Classifications

• • 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
  • C08G63/46—Polyesters chemically modified by esterification
  • C08G63/48—Polyesters chemically modified by esterification by unsaturated higher fatty oils or their acids; by resin acids
• • 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
  • C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
• • 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
  • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
  • C09D125/02—Homopolymers or copolymers of hydrocarbons
  • C09D125/04—Homopolymers or copolymers of styrene
  • C09D125/08—Copolymers of styrene
  • C09D125/14—Copolymers of styrene with unsaturated esters
• • 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
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09D133/08—Homopolymers or copolymers of acrylic acid esters
• • 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
  • C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
• • 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
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate

Definitions

• the present invention relates to a water-based coating agent, an article, and a method for producing a rosin-modified polyester resin.
• water-based coating agents are known.
• the water-based coating agent is applied, for example, to a substrate to form a coating film.
• the water-based coating agent contains, for example, a resin obtained by the following method. First, 185.2 g of fatty acid dimer, 1453.3 g of pine oil rosin, 6 g of phenolsulfonic acid and 185.2 g of polyglycerol are mixed. The mixture is then heated to 250-270° C. and reacted until the acid value reaches 6 mgKOH/g. Thereby, a resin coating film having excellent water resistance can be obtained (see, for example, Patent Document 1 (Example 1)).
• the present invention is a water-based coating agent capable of forming a coating film with excellent oil resistance, an article comprising a coating film obtained from the water-based coating agent, and a method for producing a rosin-modified polyester resin contained in the water-based coating agent.
• the present invention contains an aqueous medium and a polyester resin component
• the polyester resin component is a raw material containing (A) rosins, (B) an ⁇ , ⁇ -unsaturated dicarboxylic acid, and (C) a polyol.
• a rosin-modified polyester resin that is a reaction product of the components
• the acid value of the polyester resin component is 60 mgKOH/g or more and 180 mgKOH/g or less
• the hydroxyl value of the polyester resin component is 20 mgKOH/g or more and 180 mgKOH/g
• the content ratio of the (B) ⁇ , ⁇ -unsaturated dicarboxylic acid is 70 mol or more and 150 mol or less per 100 mol of the (A) rosin.
• the water-based coating agent described in [1] above is included.
• the present invention [3] comprises the water-based coating agent according to [1] or [2] above, wherein the (B) ⁇ , ⁇ -unsaturated dicarboxylic acid comprises fumaric acid and/or maleic anhydride.
• the present invention [4] includes the water-based coating agent according to any one of [1] to [3] above, wherein the raw material further includes (D) oils and/or fatty acids.
• the present invention [5] is the water-based coat according to [4] above, wherein the content of the (D) oil and/or fatty acid is 10% by mass or more and 30% by mass or less with respect to the total amount of the raw material components. contains a drug.
• the present invention [6] further includes the water-based coating agent according to any one of [1] to [5] above, which contains a styrene-(meth)acrylic copolymer.
• the present invention [7] further includes the water-based coating agent according to any one of [1] to [6] above, which contains wax.
• the present invention [8] includes an article including a coating film of the water-based coating agent according to any one of [1] to [7] above.
• the present invention [9] comprises a first step of reacting (A) a rosin with (B) an ⁇ , ⁇ -unsaturated dicarboxylic acid to obtain a first product, and after the first step, the first a second step of reacting the product with (C) the polyol to obtain a second product, wherein the reaction temperature in the second step is 230° C. or less; I'm in.
• the present invention [10] comprises a modification step of modifying the (C) polyol with (D) fats and/or fatty acids before the second step, and the reaction temperature in the modification step is 230° C. or higher and 300° C.
• the method for producing a rosin-modified polyester resin described in [9] above, which is as follows, is included.
• the acid value of the polyester resin component containing the rosin-modified polyester resin is within a predetermined range, and the hydroxyl value of the polyester resin component containing the rosin-modified polyester resin is within a predetermined range. Therefore, the water-based coating agent of the present invention can form a coating film having excellent oil resistance.
• the article of the present invention has excellent oil resistance because it contains the coating film of the water-based coating agent.
• a rosin-modified polyester resin having excellent oil resistance can be obtained.
• the aqueous coating agent of the present invention contains an aqueous medium and a polyester resin component. More specifically, the aqueous coating agent contains an aqueous medium and a polyester resin component dissolved and/or dispersed in the aqueous medium.
• aqueous media examples include water and hydrophilic solvents.
• Hydrophilic solvents include, for example, alcohols, ketones, esters, ethers, ether alcohols, ether alcohol acetates and nitriles.
• Alcohols include, for example, methanol and ethanol.
• Ketones include, for example, acetone.
• Esters include, for example, ethyl acetate and butyl acetate.
• Ethers include, for example, dioxane and tetrahydrofuran.
• Ether alcohols include, for example, cellosolve and carbitol.
• Ether alcohol acetates include, for example, cellosolve acetate and carbitol acetate.
• Nitriles include, for example, acetonitrile. These can be used alone or in combination of two or more. Water is preferably used as the aqueous medium.
• the polyester resin component contains rosin-modified polyester resin as the main component.
• the main component is a component contained in a proportion of 75% by mass or more, preferably 80% by mass or more, relative to the total amount. Further, the polyester resin component can contain unreacted raw material components as subcomponents, which will be described later in detail.
• a rosin-modified polyester resin is a polyester resin modified with rosins.
• a rosin-modified polyester resin is a reaction product of raw ingredients.
• the raw material components include (A) rosins, (B) ⁇ , ⁇ -unsaturated dicarboxylic acid, and (C) polyol as essential components.
• the raw material components consist of, for example, (A) rosins, (B) ⁇ , ⁇ -unsaturated dicarboxylic acid, and (C) polyol.
• the total amount of (A) rosins, (B) ⁇ , ⁇ -unsaturated dicarboxylic acid, and (C) polyol is 100% by mass based on the raw material components.
• (A) Rosins are plant-derived ingredients. Therefore, the rosin-modified polyester resin can contribute to carbon neutrality. More specifically, (A) rosins are compounds derived from pine. The pine is not particularly limited, and examples thereof include merukushi pine, slash pine and horsetail pine. These can be used alone or in combination of two or more.
• Rosins are not particularly limited, and include known undenatured rosins and/or derivatives thereof.
• Undenatured rosins include, for example, crude rosins and purified rosins.
• Crude rosins include, for example, gum rosins, tall rosins and wood rosins.
• Purified rosin includes purified crude rosin.
• Rosin derivatives include, for example, hydrogenated rosin, disproportionated rosin and polymerized rosin. These can be used alone or in combination of two or more.
• the production area of rosin is not particularly limited, and examples thereof include China, Vietnam, Indonesia and Brazil. These can be used alone or in combination of two or more.
• Rosins preferably include non-denatured rosins, more preferably gum rosins, from the viewpoint of film-forming properties and water resistance.
• the content of (A) rosins relative to the total amount of raw material components is, from the viewpoint of film-forming properties, water resistance, and tack resistance, for example, 20% by mass or more, preferably 25% by mass or more, more preferably 30% by mass. % or more, more preferably 35 mass % or more.
• the content of (A) rosins relative to the total amount of raw material components is, from the viewpoint of film-forming properties, water resistance and tack resistance, for example, 80% by mass or less, preferably 70% by mass or less, more preferably 65% by mass or less, more preferably 60% by mass or less, more preferably 50% by mass or less, and particularly preferably 40% by mass or less.
• (B) ⁇ , ⁇ -unsaturated dicarboxylic acid is a component that improves the oil resistance of the coating film.
• (B) ⁇ , ⁇ -unsaturated dicarboxylic acids include, for example, fumaric acid, maleic acid, itaconic acid, citraconic acid and anhydrides thereof.
• Anhydrides include, for example, maleic anhydride, itaconic anhydride and citraconic anhydride. These can be used alone or in combination of two or more.
• (B) ⁇ , ⁇ -unsaturated dicarboxylic acids preferably include fumaric acid and maleic anhydride, more preferably fumaric acid. That is, (B) ⁇ , ⁇ -unsaturated dicarboxylic acid preferably contains fumaric acid and/or maleic anhydride, more preferably fumaric acid.
• the content of (B) ⁇ , ⁇ -unsaturated dicarboxylic acid relative to the total amount of raw material components is, from the viewpoint of oil resistance, for example, 3% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more. , more preferably 12% by mass or more.
• the content of (B) ⁇ , ⁇ -unsaturated dicarboxylic acid relative to the total amount of raw material components is, from the viewpoint of oil resistance, for example 40% by mass or less, preferably 30% by mass or less, more preferably 25% by mass. % or less, more preferably 20 mass % or less.
• the content of (B) ⁇ , ⁇ -unsaturated dicarboxylic acid is, for example, 50 mol or more, preferably 70 mol or more, more preferably 70 mol or more per 100 mol of (A) rosins from the viewpoint of oil resistance. is 80 mol or more, more preferably 90 mol or more.
• the content ratio of (B) ⁇ , ⁇ -unsaturated dicarboxylic acid is, for example, 200 mol or less, preferably 150 mol or less, more preferably 150 mol or less per 100 mol of (A) rosin, from the viewpoint of oil resistance. is 120 mol or less.
• Polyols include, for example, dihydric alcohols, trihydric alcohols, and tetrahydric or higher alcohols.
• Dihydric alcohols include straight chain alkyl diols, branched chain alkyl diols and ether diols.
• Linear alkyldiols include, for example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol.
• Branched alkyldiols include, for example, propylene glycol, 1,3-butanediol, 1,2-butanediol, 3-methyl-1,5-pentanediol and 2,6-dimethyl-1-octene-3,8 - includes diols.
• Ether diols include, for example, diethylene glycol, triethylene glycol and dipropylene glycol.
• dihydric alcohols examples include 1,4-dihydroxy-2-butene, isosorbide, cyclohexanedimethanol, cyclohexanediol, tricyclodecanedimethylol, bisphenol A, hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated Bisphenol S, hydrogenated catechol, hydrogenated resorcinol, hydrogenated hydroquinone and dicyclopentadiene diallyl alcohol copolymer.
• Trihydric alcohols include, for example, glycerin, trimethylolethane, trimethylolpropane, trimethylolhexane and trimethyloloctane.
• tetrahydric or higher alcohols examples include tetrahydric to octahydric alcohols.
• Tetra- to octahydric alcohols include, for example, pentaerythritol, diglycerin, ditrimethylolpropane, sorbitan, sorbitol, dipentaerythritol, inositol and tripentaerythritol. These can be used alone or in combination of two or more.
• the (C) polyol preferably includes trihydric alcohols and tetrahydric or higher alcohols, more preferably trihydric alcohols, and still more preferably trimethylolpropane, glycerin and pentahydric alcohols. Erythritol is preferred, and glycerin is particularly preferred.
• the carbon number of (C) polyol is, for example, 2 or more, preferably 3 or more. In addition, the carbon number of (C) polyol is, for example, 30 or less, preferably 20 or less, more preferably 10 or less, and still more preferably 8 or less.
• the content of the (C) polyol with respect to the total amount of the raw material components is, from the viewpoint of oil resistance, for example, 5% by mass or more, preferably 8% by mass or more, more preferably 12% by mass or more, and still more preferably 13% by mass. % or more, particularly preferably 15 mass % or more.
• the content of (C) polyol relative to the total amount of raw material components is, for example, 40% by mass or less, preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably, It is 20% by mass or less.
• the raw material component can contain (D) oils and/or fatty acids as optional components. If the raw material component contains (D) oil and/or fatty acid, the oil resistance of the coating film can be improved.
• the raw material components consist of, for example, (A) rosins, (B) ⁇ , ⁇ -unsaturated dicarboxylic acids, (C) polyols, and (D) fats and/or fatty acids.
• the total amount of (A) rosins, (B) ⁇ , ⁇ -unsaturated dicarboxylic acid, (C) polyol, and (D) oils and/or fatty acids is 100% by mass based on the raw material components. is.
• fats and oils examples include linseed oil, yuzu oil, pistachio oil, rice oil, safflower oil, apricot oil, cottonseed oil, sesame oil, corn oil, watermelon oil, soybean oil, poppy oil, apple oil, sunflower oil, and cactus oil. Oil, tall oil, walnut oil, tung oil, and castor oil.
• fatty acids include fatty acids derived from the above oils and fats.
• fatty acids more specifically, linseed oil fatty acid, yuzu oil fatty acid, pistachio oil fatty acid, rice oil fatty acid, safflower oil fatty acid, apricot oil fatty acid, cottonseed oil fatty acid, sesame oil fatty acid, corn oil fatty acid, watermelon oil fatty acid, soybean oil Fatty acids include poppy oil fatty acid, apple oil fatty acid, sunflower oil fatty acid, cactus oil fatty acid, tall oil fatty acid, walnut oil fatty acid, tung oil fatty acid and castor oil fatty acid. These can be used alone or in combination of two or more.
• the content of (D) oils and/or fatty acids (the total amount thereof when used in combination) with respect to the total amount of raw material components is, from the viewpoint of flexibility, water resistance and oil resistance, for example, 0% by mass or more, preferably It is 10% by mass or more, more preferably 12% by mass or more, still more preferably 15% by mass or more, and particularly preferably 17% by mass or more.
• the content ratio of (D) oils and/or fatty acids (the total amount thereof when used in combination) to the total amount of raw material components is, for example, 40% by mass or less, preferably from the viewpoint of flexibility, water resistance, and oil resistance. is 35% by mass or less, more preferably 30% by mass or less, and still more preferably 25% by mass or less.
• Fats and/or fatty acids preferably include oils and/or fatty acids having a predetermined iodine value from the viewpoint of oil resistance. More specifically, the iodine value of the (D) oil and/or fatty acid is, from the viewpoint of oil resistance, for example, 50 mg/100 mg or more, preferably 70 mg/100 mg or more, more preferably 100 mg/100 mg or more. .
• oils and/or fatty acids contain oils and/or fatty acids having an iodine value of 100 mg/100 g or more as main components from the viewpoint of oil resistance.
• the main component is 80% by mass or more, preferably 90% by mass or more, more preferably 95% by mass or more. That is, (D) the content of fats and/or fatty acids with an iodine value of 100 or more is, for example, 80% by mass or more, preferably 90% by mass or more, more preferably, with respect to the total amount of fats and/or fatty acids It is 95% by mass or more.
• (D) fats and/or fatty acids consist of fats and/or fatty acids having an iodine value of 100 mg/100 g or more.
• Fats and/or fatty acids with an iodine value of 100 mg/100 g or more include, for example, linseed oil, yuzu oil, pistachio oil, rice oil, safflower oil, apricot oil, cottonseed oil, sesame oil, corn oil, watermelon oil, soybean oil, poppy seed oil.
• the iodine value is a value measured according to "2.3.4.1-1996 (Wiiss-Cyclohexane method)" of the standard oil analysis test method (Japan Oil Chemistry Society). Specifically, in the measurement of the iodine value, first, 0.15 g of the vegetable oil to be measured is dissolved in 10 ml of cyclohexane. Then, 25 mL of Wiiss' solution is added to these lysates and allowed to stand in the dark for about 1 hour. After that, the solution is titrated with a 0.1 mol/L sodium thiosulfate standard solution.
• the iodine value is calculated based on the amount of sodium thiosulfate standard solution dropped until reaching the end point.
• the raw material component can contain (E) other carboxylic acid as an optional component.
• E) Other carboxylic acids are carboxylic acids other than (A) rosins, (B) ⁇ , ⁇ -unsaturated dicarboxylic acids, and (D) fats and/or fatty acids.
• the raw material components include, for example, (A) rosins, (B) ⁇ , ⁇ -unsaturated dicarboxylic acids, (C) polyols, (D) fats and/or fatty acids, and (E ) and other carboxylic acids.
• the total amount of (A) rosins, (B) ⁇ , ⁇ -unsaturated dicarboxylic acids, (C) polyols, (D) oils and/or fatty acids, and (E) other carboxylic acids is , 100% by mass with respect to the raw material components.
• raw material components include, for example, (A) rosins, (B) ⁇ , ⁇ -unsaturated dicarboxylic acids, (C) polyols, and (E) other carboxylic acids.
• the total amount of (A) rosins, (B) ⁇ , ⁇ -unsaturated dicarboxylic acid, (C) polyol, and (E) other carboxylic acid is 100% by mass based on the raw material components. be.
• carboxylic acids include, for example, ⁇ , ⁇ -unsaturated monocarboxylic acids and carboxylic acids having no unsaturated bond between the ⁇ - and ⁇ -position carbons.
• ⁇ , ⁇ -unsaturated monocarboxylic acids include, for example, acrylic acid and methacrylic acid. These can be used alone or in combination of two or more.
• the content of the ⁇ , ⁇ -unsaturated monocarboxylic acid with respect to the total amount of raw material components is, from the viewpoint of oil resistance, for example, 0% by mass or more, preferably 5% by mass or more, more preferably 8% by mass or more, and further Preferably, it is 10% by mass or more.
• the content of the ⁇ , ⁇ -unsaturated monocarboxylic acid relative to the total amount of raw material components is, from the viewpoint of oil resistance, for example, 40% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less. , more preferably 15% by mass or less.
• carboxylic acids having no unsaturated bond between the ⁇ - and ⁇ -carbons include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecane di acid, tetradecanedioic acid, hexadecanedioic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, oxaloacetic acid, methylmalonic acid, dimethylmalonic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, methylglutaric acid, dimethyl Glutaric acid, diglycolic acid, 1,3-acetonedicarboxylic acid, ketoglutaric acid, cyclopropane-1,1-dicarboxylic acid, cyclobutane-1,1-dicarboxylic acid, cyclohexane-1,1-dicarboxylic
• Carboxylic acids having no unsaturated bond between the ⁇ - and ⁇ -position carbons preferably include succinic acid and adipic acid.
• a carboxylic acid having no unsaturated bond between the ⁇ - and ⁇ -position carbons can improve oil resistance.
• the content of the carboxylic acid having no unsaturated bond between the ⁇ -position carbon and the ⁇ -position carbon relative to the total amount of the raw material components is, for example, 0% by mass or more, preferably 5% by mass or more. , more preferably 8% by mass or more, and still more preferably 10% by mass or more.
• the content of the carboxylic acid having no unsaturated bond between the ⁇ -position carbon and the ⁇ -position carbon relative to the total amount of the raw material components is, from the viewpoint of oil resistance, for example, 30% by mass or less, preferably 25% by mass. % or less, more preferably 20 mass % or less, and still more preferably 15 mass % or less.
• the above ⁇ , ⁇ -unsaturated monocarboxylic acid and a carboxylic acid having no unsaturated bond between the ⁇ - and ⁇ -position carbons may be used in combination.
• the total amount of the ⁇ , ⁇ -unsaturated monocarboxylic acid and the carboxylic acid having no unsaturated bond between the ⁇ -position carbon and the ⁇ -position carbon is, with respect to the total amount of the raw material components, for example, It is 0% by mass or more, preferably 5% by mass or more.
• the total amount of the ⁇ , ⁇ -unsaturated monocarboxylic acid and the carboxylic acid having no unsaturated bond between the ⁇ -position carbon and the ⁇ -position carbon is, for example, 60% by mass with respect to the total amount of the raw material components. Below, preferably, it is 40 mass % or less.
• the rosin-modified polyester resin can be obtained as a reaction product obtained by reacting the above raw material components.
• the above raw material components may be reacted all at once, or the raw material components may be reacted in multiple stages.
• the raw material components are reacted in multiple stages.
• the reaction order is not particularly limited.
• (A) rosins and (B) ⁇ , ⁇ -unsaturated dicarboxylic acid are reacted to obtain the first product.
• the first product and (C) polyol are reacted to obtain a second product containing the rosin-modified polyester resin.
• the double bond in (B) the ⁇ , ⁇ -unsaturated dicarboxylic acid undergoes a Diels-Alder reaction with the conjugated double bond in (A) the rosin.
• the reaction temperature in the first step is, for example, 150°C or higher, preferably 170°C or higher, more preferably 180°C or higher.
• the reaction temperature in the first step is, for example, 230° C. or lower, preferably 220° C. or lower, more preferably 200° C. or lower, from the viewpoint of adjusting the acid value and hydroxyl value of the rosin-modified polyester resin.
• the reaction time in the first step is, for example, 0.1 hour or longer, preferably 0.5 hour or longer.
• the reaction time in the first step is, for example, 5 hours or less, preferably 3 hours or less, from the viewpoint of adjusting the acid value and hydroxyl value of the rosin-modified polyester resin.
• a known reaction catalyst can be added in an appropriate proportion, if necessary.
• the raw material components may be reacted in the absence of a solvent, or may be reacted in the presence of a known solvent.
• the first product comprises (A) a tertiary carboxy group derived from rosins (a tertiary carboxy group of an abietic acid monomer) and (B) a secondary carboxy group derived from an ⁇ , ⁇ -unsaturated dicarboxylic acid. contains.
• the (C) polyol is blended in the above ratio with respect to the first product. Then, the first product and (C) the polyol are reacted. Thereby, a second product is obtained (second step).
• the carboxy groups contained in the first product and the hydroxyl groups contained in the (C) polyol are subjected to an esterification reaction.
• the reaction temperature in the second step is, for example, 150°C or higher, preferably 160°C or higher, more preferably 170°C or higher, and still more preferably 180°C. °C or higher.
• the reaction temperature in the second step is, for example, 230° C. or lower, preferably 220° C. or lower, more preferably 210° C. or lower, and even more preferably 210° C. or lower. , 200° C. or less.
• reaction temperature is within the above range, (A) the reaction of tertiary carboxy groups derived from rosins is suppressed, and (B) the secondary carboxy groups derived from ⁇ , ⁇ -unsaturated dicarboxylic acids are allowed to react. can be done. Therefore, film-forming properties and oil resistance are improved.
• reaction temperature exceeds the above upper limit
• (A) the tertiary carboxyl group derived from the rosin reacts with the (C) hydroxyl group contained in the polyol, and the polyester resin component forms a network structure. becomes easier. Therefore, when a rosin-modified polyester resin is used in a water-based coating agent, the oil resistance may be lowered. On the other hand, if the reaction temperature is lower than the above lower limit, the reaction may not proceed sufficiently and the oil resistance may decrease.
• the reaction time in the second step is, for example, 1 hour or longer, preferably 3 hours or longer.
• the reaction time in the second step is, for example, 48 hours or less, preferably 24 hours or less, from the viewpoint of adjusting the acid value and hydroxyl value of the rosin-modified polyester resin.
• the condensation water produced by the esterification reaction can be distilled off by a known method.
• fats and/or fatty acids can be added and reacted in the above ratio together with the first product and (C) polyol, if necessary. More specifically, (D) the carboxy groups contained in the fat and/or fatty acid and (C) the hydroxyl groups contained in the polyol can be esterified.
• (E) other carboxylic acid can be added in the above ratio and reacted with the first product and (C) polyol, if necessary. More specifically, the carboxy group contained in (E) other carboxylic acid and the hydroxyl group contained in (C) polyol can be esterified.
• a known reaction catalyst can be added in an appropriate proportion, if necessary.
• the raw material components may be reacted in the absence of a solvent, or may be reacted in the presence of a known solvent.
• the second product is a resin composition containing a rosin-modified polyester resin.
• the second product (resin composition) can be used as the polyester resin component of water-based coating agents.
• (C) polyol can be modified with (D) oil and/or fatty acid (modified process).
• the blending ratio in the modification step is appropriately set, but for example, the hydroxyl group of the (C) polyol is, for example, 3 mol or more, preferably 10 mol or more, per 1 mol of the (D) oil and/or fatty acid. Yes, for example, 50 mol or less, preferably 40 mol or less.
• the reaction temperature in the modification step is, for example, 230°C or higher, preferably 240°C or higher, more preferably 250°C or higher, from the viewpoint of oil resistance and film-forming properties.
• the reaction temperature in the modification step is, for example, 300° C. or lower, preferably 280° C. or lower, more preferably 270° C. or lower, from the viewpoint of oil resistance and film-forming properties. If the reaction temperature is too low, the reaction in the modification step may not proceed, and (D) fats and/or fatty acids may not be incorporated into the resin. Therefore, the oil resistance and film-forming properties may deteriorate. On the other hand, if the reaction temperature is excessively high, a decomposition reaction may occur, causing an increase in low-molecular-weight components. Therefore, the oil resistance and film-forming properties may deteriorate.
• the reaction time in the modification step is, for example, 0.5 hours or longer, preferably 1 hour or longer.
• the reaction time in the modification step is, for example, 20 hours or less, preferably 10 hours or less, from the viewpoint of oil resistance and film-forming properties.
• a known reaction catalyst can be added in an appropriate ratio as necessary.
• the raw material components may be reacted in the absence of a solvent, or may be reacted in the presence of a known solvent.
• (D) oil and/or fatty acid-modified (C) polyol is obtained.
• (D) Fat and/or fatty acid-modified (C) polyol is used in the second step. That is, the first product and (D) fat and/or fatty acid-modified (C) polyol undergo an esterification reaction.
• the second product is a resin composition containing a rosin-modified polyester resin.
• the second product (resin composition) can be used as the polyester resin component of water-based coating agents.
• the weight average molecular weight (converted to standard polystyrene) of the rosin-modified polyester resin is, for example, 1,000 or more, preferably 3,000 or more, more preferably 5,000 or more. Also, the weight average molecular weight (converted to standard polystyrene) of the rosin-modified polyester resin is, for example, 100,000 or less, preferably 70,000 or less, more preferably 50,000 or less.
• the softening point of the rosin-modified polyester resin is, from the viewpoint of film-forming properties and tack resistance, for example, 70°C or higher, preferably 75°C or higher, more preferably 80°C or higher.
• the softening point of the rosin-modified polyester resin is, from the viewpoint of film-forming properties and tack resistance, for example, 150° C. or less, preferably 130° C. or less, more preferably 120° C. or less. .
• the content of the rosin-modified polyester resin is, for example, 75% by mass or more, preferably 80% by mass or more, relative to the total amount of the polyester resin component.
• the content of the rosin-modified polyester resin is, for example, 100% by mass or less, preferably 90% by mass or less, relative to the total amount of the polyester resin component.
• the polyester resin component may contain unreacted raw material components in addition to the rosin-modified polyester resin.
• unreacted raw material components include (A) unreacted rosins, (B) unreacted ⁇ , ⁇ -unsaturated dicarboxylic acids, (C) unreacted polyols, (D) unreacted oils and fats, and and/or fatty acids and (E) other unreacted carboxylic acids. Unreacted raw material components are removed from the resin composition as necessary.
• the molecular weight of unreacted raw material components is usually 500 or less.
• unreacted raw material components are referred to as components having a molecular weight of 500 or less.
• the content of the component having a molecular weight of 500 or less is, for example, 25% by mass or less, preferably 20% by mass or less, relative to the total amount of the resin composition (polyester resin component).
• the content of the component having a molecular weight of 500 or less is, for example, 0% by mass or more, preferably 10% by mass or more, relative to the total amount of the resin composition (polyester resin component).
• the film formability and oil resistance may deteriorate.
• the content of components having a molecular weight of 500 or less is measured by gel permeation chromatography in accordance with the examples described later.
• the acid value of the polyester resin component is 60 mgKOH/g or more, preferably 80 mgKOH/g or more, more preferably 100 mgKOH/g or more, still more preferably 120 mgKOH/g or more.
• the acid value of the polyester resin component is 180 mgKOH/g or less, preferably 170 mgKOH/g or less, more preferably 160 mgKOH/g or less, even more preferably 150 mgKOH/g or less, and particularly preferably 150 mgKOH/g or less. , 130 mg KOH/g or less.
• the acid value of the polyester resin component is measured according to JIS K 5601-2-1 (1999).
• the hydroxyl value of the polyester resin component is 20 mgKOH/g or more, preferably 40 mgKOH/g or more, more preferably 60 mgKOH/g or more, still more preferably 80 mgKOH/g or more, still more preferably 120 mgKOH. /g or more, particularly preferably 130 mgKOH/g or more.
• the hydroxyl value of the polyester resin component is 180 mgKOH/g or less, preferably 170 mgKOH/g or less, more preferably 160 mgKOH/g or less, even more preferably 150 mgKOH/g or less, and particularly preferably 150 mgKOH/g or less. , 140 mg KOH/g or less.
• the hydroxyl value is measured according to JIS K 0070 (1992).
• the blending amount of the raw material components is adjusted to the above ratio, and the reaction temperature and reaction time are adjusted to the above conditions. do.
• an aqueous coating agent is obtained by dissolving and/or dispersing the above polyester resin component in an aqueous medium.
• the ratio of the aqueous medium and the polyester resin component is appropriately set according to the purpose and application.
• the aqueous medium is, for example, 5% by mass or more, preferably 10% by mass or more, relative to the total amount of the aqueous medium and the polyester resin component.
• the aqueous medium is, for example, 80% by mass or less, preferably 70% by mass or less, relative to the total amount of the aqueous medium and the polyester resin component.
• the polyester resin component is, for example, 20% by mass or more, preferably 30% by mass or more, relative to the total amount of the aqueous medium and the polyester resin component.
• the polyester resin component is, for example, 95% by mass or less, preferably 90% by mass or less, relative to the total amount of the aqueous medium and the polyester resin component. If the ratio of the aqueous medium and the polyester resin component is within the above range, a rapid increase in viscosity can be suppressed, and the productivity, coating properties and drying properties of the aqueous coating agent can be improved.
• the water-based coating agent can contain other resins in addition to the water-based medium and the polyester resin component.
• Other resins are resins other than the above polyester resin component.
• resins include, for example, acrylic resins, styrene-modified acrylic resins, silicone acrylic resins, modified silicone acrylic resins, rosin phenol resins, rosin ester resins, terpene phenol resins, coumarone-indene resins, petroleum resins, epoxy resins, and modified epoxy resins.
• resins polyester resins, vinyl acetate resins, ethylene-vinyl acetate resins, urethane resins, urea resins, melamine resins and cellulose resins. These can be used alone or in combination of two or more.
• Other resins preferably include styrene-modified acrylic resins.
• styrene-modified acrylic resins When the water-based coating agent contains a styrene-modified acrylic resin, better oil resistance can be obtained.
• the styrene-modified acrylic resin includes a styrene-(meth)acrylic copolymer.
• the aqueous coating agent preferably contains a styrene-(meth)acrylic copolymer.
• (Meth)acryl means acryl and/or methacryl.
• a styrene-(meth)acrylic copolymer is obtained, for example, by copolymerizing a monomer component containing styrenes and a (meth)acrylic monomer copolymerizable with styrenes.
• styrenes examples include styrene, ⁇ -methylstyrene, vinyltoluene, ethylvinyltoluene, and chloromethylstyrene. These can be used alone or in combination of two or more. Styrenes are preferably styrene.
• the content of styrenes is, for example, 10% by mass or more, preferably 20% by mass or more, relative to the total amount of the monomer components. Moreover, the content of styrenes is, for example, 80% by mass or less, preferably 70% by mass or less, relative to the total amount of the monomer components. If the content of styrenes is within the above range, particularly excellent oil resistance can be obtained.
• (Meth)acrylic monomers include, for example, (meth)acrylic acid esters and hydrophilic group-containing (meth)acrylic monomers.
• (Meth)acrylic acid esters include, for example, (meth)acrylic acid esters having an alkyl group having 1 to 24 carbon atoms.
• the alkyl group may be linear or branched, and may have a carbon ring (alicyclic and/or aromatic ring).
• (meth) acrylic acid ester more specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, (meth) ) n-butyl acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, i-decyl (meth)acrylate, lauryl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate, cyclohexyl (meth)acrylate, and benzyl (meth)acrylate. These can be used alone or in combination of two or more.
• (Meth)acrylic acid esters preferably include methyl (meth)acrylate, n-butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate, more preferably methyl methacrylate and butyl acrylate. , and 2-ethylhexyl acrylate. Further, as the (meth)acrylic acid ester, a combination of methyl methacrylate, butyl acrylate and 2-ethylhexyl acrylate is more preferable. Further, as the (meth)acrylic acid ester, a combination of methyl methacrylate and butyl acrylate is more preferable.
• hydrophilic group-containing (meth)acrylic monomers examples include hydroxyl group-containing monomers, carboxyl group-containing monomers, amino group-containing monomers, amide group-containing monomers, and heterocyclic ring-containing monomers.
• hydroxyl group-containing monomers examples include 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, N-hydroxyethylacrylamide, methylol (meth)acrylamide, polyalkylene glycol (meth)acrylate, and glycerol mono (Meth)acrylates are mentioned. These can be used alone or in combination of two or more.
• 2-hydroxyethyl methacrylate is preferably used as the hydroxyl group-containing monomer.
• Carboxyl-containing monomers include, for example, monocarboxylic acid-containing monomers, dicarboxylic acid-containing monomers, and acid anhydrides.
• Monocarboxylic acid-containing monomers include, for example, (meth)acrylic acid and crotonic acid.
• Dicarboxylic acid-containing monomers include, for example, maleic acid, fumaric acid, itaconic acid, and citraconic acid.
• Acid anhydrides include anhydrides of monocarboxylic acid-containing monomers and dicarboxylic acid-containing monomers. These can be used alone or in combination of two or more.
• Carboxyl-containing monomers preferably include monocarboxylic acid-containing monomers, more preferably methacrylic acid.
• amino group-containing monomers examples include 2-(dimethylamino)ethyl (meth)acrylate and dimethylaminopropyl(meth)acrylamide. These can be used alone or in combination of two or more.
• Amide group-containing monomers include, for example, acrylamide, methacrylamide, N-isopropylacrylamide, N-vinylformamide, N-vinylacetamide, and N,N'-dimethylacrylamide. These can be used alone or in combination of two or more.
• heterocyclic ring-containing monomers examples include N-vinylpyrrolidone. These can be used alone or in combination of two or more.
• hydrophilic group-containing (meth)acrylic monomers can be used alone or in combination of two or more.
• Hydrophilic group-containing (meth)acrylic monomers preferably include hydroxyl group-containing monomers and carboxyl group-containing monomers.
• the (meth)acrylic monomers can be used alone or in combination of two or more.
• the (meth)acrylic monomer preferably includes a (meth)acrylic acid ester and a hydrophilic group-containing (meth)acrylic monomer, more preferably a (meth)acrylic acid ester and a hydrophilic group-containing ( A combined use with a meth)acrylic monomer is mentioned.
• the monomer component preferably contains styrenes, (meth)acrylic acid alkyl esters, and hydrophilic group-containing (meth)acrylic monomers.
• the monomer component more preferably contains styrenes, (meth)acrylic acid alkyl esters, and hydroxyl group-containing monomers and/or carboxyl group-containing monomers.
• the monomer component more preferably consists of styrenes, (meth)acrylic acid alkyl esters, and hydroxyl group-containing monomers and/or carboxyl group-containing monomers.
• the content ratio of the (meth)acrylic monomer is appropriately set according to the purpose and application.
• the content ratio (total amount) of the (meth)acrylic acid alkyl ester is, for example, 10 to the total amount of the monomer components. It is at least 20% by mass, preferably at least 20% by mass. Moreover, the content ratio (total amount) of the (meth)acrylic acid alkyl ester is, for example, 90% by mass or less, preferably 80% by mass or less, relative to the total amount of the monomer components.
• the content ratio (total amount) of the hydroxyl group-containing monomer is, for example, 5% by mass or more, preferably 10% by mass, relative to the total amount of the monomer components. % by mass or more. Moreover, the content ratio (total amount) of the hydroxyl group-containing monomer is, for example, 60% by mass or less, preferably 50% by mass or less, relative to the total amount of the monomer components.
• the content ratio (total amount) of the hydroxyl group-containing monomer is, for example, 1% by mass or more with respect to the total amount of the monomer components, preferably It is 3 mass % or more.
• the content ratio (total amount) of the carboxyl group-containing monomer is, for example, 20% by mass or less, preferably 10% by mass or less, relative to the total amount of the monomer components.
• the content ratio (total amount) of the (meth)acrylic monomer is, for example, 20% by mass or more, preferably 30% by mass or more, relative to the total amount of the monomer components.
• the content ratio (total amount) of the (meth)acrylic monomer is, for example, 90% by mass or less, preferably 90% by mass or less, more preferably 80% by mass or less, relative to the total amount of the monomer components. be.
• a styrene-(meth)acrylic copolymer can be obtained, for example, by polymerizing the above monomer components by a known method. More specifically, for example, first, the above monomer components are mixed to prepare a monomer composition. Then, the monomer composition is subjected to emulsion polymerization in the presence of a known aqueous solvent. Examples of the aqueous solvent include the above-described aqueous media.
• the method of adding the monomer composition is not particularly limited, and examples thereof include all-at-once charging, divided charging, total dropping, and partial dropping.
• a chain transfer agent can be blended if necessary.
• a chain transfer agent can adjust the weight average molecular weight of the styrene-(meth)acrylic copolymer.
• Chain transfer agents include, for example, oil-soluble chain transfer agents and water-soluble chain transfer agents.
• Oil-soluble chain transfer agents include, for example, t-dodecyl mercaptan, n-dodecyl mercaptan, n-octyl mercaptan, mercaptopropionic acid dodecyl ester, cumene, carbon tetrachloride, ⁇ -methylstyrene dimer, and terpinolene.
• Water-soluble chain transfer agents include, for example, mercaptoethanol, thioglycolic acid, (meth)allylsulfonic acid, and salts thereof. These can be used alone or in combination of two or more. The type and blending amount of the chain transfer agent are appropriately set according to the purpose and application.
• a polymerization initiator can be blended, if necessary.
• Polymerization initiators include, for example, azo initiators and peroxide polymerization initiators.
• Azo initiators include, for example, azobismethylbutyronitrile, dimethylazobisisobutyrate, azobisdimethylvaleronitrile, azobisisobutyronitrile, and azobis-2-amidinopropane hydrochloride.
• Peroxide-based polymerization initiators include, for example, persulfate, hydrogen peroxide, benzoyl peroxide, t-butyl peroxybenzoate, t-butyl peroxy isopropyl monocarbonate, t-butyl peroxy-2-ethylhexa Noate and cumene hydroperoxide.
• a redox initiator can also be used as the polymerization initiator. These can be used alone or in combination of two or more. The type and amount of the polymerization initiator are appropriately set according to the purpose and application.
• Emulsifiers include, for example, low molecular weight emulsifiers and polymeric emulsifiers.
• low-molecular emulsifiers examples include sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkylphenyl ether sulfate, ammonium polyoxyethylene alkylphenyl ether sulfate, and polyoxyethylene alkyl.
• polyoxyalkylene polycyclic phenyl ether sulfate e.g., sodium polyoxyethylene polycyclic phenyl ether sulfate, ammonium polyoxyethylene polycyclic phenyl ether sulfate, sodium polyoxypropylene polycyclic phenyl ether sulfate, polyoxypropylene polycyclic phenyl ether sulfate ester ammonium, etc.
• polyoxyethylene alkyl ethers polyoxyethylene alkylphenyl ethers
• Polyoxyethylene emulsifiers include, for example, polyvinyl alcohol and polyethylene oxide. These can be used alone or in combination of two or more.
• examples of emulsifiers include reactive emulsifiers.
• examples of reactive emulsifiers include sulfate salts of polyoxyalkylene phenyl ether having at least one functional group containing an ethylenically unsaturated bond, and polyoxyethylene alkyl having at least one functional group containing an ethylenically unsaturated bond.
• Ester salts include, for example, ester sodium salts and ester ammonium salts. These can be used alone or in combination of two or more.
• the type, blending amount, and timing of the emulsifier are appropriately set according to the purpose and application.
• the polymerization conditions are not particularly limited, and are appropriately set according to the types of monomer components, the types of polymerization initiators, and their amounts.
• the polymerization temperature is, for example, 80° C. or higher, preferably 85° C. or higher.
• the polymerization temperature is, for example, 120° C. or lower, preferably 115° C. or lower.
• the polymerization time is, for example, 2 hours or longer, preferably 3 hours or longer.
• the polymerization time is, for example, 6 hours or less, preferably 5 hours or less.
• a solution and/or dispersion of a styrene-(meth)acrylic copolymer is obtained by the above polymerization.
• the solid content concentration of the styrene-(meth)acrylic copolymer is, for example, 5% by mass or more, preferably 10% by mass or more. Further, the solid content concentration of the styrene-(meth)acrylic copolymer is, for example, 50% by mass or less, preferably 40% by mass or less.
• the viscosity (25°C) of the styrene-(meth)acrylic copolymer solution and/or dispersion is, for example, 1 mPa ⁇ s or more, preferably 5 mPa ⁇ s or more. Further, the viscosity (25° C.) of the styrene-(meth)acrylic copolymer solution and/or dispersion is, for example, 500 mPa ⁇ s or less, preferably 200 mPa ⁇ s or less, more preferably 100 mPa ⁇ s or less. be.
• the viscosity is measured with a B-type viscometer conforming to JIS K 7117-1 (1999).
• a neutralizing agent is added to the solution and/or dispersion of the styrene-(meth)acrylic copolymer.
• An alkali salt solution of a styrene-(meth)acrylic copolymer is thus obtained.
• Neutralizing agents include, for example, ammonia.
• the pH of the styrene-(meth)acrylic copolymer solution and/or dispersion is, for example, 3 or higher, preferably 4 or higher.
• the pH of the styrene-(meth)acrylic copolymer solution and/or dispersion is, for example, 10 or less, preferably 9 or less.
• the glass transition temperature of the styrene-(meth)acrylic copolymer is, for example, -30°C or higher, preferably -10°C or higher. Further, the glass transition temperature of the styrene-(meth)acrylic copolymer is, for example, 120° C. or lower, preferably 100° C. or lower. The glass transition temperature is calculated by the FOX formula.
• the weight average molecular weight of the styrene-(meth)acrylic copolymer is, for example, 5000 or more, preferably 10000 or more. Also, the weight average molecular weight of the styrene-(meth)acrylic copolymer is, for example, 300,000 or less, preferably 200,000 or less. In addition, a weight average molecular weight is measured as a standard polystyrene equivalent molecular weight by a gel permeation chromatography.
• the content ratio of other resins in the water-based coating agent is appropriately set according to the purpose and application.
• other resin preferably styrene-(meth)acrylic copolymer
• other resin is, for example, 1000 parts by mass or less, preferably 500 parts by mass or less with respect to 100 parts by mass of the polyester resin component.
• the water-based coating agent can contain wax.
• the aqueous coating agent preferably contains wax.
• waxes examples include fatty acid amide wax, carnauba wax, rice wax, polyolefin wax, paraffin wax, Fischer-Tropsch wax, beeswax, microcrystalline wax, polyethylene oxide wax, and amide wax. These can be used alone or in combination of two or more.
• the wax preferably includes fatty acid amide wax, carnauba wax, polyolefin wax, paraffin wax and microcrystalline wax, more preferably carnauba wax, polyolefin wax and paraffin wax.
• Fatty acid amide waxes more specifically, for example, pelargonic acid amide, capric acid amide, undecylic acid amide, lauric acid amide, tridecylic acid amide, myristic acid amide, pentadecylic acid amide, palmitic acid amide, heptadecylic acid amide, stearin Acid amides, nonadecanic acid amides, arachidic acid amides, behenic acid amides, lignoceric acid amides, oleic acid amides, cetenoic acid amides, linoleic acid amides, linolenic acid amides, and mixtures thereof.
• Fatty acid amide waxes also include animal and vegetable oil fatty acid amides. These can be used alone or in combination of two or more.
• carnauba wax examples include, more specifically, MICROK LEAR 418 (manufactured by Micro Powders, Inc.) and refined carnauba wax No. 1 powder (Nippon Wax Co., Ltd.). These can be used alone or in combination of two or more.
• olefin wax examples include polyethylene wax, polypropylene wax, MPP-635VF (Micro Powders, Inc.), and MP-620VF XF (Micro Powders, Inc.). These can be used alone or in combination of two or more.
• paraffin waxes include MP-28C, MP-22XF and MP-28C (Micro Powders, Inc.). These can be used alone or in combination of two or more.
• the melting point of wax is, for example, 60°C or higher and, for example, 130°C or lower.
• the content of wax in the water-based coating agent is appropriately set according to the purpose and application.
• the wax is, for example, 0 parts by mass or more, preferably 1 part by mass or more, and more preferably 3 parts by mass or more.
• the wax is, for example, 50 parts by mass or less, preferably 30 parts by mass or less, relative to 100 parts by mass of the polyester resin component.
• the water-based coating agent preferably contains a polyester resin component, another resin (preferably a styrene-(meth)acrylic copolymer), and/or wax.
• the water-based coating agent more preferably contains a polyester resin component, another resin (preferably a styrene-(meth)acrylic copolymer), and wax.
• the aqueous coating agent contains a polyester resin component and a styrene-(meth)acrylic copolymer and does not contain wax
• the total amount of the polyester resin component and the styrene-(meth)acrylic copolymer is
• the polyester resin component is, for example, 10% by mass or more, preferably 20% by mass or more.
• the polyester resin component is, for example, 80% by mass or less, preferably 50% by mass or less, based on the total amount of the polyester resin component and the styrene-(meth)acrylic copolymer.
• the styrene-(meth)acrylic copolymer is, for example, 20% by mass or more, preferably 50% by mass or more, based on the total amount of the polyester resin component and the styrene-(meth)acrylic copolymer. Further, the styrene-(meth)acrylic copolymer is, for example, 90% by mass or less, preferably 80% by mass or less, based on the total amount of the polyester resin component and the styrene-(meth)acrylic copolymer.
• the polyester resin component is, for example, 10% with respect to the total amount of the polyester resin component and wax. It is at least 20% by mass, preferably at least 20% by mass.
• the polyester resin component is, for example, 80% by mass or less, preferably 50% by mass or less, relative to the total amount of the polyester resin component and the wax.
• the wax is, for example, 20% by mass or more, preferably 50% by mass or more, relative to the total amount of the polyester resin component and the wax.
• the wax is, for example, 90% by mass or less, preferably 80% by mass or less, based on the total amount of the polyester resin component and the wax.
• the aqueous coating agent contains a polyester resin component, a styrene-(meth)acrylic copolymer and wax
• the polyester resin component is, for example, 10% by mass or more, preferably 20% by mass or more.
• the polyester resin component is, for example, 90% by mass or less, preferably 80% by mass or less, based on the total amount of the polyester resin component, the styrene-(meth)acrylic copolymer, and the wax.
• the styrene-(meth)acrylic copolymer is, for example, 10% by mass or more, preferably 20% by mass or more, based on the total amount of the polyester resin component, the styrene-(meth)acrylic copolymer and the wax. be. Further, the styrene-(meth)acrylic copolymer is, for example, 90% by mass or less, preferably 80% by mass, with respect to the total amount of the polyester resin component, the styrene-(meth)acrylic copolymer, and the wax. It is below.
• the wax is, for example, 1% by mass or more, preferably 5% by mass or more, based on the total amount of the polyester resin component, the styrene-(meth)acrylic copolymer, and the wax. Further, the wax is, for example, 20% by mass or less, preferably 10% by mass or less, based on the total amount of the polyester resin component, the styrene-(meth)acrylic copolymer, and the wax.
• the aqueous coating agent can contain a dispersant.
• a dispersant is an additive for stably dispersing the rosin-modified polyester resin in an aqueous medium.
• examples of dispersants include anionic surfactants, nonionic surfactants, cationic surfactants, polycarboxylic acid-based dispersants, naphthalene condensation-based dispersants, aliphatic alcohol sulfate-based dispersants, polyester-based dispersants, and polyethers.
• examples include system dispersants, vinyl polymer system dispersants, acetylene diol system dispersants and polyaminoamide system dispersants. These can be used alone or in combination of two or more.
• the blending amount of the dispersant is not particularly limited, and is appropriately set according to the purpose and application.
• the aqueous coating agent can contain a neutralizer. That is, the carboxyl groups of the above polyester resin component can be neutralized with a neutralizing agent. Neutralization can improve the stability of the rosin-modified polyester resin in an aqueous medium.
• neutralizing agents include basic compounds.
• Basic compounds include, for example, ammonia, triethylamine, N,N-dimethylethanolamine, isopropylamine, aminoethanol, dimethylaminoethanol, diethylaminoethanol, ethylamine, diethylamine, isobutylamine, dipropylamine, 3-ethoxypropylamine, 3-diethylaminopropylamine, sec-butylamine, propylamine, n-butylamine, 2-methoxyethylamine, 3-methoxypropylamine, 2,2-dimethoxyethylamine, monoethanolamine, morpholine, N-methylmorpholine, N-ethylmorpholine , pyrrole and pyridine. These can be used alone or in combination of two or more.
• the amount of the neutralizing agent is not particularly limited, and is set appropriately according to the purpose and application. More specifically, from the viewpoint of the stability of the water-based coating agent, the amount of the neutralizing agent to be blended is, for example, 0.5 equivalents or more, preferably 0.5 equivalents, relative to the carboxyl groups in the rosin-modified polyester resin. Eight equivalents or more. From the viewpoint of the stability of the aqueous coating agent, the amount of the neutralizing agent is, for example, 30 equivalents or less, preferably 10 equivalents or less with respect to the carboxyl groups in the rosin-modified polyester resin.
• the water-based coating agent can further contain additives in an appropriate proportion.
• Additives include, for example, fillers, thickeners, foaming agents, antioxidants, light stabilizers, heat stabilizers, and flame retardants. These can be used alone or in combination of two or more.
• the acid value of the polyester resin component containing the rosin-modified polyester resin is within a predetermined range, and the hydroxyl value of the polyester resin component containing the rosin-modified polyester resin is within a predetermined range. Therefore, the water-based coating agent can form a coating film having excellent oil resistance.
• the above polyester resin component has a relatively high acid value in order to improve oil resistance.
• a relatively large amount of ⁇ , ⁇ -unsaturated dicarboxylic acid is simply used to increase the acid value and a polyester resin component is obtained by a general esterification reaction, gelation tends to occur in the esterification reaction. Become.
• the temperature conditions in the esterification reaction are adjusted relatively low. Therefore, gelation in the esterification reaction is suppressed.
• the reaction temperature in the esterification reaction to the above upper limit or less, (A) the reaction of the tertiary carboxy group derived from the rosin is suppressed, and (B) the ⁇ , ⁇ -unsaturated dicarboxylic acid is produced.
• a carboxyl group derived from can be reacted. Therefore, according to the above method, a polyester resin component having a relatively high acid value can be obtained while suppressing gelation. Therefore, the water-based coating agent containing the polyester resin component can form a coating film having excellent oil resistance.
• the present invention includes an article including a coating film of a water-based coating agent. More specifically, the article includes a substrate and a dry coating of a water-based coating formed on the substrate.
• base materials include plastic films, vapor-deposited films, metal foils, paper, woven fabrics, and non-woven fabrics.
• Substrates preferably include plastic films and paper.
• Coating methods include, for example, a spray method, a curtain coater method, a flow coater method, a roll coater method, a brush coating method, an immersion method, and a flexographic printing method.
• the water-based coating agent is dried by a known method. Drying conditions may be natural drying at room temperature or heat drying. Heat drying is preferred.
• the drying temperature in heat drying is, for example, 40° C. or higher, preferably 50° C. or higher.
• the drying temperature is, for example, 250° C. or lower, preferably 230° C. or lower.
• the drying time is, for example, 1 second or longer, preferably 5 seconds or longer.
• the drying time is, for example, 600 seconds or less, preferably 500 seconds or less.
• Data processing device Product number Agilent 1260 Infinity II (manufactured by Agilent)
• Refractive index detector RI detector (G7162A) built into part number Agilent 1260 Infinity II
• Column product number PL gelmixed-B7.5 ⁇ 300 mm (manufactured by Agilent), 3 Mobile phase: Tetrahydrofuran
• Sample concentration 2.0 g/L
• Injection volume 10 ⁇ L
• Measurement temperature 30°C
• Molecular weight marker standard polystyrene (using Agilent EasiCal Polystyrene Standards PS-1)
• Synthesis example 1 (resin 1) A four-necked flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer was charged with 39.6 parts of gum rosin while blowing nitrogen gas, and the temperature was raised to 210°C. Then, 12.9 parts of fumaric acid was added to the flask and stirred at 210° C. for about 30 minutes. As a result, gum rosin and fumaric acid were subjected to a Diels-Alder reaction to obtain a first product (first step).
• the second product was a polyester resin component containing a rosin-modified polyester resin (hereinafter referred to as resin 1).
• resin 1 The acid value of Resin 1 was 125 mgKOH/g.
• the hydroxyl value of Resin 1 was 134 mgKOH/g.
• the content of components having a molecular weight of 500 or less was 18% by mass.
• Synthesis example 2 (resin 2) 17.8 parts of linseed oil (iodine value: 180 mg/100 g) and 18.1 parts of glycerin were introduced into a four-necked flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer while blowing nitrogen gas. and 0.1 part of lithium acetate (catalyst) were added, and the temperature was raised to 255°C. Then, the mixture was stirred at 255° C. for 3 hours. As a result, linseed oil modified glycerin to obtain linseed oil-modified glycerin (denaturation step).
• the second product was a polyester resin component containing a rosin-modified polyester resin (hereinafter referred to as resin 2).
• resin 2 The acid value of Resin 2 was 122 mgKOH/g.
• the hydroxyl value of Resin 2 was 130 mgKOH/g.
• Resin 2 the content of components having a molecular weight of 500 or less was 15% by mass.
• Synthesis Examples 3-8 and 15-16 Resins 3-8 and 15-16 (Resins 3-8 and 15-16) Resins 3 to 8 and 15 to 16 were obtained in the same manner as in Synthesis Example 2, except that the formulations were changed to those shown in Tables 1 to 4. The reaction conditions were set as shown in Tables 1-4.
• Synthesis Example 11 (Resin 11) A four-necked flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer was charged with 37.5 parts of gum rosin while blowing nitrogen gas, and the temperature was raised to 210°C. Then, 12.2 parts of fumaric acid was added to the flask and stirred at 210° C. for about 30 minutes. As a result, gum rosin and fumaric acid were subjected to a Diels-Alder reaction to obtain a first product (first step).
• the second product was a polyester resin component containing a rosin-modified polyester resin (hereinafter referred to as resin 11).
• resin 11 The acid value of Resin 11 was 120 mgKOH/g.
• the hydroxyl value of Resin 11 was 140 mgKOH/g.
• Resin 11 the content of components having a molecular weight of 500 or less was 21% by mass.
• Synthesis Examples 12-13 and 18 (Resins 12-13 and 18) Resins 12 to 13 and 18 were obtained in the same manner as in Synthesis Example 11, except that the formulations were changed to those shown in Tables 1 to 4. The reaction conditions were set as shown in Tables 1-4.
• Examples 1-16 and Comparative Examples 1-3 Aqueous coating agents 1 to 16 were obtained with the formulations shown in Tables 1 to 4. That is, 30 parts of resin, 10 parts of 25% aqueous ammonia solution, and 60 parts of distilled water were placed in an Erlenmeyer flask equipped with a reflux tube, and stirred at 70° C. for about 2 hours. As a result, the resin was neutralized and dissolved to obtain an aqueous solution.
• each water-based coating agent was coated on a paperboard of 250 g/m using a 6 ⁇ m bar coater. Thereafter, the water-based coating agent was dried to obtain a coating film of the water-based coating agent. Also, an article (coated paper) provided with a coating film of the water-based coating agent was obtained.
• the monomer composition and the aqueous polymerization initiator solution were each continuously injected over 6 hours, polymerized while maintaining the temperature at 90°C or less, and aged for 30 minutes. It was then heated to 95°C to complete polymerization and then cooled to 40°C.
• Production example 2 104 parts of styrene, 17 parts of methacrylic acid, 34 parts of n-butyl methacrylate, 138 parts of 2-hydroxyethyl methacrylate, 52 parts of methyl methacrylate, and 2 parts of n-dodecyl mercaptan as a chain transfer agent are mixed, A monomer composition was obtained.
• Examples 17-22 Aqueous coating agents 17 to 22 were obtained with the formulations shown in Table 5. That is, a polyester resin component, a styrene-(meth)acrylic copolymer and/or wax were mixed so as to obtain a solid content mass part shown in Table 5 to obtain a resin mixture.
• each water-based coating agent was temperature-controlled to 25° C. and applied to a paperboard of 250 g/m using a bar coater No. 1. 22 was used to coat. Thereafter, the water-based coating agent was dried to obtain a coating film of the water-based coating agent. Also, an article (coated paper) provided with a coating film of the water-based coating agent was obtained. The amount of adhered solid content (resin component) was 7 to 8 g/m 2 .
• the coated paper was conditioned in a constant temperature and humidity environment (22°C, relative humidity of 50%) for 12 hours. The coated paper was then subjected to oil resistance evaluation.
• the water-based coating agent, article, and method for producing a rosin-modified polyester resin of the present invention are suitably used in the field of coating for various substrates.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Wood Science & Technology (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Life Sciences & Earth Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• General Chemical & Material Sciences (AREA)
• Polyesters Or Polycarbonates (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Publications (1)

Family

ID=84140446

Family Applications (1)

Country Status (5)

Cited By (3)

Citations (7)

Family Cites Families (4)

• 2021
  • 2021-09-02 US US18/559,191 patent/US20240228824A1/en active Pending
  • 2021-09-02 EP EP21940889.5A patent/EP4342956A4/en active Pending
  • 2021-09-02 CN CN202180097932.0A patent/CN117677681A/zh active Pending
  • 2021-09-02 WO PCT/JP2021/032259 patent/WO2022244278A1/ja not_active Ceased
  • 2021-09-02 JP JP2023522196A patent/JP7814382B2/ja active Active

Patent Citations (7)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events