WO2018084064A1 - Résine de polyester polyol, et revêtement - Google Patents

Résine de polyester polyol, et revêtement Download PDF

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Publication number
WO2018084064A1
WO2018084064A1 PCT/JP2017/038679 JP2017038679W WO2018084064A1 WO 2018084064 A1 WO2018084064 A1 WO 2018084064A1 JP 2017038679 W JP2017038679 W JP 2017038679W WO 2018084064 A1 WO2018084064 A1 WO 2018084064A1
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Prior art keywords
polyester polyol
mass
resin
polyol resin
compound
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PCT/JP2017/038679
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English (en)
Japanese (ja)
Inventor
グラン マルティネス アレハンドロ
美桜 松下
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Dic株式会社
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Publication of WO2018084064A1 publication Critical patent/WO2018084064A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672—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
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • the present invention relates to a polyester polyol resin that is highly soluble in a weak solvent, has a good balance between hardness and flexibility in a cured coating film and is excellent in solvent resistance, a curable resin composition using the same, a paint, and a coated steel sheet.
  • PCM pre-coated metal
  • a weak solvent high solubility in a solvent having a low environmental load generally called a weak solvent, storage stability of the weak solvent solution, and the like are also important performances.
  • Various types of paint such as two-component curing type, ultraviolet curing type, and volatile drying type are used for PCM paint, and there are various types of resin such as polyester resin, fluorine resin, acrylic resin, etc.
  • a two-component curable coating mainly comprising a polyester resin is widely used.
  • polyester resins examples include, for example, number average molecular weights using terephthalic acid, isophthalic acid, 2-methyl-1,3-propanediol, and 1,6-hexanediol as reaction raw materials (although a coating mainly composed of a polyester resin having a Mn of 11,000 is known (see Patent Document 1), the polyester resin described in Patent Document 1 has low solubility in a weak solvent and surface hardness in a cured coating film. The balance between performance and flexibility and solvent resistance was not sufficient.
  • the problem to be solved by the present invention is a polyester polyol resin having high solubility in a weak solvent, excellent balance between hardness and flexibility in a cured coating film and excellent solvent resistance, and a curable resin composition using the same It is in providing a thing, a paint, and a coated steel plate.
  • polyester polyol resin using an aromatic dicarboxylic acid compound or a derivative thereof as an essential reaction raw material has a high solubility in a weak solvent, and is found to have excellent balance between hardness and flexibility in a cured coating film and excellent solvent resistance.
  • the present invention has been completed.
  • the present invention relates to a polyester polyol resin having a weight average molecular weight (Mw) in the range of 3,000 to 120,000, comprising 2-methyl-1,3-propanediol (A), ether in the molecular structure.
  • Mw weight average molecular weight
  • the present invention relates to a polyester polyol resin comprising a diol compound (B) having a binding site and an aliphatic dicarboxylic acid compound having 4 to 8 carbon atoms or a derivative (C) thereof as essential reaction materials.
  • the present invention further relates to a curable resin composition
  • a curable resin composition comprising a main component containing the polyester polyol resin and a curing agent.
  • the present invention further relates to a paint comprising the curable resin composition.
  • the present invention further relates to a coated steel sheet having a coating film made of the paint.
  • a polyester polyol resin having a high solubility in a weak solvent, a balance between hardness and flexibility in a cured coating film and excellent solvent resistance, a curable resin composition using the same, a paint, and a coated steel sheet can be provided.
  • the polyester polyol resin of the present invention is a polyester polyol resin having a weight average molecular weight (Mw) in the range of 3,000 to 120,000, wherein 2-methyl-1,3-propanediol (A) has a molecular structure of A diol compound (B) having an ether bond site and an aliphatic dicarboxylic acid compound having 4 to 8 carbon atoms or a derivative thereof (C) are essential reaction materials.
  • Mw weight average molecular weight
  • the diol compound (B) having an ether bond site in the molecular structure is not particularly limited as long as it is a diol compound having one or more ether bond sites in the molecular structure, and various compounds can be used. it can.
  • Specific examples of the diol compound (B) having an ether bond site in the molecular structure include, for example, the following structural formula (1)
  • each R is independently an aliphatic hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 or more.
  • R is an aliphatic hydrocarbon group having 1 to 6 carbon atoms, and may be linear or branched. Specifically, methylene group, ethylene group, 1,2-propylene group, 1,3-propylene group, tetramethylene group, 2-methyl-1,3-propylene group, pentamethylene group, 2,2-dimethyl- Examples include 1,3-propylene group, hexamethylene group, 3-methyl-1,5-pentylene group and the like. Among these, an aliphatic hydrocarbon group having 2 to 4 carbon atoms is preferable because of excellent balance between hardness and flexibility in a cured coating film and excellent solvent resistance.
  • N in the structural formula (1) is an integer of 1 or more. Among these, an integer of 1 to 4 is preferable because a balance between hardness and flexibility in a cured coating film and solvent resistance are excellent, and a compound in which n is 1 is particularly preferable.
  • the polyester polyol resin of the present invention comprises 2-methyl-1,3-propanediol (A) as a raw material diol component and a diol compound (B) having an ether bond site in the molecular structure as essential components.
  • Other diol compounds other than these may be used in combination.
  • Other diol compounds include, for example, other aliphatic diol compounds other than 2-methyl-1,3-propanediol (A); alicyclic structure-containing diol compounds such as cyclohexanediol and cyclohexanedialcohol; biphenols and bisphenols Aromatic ring-containing diol compounds; polycarbonate diol and the like.
  • Examples of the other aliphatic diol compounds include 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9- Linear aliphatic diol compounds such as nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol neopentyl glycol; 2-ethyl-1,3-propanediol, 2-methyl 1,4-butanediol, 2-ethyl-2-methyl-1,3-propanediol, 2-ethylbutane-14-butanediol, 2,3-dimethyl-1,4-butanediol, 3-methyl-1 , 5-pentanediol, 2,4-dimethyl-1,5-pentan
  • the polyester polyol resin of the present invention is highly soluble in a weak solvent, exhibits a sufficient balance between hardness and flexibility in a cured coating film and excellent solvent resistance, so the total mass of the diol raw material
  • the total mass of 2-methyl-1,3-propanediol (A) and the diol compound (B) having an ether bond site in the molecular structure is preferably 60% by mass or more, and 90% by mass. More preferably.
  • the ratio of 2-methyl-1,3-propanediol (A) to the total mass of the diol raw material is preferably in the range of 40 to 95% by mass, and more preferably in the range of 55 to 90% by mass. A range of 60 to 80% by mass is particularly preferable.
  • the ratio of the diol compound (B) having an ether bond site in the molecular structure to the total mass of the diol raw material is preferably in the range of 5 to 50% by mass, and more preferably in the range of 10 to 45% by mass. Further, the mass ratio [(A) / (B)] of 2-methyl-1,3-propanediol (A) and the diol compound (B) having an ether bond site in the molecular structure is 55/45 to 90 A range of / 10 is preferable.
  • Examples of the aliphatic dicarboxylic acid compound having 4 to 8 carbon atoms or the derivative (C) thereof include succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and acid anhydrides thereof. And acid halides.
  • the aliphatic dicarboxylic acid compound having 4 to 8 carbon atoms or the derivative (C) thereof may be used alone or in combination of two or more.
  • polyester polyol resin of the present invention in addition to the aliphatic dicarboxylic acid compound having 4 to 8 carbon atoms or its derivative (C), other dicarboxylic acid compound or its derivative may be used as a part of the reaction raw material.
  • dicarboxylic acid compounds or derivatives thereof include, for example, aliphatic dicarboxylic acid compounds having 1 to 3 or 9 or more carbon atoms such as oxalic acid, malonic acid, azelaic acid, sebacic acid or the like; phthalic acid, isophthalic acid, Terephthalic acid, aromatic dicarboxylic acid compounds such as acid anhydrides and acid halides thereof or derivatives thereof (C ′); hexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, and acid anhydrides and acids thereof Examples thereof include alicyclic dicarboxylic acid compounds such as halides or derivatives thereof (C ′′). Among them, since they are excellent in the balance between hardness and flexibility in cured coating films and solvent resistance, aromatic dicarboxylic acid compounds or It is preferable to use the derivative (C ′).
  • the polyester polyol resin of the present invention is highly soluble in a weak solvent, exhibits a sufficient balance between hardness and flexibility in a cured coating film and is excellent in solvent resistance.
  • the aliphatic dicarboxylic acid compound having 4 to 8 carbon atoms or the derivative (C) is preferably used in an amount of 1% by mass or more, more preferably 3 to 30% by mass, based on the mass. Further, the total mass of the aliphatic dicarboxylic acid compound or derivative (C) and the aromatic dicarboxylic acid compound or derivative (C ′) is preferably 60% by mass or more based on the total mass of the dicarboxylic acid raw material. 90% by mass or more is more preferable.
  • the mass ratio [(C) / (C ′)] of the aliphatic dicarboxylic acid compound or derivative (C) to the aromatic dicarboxylic acid compound or derivative (C ′) is 3/97 to 30/70.
  • a range is preferable.
  • isophthalic acid and terephthalic acid are used in combination as the aromatic dicarboxylic acid compound or derivative (C ′), and the mass ratio [isophthalic acid / terephthalic acid] is 40/60 to 90/10.
  • the range is preferable, and the range of 60/40 to 85/15 is more preferable.
  • the polyester polyol resin of the present invention may use a trifunctional or higher functional polyol compound (D1), a trifunctional or higher functional polycarboxylic acid compound or a derivative thereof (D2) as a reaction raw material. good.
  • a trifunctional or higher functional polyol compound (D1), a trifunctional or higher functional polycarboxylic acid compound or a derivative thereof (D2) is 10% by mass or less based on the total mass. It is more preferable to use so that it may become% or less.
  • the tri- or higher functional polyol compound (D1) is not particularly limited as long as it is a compound having three or more hydroxyl groups in one molecule, and a wide variety of compounds can be used.
  • Specific examples of the tri- or higher functional polyol compound (D1) include, for example, aliphatic polyol compounds such as trimethylolethane, trimethylolpropane, glycerin, hexanetriol, and pentaerythritol; aromatic polyol compounds such as trihydroxybenzene; Obtained by ring-opening polymerization of the aliphatic polyol compound or aromatic polyol compound and a cyclic ether compound such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether.
  • the tri- or higher functional polycarboxylic acid compound or derivative thereof (D2) is not particularly limited as long as it is a compound having three or more carboxy groups in one molecule, and various compounds are used. Can do.
  • Specific examples of the trifunctional or higher functional polycarboxylic acid compound or derivative (D2) include aliphatic polycarboxylic acid compounds such as 1,2,5-hexanetricarboxylic acid and 1,2,4-cyclohexanetricarboxylic acid.
  • aromatic polycarboxylic acid compounds such as trimellitic acid, trimellitic anhydride, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, and the like
  • trimellitic acid trimellitic anhydride
  • 1,2,5-benzenetricarboxylic acid 1,2,5-benzenetricarboxylic acid
  • 2,5,7-naphthalenetricarboxylic acid and the like
  • An acid anhydride, an acid halide, etc. are mentioned. These may be used alone or in combination of two or more.
  • the production method of the polyester polyol resin of the present invention is not particularly limited, and may be produced by any method. Specifically, all of the reaction raw materials may be reacted in a lump, or may be produced by a method of adding a part of the reaction raw materials in a divided manner.
  • the reaction temperature is preferably about 180 to 300 ° C., similar to the reaction temperature of general polyester resins, and a known and usual esterification catalyst may be used if necessary.
  • the polyester polyol resin of the present invention may be reacted in an organic solvent as necessary, or the viscosity or the like may be adjusted by adding an organic solvent after completion of the reaction.
  • the organic solvent is not particularly limited as long as it can dissolve the polyester polyol resin, and known and conventional solvents can be used.
  • the polyester polyol resin of the present invention has high solubility in an organic solvent of a kind generally called a weak solvent. Examples of organic solvents generally called weak solvents include “Naphtha No.
  • examples of the organic solvent having high solubility of the polyester polyol resin of the present invention include alkylene glycols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, and propylene glycol monomethyl ether.
  • Monoalkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, etc.
  • the dilution rate with these organic solvents is appropriately adjusted depending on the application, etc.
  • the polyester polyol resin when used for coating, it is preferable to dilute the non-volatile content to 40 to 80% by mass. .
  • the weight average molecular weight (Mw) of the polyester polyol resin of the present invention is preferably in the range of 3,000 to 120,000 in terms of excellent balance between hardness and flexibility in a cured coating film and excellent solvent resistance. A range of 5,000 to 50,000 is more preferable, and a range of 5,000 to 3,000 is particularly preferable.
  • the number average molecular weight (Mn) is preferably in the range of 2,000 to 10,000, more preferably in the range of 2,500 to 6,000.
  • the molecular weight distribution (Mw) / (Mn) is preferably in the range of 1.2 to 20, more preferably in the range of 1.5 to 6.
  • the molecular weight of the polyester polyol resin is a value measured by gel permeation chromatography (GPC) under the following conditions.
  • Measuring device HLC-8320GPC manufactured by Tosoh Corporation Column: Tosoh Corporation TSKgel 4000HXL, TSKgel 3000HXL, TSKgel 2000HXL, TSKgel 1000HXL Detector: RI (differential refractometer) Data processing; Multi-station GPC-8020 model II manufactured by Tosoh Corporation Measurement conditions; Column temperature 40 ° C Solvent Tetrahydrofuran Flow rate 0.35 ml / min Standard; Monodisperse polystyrene Sample; Filtered 0.2% tetrahydrofuran solution in terms of resin solids with a microfilter (100 ⁇ l)
  • the hydroxyl value of the polyester polyol resin of the present invention is preferably in the range of 2 to 100 mgKOH / g, more preferably in the range of 5 to 50 mgKOH / g, since it becomes a resin having excellent curability. A range of 30 mg OH / g is particularly preferred. Moreover, it is preferable that the acid value of the polyester polyol resin of this invention is 10 mgKOH / g or less.
  • the curable resin composition of the present invention comprises a main agent containing the polyester polyol resin and a curing agent.
  • the main agent may contain other resins other than the polyester polyol resin of the present invention.
  • other resins include other polyol resins other than the polyester polyol resin of the present invention.
  • the polyester polyol resin of the present invention is preferably used in an amount of 50% by mass or more, more preferably 80% by mass or more based on the total mass of the resin components contained in the main agent.
  • the curing agent only needs to contain a component capable of causing a curing reaction with the polyester polyol resin of the present invention.
  • a component capable of causing a curing reaction with the polyester polyol resin of the present invention.
  • examples of such a component include an amino resin, a polyisocyanate resin, a resole resin, and an epoxy resin. Can be mentioned. These may be used alone or in combination of two or more.
  • the components of the curing agent are appropriately selected according to the use and use environment of the curable resin composition, desired cured product properties, etc., as long as the polyester polyol resin of the present invention is used as the main agent, any curing agent was used. Even if it is a case, the effect which is excellent in the balance of the hardness and the softness
  • the amino resin include, for example, a methylolated amino resin synthesized from at least one of melamine, urea, and benzoguanamine and formaldehyde; methanol or a part or all of the methylol group of the methylolated amino resin;
  • alkyl etherified compounds with lower monohydric alcohols such as ethanol, propanol, isopropanol, butanol, and isobutanol.
  • amino resin products include, for example, “Cymel 303” (methylated melamine resin) manufactured by Allnex, “Cymel 350” (methylated melamine resin), “Uban 520” manufactured by Mitsui Chemicals, Inc. ( n-Butylated Modified Melamine Resin), “Uban 20-SE-60” (n-Butylated Modified Melamine Resin), “Uban 2021” (n-Butylated Modified Melamine Resin), “Uban 220” (n-Butylated) Modified melamine resin), “Uban 22R” (n-butylated modified melamine resin), “Uban 2028” (n-butylated modified melamine resin), “Uban 165” (isobutylated modified melamine resin), “Uban 114” ( Isobutylated modified melamine resin), “Uban 62” (isobutylated modified melamine resin), “you Emissions 60R "(isobutyl-modified melamine
  • polyisocyanate resin examples include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; norbornane diisocyanate, Cycloaliphatic diisocyanate compounds such as isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate; aromatic diisocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate
  • R 1 is independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.
  • R 2 is each independently an alkyl group having 1 to 4 carbon atoms or a bonding point linked to a structural moiety represented by the structural formula (2) via a methylene group marked with *.
  • m is 0 or an integer of 1 to 3
  • l is an integer of 1 or more.
  • the epoxy resin examples include a polyglycidyl ether of a polyol compound, a polyglycidyl ester of a polycarboxylic acid compound, a bisphenol type epoxy resin, a novolac type epoxy resin, and the like.
  • the curable resin composition of the present invention includes a curing catalyst, a curing accelerator, a pigment, a pigment dispersant, a matting agent, a leveling agent, a drying inhibitor, an ultraviolet absorber, an antifoaming agent, a thickener, an antisettling agent, An organic solvent or the like may be added.
  • the blending ratio of these components and the kind of the 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 a one-pack type or a two-pack type. When the curable resin composition of the present invention is a two-pack type, the various additives can be added to either or both of the main agent and the curing agent.
  • the use of the curable resin composition of the present invention is not particularly limited, it can be preferably used for paints and adhesives because it is excellent in the balance between hardness and flexibility in a cured coating film and solvent resistance. It can be suitably used as a paint for steel plates.
  • the coated steel sheet of the present invention can be used, for example, for various metal parts such as home appliances, automobile parts, building materials, pre-coated metal for metal molded products, can manufacturing applications, and the like.
  • the coating may be one layer or multiple layers.
  • one or more of the paints of the present invention may be applied in layers, or the paint of the present invention may be applied in combination with other paints.
  • Other paints include, for example, paints mainly composed of polyester resin, urethane resin, epoxy resin or the like.
  • a method of applying a layer called a primer layer on a steel plate after coating a layer called a primer layer on the steel plate is widely used for coating a steel plate.
  • the paint of the present invention can be used as a primer layer or a top coat layer.
  • the thickness of the primer layer is preferably about 0.5 to 30 ⁇ m.
  • the film thickness of the top coat layer is preferably about 1 to 60 ⁇ m. Any known and commonly used method can be used for applying the paint, and examples thereof include spray coating, dip coating, spin coating, flow coating, and roller coating. The curing conditions of the coating are appropriately adjusted depending on the selection of the curing agent, the film thickness, and the like, but a method of heat curing for about several seconds to several minutes in a temperature range of about 120 to 350 ° C. is preferable.
  • the number average molecular weight (Mn), the weight average molecular weight (Mw), and the molecular weight distribution (Mw / Mn) were measured by gel permeation chromatography (GPC) under the following conditions.
  • Measuring device HLC-8320GPC manufactured by Tosoh Corporation Column: Tosoh Corporation TSKgel 4000HXL, TSKgel 3000HXL, TSKgel 2000HXL, TSKgel 1000HXL Detector: RI (differential refractometer) Data processing; Multi-station GPC-8020 model II manufactured by Tosoh Corporation Measurement conditions; Column temperature 40 ° C Solvent Tetrahydrofuran Flow rate 0.35 ml / min Standard; Monodisperse polystyrene Sample; Filtered 0.2% tetrahydrofuran solution in terms of resin solids with a microfilter (100 ⁇ l)
  • Example 1 Production of Polyester Polyol Resin (1) Solution In a reaction vessel equipped with a stirrer, a condenser and a thermometer, 988.8 parts by mass of 2-methyl-1,3-propanediol, 360 parts by mass of diethylene glycol, 372 parts by mass of terephthalic acid Parts, 180 parts by mass of adipic acid, and 0.78 parts by mass of a titanium phosphate catalyst (“Orgatechs TA-21” manufactured by Matsumoto Fine Chemical Co., Ltd.) were added. The reaction was carried out at 200 to 250 ° C. for 4 hours with stirring under a nitrogen stream.
  • a titanium phosphate catalyst (“Orgatechs TA-21” manufactured by Matsumoto Fine Chemical Co., Ltd.)
  • polyester polyol resin (1) was dissolved in a mixed solvent of 1285.2 parts by mass of “Solvesso 100” manufactured by ExxonMobil Co., Ltd. and 142.8 parts by mass of propylene glycol monomethyl ether acetate, and a nonvolatile content of 65.9 masses. % Polyester polyol resin (1) solution.
  • the Gardner viscosity of the polyester polyol resin (1) solution was Z4 2 -Z5.
  • Polyester polyol resin (1) 71.6 parts by mass of solution, titanium oxide 94.5 parts by mass, silica 0.9 part by mass, mixed solvent 35.2 parts by mass, Dispersion was performed with a paint shaker until the particle size of titanium oxide became 10 ⁇ m or less.
  • 71.6 parts by mass of a polyester polyol resin (1) solution, 16.7 parts by mass of an amino resin, 0.9 parts by mass of a curing accelerator, 0.9 parts by mass of a matting agent, and 1.5 parts by mass of a leveling agent are mixed.
  • 6.2 parts by mass of the solvent was added and mixed, and the viscosity was adjusted with a mixed solvent so that the Ford Cup # 4 viscosity at 25 ° C. was about 100 seconds to obtain a topcoat paint (1).
  • polyester polyol resin having a weight average molecular weight (Mw) of 8,500, an acid value of 2.8 mgKOH / g, and a hydroxyl value of 20 mgKOH / g.
  • Mw weight average molecular weight
  • the obtained polyester polyol resin was dissolved in a mixed solvent of 1449 parts by mass of “Solvesso 100” manufactured by ExxonMobil Co., Ltd. and 161 parts by mass of propylene glycol monomethyl ether acetate, and a polyester having a nonvolatile content of 66.4% by mass and a Gardner viscosity Z3 A polyol resin solution was obtained.
  • Production Example 2 Production of Primer Paint (1) 70.5 parts by mass of polyester polyol resin solution obtained in Production Example 1, 23.9 parts by mass of calcium phosphate, 70.6 parts by mass of titanium oxide, 0.9 parts by mass of silica, mixing 38.3 parts by mass of the solvent was mixed and dispersed with a paint shaker until the particle size of titanium oxide was 10 ⁇ m or less. Next, 70.5 parts by mass of a polyester polyol resin solution, 16.7 parts by mass of an amino resin, 0.9 part by mass of a curing accelerator, 0.9 part by mass of a matting agent, and 6.8 parts by mass of a mixed solvent are added and mixed. Further, the Ford Cup # 4 viscosity at 25 ° C. was adjusted with a mixed solvent so that the viscosity was about 100 seconds to obtain a primer paint (1).
  • Titanium oxide “Ti-Pure R960” manufactured by Dupont Silica: “Aerosil R972” manufactured by Evonik Industries Mixed solvent: “Solvesso 100” manufactured by ExxonMobil Co., Ltd.
  • Primer paint is applied to a 0.5mm thick hot dip galvanized chromate-treated steel sheet with a bar coater and heat-dried in an oven at 250 ° C for 20 seconds (metal peak temperature is 199 to 204 ° C) to form a dry film A primer layer having a thickness of 5 ⁇ m was formed.
  • a top coat paint is applied onto the primer layer with a bar coater, and heated and dried in an oven at 250 ° C. for 40 seconds (metal peak temperature is 232 to 241 ° C.), and a coated steel sheet having a top coat layer with a dry film thickness of 15 ⁇ m.

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  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
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Abstract

L'invention fournit une résine de polyester polyol dotée d'une dissolubilité élevée dans un solvant faible, et présentant un excellent équilibre entre dureté et souplesse dans un film de revêtement durci ainsi qu'une excellente résistance aux solvants, une composition de résine durcissable mettant en œuvre cette résine, un revêtement, et une tôle d'acier revêtue. Cette résine de polyester polyol présente une masse moléculaire en poids (Mw) comprise dans une plage de 3000 à 120000, et est caractéristique en ce qu'elle a pour matières premières réactives essentielles : (A) un 2-méthyl-1,3-propanediol, (B) un composé diol possédant une région de liaison éther dans sa structure moléculaire, et (C) un composé acide dicarboxylique aliphatique de 4 à 8 atomes de carbone ou un dérivé de celui-ci.
PCT/JP2017/038679 2016-11-04 2017-10-26 Résine de polyester polyol, et revêtement WO2018084064A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016216191 2016-11-04
JP2016-216191 2016-11-04

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JP2002302643A (ja) * 2001-04-04 2002-10-18 Unitika Ltd 金属缶内面被膜形成用共重合ポリエステル樹脂
JP2006206860A (ja) * 2004-12-27 2006-08-10 Toyobo Co Ltd ポリエステル樹脂の製造方法
JP2013227467A (ja) * 2012-03-30 2013-11-07 Unitika Ltd 活性エネルギー線硬化型ポリエステル樹脂
JP2015193835A (ja) * 2014-03-28 2015-11-05 東洋インキＳｃホールディングス株式会社 ポリエステル樹脂および缶用塗料
JP2016079243A (ja) * 2014-10-14 2016-05-16 日本エステル株式会社 接着剤用共重合ポリエステル樹脂
JP2016113615A (ja) * 2014-12-10 2016-06-23 ユニチカ株式会社 ポリエステル樹脂およびそれを用いた積層体
JP2016145276A (ja) * 2015-02-06 2016-08-12 東洋インキＳｃホールディングス株式会社 塗料組成物および缶蓋
JP2017002158A (ja) * 2015-06-09 2017-01-05 東洋インキＳｃホールディングス株式会社 ポリエステル樹脂およびそれを含む缶被覆用樹脂組成物
WO2017047197A1 (fr) * 2015-09-16 2017-03-23 東洋紡株式会社 Polyester copolymérisé et matériau de couche d'apprêt pour métal utilisant un tel polyester

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6197419A (ja) * 1984-10-15 1986-05-15 Daicel Chem Ind Ltd ポリエステル繊維
JP2002302643A (ja) * 2001-04-04 2002-10-18 Unitika Ltd 金属缶内面被膜形成用共重合ポリエステル樹脂
JP2006206860A (ja) * 2004-12-27 2006-08-10 Toyobo Co Ltd ポリエステル樹脂の製造方法
JP2013227467A (ja) * 2012-03-30 2013-11-07 Unitika Ltd 活性エネルギー線硬化型ポリエステル樹脂
JP2015193835A (ja) * 2014-03-28 2015-11-05 東洋インキＳｃホールディングス株式会社 ポリエステル樹脂および缶用塗料
JP2016079243A (ja) * 2014-10-14 2016-05-16 日本エステル株式会社 接着剤用共重合ポリエステル樹脂
JP2016113615A (ja) * 2014-12-10 2016-06-23 ユニチカ株式会社 ポリエステル樹脂およびそれを用いた積層体
JP2016145276A (ja) * 2015-02-06 2016-08-12 東洋インキＳｃホールディングス株式会社 塗料組成物および缶蓋
JP2017002158A (ja) * 2015-06-09 2017-01-05 東洋インキＳｃホールディングス株式会社 ポリエステル樹脂およびそれを含む缶被覆用樹脂組成物
WO2017047197A1 (fr) * 2015-09-16 2017-03-23 東洋紡株式会社 Polyester copolymérisé et matériau de couche d'apprêt pour métal utilisant un tel polyester

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