WO2019102626A1 - Résine de polyester modifiée avec un groupe (méth)acrylique, composition de résine durcissable, matériau de revêtement, et tôle d'acier revêtue - Google Patents

Résine de polyester modifiée avec un groupe (méth)acrylique, composition de résine durcissable, matériau de revêtement, et tôle d'acier revêtue Download PDF

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Publication number
WO2019102626A1
WO2019102626A1 PCT/JP2017/044868 JP2017044868W WO2019102626A1 WO 2019102626 A1 WO2019102626 A1 WO 2019102626A1 JP 2017044868 W JP2017044868 W JP 2017044868W WO 2019102626 A1 WO2019102626 A1 WO 2019102626A1
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Prior art keywords
meth
polyester resin
acrylic
mass
modified polyester
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PCT/JP2017/044868
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English (en)
Japanese (ja)
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グラン マルティネス アレハンドロ
正澄 澪川
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Dic株式会社
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Priority to DE112017008223.4T priority Critical patent/DE112017008223T5/de
Priority to CN201780097073.9A priority patent/CN111448229B/zh
Priority to JP2019556082A priority patent/JP6725895B2/ja
Publication of WO2019102626A1 publication Critical patent/WO2019102626A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G63/181—Acids containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
    • 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
    • C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
    • 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
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/916—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
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates to a (meth) acrylic-modified polyester resin, a curable resin composition containing the same, a paint comprising the curable resin composition, and a coated steel plate having a coating of the paint.
  • PCM pre-coated metal
  • paints of various forms such as two-component curing type, UV curing type, and volatilization drying type are used, and the resin system is also various as polyester resin, fluorine resin, acrylic resin, etc.
  • the resin system is also various as polyester resin, fluorine resin, acrylic resin, etc.
  • a two-component curable coating mainly composed of a polyester resin is widely used because it has excellent processability.
  • Examples of the two-component curable paint containing the polyester resin as a main component include, for example, terephthalic acid, isophthalic acid, 2-methyl-1,3-propanediol, and a number average molecular weight using 1,6-hexanediol as a reaction raw material Paints based on polyester resins of 11,000 Mn are known (see, for example, Patent Document 1), but although excellent in processability, standards that are recently required in terms of high solidification of the paint It did not cover the
  • the problem to be solved by the present invention is (meth) acrylic-modified polyester resin capable of forming a coating having high processability and weatherability, which is capable of achieving high solidification of paint, and curability containing the same. It is providing a resin composition, a paint, and a coated steel plate.
  • a (meth) acrylic-modified polyester comprising a saturated polyester resin (A) and a (meth) acrylic monomer mixture (B) containing a hydroxyl group-containing (meth) acrylic monomer as essential reaction raw materials It is a resin, and the saturated polyester resin (A) is a polycondensate of an aliphatic diol (a1) and a dicarboxylic acid (a2) containing an aliphatic dicarboxylic acid, and the content of the aliphatic dicarboxylic acid
  • the present invention relates to a (meth) acrylic-modified polyester resin having a content of 5% by mass or more in the dicarboxylic acid (a2), a curable resin composition containing the same, a paint, and a coated steel sheet.
  • the (meth) acrylic-modified polyester resin of the present invention enables high-solidification of the paint, that is, high non-volatile differentiation, and can form a coating film having excellent processability and weather resistance. It can be suitably used for automotive paints such as top coats and automotive repair paints.
  • “high solid” indicates that the non-volatile content of the paint is 65% by mass or more.
  • the (meth) acrylic-modified polyester resin of the present invention is characterized in that the saturated polyester resin (A) and the (meth) acrylic monomer mixture (B) are essential reaction raw materials.
  • the saturated polyester resin (A) refers to a polyester resin substantially having no aliphatic carbon-carbon double bond.
  • saturated polyester resin (A) what was obtained by carrying out the polycondensation reaction of aliphatic diol (a1) and dicarboxylic acid (a2) is used.
  • the aliphatic diol (a1) it is possible to form a coating having high processability and weatherability, and to obtain a (meth) acrylic-modified polyester resin capable of achieving high-solidification of the coating, so that at least at least Those containing an asymmetric diol having one side chain and / or a linear diol having no side chain are preferred.
  • the term "asymmetric diol” refers to a diol having an asymmetric structure.
  • Examples of the asymmetric diol having at least one side chain include 2-butyl-2-ethyl-1,3-propanediol, 2-methyl-1,4-butanediol, and 2-ethyl-1,4-butane.
  • Diol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 3-methyl-1,5-heptanediol and the like can be mentioned.
  • These unsymmetrical diols having at least one side chain can be used alone or in combination of two or more. Also among these, 2-methyl-1,3-propanediol is preferred.
  • linear diol having no side chain examples include ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and the like.
  • linear diols having no side chain can be used alone or in combination of two or more. Further, among these, 1,6-hexane, because it is possible to obtain a (meth) acrylic-modified polyester resin capable of forming a paint film having high processability and weather resistance, while being able to make the paint highly solid. Diols are preferred.
  • aliphatic diol (a1) other diol can be used as needed other than the unsymmetrical diol which has the said at least 1 side chain, and the linear diol which does not have a side chain.
  • Examples of the other aliphatic diols include neopentyl glycol, hydrogenated bisphenol A, hydrogenated bisphenol F, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,2-butanediol, and 1,3-butanediol.
  • dicarboxylic acid (a2) an aliphatic dicarboxylic acid is contained as an essential component because a (meth) acrylic-modified polyester resin capable of forming a coating film having excellent processability and weatherability is obtained.
  • aliphatic dicarboxylic acids examples include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, cyclohexanedicarboxylic acid, dimer acid, fumaric acid and the like, and aliphatics thereof
  • the methyl ester of dicarboxylic acid, an acid chloride, etc. are mentioned.
  • These aliphatic dicarboxylic acids can be used alone or in combination of two or more. Among these, adipic acid is preferred.
  • the content of the aliphatic dicarboxylic acid is 5% by mass or more in the dicarboxylic acid (a2) because it is excellent in compatibility with the (meth) acrylic monomer mixture (B), and 10
  • the range of -20% by mass is more preferable.
  • dicarboxylic acid (a2) alicyclic dicarboxylic acid, aromatic dicarboxylic acid, or these acid anhydrides can also be contained as needed.
  • alicyclic dicarboxylic acid examples include 1,3-cyclopentane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid and the like.
  • aromatic dicarboxylic acid examples include terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acid, p-hydroxybenzoic acid P- (2-hydroxyethoxy) benzoic acid, trimellitic acid, pyromellitic acid, phthalic anhydride and the like.
  • an esterification catalyst can also be used, if necessary.
  • esterification catalyst examples include metal salts such as titanium, tin, zinc, aluminum, zirconium, magnesium, hafnium, germanium and the like; titanium tetraisopropoxide, titanium tetrabutoxide, titanium oxyacetylacetonate, dibutyl tin oxide, dibutyl tin oxide Tin diacetate, dibutyltin dilaurate, tin octanoate, 2-ethylhexanetin, zinc acetylacetonate, zirconium tetrachloride, zirconium tetrachloride tetrahydrofuran complex, hafnium tetrachloride, hafnium tetrachloride tetrahydrofuran complex, germanium oxide, tetraethoxygermanium, etc. And the like.
  • metal salts such as titanium, tin, zinc, aluminum, zirconium, magnesium, hafnium, germanium
  • reaction of the aliphatic diol (a1) and the dicarboxylic acid (a2) can be carried out, for example, in the absence of a solvent or in the presence of an organic solvent.
  • reaction of the aliphatic diol (a1) and the dicarboxylic acid (a2) is carried out without a solvent, it can be used after being dissolved in an organic solvent after the reaction.
  • organic solvent examples include ketone solvents such as methyl ethyl ketone, acetone and isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate and butyl acetate; and aroma such as toluene, xylene and solvent naphtha Solvents; cycloaliphatic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol and propylene glycol monomethyl ether; alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, dialkylene glycol Examples thereof include glycol ether solvents such as monoalkyl ether acetate. These organic solvents can be used alone or in combination of two or more.
  • the weight average molecular weight of the saturated polyester resin (A) is such that a (meth) acrylic-modified polyester resin capable of forming a paint film having high processability and weatherability can be obtained. Therefore, the range of 1,000 to 5,000 is preferable, and the range of 2,000 to 3,000 is more preferable.
  • the weight average molecular weight of the saturated polyester resin (A) is a value measured by gel permeation chromatography (GPC).
  • the (meth) acrylic monomer mixture (B) essentially contains a hydroxyl group-containing (meth) acrylic monomer.
  • hydroxyl group-containing (meth) acrylic monomer examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and mono (meth) glycerin. And (meth) acrylic monomers having a hydroxyl group in the molecule such as acrylic acid ester. These hydroxyl group-containing (meth) acrylic monomers can be used alone or in combination of two or more.
  • the content of the hydroxyl group-containing (meth) acrylic monomer is preferably 10% by mass or more in the (meth) acrylic monomer mixture.
  • the range of 20 to 40% by mass is more preferable, and in the case of using for PCM coating etc.
  • the range of% is more preferable.
  • the (meth) acrylic monomer mixture can also contain other (meth) acrylic monomers other than the hydroxyl group-containing (meth) acrylic monomer.
  • Examples of the other (meth) acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, and (meth) T-butyl acrylate, 2-ethylhexyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, dodecyl (meth) acrylate, (Meth) acrylic acid alkyl esters such as stearyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate; (meth) Acrylic acid, ⁇ -carboxyethyl (
  • the mass ratio [(A) / (B)] of the saturated polyester resin (A) to the (meth) acrylic monomer mixture (B) enables high-solidification of the paint and excellent processability And the range of 15/85 to 50/50 is preferable, and the range of 25/75 to 35/65 is more preferable, since a (meth) acrylic-modified polyester resin capable of forming a coating film having weather resistance is obtained.
  • the (meth) acrylic-modified polyester resin of the present invention is prepared, for example, by adding the (meth) acrylic monomer mixture (B) and the polymerization initiator to the organic solvent solution of the saturated polyester resin (A) dropwise and reacting them. Can be obtained by:
  • polymerization initiator examples include azo compounds such as 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2-methylbutyronitrile) and azobiscyanovaleric acid; tert-butylperoxy Pivalate, tert-butylperoxybenzoate, tert-butylperoxy-2-ethylhexanoate, di-tert-butyl peroxide, cumene hydroperoxide, benzoyl peroxide, t-butyl hydroperoxide, tert-butyl Organic peroxides such as peroxy-2-ethylhexyl monocarbonate; and inorganic peroxides such as hydrogen peroxide, ammonium persulfate, potassium persulfate and sodium persulfate. These polymerization initiators can be used alone or in combination of two or more.
  • azo compounds such as 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2-
  • the weight average molecular weight of the (meth) acrylic-modified polyester resin of the present invention is such that the paint can be made into a high solid solution, and a (meth) acrylic-modified polyester resin capable of forming a coating having excellent processability and weatherability From the viewpoint of obtaining, the range of 5,000 to 20,000 is preferable, and the range of 7,500 to 12,500 is more preferable.
  • the hydroxyl value of the (meth) acrylic acid polyester resin of the present invention makes it possible to solidify the paint, and can form a (meth) acrylic-modified polyester resin having excellent processability and weatherability.
  • the range of 60 to 150 is preferable because In particular, when the (meth) acrylic modified polyester resin of the present invention is used for industrial coatings such as automobiles and heavy machinery, the range of 100 to 150 is more preferable, and when it is used for PCM coatings, the range of 60 to 100 is More preferable.
  • the curable resin composition of the present invention essentially contains the (meth) acrylic-modified polyester resin and a curing agent.
  • the curing agent may contain a component capable of causing a curing reaction with the (meth) acrylic-modified polyester resin of the present invention, and as such a component, for example, amino resin, polyisocyanate resin, resol resin And epoxy resins. These may be used alone or in combination of two or more.
  • the components of the curing agent are appropriately selected according to the application and use environment of the curable resin composition, the physical properties of the desired cured product, and the like, as long as the (meth) acrylic-modified polyester resin of the present invention is used as the main agent, Even when any curing agent is used, the effect excellent in the balance between the processability and the weather resistance in the cured coating film exhibited by the present invention is sufficiently exhibited.
  • amino resin for example, a methylolated amino resin synthesized from at least one selected from the group consisting of melamine, urea and benzoguanamine and formaldehydes; part or all of the methylol groups of the methylolated amino resin Those obtained by alkyl etherification with lower monohydric alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol and the like can be mentioned.
  • Examples of commercial products of the amino resin include “Cymel 303” (methylated melamine resin) manufactured by Allnex, “Cymel 350” (methylated melamine resin), “Yuban 520” manufactured by Mitsui Chemicals, Inc. (n- Butylated Modified Melamine Resin), “U-Ban 20-SE-60” (n-Butylated Modified Melamine Resin), “U-Ban 2021” (n-Butylated Modified Melamine Resin), “U-Bon 220” (n-Butylated Modified Melamine) Resin), “U-Bane 22R” (n-butylated modified melamine resin), “U-Ban 2028” (n-butylated modified melamine resin), “U-Bang 165” (isobutylated modified melamine resin), “U-Bang 114” (isobutylated) Modified melamine resin), “U-ban 62” (isobutylated modified melamine resin), “U
  • 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, isophorone diisocyanate, Alicyclic alicyclic compounds such as hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate; tolylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, diphenylmethane diisocyanate, aromatic diisocyanate compounds such as 1,5-naphthalene diisocyanate; Polymethylene polypheny having a repeating structure represented by formula (1) Polyisocyanates; these isocyanurate modified product, a biuret modified product, an allophanate modified product, and a blocked poly
  • each R 1 independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.
  • R 2 each independently represents an alkyl group having 1 to 4 carbon atoms, or a bonding point which is linked to the structural moiety represented by the structural formula (1) via a methylene group marked with an asterisk (*).
  • m is an integer of 0 or 1 to 3
  • l is an integer of 1 or more.
  • epoxy resin examples include polyglycidyl ethers of polyol compounds, polyglycidyl esters of polycarboxylic acid compounds, bisphenol type epoxy resins, and novolac type epoxy resins.
  • the curable resin composition of the present invention may be, if necessary, a curing catalyst, a curing accelerator, a pigment, a pigment dispersant, a matting agent, a leveling agent, a drying inhibitor, an ultraviolet absorber, an antifoamer, a thickener. An anti-settling agent, an organic solvent and the like may be added.
  • the compounding ratio of each of these components and the kind of compound are suitably adjusted by the use and desired performance of a curable resin composition.
  • the curable resin composition of the present invention may be one-pack type or two-pack type. When the curable resin composition of the present invention is a two-component type, the various additives can be added to either or both of the main agent and the curing agent.
  • the application of the curable resin composition of the present invention is not particularly limited, it can be used for paints and adhesives because it can form a cured coating film having excellent processability and weather resistance, and in particular, it can be used for PCM paints and automobiles. It can be suitably used as a paint for coated steel plates such as top paints, paints for automobiles such as paints for car repair, etc.
  • the coated steel sheet of the present invention refers to a coated steel sheet having a cured coating film of a coating comprising the curable resin composition on the surface of the steel sheet, and the steel sheet refers to, for example, plating of galvanized steel sheet, aluminum-zinc alloy steel sheet, etc.
  • a steel plate, a zinc-aluminium-magnesium alloy plated steel plate, an aluminum plate, an aluminum alloy plate, an electromagnetic steel plate, a copper plate, a stainless steel plate and the like can be mentioned.
  • the number average molecular weight (Mn) and weight average molecular weight (Mw) of the saturated polyester resin used in the present invention, and the number average molecular weight (Mn) of the (meth) acrylic-modified polyester resin of the present invention, and weight average molecular weight (Mw) ) Shows values obtained by measurement under the following conditions by gel permeation chromatography (GPC).
  • Measuring device High-speed GPC device ("HLC-8220GPC” manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were used in series connection. "TSKgel G5000" (7.8 mm ID ⁇ 30 cm) ⁇ 1 "TSK gel G 4000” (7.8 mm ID ⁇ 30 cm) ⁇ 1 "TSK gel G 3000" (7.8 mm ID ⁇ 30 cm) ⁇ 1 This "TSKgel G2000" (7.8 mm ID ⁇ 30 cm) ⁇ 1 detector: RI (differential refractometer) Column temperature: 40 ° C Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 mL / min Injection volume: 100 ⁇ L (tetrahydrofuran solution with a sample concentration of 0.4% by mass) Standard sample: A calibration curve was prepared using the following standard polystyrene.
  • the saturated polyester resin (1) had a number average molecular weight (Mn) of 1,094, a weight average molecular weight (Mw) of 2,114, an acid value of 2.8 mg KOH / g and a hydroxyl value of 137 mg KOH / g.
  • the obtained saturated polyester resin (1) was dissolved in butyl acetate to obtain a saturated polyester resin (1) solution having a nonvolatile content of 81.4% by mass.
  • the Gardner viscosity of this saturated polyester resin (1) solution was Z4-Z5.
  • the saturated polyester resin (2) had a number average molecular weight (Mn) of 988, a weight average molecular weight (Mw) of 2,026, an acid value of 2.1 mg KOH / g, and a hydroxyl value of 141.3 mg KOH / g.
  • the obtained saturated polyester resin (2) was dissolved in butyl acetate to obtain a saturated polyester resin (2) solution having a nonvolatile content of 83.1% by mass.
  • the Gardner viscosity of this saturated polyester resin (2) solution was Z3-Z4.
  • the saturated polyester resin (3) had a number average molecular weight (Mn) of 667, a weight average molecular weight (Mw) of 1,441, an acid value of 7.2 mg KOH / g, and a hydroxyl value of 169.2 mg KOH / g.
  • the obtained saturated polyester resin (3) was dissolved in butyl acetate to obtain a saturated polyester resin (3) solution having a nonvolatile content of 87% by mass.
  • the Gardner viscosity of this saturated polyester resin (3) solution was Z2-Z3.
  • the saturated polyester resin (4) had a number average molecular weight (Mn) of 2,149, a weight average molecular weight (Mw) of 4,968, an acid value of 4.7 mg KOH / g and a hydroxyl value of 78.6 mg KOH / g. .
  • the obtained saturated polyester resin (4) is dissolved in a mixed solvent of 800 parts by mass of an aromatic solvent ("Solvesso 100" manufactured by Exxon Mobil Co., Ltd.) and 200 parts by mass of propylene glycol monomethyl ether acetate, and the non volatile matter 78 A 0.3% by mass saturated polyester resin (4) solution was obtained.
  • the Gardner viscosity of this saturated polyester resin (4) solution was Z-Z1.
  • Production Example 5 Production of a Saturated Polyester Resin (5) Solution
  • a reaction vessel equipped with a stirrer, a condenser and a thermometer 30.81 parts by mass of 2-methyl-1,3-propanediol, 6.85 parts by mass of 1,6-hexanediol, 1.17 parts by mass of trimethylolpropane, 4.25 parts by mass of neopentyl glycol, 38.44 parts by mass of isophthalic acid, 18.49 parts by mass of adipic acid, and 0.01 parts by mass of tetraisopropyl orthotitanate were charged.
  • the esterification reaction was carried out at 200 to 250 ° C.
  • the number average molecular weight (Mn) of this saturated polyester resin (5) was 1,234, the weight average molecular weight (Mw) was 2,998, the acid value was 6 mg KOH / g, and the hydroxyl value was 113.5 mg KOH / g.
  • the obtained saturated polyester resin (5) was dissolved in butyl acetate to obtain a saturated polyester resin (5) solution having a nonvolatile content of 82.2% by mass.
  • the Gardner viscosity of this saturated polyester resin (5) solution was XY.
  • Production Example 6 Production of Saturated Polyester Resin (6) Solution
  • 25.76 parts by mass of 2-methyl-1,3-propanediol In a reaction vessel equipped with a stirrer, a condenser and a thermometer, 25.76 parts by mass of 2-methyl-1,3-propanediol, 2.02 parts by mass of trimethylolpropane, 12.63 parts by mass of neopentyl glycol, and 40 parts of isophthalic acid .4 parts by mass, 16.67 parts by mass of terephthalic acid, 2.53 parts by mass of adipic acid, and 0.01 parts by mass of tetraisopropyl orthotitanate were charged.
  • the esterification reaction was carried out at 200 to 250 ° C. for 12 hours while stirring under a nitrogen stream to obtain a saturated polyester resin (6).
  • the number average molecular weight (Mn) of this saturated polyester resin (6) was 1,763, the weight average molecular weight (Mw) was 4,028, the acid value was 4.5 mg KOH / g, and the hydroxyl value was 94.4 mg KOH / g .
  • the obtained saturated polyester resin (6) was dissolved in butyl acetate to obtain a saturated polyester resin (6) solution having a nonvolatile content of 72% by mass.
  • the Gardner viscosity of this saturated polyester resin (6) solution was Z1-Z2.
  • Example 1 Preparation of (Meth) Acryl-Modified Polyester Resin (1) Solution
  • a reaction vessel equipped with a stirrer, a condenser and a thermometer 17.41 parts by mass of the saturated polyester resin (1) solution obtained in Production Example 1 and 20.38 parts by mass of butyl acetate are charged, and the temperature rises to 120 to 130 ° C. It warmed.
  • Example 2 Preparation of (meth) acrylic modified polyester resin (2)
  • the temperature was raised to 120 to 130.degree.
  • the (meth) acrylic monomer mixture described in Table 1 and 4.02 parts by mass of (2-ethylhexanoyl) (tert-butyl) peroxide were added dropwise over 4 to 6 hours.
  • Example 3 Preparation of (meth) acrylic modified polyester resin (3)
  • a reaction vessel equipped with a stirrer, a condenser, and a thermometer 18.30 parts by mass of the saturated polyester resin (3) solution obtained in Production Example 3 and 21.26 parts by mass of butyl acetate are charged, and the temperature rises to 120 to 130 ° C. It warmed.
  • (meth) acrylic monomer mixture described in Table 1 4.89 parts by mass of (2-ethylhexanoyl) (tert-butyl) peroxide, and 0.5 mass of 1-dodecanethiol over 4 to 6 hours The part was dropped.
  • Example 4 Preparation of (meth) acrylic-modified polyester resin (4)
  • a reaction vessel equipped with a stirrer, a condenser and a thermometer 22.05 parts by mass of the saturated polyester resin (4) solution obtained in Production Example 4; 12.88 parts by mass of butyl acetate; 19.24 parts by mass of propylene glycol monomethyl ether acetate
  • the temperature was raised to 120 to 130 ° C.
  • the (meth) acrylic monomer mixture described in Table 1 3.15 parts by mass of (2-ethylhexanoyl) (tert-butyl) peroxide, and 0.45 parts by mass of 1-dodecanethiol.
  • the part was dropped.
  • Example 5 Preparation of (Meth) Acryl-Modified Polyester Resin (5) In a reaction vessel equipped with a stirrer, a condenser, and a thermometer, 25.25 parts by mass of the saturated polyester resin (5) solution obtained in Production Example 5; 17.04 parts by mass of butyl acetate; 3.01 parts by mass of propylene glycol monomethyl ether acetate The temperature was raised to 120 to 130 ° C. Then, (meth) acrylic monomer mixture described in Table 1, 4.94 parts by mass of (2-ethylhexanoyl) (tert-butyl) peroxide, and 0.54 mass of 1-dodecanethiol over 4 to 6 hours The part was dropped.
  • compositions of the (meth) acrylic modified polyester resins (1) to (5) obtained in Examples 1 to 5 are shown in Table 1.
  • Comparative Preparation Example 1 Preparation of Acrylic Resin Solution (C1-1) In a reaction vessel equipped with a stirrer, a condenser, and a thermometer, butyl acetate was charged, and the temperature was raised to 120 to 130.degree. Then, the acrylic monomer mixture used in Example 5 was dropped over 4 to 6 hours. Thereafter, tert-butyl benzoyl peroxide was added, and allowed to stand at 120 to 130 ° C. for 2 hours to obtain an acrylic resin solution (C1-1) having a nonvolatile content of 70.8% by mass.
  • the acrylic resin solution (C1-1) has a number average molecular weight (Mn) of 2,742, a weight average molecular weight (Mw) of 7,841, an acid value of 6.6 mg KOH / g, and a hydroxyl value (solid content) of 73. 3 mg KOH / g, Gardner viscosity was YZ.
  • Comparative Example 1 Preparation of Mixed Solution (C1) of Acrylic Resin and Polyester Resin
  • the acrylic resin solution (C1-1) obtained in Comparative Production Example 1 and the saturated polyester resin (5) solution obtained in Production Example 5 are mixed at 25 ° C. so that the same polyester amount as in Example 5 can be obtained.
  • a mixed solution (C1) of an acrylic resin and a polyester resin was obtained.
  • Example 6 Preparation of White Paint (1) In a reaction vessel equipped with a stirrer, a condenser and a thermometer, 26.4 parts by mass of the (meth) acrylic-modified polyester resin (4) solution obtained in Example 4 and titanium oxide ("Ti-Pure R960” manufactured by Dupont 34) .3 parts by mass, 0.3 parts by mass of silica ("Aerosil R 972” manufactured by Evonik Industries), aromatic solvent (“Sorvesso 100” manufactured by Exxon Mobil Limited) and propylene glycol monomethyl ether acetate at a mass ratio of 7: 3 The mixed solvent was mixed with 4.1 parts by mass of the mixed solvent and dispersed until the particle size became 10 .mu.m or less ..
  • Solid 100 1.0 part by mass of a mixed solvent in which propylene glycol monomethyl ether acetate is mixed in a mass ratio of 7: 3 are added and mixed, and the Ford cup # 4 viscosity at 25 ° C. is about
  • the white paint (1) was obtained by adjusting to 100 seconds.
  • Example 7 Preparation of White Paint (2)
  • Example 6 was repeated except that the (meth) acrylic modified polyester resin (5) solution obtained in Example 5 was used instead of the (meth) acrylic modified polyester resin (4) solution used in Example 6.
  • White paint (2) was obtained.
  • Example 6 is the same as Example 6, except that the mixed solution (C1) of the acrylic resin and polyester resin obtained in Comparative Example 1 is used instead of the (meth) acrylic modified polyester resin (4) solution used in Example 6.
  • White paint (3) was obtained.
  • Example 6 was carried out in the same manner as Example 6, except that a saturated polyester resin solution ("Beckolite GS-13" manufactured by DIC Corporation) was used instead of the (meth) acrylic modified polyester resin (4) solution used in Example 6. White paint (4) was obtained.
  • Example 6 Preparation of White Paint (5)
  • Example 6 was repeated except that a saturated polyester resin solution ("Beckolite GS-37-1" manufactured by DIC Corporation) was used instead of the (meth) acrylic modified polyester resin (4) solution used in Example 6.
  • a white paint (5) was obtained in the same manner.
  • Example 6 was carried out in the same manner as Example 6, except that a saturated polyester resin solution ("Beckolite GS-12" manufactured by DIC Corporation) was used instead of the (meth) acrylic modified polyester resin (4) solution used in Example 6.
  • White paint (7) was obtained.
  • the coated steel plate was produced using the white paint obtained by said Example and comparative example.
  • Examples 8 and 9 Preparation of coated steel sheets (A) and (B)
  • the white paints (1) and (2) obtained in Examples 5 and 6 were each coated with a bar coater to a film thickness of 15 to 20 ⁇ m on a 0.5 mm thick hot-dip galvanized chromate-treated steel sheet, It heat-dried in 20 degreeC oven for 20 seconds (metal peak temperature is 210 degreeC), and obtained the coated steel plates (A) and (B).
  • Comparative Examples 8 to 11 Preparation of Painted Steel Sheets (C) to (F)
  • the white paints (3) to (6) obtained in Comparative Examples 3 to 6 were coated with a bar coater on a hot-dip galvanized chromate-treated steel sheet having a thickness of 0.5 mm so that the film thickness would be 15 to 20 ⁇ m.
  • the resultant was heated and dried in an oven for 40 seconds (metal peak temperature is 230.degree. C.) to obtain coated steel sheets (C) to (F).
  • Example 10 and 11 Preparation of coated steel sheets (G) and (H)
  • a saturated polyester resin (“Beckorite GS-12" manufactured by DIC Corporation) is coated on a 0.5 mm-thick hot-dip galvanized chromate-treated steel plate with a bar coater to a film thickness of 5 ⁇ m, 250 ° C Heat-dried in an oven for 20 seconds (metal peak temperature is 210 ° C.) to form a primer layer, and then the white paints (1) and (2) obtained in Examples 5 and 6 were applied to the surface of the primer layer. It coated with a bar coater so that a film thickness might be set to 15 micrometers, and it heat-dried for 40 seconds in a 250 degreeC oven (metal peak temperature is 210 degreeC), and created the coated steel plates (G) and (H).
  • a saturated polyester resin ("Beckorite GS-12" manufactured by DIC Corporation) is coated on a 0.5 mm-thick hot-dip galvanized chromate-treated steel plate with a bar coater to a film thickness of 5 ⁇ m, 250 ° C (The metal peak temperature is 210 ° C.) to form a primer layer, and then the white paints (3), (6) and (7) obtained in Comparative Examples 3, 6 and 7 are prepared.
  • the primer layer is coated with a bar coater to a film thickness of 15 ⁇ m and dried by heating in an oven at 250 ° C. for 40 seconds (metal peak temperature is 230 ° C.) to produce coated steel plates (I) to (K) did.
  • Example 12 Preparation of Clear Paint (1) In a reaction vessel equipped with a stirrer, a condenser and a thermometer, 87.8 parts by mass of the (meth) acrylic-modified polyester resin (5) solution obtained in Example 5; amino resin ("Cymel 303LF” manufactured by Allnex) 10. 0 parts by mass, 0.9 parts by mass of a catalyst ("Nacure 5225” manufactured by King), 0.5 parts by mass of a leveling agent ("Modaflow 2100” manufactured by Allnex), aromatic solvent (“Solvesso 100” manufactured by Exxon Mobil Co., Ltd. ) And propylene glycol monomethyl ether acetate in a mass ratio of 7: 3 are added and mixed, and the mixture is further adjusted so that the Ford cup # 4 viscosity at 25 ° C. becomes about 100 seconds And got clear paint (1).
  • amino resin (“Cymel 303LF” manufactured by Allnex) 10. 0 parts by mass, 0.9 parts by mass of a catalyst ("Nacure 5225"
  • Example 13 Preparation of a coated steel sheet (L)
  • the clear paint (1) obtained in Example 12 was coated on a 0.5 mm thick hot-dip galvanized chromate-treated steel sheet to a film thickness of 15 to 20 ⁇ m with a bar coater, and kept for 20 seconds in an oven at 250 ° C. It heat-dried (metal peak temperature is 210 degreeC) and obtained the coated steel plate (L).
  • Examples 8 and 9 shown in Table 3 are examples of the white paint using the (meth) acrylic modified polyester resin of the present invention, both have a high nonvolatile content such as 73.3% by mass of nonvolatile content. It was confirmed that high solid paint could be made. In addition, it has been confirmed that the coating film of the white paint is excellent not only in excellent processability and weatherability but also in coating film hardness and stain resistance.
  • Comparative Example 8 is an example of a white paint using a mixed solution of an acrylic resin and a polyester resin, but it has a high non-volatile content and although a high solid paint can be produced, the paint film of the paint is It was confirmed that the gloss retention was as low as 60% and the weather resistance was insufficient.
  • Comparative Examples 9 and 10 are examples of the white paint using a saturated polyester resin, but the nonvolatile content is as low as 64.3 mass% (Comparative Example 9) and 63.2 mass% (Comparative Example 10), and is a high solid. It could be confirmed that it was not possible to make a good paint. In addition, it was confirmed that the coating film of the white paint had an extremely low gloss retention of 30% (Comparative Example 9) and 55% (Comparative Example 10), and the weather resistance was extremely insufficient.
  • Comparative Example 11 is an example of a white paint using an acrylic resin solution, but although a high non-volatile content and high solid paint can be produced, the paint film of the paint has insufficient processability. It has been confirmed that there is.
  • Examples 10 and 11 and Comparative Examples 12 to 14 shown in Table 4 relate to a coated steel plate provided with a primer layer between the steel plate and the white paint. It was confirmed that the coating film of the white paint in the coated steel sheet obtained in Examples 10 and 11 was excellent not only in the excellent processability and the weather resistance but also in the coating film hardness and the stain resistance.
  • Example 13 shown in Table 5 is an example of a clear paint using the (meth) acrylic-modified polyester resin of the present invention. It was confirmed that the coating film of the clear paint in the coated steel sheet obtained in Example 13 is excellent not only in the excellent processability and the weather resistance but also in the film hardness and the stain resistance.

Abstract

La présente invention concerne une résine de polyester modifiée avec un groupe (méth)acrylique formée de matériaux de départ par réaction essentiels comprenant une résine de polyester saturée (A) et un mélange de monomères (méth)acryliques (B) qui contient un monomère (méth)acrylique portant un groupe hydroxyle, la résine de polyester modifiée avec un groupe (méth)acrylique étant caractérisée en ce que la résine de polyester saturée (A) est le polycondensat d'un diol aliphatique (a1) et d'un acide dicarboxylique (a2) contenant un acide dicarboxylique aliphatique et la teneur en acide dicarboxylique aliphatique dans l'acide dicarboxylique (a2) est d'au moins 5 % en masse. Cette résine de polyester modifiée avec un groupe (méth)acrylique peut fournir une solidification élevée d'un matériau de revêtement et peut former un film de revêtement qui fait preuve d'une excellente aptitude au façonnage et d'une excellente résistance aux intempéries.
PCT/JP2017/044868 2017-11-21 2017-12-14 Résine de polyester modifiée avec un groupe (méth)acrylique, composition de résine durcissable, matériau de revêtement, et tôle d'acier revêtue WO2019102626A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
DE112017008223.4T DE112017008223T5 (de) 2017-11-21 2017-12-14 (Meth)acrylmodifiziertes Polyesterharz, härtbare Harzzusammensetzung, Lack und lackiertes Stahlblech
CN201780097073.9A CN111448229B (zh) 2017-11-21 2017-12-14 (甲基)丙烯酸类改性聚酯树脂、固化性树脂组合物、涂料及涂装钢板
JP2019556082A JP6725895B2 (ja) 2017-11-21 2017-12-14 （メタ）アクリル変性ポリエステル樹脂、硬化性樹脂組成物、塗料及び塗装鋼板

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5016396B1 (fr) * 1970-08-26 1975-06-12
JP2000327727A (ja) * 1999-03-16 2000-11-28 Toyo Ink Mfg Co Ltd ポリエステル変性樹脂および該樹脂を用いた樹脂組成物ならびに該樹脂を用いた硬化物
JP2003025491A (ja) * 2001-07-11 2003-01-29 Nippon Yushi Basf Coatings Kk 塗装鋼板
JP2008201842A (ja) * 2007-02-16 2008-09-04 Basf Coatings Japan Ltd 塗料組成物
JP2012184370A (ja) * 2011-03-08 2012-09-27 Toyo Ink Sc Holdings Co Ltd 水性塗料組成物とその製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5016396B1 (fr) * 1970-08-26 1975-06-12
JP2000327727A (ja) * 1999-03-16 2000-11-28 Toyo Ink Mfg Co Ltd ポリエステル変性樹脂および該樹脂を用いた樹脂組成物ならびに該樹脂を用いた硬化物
JP2003025491A (ja) * 2001-07-11 2003-01-29 Nippon Yushi Basf Coatings Kk 塗装鋼板
JP2008201842A (ja) * 2007-02-16 2008-09-04 Basf Coatings Japan Ltd 塗料組成物
JP2012184370A (ja) * 2011-03-08 2012-09-27 Toyo Ink Sc Holdings Co Ltd 水性塗料組成物とその製造方法

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JPWO2019102626A1 (ja) 2020-07-02
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JP6725895B2 (ja) 2020-07-22

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