WO2020149082A1 - 共重合ポリエステルおよび水分散体 - Google Patents
共重合ポリエステルおよび水分散体 Download PDFInfo
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- WO2020149082A1 WO2020149082A1 PCT/JP2019/049628 JP2019049628W WO2020149082A1 WO 2020149082 A1 WO2020149082 A1 WO 2020149082A1 JP 2019049628 W JP2019049628 W JP 2019049628W WO 2020149082 A1 WO2020149082 A1 WO 2020149082A1
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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
- 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
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
-
- 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
- C08G63/123—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/137—Acids or hydroxy compounds containing cycloaliphatic rings
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/07—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from polymer solutions
-
- 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
- C09D17/00—Pigment pastes, e.g. for mixing in paints
- C09D17/001—Pigment pastes, e.g. for mixing in paints in aqueous medium
-
- 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
- C09D17/00—Pigment pastes, e.g. for mixing in paints
- C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
- C09D17/007—Metal oxide
- C09D17/008—Titanium dioxide
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
- C09D5/022—Emulsions, e.g. oil in water
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
- C09D5/024—Emulsion paints including aerosols characterised by the additives
- C09D5/028—Pigments; Filters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
-
- 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
Definitions
- the present invention relates to a copolyester and an aqueous dispersion. More specifically, it relates to a copolyester and an aqueous dispersion which are excellent in storage stability, water-resistant adhesion, processability, weather resistance and leveling property.
- Copolyester is widely used as a raw material for resin compositions used in coating agents, inks and adhesives, and is generally composed of polycarboxylic acids and polyhydric alcohols. Since flexibility and molecular weight can be freely controlled by selecting and combining polyhydric carboxylic acids and polyhydric alcohols, they are widely used in various applications including coating agents and adhesives.
- the copolyester having an alicyclic skeleton in the resin has excellent processability and weather resistance, and is used for paints with outdoor durability (for example, Patent Document 1).
- Patent Document 1 JP-A-5-239196
- an object of the present invention is to provide a copolyester effective as a resin component that exhibits long-term stability when dispersed in water, and further, a condition assuming exposure under humid conditions for a long period of time.
- Water-dispersed polyester resin capable of forming a coating film that has water-resistant adhesion to substrates and weatherability, and has processability (high flexibility) equivalent to that of high-molecular-weight polyester, and that has excellent leveling properties.
- the present inventors have found that the above-mentioned problems can be solved by the means described below, and arrived at the present invention. That is, the present invention has the following configurations.
- the polyvalent carboxylic acid component and the polyhydric alcohol component are used as copolymerization components and the polyvalent carboxylic acid component is 100 mol %, the alicyclic polyvalent carboxylic acid component is 50 mol% or more and the acid value is 170 equivalents/ A copolyester having a weight ratio of 10 6 to 1,000 equivalents/10 6 g.
- the alicyclic polyvalent carboxylic acid component is preferably 1,4-cyclohexanedicarboxylic acid or tetrahydrophthalic anhydride.
- the glass transition temperature of the copolyester is preferably 5° C. or lower.
- the number average molecular weight of the copolyester is preferably 10,000 or less.
- An aqueous dispersion of copolyester obtained by dispersing the copolyester in water.
- the water dispersion using the copolyester of the present invention is excellent in weather resistance, leveling property, processability (flexibility), and water resistance adhesion, and exhibits good storage stability. Therefore, it is suitable for a water-based coating applied to a metal or plastic substrate.
- An aqueous dispersion (hereinafter, also simply referred to as an aqueous dispersion) using the copolyester of the present invention exhibits excellent weather resistance, leveling property, processability, water-resistant adhesiveness, and storage stability. Therefore, it is suitable for a water-based paint that is exposed to an outdoor environment after coating, and a product produced using the copolyester of the present invention can obtain a smooth coating film having high flexibility and high water resistance.
- the copolyester of the present invention has a chemical structure that can be obtained by a polycondensation product of a polyvalent carboxylic acid component and a polyhydric alcohol component, and the polyvalent carboxylic acid component and the polyhydric alcohol component are each one or two. It is composed of at least one selected ingredient.
- the alicyclic polyvalent carboxylic acid component is 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more, and further preferably It is 80 mol% or more, particularly preferably 90 mol% or more, and 100 mol% is also acceptable.
- the leveling property of the aqueous dispersion produced using the copolyester is excellent, and the processability and weather resistance of the coating film tend to be improved.
- the total amount of the polyvalent carboxylic acid component and the polyhydric alcohol component may exceed 200 mol %.
- the total amount of the composition excluding the component to which the acid anhydride or the like is added later (added after) is calculated as 200 mol %.
- the alicyclic polycarboxylic acid constituting the copolyester of the present invention is preferably an alicyclic dicarboxylic acid.
- the alicyclic dicarboxylic acid is not particularly limited, and 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, tetrahydrophthalic acid anhydride, methyltetrahydrophthalic acid anhydride And hydrogenated naphthalenedicarboxylic acid, and derivatives thereof can be used.
- the alicyclic dicarboxylic acid components may be used alone or in combination of two or more.
- 1,4-cyclohexanedicarboxylic acid or tetrahydrophthalic anhydride is preferable, and it is more preferable to use 1,4-cyclohexanedicarboxylic acid and tetrahydrophthalic anhydride together.
- 1,4-cyclohexanedicarboxylic acid and tetrahydrophthalic anhydride are used in combination, 1,4-cyclohexanedicarboxylic acid/tetrahydrophthalic anhydride is preferably 90 to 50/10 to 50 (molar ratio), It is more preferably 80 to 60/20 to 40 (molar ratio).
- the polycarboxylic acid component other than the alicyclic polycarboxylic acid component is preferably an aromatic polycarboxylic acid or an aliphatic polycarboxylic acid, and an aromatic dicarboxylic acid or More preferably, it is an aliphatic dicarboxylic acid.
- a polyvalent carboxylic acid component other than the aromatic polyvalent carboxylic acid component or the aliphatic polyvalent carboxylic acid component is contained as the copolymerization component, the storage stability of the aqueous dispersion may be reduced.
- the total amount of the aromatic polyvalent carboxylic acid and the aliphatic polyvalent carboxylic acid is 50 mol% or less, preferably 40 mol% or less, more preferably 30 mol, based on 100 mol% of all the polyvalent carboxylic acid components. % Or less, more preferably 20 mol% or less, particularly preferably 10 mol% or less, and 0 mol% is also acceptable.
- the aromatic dicarboxylic acid constituting the copolyester of the present invention is not particularly limited, but terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, 4,4′-dicarboxybiphenyl, 5-sodium sulfoisophthalic acid, And these derivatives (dimethyl terephthalate, dimethyl isophthalate) etc. can be used. Of these, terephthalic acid and isophthalic acid are preferable.
- the aliphatic dicarboxylic acid is not particularly limited, and succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and derivatives thereof (dimethyl adipate, dimethyl sebacate), etc. should be used. You can Of these, adipic acid is preferred.
- the acid value of the copolyester of the present invention must be 170 to 1000 equivalents/10 6 g.
- the acid value is preferably 200 equivalent/10 6 g or more, more preferably 300 equivalent/10 6 g or more.
- the amount is 170 equivalents/10 6 g or more, the stability of the aqueous dispersion of the copolyester becomes good.
- it is preferably 800 equivalent/10 6 g or less, and more preferably 600 equivalent/10 6 g or less.
- the amount is 1000 equivalents/10 6 g or less, the water-resistant adhesiveness is improved, which is suitable for applications requiring durability.
- the polyhydric alcohol constituting the copolyester of the present invention is not particularly limited, but ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol.
- 1,4-butanediol 2-methyl-1,3-propanediol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1- Methyl-1,8-octanediol, 2-methyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-ethyl-2-n-propyl-1,3 -Propanediol, 2,2-di-n-propyl-1,3-propanediol, 2-n-butyl-2-ethyl-1,3-propanediol, 2,2-di-n-butyl-1,3- Propanediol, 2,4-diethyl-1,5-pentanediol, 2-ethyl-1,3-hexan
- Glycol components such as polyalkylene ether glycol, glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, ⁇ -methylglucose, mannitol and sorbitol can be used, and one or more of them can be used.
- the copolymerized polyester of the present invention is preferably copolymerized with a trivalent or higher polyvalent carboxylic acid component and/or a trivalent or higher polyhydric alcohol component.
- the trivalent or higher polycarboxylic acid component include aromatic carboxylic acids such as trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, trimesic acid, trimellitic anhydride (TMA), and pyromellitic anhydride (PMDA).
- aliphatic carboxylic acids such as 1,2,3,4-butanetetracarboxylic acid, and the like, and these can be used alone or in combination of two or more.
- the copolymerization amount of the trivalent or higher polyvalent carboxylic acid component is preferably 1 mol% or more, more preferably 3 mol% or more, when the total polyvalent carboxylic acid component is 100 mol %. , And more preferably 5 mol% or more. Further, it is preferably 30 mol% or less, more preferably 20 mol% or less, and further preferably 10 mol% or less. If it exceeds 30 mol %, gelation may occur during polymerization.
- the trihydric or higher polyhydric alcohol component examples include glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, ⁇ -methylglucose, mannitol, and sorbitol, and one or more of them may be used. It is possible.
- the copolymerization amount of the trihydric or higher polyhydric alcohol component is preferably 10 mol% or more, more preferably 15 mol% or more, and further preferably, when the total polyhydric alcohol component is 100 mol %. Is 20 mol% or more, particularly preferably 30 mol% or more. Further, it is preferably 50 mol% or less, and more preferably 40 mol% or less.
- the copolyester When the copolymerization amount of the trivalent or higher polyvalent carboxylic acid component and/or the trivalent or higher polyvalent alcohol component is within the above range, the copolyester can be appropriately branched, and the copolyester water The storage stability and water-resistant adhesion of the dispersion will be good. On the other hand, when the amount of the polyhydric alcohol component copolymerized is more than 50 mol %, gelation may occur during the polymerization.
- the glass transition temperature of the copolyester of the present invention is preferably 5° C. or lower, more preferably 0° C. or lower, further preferably ⁇ 10° C. or lower, particularly preferably ⁇ 20° C. or lower.
- the glass transition temperature is in the range of 5° C. or lower, both good leveling property and processability of the coating film can be achieved.
- the number average molecular weight of the copolyester of the present invention is preferably 10,000 or less, more preferably 6000 or less. Further, it is preferably 1000 or more, and more preferably 2000 or more. When the number average molecular weight is within the above range, the leveling property becomes good.
- a polyvalent carboxylic acid and a polyhydric alcohol are heated in the presence of a known catalyst, a dehydration esterification step is performed, and a polyhydric alcohol is removed.
- a dehydration esterification step is performed, and a polyhydric alcohol is removed.
- part or all of the acid component may be replaced with an acid anhydride.
- conventionally known polymerization catalysts for example, titanium compounds such as tetra-n-butyl titanate, tetraisopropyl titanate, titanium oxyacetylcetonate, antimony trioxide, and tritium oxide. It is possible to use antimony compounds such as butoxyantimony, germanium compounds such as germanium oxide and tetra-n-butoxygermanium, and acetates such as magnesium, iron, zinc, manganese, cobalt and aluminum. These catalysts can be used alone or in combination of two or more.
- a method for increasing the acid value of the copolyester of the present invention for example, (1) after completion of the polycondensation reaction, a trivalent or higher polyvalent carboxylic acid and/or a trivalent or higher polyvalent anhydrous carboxylic acid is added, There are a method of reacting (acid addition) and a method of intentionally changing the resin by allowing heat, oxygen, water, etc. to act during the (2) polycondensation reaction, and these can be arbitrarily performed.
- the polycarboxylic acid anhydride used for the acid addition in the acid addition method is not particularly limited, and examples thereof include phthalic anhydride, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, trimellitic anhydride, and anhydrous. Pyromellitic acid, hexahydrophthalic anhydride, 3,3,4,4-benzophenone tetracarboxylic dianhydride, 3,3,4,4-biphenyltetracarboxylic dianhydride, ethylene glycol bisanhydrotrimellitate And the like, and these can be used alone or in combination of two or more. Preferred is trimellitic anhydride.
- the trivalent or higher polyvalent carboxylic acid component and/or the trivalent or higher polyvalent anhydrous carboxylic acid component used in the acid addition are not included in the calculation when the polyvalent carboxylic acid component is 100 mol %.
- the water dispersion is a composition containing the copolyester and water, and preferably a composition in which the copolyester is dispersed in an organic solvent and water.
- organic solvent those having hydrophilicity are preferable, alcohols such as methanol, ethanol, isopropanol and 2-ethylhexanol, ethers such as n-butyl cellosolve, t-butyl cellosolve, propylene glycol monomethyl ether and dipropylene glycol monomethyl ether, Examples thereof include glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 2-methyl-1,3-propanediol and 1,4-butanediol.
- cyclohexanone which has low hydrophilicity
- ketones such as isophorone
- ethers are preferable, and glycol ether type is more preferable.
- the amount of the organic solvent is preferably 20 parts by mass or more with respect to 100 parts by mass of the copolyester, and when the organic solvent is within the above range, long-term storage stability becomes good.
- the solid content concentration of the water dispersion is preferably 45 parts by mass or less, and the workability becomes good when the solid content concentration is within the above range.
- a base component In order to improve the dispersibility in water of the copolyester of the present invention, it is preferable to neutralize the acid component in the copolyester with a base component to form a neutralized salt.
- the base component that can be used is not particularly limited, but from lithium hydroxide, sodium hydroxide, alkali metal salts such as potassium hydroxide, ammonia, monoethanolamine, triethylamine, dimethylaminoethanol, organic amines such as diazabicycloundecene, and the like. You can choose freely.
- the neutralized salt can be used as an aqueous dispersion having good storage stability.
- the base component is preferably 1 part by mass or more, more preferably 1.5 parts by mass or more, and further preferably 2 parts by mass or more with respect to 100 parts by mass of the copolyester. Further, it is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and further preferably 3 parts by mass or less.
- Copolyester (a1) In a reaction vessel equipped with a stirrer, a condenser, and a thermometer, 453 parts of 1,4-cyclohexanedicarboxylic acid, 174 parts of tetrahydrophthalic anhydride, 113 parts of trimethylolpropane, and 1,6-hexane. 566 parts of diol and tetrabutyl orthotitanate as a catalyst were charged in an amount of 0.03 mol% with respect to all acid components, and the temperature was raised from 160° C. to 220° C. over 4 hours, and an esterification reaction was carried out through a dehydration step.
- the pressure in the system was reduced to 5 mmHg over 20 minutes, and the temperature was further raised to 250°C. Then, the pressure was reduced to 0.3 mmHg or less, and a polycondensation reaction was performed for 60 minutes. Then, the mixture was cooled to 180° C., 30 parts of trimellitic anhydride was added, and the reaction was carried out for 30 minutes. I took this out.
- the number average molecular weight was 6000, the glass transition temperature was ⁇ 20° C., and the acid value was 396 equivalents/10 6 g.
- Table 1 The results are shown in Table 1.
- the polyester aqueous dispersions (b1) to (b15) were allowed to stand at 5° C. and 25° C. for 3 months, and changes in solution viscosity at each temperature were confirmed. The smaller the increase in viscosity, the better the storage stability.
- the solution viscosity was measured by filling a polyester water dispersion in a glass container and measuring it at 25° C. with a BL type viscometer manufactured by Toki Sangyo Co., Ltd. The rotation speed was 30 rpm.
- Example 1 Preparation of water-based paint
- 100 parts of titanium oxide (CR-93: made by Ishihara Sangyo Co., Ltd.), 179 parts of ion-exchanged water, and 289 parts of glass beads were put in a glass container and dispersed for 6 hours with a Shinto machine to obtain a pigment paste (X).
- a water-based paint (A1) was obtained by mixing 3 parts in a container and stirring.
- Bonded (registered trademark) steel plate having a thickness of 0.5 mm was coated with the water-based paint obtained in the above-mentioned Examples and Comparative Examples so that the film thickness after drying was 12 ⁇ m, and dried at 250° C. for 50 seconds. The test piece of was obtained.
- the metal coated plate test piece was irradiated with a super UV tester (acceleration test of aging change) for 48 hours (measurement condition: UV lamp irradiation amount 100 mW under conditions of temperature 50° C. and humidity 50%) (48 hour test).
- the weather resistance was evaluated by the gloss retention rate before and after the 48-hour test.
- the gloss was measured by using GLOSS METER (manufactured by Tokyo Denshoku Co., Ltd.) to measure reflection at 60 degrees.
- ⁇ Gloss retention 70% to less than 90%
- ⁇ Gloss retention 50% to less than 70%
- X Gloss retention less than 50%
- copolyester of the present invention and the water dispersion are excellent in storage stability, water-resistant adhesion, processability, water resistance, weather resistance and leveling property, and are useful as resins for water-based paints.
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Abstract
Description
すなわち、本発明は、以下の構成からなる。
本発明の共重合ポリエステルを用いた水分散体(以下、単に水分散体ともいう。)は優れた耐候性、レベリング性、加工性耐水密着性、および保存安定性を発揮する。このため、コーティング後に屋外環境下に曝されるような水性塗料に好適であり、本発明の共重合ポリエステルを用いて製造された製品は高屈曲性、高耐水性を有する平滑な塗膜が得られる。
なお、前記酸付加で用いる3価以上の多価カルボン酸成分および/または3価以上の無水多価カルボン酸成分は、多価カルボン酸成分を100モル%としたときの計算には含めない。
水分散体は、前記共重合ポリエステルおよび水を含有する組成物であり、好ましくは共重合ポリエステルを有機溶媒および水に分散した組成物である。有機溶剤としては親水性を有するものが好ましく、メタノール、エタノール、イソプロパノール、2-エチルヘキサノールなどのアルコール類、n-ブチルセロソルブ、t-ブチルセロソルブ、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテルなどのエーテル類、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ジプロピレングリコール、トリプロピレングリコール、2-メチル-1,3-プロパンジオール、1,4-ブタンジオール等のグリコール類があげられる。また、水分散体としたときに分離しないものであれば、親水性の低いシクロヘキサノン、イソホロンなどのケトン類なども使用することができ、溶解性、蒸発速度(乾燥性)などを考慮して任意に選択、配合される。なかでもエーテル類が好ましく、グリコールエーテル系がより好ましい。有機溶媒は共重合ポリエステル100質量部に対して20質量部以上であることが好ましく、有機溶媒が前記範囲内であると長期の保存安定性が良好となる。水分散体の固形分濃度としては、45質量部以下であることが好ましく、固形分濃度が前記範囲内であると作業性が良好となる。
400MHzの1H-核磁気共鳴スペクトル装置(以下、NMRと略記することがある)を用い、共重合ポリエステルを構成する多価カルボン酸成分、多価アルコール成分のモル比定量を行った。溶媒には重クロロホルムを使用した。なお、酸後付加により共重合ポリエステルの酸価を上げた場合には、酸後付加に用いた酸成分以外の酸成分の合計を100モル%として、各成分のモル比を算出した。
試料(共重合ポリエステル)4mgを、4mLのテトラヒドロフランに溶解した後、孔径0.2μmのポリ四フッ化エチレン製メンブランフィルターでろ過した。これを試料溶液とし、ゲル浸透クロマトグラフィー(GPC)で分析を行った。装置はTOSOH HLC-8220、検出器は示差屈折率検出器、移動相はテトラヒドロフランを用い、流速1mL/分、カラム温度40℃で測定した。カラムは昭和電工製KF-802、804L、806Lを直列で用いた。分子量標準には単分散ポリスチレンを使用し、数平均分子量は標準ポリスチレン換算値とし、分子量1000未満に相当する部分を省いて算出した。
示差走査型熱量計(SII社、DSC-200)を用いて測定した。試料(共重合ポリエステル)5mgをアルミニウム抑え蓋型容器に入れ密封し、液体窒素を用いて-50℃まで冷却した。次いで150℃まで20℃/分の昇温速度にて昇温させ、昇温過程にて得られる吸熱曲線において、吸熱ピークが出る前(ガラス転移温度以下)のベースラインの延長線と、吸熱ピークに向かう接線(ピークの立ち上がり部分からピークの頂点までの間での最大傾斜を示す接線)との交点の温度をもって、ガラス転移温度(Tg、単位:℃)とした。
試料(共重合ポリエステル)0.2gを精秤しクロロホルム40mlに溶解した。次いで、0.01Nの水酸化カリウムのエタノール溶液で滴定を行った。指示薬にはフェノールフタレインを用いた。試料に対して、水酸化カリウム当量を求め、測定値を試料106gあたりの当量に換算し、単位は当量/106gとした。
試料(共重合ポリエステル)0.1±0.005gおよびフェノール/テトラクロロエタン(重量比6/4)の混合溶媒25ccに溶かし、ウベローデ粘度管を用いて30℃で測定した。
攪拌機、コンデンサー、温度計を具備した反応容器に1,4-シクロヘキサンジカルボン酸453部、テトラヒドロフタル酸無水物174部、トリメチロールプロパン113部、1,6-ヘキサンジオール566部、触媒としてオルトチタン酸テトラブチルを全酸成分に対して0.03モル%仕込み、160℃から220℃まで4時間かけて昇温、脱水工程を経ながらエステル化反応を行った。次に重縮合反応工程は、系内を20分かけて5mmHgまで減圧し、さらに250℃まで昇温を進めた。次いで、0.3mmHg以下まで減圧し、60分間の重縮合反応を行った。その後、180℃まで冷却し、無水トリメリット酸30部を投入し、30分間反応させた。これを取り出した。得られた共重合ポリエステル(a1)はNMRによる組成分析の結果、モル比で1,4-シクロヘキサンジカルボン酸/テトラヒドロフタル酸無水物/トリメチロールプロパン/1,6-ヘキサンジオール=70/30/15/85[モル比]であった。また、数平均分子量は6000、ガラス転移温度は-20℃、酸価は396当量/106gであった。結果を表1に記載した。
共重合ポリエステル(a1)の製造例に準じ、原料の種類と配合比率を変更して、共重合ポリエステル(a2)~(a15)を合成した。結果を表1に記載した。
上記共重合ポリエステル(a1)500部をノルマルブチルセロソルブ188部に溶解し、ジメチルアミノエタノール13部を添加後、イオン交換水549部を添加して、水分散体(b1)を得た。結果を表1に記載した。
水分散体(b1)の製造例に準じ、原料の種類と配合比率を変更して、本発明の水分散体(b2)~(b15)を製造した。結果を表1に記載した。
ポリエステル水分散体(b1)~(b15)を5℃、および25℃下に3か月間静置し、各温度での溶液粘度の変化を確認した。粘度の上昇が小さいほど保存安定性は良好である。溶液粘度の測定は、ポリエステル水分散体をガラス容器に充填し、25℃下で、東機産業社製BL型粘度計で測定した。回転数は30rpmとした。
評価基準
溶液粘度の変化幅=|静置後の溶液粘度/静置前の溶液粘度|
○:溶液粘度の変化幅≦100%
△:溶液粘度の変化幅>100%
×:溶液が固化した。
合成直後のポリエステル水分散体(b1)~(b15)を撹拌しながら加熱することで固形分濃度50質量%まで溶媒を蒸発させ、溶液粘度をBROOKFIELD社製コーンプレート型粘度計(HBDV-II+P CP)で測定した。固形分濃度50質量%での溶液粘度が低いほどレベリング性は良好である。
評価基準
○:500Pa・s以下
△:500Pa・sを超えて1000Pa・s以下
×:1000Pa・sを超える
酸化チタン(CR-93:石原産業製)100部、イオン交換水 179部、ガラスビーズ289部をガラス容器に入れ、しんとう機にて6時間分散し、顔料ペースト(X)を得た。次いで、水分散体(b1)100部、メラミン樹脂(サイメル(登録商標)327:オルネクス社)11部、顔料ペースト(X)140部、レベリング剤(BYK(登録商標)-381:BYK社)0.3部を容器に配合し、撹拌することで水性塗料(A1)を得た。
水性塗料(A1)と同様の方法にて、本発明の実施例または比較例である水性塗料(A2)~(A15)を得た。
(試験片の作成)
0.5mm厚のボンデ(登録商標)鋼板に前記実施例及び比較例で得られた水性塗料を乾燥後の膜厚が12μmとなる様に塗装し、250℃で50秒間乾燥し、金属塗装板の試験片を得た。
前記金属塗装板試験片を25℃下で塗膜面を外側に180°折り曲げ試験を行い、目視にて、塗膜の割れを確認した。例えば、2Tとは、金属板塗装板試験片と同じ厚さの金属板を2枚挟んで折り曲げた際に塗膜の割れが発生しないことである。数字が小さいほど屈曲性が良好である。
評価基準
○:1T以上
△:2~3T
×:4T以下
前記金属塗装板試験片の端部をテープで保護し、95℃温水中に24時間浸漬させた。浸漬後、取り出した金属塗装板試験片上の塗膜に、素地に達するように1mm間隔の碁盤目状にクロスカットを入れ、大きさ1mm×1mmの碁盤目を100個作った。その表面に粘着セロハンテープを貼着し、20℃においてそのテープを急激に剥離した後の碁盤目塗膜の残存数を調べた。
評価基準
◎:塗膜残存マス数80個以上
○:塗膜残存マス数30~79個
△:塗膜残存マス数78~39個
×:塗膜残存マス数38個以下
前記金属塗装板試験片をスーパーUVテスター(経時変化の加速試験)で48時間照射(測定条件:温度50℃、湿度50%の条件下で、UVランプ照射量100mW)した(48時間試験)。48時間試験前後の光沢保持率により耐候性の評価を行った。ここで光沢は、GLOSS METER(東京電飾社製)を用いて、60度での反射を測定した。
評価基準
◎:光沢保持率90%以上
○:光沢保持率70%以上90%未満
△:光沢保持率50%以上70%未満
×:光沢保持率50%未満
Claims (5)
- 多価カルボン酸成分と多価アルコール成分を共重合成分とし、多価カルボン酸成分を100モル%としたとき脂環族多価カルボン酸成分が50モル%以上であり、酸価が170当量/106g~1000当量/106gである共重合ポリエステル。
- 脂環族多価カルボン酸成分が、1,4-シクロヘキサンジカルボン酸またはテトラヒドロフタル酸無水物である請求項1に記載の共重合ポリエステル。
- ガラス転移温度が5℃以下である請求項1または2に記載の共重合ポリエステル。
- 数平均分子量が10000以下であることを特徴とする請求項1~3のいずれかに記載の共重合ポリエステル。
- 請求項1~4のいずれかに記載の共重合ポリエステルと水を含有する共重合ポリエステル水分散体。
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EP19910839.0A EP3913013A4 (en) | 2019-01-17 | 2019-12-18 | COPOLYESTER AND AQUEOUS DISPERSION |
JP2020532830A JP7415282B2 (ja) | 2019-01-17 | 2019-12-18 | 共重合ポリエステルおよび水分散体 |
EP23165491.4A EP4223827A1 (en) | 2019-01-17 | 2019-12-18 | Copolymerized polyester and water dispersion |
CA3118423A CA3118423A1 (en) | 2019-01-17 | 2019-12-18 | Copolymerized polyester and water dispersion |
KR1020217019295A KR20210114396A (ko) | 2019-01-17 | 2019-12-18 | 공중합 폴리에스테르 및 수분산체 |
CN201980086613.2A CN113227198B (zh) | 2019-01-17 | 2019-12-18 | 共聚聚酯及其水分散体 |
MX2021006898A MX2021006898A (es) | 2019-01-17 | 2019-12-18 | Poliester copolimerizado y dispersion acuosa. |
US17/290,393 US20210371581A1 (en) | 2019-01-17 | 2019-12-18 | Copolymerized polyester and water dispersion |
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