WO2018084065A1 - Résine de polyester polyol, et revêtement - Google Patents

Résine de polyester polyol, et revêtement Download PDF

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Publication number
WO2018084065A1
WO2018084065A1 PCT/JP2017/038680 JP2017038680W WO2018084065A1 WO 2018084065 A1 WO2018084065 A1 WO 2018084065A1 JP 2017038680 W JP2017038680 W JP 2017038680W WO 2018084065 A1 WO2018084065 A1 WO 2018084065A1
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WIPO (PCT)
Prior art keywords
polyester polyol
mass
polyol resin
compound
resin
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PCT/JP2017/038680
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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 WO2018084065A1 publication Critical patent/WO2018084065A1/fr

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Classifications

    • 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
    • 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

Definitions

  • the present invention relates to a polyester polyol resin having high solubility in a weak solvent and excellent balance between hardness and flexibility in a cured coating film, 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 was not sufficient.
  • the problem to be solved by the present invention is a polyester polyol resin having high solubility in a weak solvent and excellent balance between hardness and flexibility in a cured coating film, a curable resin composition using the same, a coating material, and a coating material. It is to provide a coated steel sheet.
  • a diol compound having an ether bond site in the molecular structure an aliphatic diol compound having a branched structure in the molecular structure, and a trifunctional or higher functional polyol compound.
  • a polyester polyol resin using a polycarboxylic acid compound having three or more functionals as an essential reaction raw material has been found to have a high solubility in a weak solvent and an excellent balance between hardness and flexibility in a cured coating film. It came to complete.
  • the present invention is a polyester polyol resin having a weight average molecular weight (Mw) in the range of 3,000 to 120,000, comprising the following (A) and (B) and (C1) or (C2):
  • the present invention relates to a polyester polyol resin characterized by being an essential reaction raw material.
  • Diol compound having an ether bond site in the molecular structure A) Aliphatic diol compound (B) having a branched structure in the molecular structure Trifunctional or higher polyol compound (C1) Trifunctional or higher polycarboxylic acid compound or derivative (C2)
  • 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 high solubility in a weak solvent and excellent balance between hardness and flexibility in a cured coating film, a curable resin composition using the same, a paint, and a coated steel sheet are provided. Can do.
  • the polyester polyol resin of the present invention has a weight average molecular weight (Mw) in the range of 3,000 to 120,000, and the following (A) and (B) and (C1) or (C2) are essential reaction raw materials. It is characterized by. Diol compound having an ether bond site in the molecular structure (A) Aliphatic diol compound (B) having a branched structure in the molecular structure Trifunctional or higher polyol compound (C1) Trifunctional or higher polycarboxylic acid compound or derivative (C2)
  • the diol compound (A) 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.
  • 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 is excellent, and it is particularly preferable to use a compound in which n is 1 as an essential component.
  • the aliphatic diol compound (B) having a branched structure in the molecular structure is an aliphatic hydrocarbon diol compound having a branched chain
  • the number and molecular weight of the branched chain are not particularly limited. May be.
  • the aliphatic diol compound (B) having a branched structure in the molecular structure may be used alone or in combination of two or more. Among them, a compound having 4 to 6 carbon atoms is preferable, and 2-methyl-1,3-propanediol is more preferable from the viewpoint of excellent balance between hardness and flexibility in a cured coating film.
  • the polyester polyol resin of the present invention uses other diol compounds as reaction raw materials. You may use as a part of.
  • Other diol compounds include, for example, linear aliphatic diol compounds, alicyclic structure-containing diol compounds such as cyclohexane diol and cyclohexane dialcohol, aromatic ring-containing diol compounds such as biphenol and bisphenol, polyether diol, polycarbonate diol, and the like. Can be mentioned.
  • the polyester polyol resin of the present invention is excellent in the balance between hardness and flexibility in the cured coating film, and sufficiently exhibits the effect of high solubility in a weak solvent.
  • the total mass of the diol compound (A) having an ether bond site in the molecular structure and the aliphatic diol compound (B) having a branched structure in the molecular structure is preferably 60% by mass or more, and 90% by mass or more. It is more preferable that Further, the ratio of the diol compound (A) having an ether bond site in the molecular structure to the total mass of the diol raw material is preferably in the range of 30 to 98% by mass, and in the range of 40 to 95% by mass. preferable.
  • the ratio of the aliphatic diol compound (B) having a branched structure in the molecular structure to the total mass of the diol raw material is preferably in the range of 1 to 70% by mass, and preferably in the range of 5 to 55% by mass. . Furthermore, the mass ratio [(A) / (B)] of the diol compound (A) having an ether bond site in the molecular structure and the aliphatic diol compound (B) having a branched structure in the molecular structure is 40 / The range of 60 to 95/5 is preferable.
  • the tri- or higher functional polyol compound (C1) 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 (C1) 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 trifunctional or higher functional polyol compound (C1) may be used alone or in combination of two or more. Especially, it is preferable to use an aliphatic polyol compound and it is more preferable to use a trifunctional aliphatic polyol compound at the point which is excellent in the balance of the hardness and the softness
  • the tri- or higher functional polycarboxylic acid compound or derivative thereof (C2) 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 (C2) 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 trifunctional or higher functional polyol compound (C1) and the trifunctional or higher functional polycarboxylic acid compound or its derivative (C2) are components used for introducing a branched structure into the resin structure. Both can be used equally.
  • the polyester polyol resin of the present invention is excellent in the balance between hardness and flexibility in a cured coating film, and sufficiently exhibits the effect of high solubility in a weak solvent.
  • the trifunctional or higher functional polyol compound (C1) or the trifunctional or higher functional polycarboxylic acid compound or its derivative (C2) is preferably used in the range of 0.05 to 15% by mass, preferably in the range of 0.1 to 10% by mass. It is more preferable to use in.
  • the polyester polyol resin of the present invention preferably uses a dicarboxylic acid compound or a derivative thereof as a reaction raw material in addition to the component (A), the component (B), the component (C1) or the component (C2).
  • the dicarboxylic acid compound or derivative thereof include, for example, an aliphatic dicarboxylic acid compound or derivative thereof (D1), an aromatic dicarboxylic acid compound or derivative thereof (D2), an alicyclic dicarboxylic acid compound or derivative thereof (D3), and the like. Is mentioned.
  • Examples of the aliphatic dicarboxylic acid compound or derivative (D1) thereof include oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and These acid anhydrides and acid halides can be mentioned.
  • Examples of the aromatic dicarboxylic acid compound or derivative (D2) include phthalic acid, isophthalic acid, terephthalic acid, and acid anhydrides and acid halides thereof.
  • Examples of the alicyclic dicarboxylic acid compound or derivative (D3) thereof include hexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, and acid anhydrides and acid halides thereof. These may be used alone or in combination of two or more.
  • the aliphatic dicarboxylic acid compound or a derivative thereof (D1) is preferably used from the viewpoint of excellent flexibility in a cured coating film, and a linear saturated aliphatic dicarboxylic acid compound having 4 to 8 carbon atoms or a derivative thereof. It is more preferable to use Moreover, it is preferable to use the said aromatic dicarboxylic acid compound or its derivative (D2) in the point which is excellent in the hardness in a cured coating film.
  • the polyester polyol resin of the present invention is excellent in the balance between hardness and flexibility in the cured coating film, and since the effect of high solubility in a weak solvent is sufficiently exerted, relative to the total mass of the dicarboxylic acid raw material,
  • the aliphatic dicarboxylic acid compound or derivative thereof (D1) is preferably used in an amount of 1% by mass or more, more preferably 1-30% by mass.
  • the aromatic dicarboxylic acid compound or derivative thereof (D2) is preferably used in an amount of 70% by mass or more, more preferably 75 to 99% by mass, based on the total mass of the dicarboxylic acid raw material.
  • the total mass of the aliphatic dicarboxylic acid compound or derivative (D1) and the aromatic dicarboxylic acid compound or derivative (D2) 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. Further, the mass ratio [(D1) / (D2)] of the aliphatic dicarboxylic acid compound or derivative (D1) and the aromatic dicarboxylic acid compound or derivative (D2) is in the range of 1/97 to 30/70. It is preferable that
  • 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 at once, 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 the cured coating film. More preferably, it is in the range of 100,000.
  • the number average molecular weight (Mn) is preferably in the range of 2,000 to 10,000.
  • the molecular weight distribution (Mw) / (Mn) is preferably in the range of 2-20.
  • 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 5 to 50 mgKOH / g, since it becomes a resin having excellent curability. 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 main agent is contained because the effect of excellent balance between hardness and flexibility in the cured coating film produced by the present invention and high solubility in weak solvents is exhibited.
  • 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 component to be processed.
  • 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 of its excellent balance between hardness and flexibility in a cured coating, and is particularly suitable as a paint for coated steel sheets. Can be used.
  • 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 paint of the present invention When the paint of the present invention is used for a coated steel sheet, the paint may be applied directly to the steel sheet, or after forming a primer layer on the steel sheet, the paint of the present invention may be applied thereon.
  • the primer layer can be formed using, for example, a primer coating mainly composed of polyester resin, urethane resin, epoxy resin, or the like.
  • the thickness of the primer layer is preferably about 0.5 to 30 ⁇ 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 film thickness when applying the paint is preferably about 1 to 60 ⁇ m.
  • 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, 528.4 parts by mass of 2-methyl-1,3-propanediol, 650 parts by mass of diethylene glycol, 172 of trimethylolpropane Part by mass, 1549 parts by mass of terephthalic acid, 100 parts by mass of adipic acid, 450 parts by mass of isophthalic acid, and 1.72 parts by mass of a titanium phosphate catalyst (“Orgatechs TA-21” manufactured by Matsumoto Fine Chemical Co., Ltd.) were added. The mixture was reacted for 10 hours at 200 to 250 ° C.
  • a polyester polyol resin (1) was obtained.
  • the obtained polyester polyol resin (1) was dissolved in a mixed solvent of 1452 parts by mass of “Solvesso 100” manufactured by ExxonMobil Co., Ltd. and 622 parts by mass of propylene glycol monomethyl ether acetate, and the non-volatile content was 56.9% by mass and the Gardner viscosity.
  • a polyester polyol resin (1) solution of Z3 2 -Z4 was obtained.
  • Example 2 Production of Polyester Polyol Resin (2) Solution
  • a reaction vessel equipped with a stirrer, a condenser and a thermometer 146.3 parts by mass of 2-methyl-1,3-propanediol, 1200 parts by mass of diethylene glycol, 1700 parts by mass of terephthalic acid Parts, 200 parts by mass of adipic acid, 100 parts by mass of trimellitic anhydride, and 1.67 parts by mass of a titanium phosphate catalyst (“Orgatechs TA-21” manufactured by Matsumoto Fine Chemical Co., Ltd.).
  • the reaction was carried out at 200 to 250 ° C.
  • polyester polyol resin (2) is dissolved in a mixed solvent of 1233 parts by mass of “Solvesso 100” manufactured by ExxonMobil Co., Ltd. and 528 parts by mass of propylene glycol monomethyl ether acetate, and has a nonvolatile content of 59.7% by mass and a Gardner viscosity.
  • a polyester polyol resin (2) solution of Z2 2 -Z3 was obtained.
  • the polyester polyol resin (1 ′) having a weight average molecular weight (Mw) of 12,000, an acid value of 8.5 mgKOH / g, and a hydroxyl value of 52 mgKOH / g was reacted by stirring for 13 hours at 180 to 250 ° C. with stirring in a nitrogen stream. Obtained.
  • the obtained polyester polyol resin (1 ′) was dissolved in a mixed solvent of 1364.4 parts by mass of “Solvesso 100” manufactured by ExxonMobil Co., Ltd. and 151.8 parts by mass of propylene glycol monomethyl ether acetate to give a nonvolatile content of 65.0.
  • a mass% polyester polyol resin (1 ′) solution was obtained.
  • the Gardner viscosity of the polyester polyol resin (1 ′) solution was ZZ1.
  • polyester polyol resin solutions obtained in Examples 1 and 2 and Comparative Example 1 were stored at room temperature of 25 ° C., and the state after one month was visually evaluated.
  • Polyester polyol resin (1 ′) had no cloudiness and fluidity was good.
  • Example 3 Production of Top Coat Paint (1) 82.9 parts by mass of polyester polyol resin (1) solution, 94.5 parts by mass of titanium oxide, 0.9 part by mass of silica, 16 parts by mass of mixed solvent (1) Dispersion was performed with a paint shaker until the particle size of titanium oxide became 10 ⁇ m or less. Next, 82.9 parts by mass of the polyester polyol resin (1) solution, 16.7 parts by mass of the amino resin, 0.9 parts by mass of the curing accelerator, 0.9 parts by mass of the matting agent, and 1.5 parts by mass of the leveling agent are mixed. 2.8 parts by mass of the solvent (1) was added and mixed, and further the Ford Cup # 4 viscosity at 25 ° C. was adjusted with the mixed solvent to be about 100 seconds to obtain a topcoat paint (1).
  • Example 4 Production of Top Coat Paint (2) 78.8 parts by mass of polyester polyol resin (2) solution, 94.5 parts by mass of titanium oxide, 0.9 part by mass of silica, 23 parts by mass of mixed solvent (1) Dispersion was performed with a paint shaker until the particle size of titanium oxide became 10 ⁇ m or less. Next, 78.8 parts by mass of polyester polyol resin (2) solution, 16.7 parts by mass of amino resin, 0.9 parts by mass of curing accelerator, 0.9 parts by mass of matting agent, 1.5 parts by mass of leveling agent, and mixing 4.1 parts by weight of solvent (1) 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 (2).
  • Production Example 1 Production of Primer Paint
  • a reaction vessel equipped with a stirrer, a condenser and a thermometer 946 parts by mass of neopentyl glycol, 178 parts by mass of trimethylolpropane, 371 parts by mass of 1,6-hexanediol, 1881 parts by mass of isophthalic acid, 176 parts by mass of adipic acid was added.
  • the mixture was reacted at 200 to 250 ° C. for 12 hours with stirring under a nitrogen stream to obtain a polyester polyol resin having a weight average molecular weight (Mw) of 4,500, an acid value of 10.8 mgKOH / g, and a hydroxyl value of 55 mgKOH / g.
  • Mw weight average molecular weight
  • the obtained polyester polyol resin was dissolved in a mixed solvent of 1151.3 parts by mass of “Solvesso 100” manufactured by ExxonMobil Co., Ltd. and 127.9 parts by mass of butyl cellosolve, and a polyester having a nonvolatile content of 70% by mass and a Gardner viscosity of Z2-Z3 A polyol resin solution was obtained. 67.5 parts by mass of the polyester polyol resin solution obtained above, 23.9 parts by mass of calcium phosphate, 70.6 parts by mass of titanium oxide, 0.9 part by mass of silica, and 43.4 parts by mass of the mixed solvent (2) were mixed. The dispersion was performed with a paint shaker until the particle size of the titanium oxide was 10 ⁇ m or less.
  • Titanium oxide “Ti-PureR960” manufactured by Dupont Silica: “Aerosil R972” manufactured by Evonik Industries
  • Mixed solvent (1) “Solvesso 100” manufactured by ExxonMobil Co., Ltd. and propylene glycol monomethyl ether acetate mixed at a mass ratio of 7: 3
  • Mixed solvent (2) “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 & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention fournit une résine de polyester polyol présentant un excellent équilibre entre dureté et souplesse dans un film de revêtement durci, et dotée d'une dissolubilité élevée dans un solvant faible, 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 les composants (A) ainsi que (B) et (C1) ou (C2) suivants. (A) composé diol possédant une région de liaison éther dans sa structure moléculaire, (B) composé diol aliphatique possédant une structure ramifiée dans sa structure moléculaire, (C1) composé polyol au moins trifonctionnel, (C2) composé acide polycarboxylique au moins trifonctionnel ou dérivé de celui-ci
PCT/JP2017/038680 2016-11-04 2017-10-26 Résine de polyester polyol, et revêtement WO2018084065A1 (fr)

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JP2016-216192 2016-11-04
JP2016216192 2016-11-04

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06157979A (ja) * 1992-11-24 1994-06-07 Toray Ind Inc 塗装鋼板用塗料組成物
JPH08337646A (ja) * 1995-06-09 1996-12-24 Mitsubishi Rayon Co Ltd 共重合ポリエステル樹脂
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
JP2009001707A (ja) * 2007-06-22 2009-01-08 Toyo Ink Mfg Co Ltd ポリエステル樹脂及び感圧式接着剤組成物
JP2009214531A (ja) * 2007-10-05 2009-09-24 Unitika Ltd 易接着フィルム
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
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
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

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06157979A (ja) * 1992-11-24 1994-06-07 Toray Ind Inc 塗装鋼板用塗料組成物
JPH08337646A (ja) * 1995-06-09 1996-12-24 Mitsubishi Rayon Co Ltd 共重合ポリエステル樹脂
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
JP2009001707A (ja) * 2007-06-22 2009-01-08 Toyo Ink Mfg Co Ltd ポリエステル樹脂及び感圧式接着剤組成物
JP2009214531A (ja) * 2007-10-05 2009-09-24 Unitika Ltd 易接着フィルム
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
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
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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