively coupled plasma mass spectrometry (ICP-MS).
• the composition of the present invention may further contain a trihydric or tetrahydric alcohol.
• trivalent or tetravalent alcohols include pentaerythritol, hexanetetrol, 2,-bis(hydroxymethyl)-1,3-propanediol (pentaerythritol), benzenetriol, 3-methylpentane-1 , 3,5-triol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, Trimethylolpropane, 1,2,3-butanetriol, 1,2,4-butanetriol, 2-hydroxymethyl-2-methyl-1,3-propanediol (trimethylolethane), 2-ethyl-2-hydroxy Methyl-1,3-propanediol (trimethylolprotane), 3-hydroxyeth
• trivalent aliphatic alcohols are more preferred, trivalent aliphatic alcohols having 3 to 10 carbon atoms are even more preferred, trivalent aliphatic alcohols having 3 to 8 carbon atoms are particularly preferred, and glycerin is most preferred. .
• the pot life can be extended without causing curing failure.
• an oxidative polymerization type curable resin composition containing a polymer made from the composition of the present invention is cured (drying) even if no curing accelerator is added or the amount of the curing accelerator is reduced. It can be maintained without delaying the time.
• the upper limit of the content of trivalent or tetravalent alcohol is preferably 2,000 mass ppm or less.
• the lower limit of the content is not particularly limited, and is preferably 0.1 mass ppm or more, more preferably 10 mass ppm or more, still more preferably 100 mass ppm or more, particularly preferably 500 mass ppm or more. Any combination of these upper and lower limits can be used. That is, the content of trivalent or tetravalent alcohol is preferably 0.1 to 2,000 mass ppm, more preferably 10 to 2,000 mass ppm, still more preferably 100 to 2,000 mass ppm, and particularly preferably is 500 to 2,000 ppm by mass.
• the content of the trivalent or tetravalent alcohol is within the above range, when reacting the 1,6-hexanediol composition to synthesize a polymer such as polyester, the polymer chain due to the trivalent or tetravalent alcohol will be removed.
• the amount of branched structure can be adjusted, and gelation can be suitably suppressed while obtaining the effects of the present invention.
• the content of trivalent or tetravalent alcohol is a value measured by gas chromatography mass spectrometry (GC-MS).
• the 1,6-hexanediol composition of the present invention may be produced so that the total content of alkali metal elements is within the above range.
• a commercially available 1,6-hexanediol composition has a total alkali metal content of less than 1 mass ppm, for example, acetic acid, phosphoric acid, nitric acid, etc.
• the total content of alkali metals may be within the above range by adding acids such as and metal salts of alkali metals.
• 1,6-hexanediol compositions contain less than 0.1 mass ppm of trihydric or tetrahydric alcohol; A trihydric or tetrahydric alcohol may be added so that the content of the trihydric or tetrahydric alcohol is within the above range.
• the thermosetting resin composition contains at least a main ingredient containing a polymer such as polyester and a curing agent, and optionally further contains an acid curing catalyst such as a sulfonic acid type.
• an acid curing catalyst such as a sulfonic acid type.
• a dryer such as cobalt, manganese, or iron is used for accelerating curing, and a curing accelerating aid, a so-called auxiliary dryer, is also used.
• the hardening accelerator includes at least one metal selected from the group consisting of alkali metals such as potassium and sodium; alkaline earth metals such as calcium and strontium; heavy metals such as zirconium and lead; and various carboxylic acids. metal salts (metal soaps).
• the 1,6-hexanediol composition since an alkali metal is contained in the 1,6-hexanediol composition, polymers such as polyester obtained by reacting the 1,6-hexanediol composition, oxidative polymerization type curable products containing the polymer, etc.
• the resin composition also contains an alkali metal. Therefore, even if the curing accelerator is not blended or the blended amount is reduced, the curing (oxidative polymerization) reaction is promoted and the drying time can be maintained without being delayed.
• biomass resources are reusable organic resources derived from animals and plants.
• Preferred resources include wood, rice straw, rice husks, rice bran, old rice, corn, sugar cane, cassava, soybeans, okara, bagasse, These are plant resources such as vegetable oils, fats and oils, waste paper, and papermaking residues.
• These biomass resources generally contain elemental nitrogen and many alkali metals and alkaline earth metals such as sodium, potassium, magnesium, and calcium.
• raw materials obtained from biomass resources are obtained by the production method described in JP-A-2020-114227.
• 1,6-hexanediol compositions derived from biomass resources such as 1,6-hexanediol compositions derived from biomass resources, can be suitably used.
• the hydrogen ion concentration (pH) of the fermentation liquid is usually adjusted using a neutralizing agent in order to proceed with the fermentation efficiently. Contains many alkali metals and alkaline earth metals in the neutralizing agent and culture solution.
• 1,6-hexanediol derived from biomass resources obtained by the production method described in JP-A-2020-114227 contains trivalent or tetravalent alcohol as an impurity. This was discovered after careful consideration. These impurities are considered unnecessary and are removed using purification methods as long as cost permits.
• the alkali metal is not an unnecessary component to coexist with 1,6-hexanediol, and the coexistence of a specific amount is rather a polymer such as polyester obtained by reacting a 1,6-hexanediol composition.
• the polymer of the present invention is obtained by reacting the 1,6-hexanediol composition of the present invention.
• the polymer is not particularly limited as long as it is a polymer having a structural unit derived from the 1,6-hexanediol composition of the present invention, and includes oligomers.
• Examples of the polymer include polyester, polyurethane, polycarbonate, polyether, epoxy polymers made from the above-mentioned epoxy group-containing 1,6-hexanediol derivatives, and the above-mentioned (meth)acryloyl group-containing 1,6-hexanediol derivatives as raw materials.
• examples include acrylic polymers. These may be used alone or in combination of two or more.
• the polymer of the present invention has at least a structural unit derived from the 1,6-hexanediol composition of the present invention, contains an alkali metal derived from the 1,6-hexanediol composition, and further contains, if necessary, an alkali metal derived from the 1,6-hexanediol composition. It has a structural unit derived from trivalent or tetravalent alcohol.
• the trihydric or tetrahydric alcohol optionally included in the 1,6-hexanediol composition is incorporated into the polymer skeleton during polymerization.
• the content of the structural unit derived from the 1,6-hexanediol composition of the present invention in 100 mass% of the polymer of the present invention is preferably 10 to 100 mass%, more preferably 20 to 100 mass%. Thereby, there is a tendency for more favorable effects to be obtained.
• the content of each structural unit in the polymer is measured by NMR.
• the total content of alkali metals (preferably the total content of one or both of sodium metal element and potassium metal element) is preferably 0.1 to 5,000 ppm by mass, more preferably 0. .2 to 5,000 ppm by mass. Thereby, there is a tendency for more favorable effects to be obtained.
• the content of structural units derived from trivalent or tetrahydric alcohol in 100% by mass of the polymer of the present invention is preferably 0.01 to 2,000 mass ppm, more preferably 0.02 to 2,000 mass ppm. be. Thereby, there is a tendency for more favorable effects to be obtained.
• the polymer may be modified. Modification is not particularly limited, and includes, for example, the modification described for 1,6-hexanediol derivatives. These may be used alone or in combination of two or more. Among these, modification with (meth)acrylic acid is preferred. In particular, when the polymer is polyester, it is preferably modified with (meth)acrylic acid.
• the weight average molecular weight (Mw) of the polymer of the present invention is preferably 2,000 to 1,000,000, more preferably 3,000 to 50,000.
• the weight average molecular weight (Mw) of a polymer is a value measured by gel permeation chromatography (GPC).
• the weight average molecular weight (Mw) is a value measured by gel permeation chromatography (GPC) under the conditions described below.
• polyester will be explained in detail, but the polymer is not limited to polyester.
• the polyester of the present invention is obtained by reacting the 1,6-hexanediol composition of the present invention.
• the polyester of the present invention is a polycondensate synthesized by dehydration condensation of a carboxylic acid and an alcohol to form an ester bond, and at least the 1,6-hexane of the present invention is used as the alcohol.
• a diol composition is used. Therefore, the polyester of the present invention is a reaction product (polycondensate) obtained by a polycondensation reaction of carboxylic acid and alcohol, and the polyester of the present invention is at least derived from the 1,6-hexanediol composition of the present invention. It has a structural unit derived from a 1,6-hexanediol composition, and further contains a structural unit derived from a trivalent or tetravalent alcohol as necessary.
• the polyester of the present invention is preferably a polyester polyol.
• the polyester polyol include condensed polyester polyols, lactone polyester polyols, and the like.
• Condensed polyester polyols include, for example, low-molecular polyhydric alcohols (ethylene glycol (EG), diethylene glycol, propylene glycol (PG), dipropylene glycol, (1,3- or 1,4-)butanediol, pentanediol, neo Low molecular polyols such as pentyl glycol, hexanediol, cyclohexanedimethanol, glycerin, 1,1,1-trimethylolpropane (TMP), 1,2,5-hexanetriol, pentaerythritol, 1,4-cyclohexanedimethanol, sugars such as sorbitol) and polybasic carboxylic acids (glutaric acid, adipic acid, azelaic
• the lactone-based polyester polyol is, for example, a polycaprolactone polyol obtained by ring-opening polymerization of a lactone such as ⁇ -caprolactone, ⁇ -methyl- ⁇ -caprolactone, and ⁇ -methyl- ⁇ -caprolactone.
• carboxylic acids examples include aliphatic polycarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, glutaric acid, pimelic acid, suberic acid, dodecanedicarboxylic acid, maleic acid, and fumaric acid; -Alicyclic polyesters such as cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, hexahydrophthalic anhydride, 1,4-cyclohexanedicarboxylic acid, etc.
• aliphatic polycarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, glutaric acid, pimelic acid, suberic acid, dodecanedicarboxylic acid, maleic acid, and fumaric acid
• Aromatic polyvalent carboxylic acids such as orthophthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, biphenyldicarboxylic acid, 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid, trimellitic acid, etc.
• Aliphatic monocarboxylic acids such as acetic acid, propionic acid, 2-ethylhexanoic acid, acrylic acid, methacrylic acid
• Aromatic monocarboxylic acids such as benzoic acid, p-tert-butylbenzoic acid, p-hydroxybenzoic acid
• Examples include fatty acids derived from various animal and vegetable oils, such as soybean oil fatty acids, tall oil fatty acids, linoleic acid, and eicosapentaenoic acid; and anhydrides thereof. These may be used alone or in combination of two or more.
• aromatic polycarboxylic acids and their anhydrides and fatty acids derived from animal and vegetable oils are preferred, and phthalic anhydride and soybean oil fatty acids are more preferred.
• the alcohol that can be used in addition to the 1,6-hexanediol composition of the present invention is not particularly limited as long as it is a compound having a hydroxyl group (alcoholic hydroxyl group or phenolic hydroxyl group).
• the alcohol include aliphatic monoalcohols such as ethanol, butanol, and 2-ethylhexanol; aliphatic polyols such as ethylene glycol, neopentyl glycol, and trimethylolpropane; and aromatic mono/polymer alcohols such as phenol, cresol, and bisphenol-A. and ethylene oxide extension products thereof, hydrogenated alicyclic groups, and the like. These may be used alone or in combination of two or more. Among them, aliphatic polyols are preferred, and neopentyl glycol and trimethylolpropane are more preferred.
• the content of the 1,6-hexanediol composition of the present invention in 100% by mass of the alcohol is preferably 1 to 100% by mass, more preferably 10 to 100% by mass. Thereby, there is a tendency for more favorable effects to be obtained.
• the polyester of the present invention can be obtained by a known method for producing polyester. Specifically, it can be synthesized by a production method in which the carboxylic acid and the alcohol are reacted at a reaction temperature of 150 to 280° C. while removing generated water from the system. Further, a reaction catalyst, an antioxidant, etc. may be used in combination during the synthesis.
• the content of the structural unit derived from the 1,6-hexanediol composition of the present invention in 100 mass% of the polyester of the present invention is preferably 10 to 70 mass%, more preferably 20 to 70 mass%. Thereby, there is a tendency for more favorable effects to be obtained.
• the content of each structural unit in polyester is measured by NMR.
• the total content of alkali metal elements is preferably 0.1 to 3,500 ppm by mass, more preferably is 0.2 to 3,500 ppm by mass. Thereby, there is a tendency for more favorable effects to be obtained.
• the content of structural units derived from trivalent or tetravalent alcohol in 100% by mass of the polyester of the present invention is preferably 0.01 to 1,400 mass ppm, more preferably 0.02 to 1,400 mass ppm. be. Thereby, there is a tendency for more favorable effects to be obtained.
• the weight average molecular weight (Mw) of the polyester of the present invention is preferably 2,000 to 120,000, more preferably 3,000 to 50,000.
• the polymer of the present invention can be used for various purposes. Specifically, it is used for coatings such as paints, inks, and adhesives; binders for nonwoven fabrics, fibers, and paper; casings for automobile parts and electrical appliances; plastic structural materials for sporting goods; vibration-proofing materials; Can be used in a wide range of applications, including rubber applications such as vibration materials.
• the polyester of the present invention can be used for various purposes. Specifically, it is used for coatings such as paints, inks, and adhesives; binders for nonwoven fabrics, fibers, and paper; casings for automobile parts and electrical appliances; plastic structural materials for sporting goods; vibration-proofing materials; Can be used in a wide range of applications, including rubber applications such as vibration materials.
• the curable resin composition of the present invention contains the polymer of the present invention (preferably the polyester of the present invention).
• the curable resin composition is not limited as long as it contains the polymer of the present invention (preferably the polyester of the present invention) and is curable.
• the curing method is not particularly limited, and the curable resin composition of the present invention includes, for example, a thermosetting resin composition that is cured by heat, an energy ray-curable resin composition that is cured by energy rays, and a resin composition that is cured by oxidative polymerization. Examples include oxidation-polymerizable curable resin compositions that harden, moisture-curable resin compositions that harden by chemical reaction with moisture, and the like. Among these, thermosetting resin compositions and oxidative polymerization type curable resin compositions are preferred.
• the content of the polymer of the present invention in 100% by mass of the composition is preferably 20 to 99.99% by mass, more preferably 50 to 99% by mass. .9% by mass.
• the content of the polymer of the present invention means the total content when a plurality of polymers of the present invention are contained. The contents of other components are also the same.
• the total content of alkali metals (preferably the total content of either or both of sodium metal and potassium metal) is preferably 0.02 to 3,496.5 ppm by mass. , more preferably 0.1 to 3,496.5 ppm by mass. Thereby, there is a tendency for more favorable effects to be obtained.
• thermosetting resin composition and the oxidative polymerization type curable resin composition will be described in detail among the curable resin compositions. It is not limited to oxidative polymerization type curable resin compositions.
• thermosetting resin composition of the present invention includes a composition containing a main ingredient containing the polymer (preferably polyester) of the present invention and a curing agent. This composition is used for thermosetting cured products in general, and can be applied to applications such as bake-cured paints, printing inks, and molded products.
• the main ingredient may contain resins other than the polymer (preferably polyester) of the present invention.
• resins other than the polymer (preferably polyester) of the present invention include polyol resins other than the polymer of the present invention.
• the polymer of the present invention preferably polyester
• the polymer of the present invention is preferably used in an amount of 20% by mass or more, more preferably 50% by mass or more based on 100% by mass of the resin component contained in the main resin. .
• the content of the main agent in 100% by mass of the composition is preferably 20 to 99.9% by mass, more preferably 50 to 90% by mass. Thereby, there is a tendency for more favorable effects to be obtained.
• the content of the polymer of the present invention (preferably the polyester of the present invention) in 100% by mass of the composition is preferably 20 to 99.9% by mass, more preferably 50 to 90% by mass. It is. Thereby, there is a tendency for more favorable effects to be obtained.
• the curing agent need only contain a component that can cause a curing reaction with the polymer of the present invention (preferably polyester), and examples of such components include amino resins, polyisocyanate resins, resol resins, and epoxy resins. Examples include resin. These may be used alone or in combination of two or more.
• the components of the curing agent are appropriately selected depending on the purpose of the curable resin composition, the usage environment, the desired physical properties of the cured product, etc., but as long as the polymer of the present invention (preferably the polyester of the present invention) is used as the main component, any The effects of the present invention can be fully exhibited even when using a curing agent of Among these, amino resins are preferred.
• amino resin examples include, for example, a methylolated amino resin synthesized from formaldehyde and at least one of melamine, urea, and benzoguanamine; Examples include those obtained by alkyl etherification with lower monohydric alcohols such as ethanol, propanol, isopropanol, butanol, and isobutanol. These may be used alone or in combination of two or more. Among these, melamine is preferred, and butylated melamine is more preferred.
• the content of the curing agent in 100% by mass of the composition is preferably 0.1 to 80% by mass, more preferably 1 to 50% by mass. Thereby, there is a tendency for more favorable effects to be obtained.
• the thermosetting resin composition may contain a curing catalyst (acid curing catalyst).
• a curing catalyst include acid compounds such as p-toluenesulfonic acid, trichloroacetic acid, phosphoric acid, monoalkylphosphoric acid, dialkylphosphoric acid, monoalkylphosphorous acid, dialkylphosphorous acid, dodecylbenzenesulfonic acid, and neutralized salts thereof. Examples include derivatives such as. These may be used alone or in combination of two or more. Among them, dodecylbenzenesulfonic acid is preferred.
• the content of the curing catalyst in 100% by mass of the composition is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass. Thereby, there is a tendency for more favorable effects to be obtained.
• An example of the oxidatively polymerizable curable resin composition of the present invention includes a composition containing the polymer of the present invention (preferably polyester) and a curing accelerator. This composition is generally used for oxidatively polymerizable cured products, and can be applied to oxidatively polymerizable paints, printing inks, molded products, and the like.
• the content of the polymer (preferably polyester) of the present invention in 100% by mass of the composition is preferably 20 to 99.99% by mass, more preferably 50 to 99.9% by mass. %. Thereby, there is a tendency for more favorable effects to be obtained.
• the curing accelerator may be a metal salt (metal soap). These may be used alone or in combination of two or more. Among these, cobalt salts are preferred, and cobalt 2-ethylhexanoate is more preferred.
• the content of the curing accelerator in 100% by mass of the composition is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass. Thereby, there is a tendency for more favorable effects to be obtained.
• the oxidative polymerization type curable resin composition may contain a curing accelerator (auxiliary dryer).
• the curing accelerator (auxiliary dryer) includes at least one metal selected from the group consisting of alkali metals such as potassium and sodium; alkaline earth metals such as calcium and strontium; and heavy metals such as zirconium and lead. , 2-ethylhexanoic acid (octylic acid), neodecanoic acid, and other metal salts (metal soaps) with various carboxylic acids. These may be used alone or in combination of two or more.
• the content of the curing accelerator in 100% by mass of the composition is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 1% by mass or less, especially Preferably it is 0.5% by mass or less, most preferably 0.1% by mass or less.
• the curable resin composition of the present invention includes a pigment, a pigment dispersant, a matting agent, a leveling agent, a drying inhibitor, an ultraviolet absorber, an antifoaming agent, a thickener, an anti-settling agent, an organic It may also contain a solvent or the like. These may be used alone or in combination of two or more. The blending ratio of each of these components and the type of blend are appropriately adjusted depending on the use and desired performance of the curable resin composition.
• the curable resin composition of the present invention may be of a one-component type or a two-component type. When the curable resin composition of the present invention is a two-component type, the various additives described above can be added to either or both of the main ingredient and the curing agent.
• the coating material of the present invention contains at least the curable resin composition of the present invention, and may contain other optional components such as pigments as appropriate.
• the curable resin compositions of the present invention the above-mentioned thermosetting resin composition can be used as a baking paint, etc.
• the above-mentioned oxidative polymerization type curable resin composition can be used as an oxidative polymerization type paint, etc.
• the method for producing the paint of the present invention include a method of mixing the curable resin composition of the present invention and other optional components in various mixers such as a homodisper.
• the coating material of the present invention can be applied to an object to be coated using a conventional method, and a coating film can be obtained by drying and curing the coating material.
• examples of the base material (object to be coated) to which the paint of the present invention can be applied include steel, plastic, wood, concrete, and the like.
• the coating (coating film) of the present invention can be applied, for example, to various metals such as home appliances, automobile parts, building materials, plastic parts, pre-coated metals for metal moldings, can manufacturing applications, woodworks such as furniture, floors, walls, etc. It can be used for a wide range of purposes, including concrete materials.
• the notation " ⁇ " means a value greater than or equal to the value before the description " ⁇ ” and less than or equal to the value after the description " ⁇ ".
• the upper and lower limits of each numerical range can be used in any combination. For example, when two numerical ranges of 0.001 to 500 mass ppm and 0.05 to 250 mass ppm are disclosed for the content of a certain compound, 0.001 to 500 mass ppm and 0.05 to 250 mass ppm are disclosed. This means that in addition to ppm, numerical ranges of 0.001 to 250 mass ppm and 0.05 to 500 mass ppm are also disclosed.
• Example 1 Preparation of 1,6-hexanediol composition 1 (1,6-HD composition 1)
• 1,6-hexanediol manufactured by Ube Industries, Ltd. whose alkali metal element content was 0.02 mass ppm sodium according to ICP-MS analysis, was melted by heating at 80°C, and acetic acid was added so that the potassium content was 500 mass ppm. Potassium was added, and 800 mass ppm of glycerin was further added and the mixture was cooled to obtain 1,6-hexanediol composition 1.
• Example 2 Preparation of 1,6-hexanediol composition 2 (1,6-HD composition 2)
• 1,6-hexanediol manufactured by Ube Industries, Ltd. whose alkali metal element content was 0.02 mass ppm sodium according to ICP-MS analysis, was melted by heating at 80°C, and acetic acid was added so that the sodium content was 995 mass ppm.
• Sodium was added, and 300 mass ppm of glycerin was added and the mixture was cooled to obtain 1,6-hexanediol composition 2.
• Example 3 Preparation of 1,6-hexanediol composition 3 (1,6-HD composition 3)
• 1,6-hexanediol manufactured by Ube Industries, Ltd. whose alkali metal element content was 0.02 mass ppm sodium according to ICP-MS analysis, was melted by heating at 80°C, and acetic acid was added so that the potassium content was 998 mass ppm. Potassium was added, and 1,900 mass ppm of glycerin was added and the mixture was cooled to obtain 1,6-hexanediol composition 3.
• Example 4 Preparation of 1,6-hexanediol composition 4 (1,6-HD composition 4)
• 1,6-hexanediol manufactured by Ube Industries, Ltd. whose alkali metal element content was 0.02 mass ppm sodium according to ICP-MS analysis, was melted by heating at 80°C, and acetic acid was added so that the potassium content was 998 mass ppm. Potassium was added, and 1,900 mass ppm of 3-methylpentane-1,3,5-triol was added and the mixture was cooled to obtain 1,6-hexanediol composition 4.
• Example 5 Preparation of 1,6-hexanediol composition 5 (1,6-HD composition 5)
• 1,6-hexanediol manufactured by Ube Industries, Ltd. whose alkali metal element content was 0.02 mass ppm sodium according to ICP-MS analysis, was melted by heating at 80°C, and acetic acid was added so that the potassium content was 998 mass ppm. Potassium was added, and 1,900 mass ppm of pentaerythritol was added and the mixture was cooled to obtain 1,6-hexanediol composition 5.
• Plasmid A was created by introducing glycerol dehydratase ⁇ , ⁇ , ⁇ subunit genes and dehydratase reactivator gene derived from Citrobacter freundii between the BamHI and HindIII restriction enzyme cleavage sites of pACYC184 (Nippon Gene). .
• MCS was introduced between the BamHI and EcoRI restriction enzyme cleavage sites to create plasmid B.
• HadB and HadC genes derived from Clostridium difficile as ⁇ and ⁇ subunit genes of 2-hydroxyisocaproyl-CoA dehydratase HadI gene derived from Clostridium difficile as 2-hydroxyisocaproyl-CoA dehydratase activating enzyme, 6- trans-2-enoyl-CoA reductase (GenBank: AE017248) gene derived from Treponema denticola as hydroxy-2,3-dehydro-hexanoyl-CoA 2,3-reductase, and the trans-2-enoyl-CoA reductase (GenBank: AE017248) gene derived from Nocardia iowensis as 6-hydroxyhexanoate 1-reductase.
• the carboxylic acid reductase (GenBank: AAR91681.1) gene and the 6-hydroxyhexanoate dehydrogenase (GenBank: AAN37489.1) gene from Rhodococcus as 6-hydroxyhexanal 1-reductase were added to pCOLADuet-1 (Novagen) with HadB, Plasmid C was created in which the HadC and HadI genes were introduced into MCS1 and the other genes were introduced into MCS2.
• Gene in this section refers to an open reading frame containing a stop codon that encodes each enzyme, and each gene has a sequence containing a T7 promoter and a ribosome binding site upstream, and a sequence containing a T7 terminator downstream.
• Plasmids A, B, and C were sequentially transformed into chemically competent cells of BL21 Star (DE3) (Invitrogen) by the heat shock method, and selected on LB plates containing appropriate antibiotics. As a result, a BL21 Star (DE3) strain containing all plasmids A, B, and C was obtained. As a result, 4,6-dihydroxy-2-oxo-hexanoate aldolase (2A in the figure of Patent No.
• Example 6 Preparation of 1,6-hexanediol composition 6 (1,6-HD composition 6)
• Autoclaved medium carbon source: glucose, glycerin, nitrogen source: enzyme extract, inorganic salts: potassium phosphate, potassium hydroxide, vitamin B12, antibiotics: carbenicillin, kanamycin, chloramphenicol, pH: 7.0
• glucose and glycerin are raw materials derived from biomass resources
• the cells were further cultured at 30°C for 3 hours to express the 1,6-HD pathway enzyme. After expression, an appropriate amount of carbon source (glucose, glycerin) was added, and the inside of the culture vessel was placed under a nitrogen atmosphere to create anaerobic conditions. Cultivation was performed under these conditions at 30°C for 48 hours to produce 1,6-hexanediol.
• carbon source glucose, glycerin
• the culture solution was centrifuged at 4°C for 20 minutes, the supernatant was collected, and the filtrate was filtered using a membrane filter with an appropriate pore size of 0.2 to 0.4 ⁇ m, and the 1,6-hexanediol composition was obtained as a filtrate. I got something.
• step (a) cation exchange was performed in a batch manner. The temperature of contact with the cation exchange resin was set at 40° C., and DIAION SK1BH manufactured by Mitsubishi Chemical Corporation was added as a cation exchange resin to the 1,6-hexanediol composition and stirred for 1 hour. After stirring, filtration was performed to obtain 1,6-hexanediol composition A as a filtrate.
• anion exchange was performed in a batch manner. The temperature of contact with the anion exchange resin was set at 40° C., and DIAION SA10AOH manufactured by Mitsubishi Chemical Corporation was added as an anion exchange resin to the 1,6-hexanediol composition and stirred for 3 hours. After stirring, filtration was performed to obtain 1,6-hexanediol composition B as a filtrate.
• a thin film distiller was used as the apparatus for step (c).
• the jacket temperature was set at 70°C, the 1,6-hexanediol-containing composition was continuously introduced, and water was distilled off from the top.
• the dehydrated 1,6-hexanediol composition C was continuously extracted from the bottom as bottoms.
• the water concentration in this 1,6-hexanediol composition C was 0.020 mass % (200 mass ppm).
• An Aldershaw distillation column was used as the distillation column in step (d).
• the 1,6-hexanediol composition C obtained in step (c) was continuously supplied to the distillation column, and the top temperature was controlled at a constant temperature of 240°C. Continuous distillation is carried out from the top of the column and continuous extraction is carried out from the bottom of the column to remove low boiling point components in 1,6-hexanediol composition C.
• the 1,6-hexanediol composition D from which the components had been removed was taken out.
• the analysis results of the obtained 1,6-HD composition 6 are shown below.
• the content of glycerin was measured by GC analysis, and the content of potassium metal element and sodium metal element was measured by ICP-MS analysis.
• Glycerin 800 mass ppm Potassium metal element: 3,080 mass ppm Sodium metal element: 1,890 mass ppm
• GC analysis details /equipment Agilent GC-MS (GC7890B/MSD5977B) ⁇ Column: Agilent J&W GC Column-DB-1 ⁇ Carrier gas: He ⁇ Flow rate: 0.966mL/min ⁇ Linear speed: 99.5cm/sec ⁇ Injection volume: 1 ⁇ L ⁇ Split ratio: 50 ⁇ Column temperature: 75°C (hold: 2 min) -10°C/min (temperature increase rate, 22.5 min) -300°C (hold: 5.5 min) ⁇ Detector: FID
• Tables 1 and 2 show the analysis results of the 1,6-hexanediol compositions obtained in the Examples and Comparative Examples. Further, in Tables 1 and 2, the detection limits for potassium metal element and sodium metal element were each 0.003 mass ppm, and the detection limit for trivalent or tetravalent alcohol was 1 mass ppm. In Tables 1 and 2, 1,6-hexanediol compositions in which potassium acetate was added were marked as ⁇ , and those in which potassium acetate was not added were marked as -. The same applies to sodium acetate, glycerin, 3-methylpentane-1,3,5-triol, and pentaerythritol.
• alcohol in the table refers to trivalent or tetravalent alcohol, and in this example, the content of glycerin, 3-methylpentane-1,3,5-triol, or pentaerythritol is described.
• polyester resin A-1 solution The weight average molecular weight (Mw) of the obtained polyester resin A-1 was 19,300, the hydroxyl value was 30 mgKOH/g, and the acid value was 8.0 mgKOH/g.
• Baking paint samples A-2 to A-9 were prepared in the same manner except that the polyester was changed to A-2 to A-9.
• Comparative Example 3 using polyester using a 1,6-hexanediol composition with a total alkali metal content exceeding 5,000 mass ppm, the hardness of the coating film was 6B or less and cured. I didn't. Further, in Comparative Examples 1 and 2 using polyesters using 1,6-hexanediol compositions having a total content of alkali metal elements of less than 1 mass ppm, the pot life could not be extended sufficiently. On the other hand, in an example using a polyester using a 1,6-hexanediol composition with a total content of alkali metal elements of 1 to 5,000 mass ppm, it was found that the pot life could be extended without causing curing failure. Do you get it.
• the prepared coating composition was coated on an SPCC steel plate with a bar coater, and the drying time (time until it became tack-free) and the pencil hardness of the coating film after drying for one day at room temperature were determined according to JIS K5600-5-4-1999. Measured according to. The evaluation results are shown in Tables 7 and 8.
• Comparative Examples 1 and 2 using polyesters using 1,6-hexanediol compositions with a total content of alkali metal elements of less than 1 mass ppm, petrochemical A system using a 1,6-HD composition of the product (Comparative Example 1-2) or a polyester using a 1,6-hexanediol composition with a total alkali metal content of 1 to 5,000 mass ppm.
• the curing (drying) time was longer than in the example using.
• the weight average molecular weight (Mw) of polyester is a value measured by gel permeation chromatography (GPC) under the following conditions.
• Measuring device HLC-8320GPC manufactured by Tosoh Corporation
• Detector; RI differential refractometer
• Data processing Multi-station GPC-8020model II manufactured by Tosoh Corporation Measurement conditions: Column temperature 40°C Solvent Tetrahydrofuran Flow rate 0.1 ml/min Standard; Monodispersed polystyrene sample; 0.2% tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (100 ⁇ l) Standard sample: A calibration curve was created using the following standard polystyrene.

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