WO2010084833A1 - Aqueous coating composition - Google Patents
Aqueous coating composition Download PDFInfo
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- WO2010084833A1 WO2010084833A1 PCT/JP2010/050464 JP2010050464W WO2010084833A1 WO 2010084833 A1 WO2010084833 A1 WO 2010084833A1 JP 2010050464 W JP2010050464 W JP 2010050464W WO 2010084833 A1 WO2010084833 A1 WO 2010084833A1
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
Definitions
- the present invention comprises a carboxyl group-containing polyester resin (A), an amino resin (B) and a phosphoric acid compound (C) as active ingredients, and is excellent in processability, coating film hardness, water resistance and the like, and also prevents air pollution.
- the present invention relates to a water-based paint composition for solving problems such as resource saving and countermeasures for dangerous substances.
- the paint as described above contains a large amount of organic solvent, it has a risk of air pollution, deterioration of working environment and fire and explosion.
- water-based paints are desired, but the actual situation is that no water-based paint for can outer surfaces satisfying high processability, coating film hardness, and water resistance has been developed. .
- Can exterior paints for beverage cans (for two-piece cans) that do not require high processing performance are being made water-based (see, for example, Patent Documents 3, 4, and 5).
- Patent Documents 3, 4, and 5 can be tried to be transferred to a bottle can that requires high processing performance, the coating film is insufficient in processability, and the coating film is damaged at the screw portion, so that it cannot be transferred. For this reason, solvent-based paints are still used as the outer paint of bottle cans.
- an outer surface water-based paint for bottle cans that has particularly high processing performance and satisfies the performance required for can outer surface applications (coating film hardness, water resistance, etc.). ing.
- the subject of this invention is providing the water-based coating composition which satisfy
- an aqueous coating composition containing, as main components, a polyester resin (A), an amino resin (B), and a phosphoric acid compound (C) containing a carboxy group is easy to process.
- the present invention has been completed by finding that it is a water-based coating composition suitable for use in can coatings having excellent properties, coating film hardness, and water resistance.
- the present invention provides an aqueous coating composition containing a polyester resin (A) containing a carboalkyl group, an amino resin (B), and a phosphoric acid compound (C).
- the water-based coating composition of the present invention can be used mainly for the outer surface of a can, and in particular, forms a coating film excellent in processability, adhesion, and coating film hardness even after bottle shape processing and after screw processing. Moreover, it has the performance of being excellent in boiling water resistance.
- the water-based coating composition of the present invention contains a polyester resin (A) containing a carboxy group, an amino resin (B), and a phosphoric acid compound (C).
- the present invention provides an aqueous coating composition that can be used for a top coating of a can (bottle can) having severe drawing and threading as well as for a two-piece can having a relatively gentle processing step.
- the number average molecular weight of the polyester resin (A) having a carboxyl group is preferably in the range of 1000 to 10,000. If it is smaller than this range, the processability of the coating film tends to be inferior. If it is larger, the viscosity of the coating becomes high and the paintability is impaired, and the stability of the coating liquid also tends to be lowered.
- the polyester resin (A) having a carboxyl group is not particularly limited, but the acid value (polyester resin solid content) from the viewpoint of improving the balance of resin viscosity, processability, coating film hardness, water resistance and coating liquid stability.
- the hit is preferably 10 to 50 (mg KOH / g), and particularly preferably 15 to 30 (mg KOH / g).
- the glass transition temperature of the polyester resin is preferably in the range of ⁇ 10 ° C. to 60 ° C.
- a method for producing a polyester resin (A) having a carboxyl group will be described.
- a method for introducing a carboxyl group for example, there is a method in which an acid component and an alcohol component are reacted in an acid component excess state so as to have a target carboxyl group.
- a method of obtaining a carboxyl group-containing polyester resin by reacting with an excess of alcohol component and adding trimellitic anhydride or phthalic anhydride to the obtained hydroxyl group-containing polyester resin can also be employed. The latter method is suitable for satisfying the total performance.
- polyester resin (A) which has a carboxyl group there is no restriction
- the well-known method by esterification reaction of an acid component and an alcohol component can be applied as it is.
- known dibasic acids, tribasic or more polybasic acids, dihydric alcohols, and trihydric or higher polyhydric alcohols can be used.
- soybean oil coconut oil, castor oil, safflower oil, or a part of these fatty acids can also be used.
- the aromatic carboxylic acids are terephthalic acid, isophthalic acid, (anhydrous) phthalic acid, (anhydrous) trimellitic acid, benzoic acid, etc.
- aliphatic carboxylic acids such as hexahydro (anhydrous) phthalic acid, tetrahydro (anhydride) phthalic acid, methyl hexahydro (anhydride) phthalic acid, 1,4-cyclohexanedicarboxylic acid include adipic acid, sebacic acid, succinic acid, ( Anhydrous) maleic acid, fumaric acid and the like.
- Typical alcohol components include (di) ethylene glycol, (di) propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, and 1,5-pentanediol.
- Examples include 2-methyl 1,3-propanediol, neopentyl glycol, trimethylol propane, trimethylol ethane, glycerin, pentaerythritol, 1,4-cyclohexane dimethanol and the like.
- a monoepoxy compound such as glycidyl ester versatate or ⁇ -olefin oxide can also be used.
- amino resin (B) used in the aqueous coating composition of the present invention examples include benzoguanamine resin, melamine resin, urea resin and the like. These may be used alone or in combination.
- benzoguanamine resins are preferable from the viewpoint of water resistance and gloss of the coating film, and the number average molecular weight is preferably in the range of 300 to 1,000. When the number average molecular weight is lower than this range, the processability of the coating film tends to be lowered, and when it is larger, the stability in the aqueous paint tends to be lowered.
- methylol groups in the methylolated melamine / benzoguanamine resin which is an addition reaction product (methylolation) of melamine or benzoguanamine and formaldehyde, are etherified with alcohols.
- a high ether type benzoguanamine resin having a formalin addition number per triazine nucleus of 2.5 or more and a degree of etherification of 1.8 or more is particularly excellent in processability.
- the phosphoric acid compound (C) used in the aqueous coating composition of the present invention includes a compound (C-0) having a hydroxyl group bonded to at least one phosphorus atom in one molecule, and at least one phosphorus atom in one molecule. It is preferably at least one selected from the group consisting of an epoxy compound (C-1) modified with a compound having a hydroxyl group bonded to. Further, compound (C-2) obtained by modifying compound (C-1) with carboxylic acid can also be mentioned. Further, the compounds (C-1) and (C-2) may be further modified with a compound such as an isocyanate, a phenol resin, or an amine. (Compound (C-3))
- Examples of the compound (C-0) having a hydroxyl group bonded to at least one phosphorus atom in one molecule include tetraphosphoric acid tetraphosphates such as metaphosphoric acid, orthophosphoric acid, pyrophosphoric acid, triphosphoric acid, and tetraphosphoric acid.
- tetraphosphoric acid tetraphosphates such as metaphosphoric acid, orthophosphoric acid, pyrophosphoric acid, triphosphoric acid, and tetraphosphoric acid.
- the acid, phosphorous acid, diphosphorous acid, hypophosphorous acid, etc. which can be hydrolyzed can be mentioned.
- epoxy compound examples include ethylene glycol, propylene glycol, hexanediol, neopentyl glycol, trimethylol propane, triethylol ethane, trimethylol propane, glycerin, diglycerin, pentaerythritol, sorbitol, spiroglycol, hydrogenated bisphenol A and the like.
- a glycidyl ether type epoxy compound obtained by reacting such an aliphatic polyol with epichlorohydrin;
- Glycidyl obtained by reacting polyols such as ethylene oxide or propylene oxide adducts of aromatic polyhydroxy compounds such as catechol, resorcinol, hydroquinone, bisphenol (A, F, S, AD) tetrahydroxyphenylmethane and the like with epichlorohydrin Ether type epoxy compounds; glycidyl compounds obtained by reacting a polyether polyol such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like with epichlorohydrin;
- Glycidyl ester type epoxy compounds obtained by reacting aliphatic or aromatic polycarboxylic acids such as propanetricarboxylic acid, butanetetracarboxylic acid, adipic acid, phthalic acid, isophthalic acid, tetraphthalic acid, trimellitic acid and epichlorohydrin; aniline A glycidylamine type epoxy compound obtained by reacting an amine such as (p, m-) aminophenol, diaminodiphenylmethane, bisaminomethylcyclohexane, metaxylylenediamine, and epichlorohydrin;
- Linear aliphatic epoxy compounds obtained by oxidizing linear aliphatic double bonds such as butadiene, hexadiene, octadiene, dodecadiene, polybutadiene, polyisoprene, and soybean oil; and further heterocyclic rings such as triazine and hydantoin. Mention may be made of polyfunctional epoxy compounds such as epoxy compounds to be contained. These may be used alone or in combination.
- carboxylic acid examples include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, Aliphatic saturated monocarboxylic acids such as stearic acid, pivalic acid, methoxyacetic acid, pyruvic acid, glyoxylic acid; (meth) acrylic acid, 3,3-dimethylacrylic acid, crotonic acid, isocrotonic acid, tiglic acid, vinylacetic acid, Ethylenically unsaturated monocarboxylic acids such as pentenoic acid and oleic acid;
- Aliphatic saturated dicarboxylic acids such as adipic acid, 3-methyladipic acid, 3-oxaadipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, diacetyltartaric acid and the like;
- Aromatic monocarboxylic acids such as benzoic acid, o-toluic acid, 1-naphthoic acid, atropaic acid, cinnamic acid; (anhydrous) phthalic acid, 4-methylphthalic acid (anhydride), homophthalic acid, isophthalic acid, terephthalic acid Acid, carboxyphenoxyacetic acid, phenylmalonic acid, phenylmalonic acid, phenylenediacetic acid, phenylsuccinic acid, benzylmalonic acid, carboxycinnamic acid and the like; and nicotinic acid, isonicotinic acid, Examples thereof include heterocyclic carboxylic acids such as 2-furancarboxylic acid and 2-thiophenecarboxylic acid, and anhydrides thereof.
- glycolic acid lactic acid, glyceric acid, 3-hydroxypropionic acid, hydroxypyruvic acid, 1-hydroxy-1-cyclopropanecarboxylic acid, hydroxybutyric acid, 2-hydroxyisovaleric acid, 2-hydroxyisovaleric acid, bis ( Hydroxymethyl) propionic acid, comenic acid, 2-hydroxycaproic acid, mevalonic acid, meconic acid, salicylic acid, 3-isopropylsalicylic acid, 2-hexahydroxysalicylic acid, p-hydroxybenzoic acid, 2,3-dihydroxybenzoic acid, resorcylic acid Gentisic acid, homogentisic acid, protocatechuic acid, shikimic acid, vanillic acid, isovanillic acid, homovanillic acid, hydroxy-o-toluic acid, hydroxy-m-toluic acid, hydroxy-p-toluic acid, hydroxyphenylacetic acid, mandelic acid, The Droxymandelic acid, vanillylmandelic acid,
- reaction between a compound having a hydroxyl group bonded to at least one phosphorus atom in one molecule and an epoxy compound, or a compound having a hydroxyl group bonded to at least one phosphorus atom in one molecule, an epoxy compound and a carboxylic acid The reaction is carried out in the absence of a solvent or in a water-soluble solvent, and a catalyst such as an amine compound may be used if necessary.
- the water-miscible organic solvent used here is not particularly limited.
- aromatic hydrocarbons such as toluene, xylene, Solvesso # 100 and Solvesso # 150
- aliphatic hydrocarbons such as hexane, heptane, octane and decane.
- ester organic solvents such as methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, amyl acetate, ethyl formate, and butyl propionate.
- Water-miscible organic solvents include alcohols such as methanol, ethanol, propanol and butanol, ketones such as acetone and methyl ethyl ketone, ethylene glycol (mono, di) methyl ether, ethylene glycol (mono, di) ethyl ether, and ethylene glycol mono Propyl ether, ethylene glycol monoisopropyl ether, monobutyl ether, diethylene glycol (mono, di) methyl ether, diethylene glycol (mono, di) ethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol (mono, di) methyl ether, Propylene glycol (mono, di) methyl ether, propylene glycol monopropyl ether, propylene glycol Over mono butyl ether, dipropylene glycol (mono, di) include various organic solvents glycol ether such as methyl
- organic solvents and water can be used alone or in combination depending on the compatibility with the resin and the performance such as the appearance after coating.
- the water-miscible organic solvent can be used alone or in combination with ion-exchanged water depending on the adjustment of the paint viscosity or the appearance of the coating film.
- the catalyst examples include the aforementioned organic amine compounds and inorganic acid salts or organic acid salts thereof; metal halides such as boron trifluoride, lithium chloride, tin chloride, lithium bromide, tin bromide; sodium hydroxide, Metal hydroxides such as lithium hydroxide; imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-failimidazole and the like, and adducts thereof such as inorganic or organic substances; triphenylphosphine, triphenyl Antimony etc. can be mentioned, These may be used individually or in mixture.
- metal halides such as boron trifluoride, lithium chloride, tin chloride, lithium bromide, tin bromide
- sodium hydroxide Metal hydroxides such as lithium hydroxide
- imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-failimidazole and the like
- the ratio of the polyester resin (A) having a carboxyl group and the amino resin (B) in the resin solid content is preferably a mass ratio of 40/60 to 80/20, more preferably 45/55 to 60/40. It is. When the ratio of the polyester resin (A) having a carboxyl group is lower than 40, the processability of the coating film becomes inferior, and when it is higher than 80, the hardness and water resistance of the coating film tend to be insufficient.
- the ratio of the phosphoric acid compound (C) in the resin solid content may be any range as long as it produces the effects of the present invention, but the total of the polyester resin (A) having a carboxyl group and the amino resin (B).
- the content ratio of the phosphoric acid compound (C) is less than 0.1, the hardness of the coating film is inferior, and when it exceeds 10, the gloss and storage properties of the coating film are inferior.
- the water-based coating composition of the present invention can be suitably used as a top coating for cans (bottle cans) having particularly severe drawing and threading, as well as two-piece cans.
- aqueous coating composition of the present invention when used as a can coating, known additives such as pigments such as titanium oxide and silica, surfactants, antifoaming agents, and dispersing agents are added as necessary. Can be blended.
- the amine neutralized product of the polyester resin (A) having a carboxyl group and the amino resin (B) as a curing agent are used for the preparation of a paint in a form dissolved and / or dispersed in an aqueous medium. This includes one in which either or both of the polyester resin (A) having a carboxyl group and the amino resin (B) as a curing agent are dissolved and partly dispersed.
- aqueous medium a mixed solvent of ion-exchanged water and a water-miscible organic solvent is usually used.
- water-soluble solvent include those mentioned above.
- a base As a basic compound used for neutralization, (mono, di, tri) methyl is used.
- Alkylamines such as amine, (mono, di, tri) ethylamine, (mono, di, tri) propylamine; (mono, di) ethanolamine, (mono, di) isopropanolamine, N-methylethanolamine, N, N Alkanolamines such as dimethylethanolamine, N, N-diethylethanolamine, 2-amino-2-methylpropanol, 2- (dimethylamino) -2-methylpropanol, N-methyldiethanolamine; ethylenediamine, diethylenetriamine, triethylenetetramine , Polyamines such as tetraethylenepentamine, etc. Organic amines and ammonia.
- the solid content concentration of the polyester resin (A) having a carboxyl group and the aqueous coating material having the amino resin (B) as a curing agent is usually 20 to 70% by mass, preferably 30 to 60% by mass. When it exceeds 70% by mass, it is difficult to handle due to high viscosity, and when it is less than 20% by mass, the viscosity of the prepared coating tends to be too low.
- Metal cans have been widely used as a kind of packaging containers for beverages, foods and the like.
- the outer surface of these cans is printed and painted for the purpose of aesthetics, rust prevention, contents display, and the like.
- the outer surface of the can body is made up of “metal substrate + ink + clear coating” in the case of cans that are not highly drawn (such as two-piece cans).
- size coating is often applied as in test pieces -1 and 2 below.
- the coating agent used for size coating provides a strong adhesion between the metal substrate and the ink or the metal substrate and the overcoat clear by providing a thin organic film on the surface of the metal substrate. It is a transparent paint that plays a role in improving drawing processability.
- Specimen-1 Metal + Size coating + Topcoat clear coating
- Specimen-2 Metal + Size coating coating + Ink + Topcoat clear coating
- Specimen-3 Metal + Size coating Film-free + Topcoat clear paint
- Specimen-4 Metal + No size coating + Ink + Topcoat clear paint
- the water-based coating composition of the present invention is applied to various substrates such as metal, plastic film, or a metal plate laminated with a plastic film by known means such as roll coating, coil coating, spray coating and brush coating.
- a plastic film such as polyethylene terephthalate (PET) and polybutylene terephthalate.
- the water-based coating composition of the present invention is a combination of the above (test specimens-1, 2, 3, 4) formed on an outer surface of a bottomed cylindrical metal formed from an aluminum plate, particularly at one end. Painted with.
- the aqueous coating composition of the present invention preferably has a film thickness of about 1 to 10 ⁇ m.
- the roll coat coating method is suitable for uniform coating. Considering the production speed of beverage cans, the coating speed of the roll coat is 200 to 400 m / min. It is estimated that it is about.
- the water-based coating composition of the present invention may be dried at room temperature, but it can exhibit more performance when thermally cured by baking.
- an electric oven, a far-infrared oven, a gas oven or the like is preferably used.
- baking condition baking for about 20 seconds to 15 minutes in a temperature atmosphere of 150 ° C. to 240 ° C. is preferably used.
- polyester resin (A-1) having a number average molecular weight of 4500, a solid content acid value of 23.5, and a nonvolatile content of 60.0%.
- the numerical value of the functional group represents the number of moles relative to 1 mole of benzoguanamine.
- Functional group JNM-EX270 manufactured by JEOL Ltd. was used as a confirmation device for functional group measurement by 13 C-NMR, and the sample was dissolved in dimethyl sulfoxide-d 6 and subjected to CNOE-proton decoupling conditions at room temperature. I went there.
- acrylic resin A-2 One hour after the completion of the dropwise addition, 3.0 parts of di-t-butyl peroxide was added and the reaction was continued for another 2 hours. Next, 375.0 parts of the solvent was distilled off from the resin solution thus obtained under reduced pressure, and neutralized with 20.0 parts of N, N-dimethylethanolamine. Subsequently, an aqueous solution of an acrylic resin having a non-volatile content of 50.6% and an acid value of 26.5 was obtained by diluting with 200.0 parts by mass of water. This is abbreviated as acrylic resin A-2.
- Test piece-2 Size paint film + ink + top clear paint
- a 6E-090 (size coat) manufactured by DIC Corporation was applied to an aluminum plate having a thickness of 0.21 mm so that the dry film thickness was 1.5 ⁇ m, and the baked coated plate was applied for 1 minute at a maximum material temperature of 200 ° C. Obtained.
- an ink metal lithographic ink MTC NS indigo made by DIC Corporation
- polyester resin as a main component of the vehicle is printed (undried film thickness is 4 ⁇ m).
- Coating was performed with a coater so that the dry film thickness was about 7 ⁇ m, and the material arrival temperature was baked at 210 ° C. for 2 minutes to obtain a top-coated clear coated plate.
- Specimen-3 No size coating + top clear coating
- Specimen-3 was obtained in the same manner as for Specimen 1 except that the size coating was not applied to an aluminum plate having a thickness of 0.21 mm.
- Test piece-4 No size coating + ink + top clear coating
- Test piece-4 was obtained in the same manner as in the case of test piece 2 except that the size coating was not applied to the aluminum plate having a thickness of 0.21 mm.
- Pencil hardness test The pencil hardness was measured according to JIS-K-5400 using a high-grade pencil specified in JIS-S-6006 for the coated plate.
- the aqueous coating composition of the present invention can be applied not only to a two-piece can having a relatively gentle processing step, but also to a bottle can having a severe processing step, and can be widely used for a paint for cans.
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Abstract
Disclosed is an aqueous coating composition for outer surfaces of cans, which can provide coating film hardness and water resistance required for use in the coating of outer surfaces of cans from the viewpoint of the protection of the global environment, is widely applicable to the coating of cans including the coating of two-piece cans which requires a relatively mild processing process as well as the coating of bottle cans which requires a severe processing process, and therefore has high processing performance. The aqueous coating composition is characterized by comprising a polyester resin (A) containing a carboxyl group, an amino resin (B) and a phosphoric acid compound (C), wherein the polyester resin (A) has a number average molecular weight of 1000 to 10000 and an acid value of 10 to 50 mgKOH/g and the amino resin (B) comprises a high-ether-type benzoguanamine resin having a number average molecular weight of 300 to 1000.
Description
本発明はカルボキシル基含有ポリエステル樹脂(A)とアミノ樹脂(B)及びリン酸系化合物(C)を有効成分とする、加工性、塗膜硬度、耐水性等に優れ、しかも、大気汚染の防止、省資源、危険物対策などの問題を解決するための、水性塗料組成物に関する。
The present invention comprises a carboxyl group-containing polyester resin (A), an amino resin (B) and a phosphoric acid compound (C) as active ingredients, and is excellent in processability, coating film hardness, water resistance and the like, and also prevents air pollution. The present invention relates to a water-based paint composition for solving problems such as resource saving and countermeasures for dangerous substances.
製缶塗料業界では、高い加工性能を要求される用途において、実用領域の塗膜性能を確保することが困難であることから、未だに溶剤型塗料が使用されている。(例えば、特許文献1,2参照)
In the can coating industry, solvent-based paints are still used because it is difficult to ensure the coating performance in the practical range in applications that require high processing performance. (For example, see Patent Documents 1 and 2)
しかしながら、上述したような塗料は、有機溶剤を多く含有するため、特に大気汚染、作業環境の悪化ならびに火災や爆発の危険性を有している。これらの問題点を回避する手段として、塗料の水性化が望まれているが、高い加工性、塗膜硬度、耐水性を満足する缶外面用の水性塗料は開発されていないのが実情である。
However, since the paint as described above contains a large amount of organic solvent, it has a risk of air pollution, deterioration of working environment and fire and explosion. As a means for avoiding these problems, water-based paints are desired, but the actual situation is that no water-based paint for can outer surfaces satisfying high processability, coating film hardness, and water resistance has been developed. .
高い加工性能を要しない飲料缶(2ピース缶用)の缶外面塗料は、塗料の水性化が進んでいる(例えば、特許文献3、4、5参照)。しかしながら、これらを、高い加工性能を必要とするボトル缶に転用しようとしても、塗膜の加工性が不足していることから、ネジ部で塗膜が損傷を受けるため、転用することはできない。この為に、ボトル缶の外面塗料は、未だに溶剤型塗料が使用されている。
Can exterior paints for beverage cans (for two-piece cans) that do not require high processing performance are being made water-based (see, for example, Patent Documents 3, 4, and 5). However, even if these are tried to be transferred to a bottle can that requires high processing performance, the coating film is insufficient in processability, and the coating film is damaged at the screw portion, so that it cannot be transferred. For this reason, solvent-based paints are still used as the outer paint of bottle cans.
従って、地球環境の保護などの観点から、特に高い加工性能を有し、缶外面用途として必要な性能(塗膜硬度、耐水性等)を満たしたボトル缶用の外面水性塗料の開発が望まれている。本発明の課題は上記の性能を満たす水性塗料組成物を提供することにある。
Therefore, from the viewpoint of protecting the global environment, it is desired to develop an outer surface water-based paint for bottle cans that has particularly high processing performance and satisfies the performance required for can outer surface applications (coating film hardness, water resistance, etc.). ing. The subject of this invention is providing the water-based coating composition which satisfy | fills said performance.
本発明者等は、鋭意検討した結果、カルボキル基を含有するポリエステル樹脂(A)とアミノ樹脂(B)及びリン酸系化合物(C)を主要成分とする水性塗料組成物が、加工性、密着性、塗膜硬度、耐水性に優れた缶用塗料に用いるに相応しい水性塗料組成物であることを見い出し、本発明を完成するに至った。
As a result of intensive studies, the present inventors have found that an aqueous coating composition containing, as main components, a polyester resin (A), an amino resin (B), and a phosphoric acid compound (C) containing a carboxy group is easy to process. The present invention has been completed by finding that it is a water-based coating composition suitable for use in can coatings having excellent properties, coating film hardness, and water resistance.
即ち、本発明は、カルボキル基を含有するポリエステル樹脂(A)とアミノ樹脂(B)及びリン酸系化合物(C)を含有する水性塗料組成物を提供する。
That is, the present invention provides an aqueous coating composition containing a polyester resin (A) containing a carboalkyl group, an amino resin (B), and a phosphoric acid compound (C).
本発明の水性塗料組成物は、主として缶外面用に用いることが出来、特に、ボトル形状加工後、及び、ネジ加工後においても加工性・密着性・塗膜硬度に優れた塗膜を形成し、且つ耐沸水性に優れるという性能を有するものである。
The water-based coating composition of the present invention can be used mainly for the outer surface of a can, and in particular, forms a coating film excellent in processability, adhesion, and coating film hardness even after bottle shape processing and after screw processing. Moreover, it has the performance of being excellent in boiling water resistance.
以下、本発明を詳細に説明する。本発明の水性塗料組成物は、カルボキル基を含有するポリエステル樹脂(A)とアミノ樹脂(B)及びリン酸系化合物(C)を含有するものである。比較的穏やかな加工工程を有する2ピース缶用はもとより、厳しい絞り加工やネジ切り加工を有する缶(ボトル缶)の上塗り塗料に使用することができる水性塗料組成物を提供するものである。
Hereinafter, the present invention will be described in detail. The water-based coating composition of the present invention contains a polyester resin (A) containing a carboxy group, an amino resin (B), and a phosphoric acid compound (C). The present invention provides an aqueous coating composition that can be used for a top coating of a can (bottle can) having severe drawing and threading as well as for a two-piece can having a relatively gentle processing step.
まず、カルボキシル基を有するポリエステル樹脂(A)について詳細に説明する。カルボキシル基を有するポリエステル樹脂(A)の数平均分子量は、1000~10000の範囲が好ましい。この範囲より小さいと塗膜の加工性が劣る傾向があり、大きい場合は塗料の粘度が高くなり塗装性が損なわれるのに加え、塗液の安定性も低下する傾向がある。また、カルボキシル基を有するポリエステル樹脂(A)は、特に限定されないが、樹脂粘度、加工性、塗膜硬度、耐水性のバランスと塗液安定性の向上の点から、酸価(ポリエステル樹脂固形分当たり)が10~50(mgKOH/g)であるものが好ましく、中でも特に15~30(mgKOH/g)であるものが特に好ましい。50mgKOH/gよりも大きいと塗膜の加工性、耐水性が劣る傾向があり、10mgKOH/gより小さいと塗液の安定性が低下する。また、ポリエステル樹脂のガラス転移温度は-10℃~60℃の範囲が好ましい。
First, the polyester resin (A) having a carboxyl group will be described in detail. The number average molecular weight of the polyester resin (A) having a carboxyl group is preferably in the range of 1000 to 10,000. If it is smaller than this range, the processability of the coating film tends to be inferior. If it is larger, the viscosity of the coating becomes high and the paintability is impaired, and the stability of the coating liquid also tends to be lowered. In addition, the polyester resin (A) having a carboxyl group is not particularly limited, but the acid value (polyester resin solid content) from the viewpoint of improving the balance of resin viscosity, processability, coating film hardness, water resistance and coating liquid stability. The hit is preferably 10 to 50 (mg KOH / g), and particularly preferably 15 to 30 (mg KOH / g). When it is larger than 50 mgKOH / g, the processability and water resistance of the coating film tend to be inferior, and when it is smaller than 10 mgKOH / g, the stability of the coating liquid is lowered. The glass transition temperature of the polyester resin is preferably in the range of −10 ° C. to 60 ° C.
カルボキシル基を有するポリエステル樹脂(A)の製造法について説明する。カルボキシル基を導入する方法としては、例えば、酸成分とアルコール成分より、目標のカルボキシル基をもつよう、酸成分過剰の状態で反応させる方法がある。又、逆にアルコール成分過剰で反応させ、得られた水酸基含有ポリエステル樹脂に無水トリメリット酸や無水フタル酸などを付加させ、カルボキシル基含有ポリエステル樹脂を得る方法等も採用できる。後者の方法がトータル性能を満足させるのに好適である。カルボキシル基を有するポリエステル樹脂(A)の製造法については特に制限は無く、酸成分とアルコール成分のエステル化反応による周知の方法が、そのまま適用できる。原料の酸成分及びアルコール成分は、各々周知の二塩基酸、三塩基以上の多塩基酸、並びに2価アルコール類及び3価以上の多価アルコール類が利用できる。
A method for producing a polyester resin (A) having a carboxyl group will be described. As a method for introducing a carboxyl group, for example, there is a method in which an acid component and an alcohol component are reacted in an acid component excess state so as to have a target carboxyl group. Conversely, a method of obtaining a carboxyl group-containing polyester resin by reacting with an excess of alcohol component and adding trimellitic anhydride or phthalic anhydride to the obtained hydroxyl group-containing polyester resin can also be employed. The latter method is suitable for satisfying the total performance. There is no restriction | limiting in particular about the manufacturing method of the polyester resin (A) which has a carboxyl group, The well-known method by esterification reaction of an acid component and an alcohol component can be applied as it is. As the raw acid component and alcohol component, known dibasic acids, tribasic or more polybasic acids, dihydric alcohols, and trihydric or higher polyhydric alcohols can be used.
更に、大豆油、ヤシ油、ヒマシ油、サフラワ油、又はこれらの脂肪酸を一部使用することもできる。
Furthermore, soybean oil, coconut oil, castor oil, safflower oil, or a part of these fatty acids can also be used.
酸成分として代表的なもののみを挙げれば、まず芳香族カルボン酸としては、テレフタル酸、イソフタル酸、(無水)フタル酸、(無水)トリメリット酸、安息香酸など、脂環式カルボン酸としては、ヘキサヒドロ(無水)フタル酸、テトラヒドロ(無水)フタル酸、メチルヘキサヒドロ(無水)フタル酸、1,4-シクロヘキサンジカルボン酸など、脂肪族カルボン酸としては、アジピン酸、セバシン酸、コハク酸、(無水)マレイン酸、フマル酸などが、それぞれ挙げられる。
If only typical acid components are listed, the aromatic carboxylic acids are terephthalic acid, isophthalic acid, (anhydrous) phthalic acid, (anhydrous) trimellitic acid, benzoic acid, etc. Examples of aliphatic carboxylic acids such as hexahydro (anhydrous) phthalic acid, tetrahydro (anhydride) phthalic acid, methyl hexahydro (anhydride) phthalic acid, 1,4-cyclohexanedicarboxylic acid include adipic acid, sebacic acid, succinic acid, ( Anhydrous) maleic acid, fumaric acid and the like.
アルコール成分として代表的なものを挙げれば、(ジ)エチレングリコール、(ジ)プロピレングリコール、1,3-ブタンジオール、1,4-ブタンジオール、1,6-ヘキサンジオール、1,5-ペンタンジオール、2メチル1,3-プロパンジオール、ネオペンチルグリコール、トリメチロールプロパン、トリメチロールエタン、グリセリン、ペンタエリスリトール、1,4-シクロヘキサンジメタノールなどが挙げられる。
Typical alcohol components include (di) ethylene glycol, (di) propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, and 1,5-pentanediol. Examples include 2-methyl 1,3-propanediol, neopentyl glycol, trimethylol propane, trimethylol ethane, glycerin, pentaerythritol, 1,4-cyclohexane dimethanol and the like.
アルコール成分の一部として、モノエポキシ化合物、例えばバーサティック酸グリシジルエステル、α-オレフィンオキサイドなども使用できる。
As a part of the alcohol component, a monoepoxy compound such as glycidyl ester versatate or α-olefin oxide can also be used.
本発明の水性塗料組成物に用いるアミノ樹脂(B)としては、ベンゾグアナミン樹脂、メラミン樹脂、尿素樹脂等を挙げることができる。これらを単独又は混合しても良い。これらのアミノ樹脂の中でも、塗膜の耐水性、光沢などの点からベンゾグアナミン樹脂であることが好ましく、数平均分子量は300~1000の範囲が好ましい。数平均分子量がこの範囲より低いと塗膜の加工性が低下する傾向があり、大きいと水性塗料中での安定性が低下する傾向がある。更に、メラミン又はベンゾグアナミンとホルムアルデヒドとの付加反応生成物(メチロール化)であるメチロール化メラミン/ベンゾグアナミン樹脂の中のメチロール基の一部又は全部をアルコール類でエーテル化したものであることが好ましい。特に、トリアジン核1個あたりのホルマリン付加数が2.5以上、エーテル化度が1.8以上の高エーテルタイプのベンゾグアナミン樹脂が加工性に特に優れる。
Examples of the amino resin (B) used in the aqueous coating composition of the present invention include benzoguanamine resin, melamine resin, urea resin and the like. These may be used alone or in combination. Among these amino resins, benzoguanamine resins are preferable from the viewpoint of water resistance and gloss of the coating film, and the number average molecular weight is preferably in the range of 300 to 1,000. When the number average molecular weight is lower than this range, the processability of the coating film tends to be lowered, and when it is larger, the stability in the aqueous paint tends to be lowered. Furthermore, it is preferable that some or all of the methylol groups in the methylolated melamine / benzoguanamine resin, which is an addition reaction product (methylolation) of melamine or benzoguanamine and formaldehyde, are etherified with alcohols. In particular, a high ether type benzoguanamine resin having a formalin addition number per triazine nucleus of 2.5 or more and a degree of etherification of 1.8 or more is particularly excellent in processability.
本発明の水性塗料組成物に用いるリン酸系化合物(C)は、一分子中に少なくとも一個のリン原子に結合した水酸基を有する化合物(C-0)、及び一分子中に少なくとも一個のリン原子に結合した水酸基を有する化合物により変性されたエポキシ化合物(C-1)からなる群から選ばれた少なくとも一種であることが好ましい。また化合物(C-1)をカルボン酸により変性した化合物(C-2)も挙げられる。また、化合物(C-1)、(C-2)はイソシアネート、フェノール樹脂、アミン等の化合物によって更に変性されても良い。(化合物(C-3))
The phosphoric acid compound (C) used in the aqueous coating composition of the present invention includes a compound (C-0) having a hydroxyl group bonded to at least one phosphorus atom in one molecule, and at least one phosphorus atom in one molecule. It is preferably at least one selected from the group consisting of an epoxy compound (C-1) modified with a compound having a hydroxyl group bonded to. Further, compound (C-2) obtained by modifying compound (C-1) with carboxylic acid can also be mentioned. Further, the compounds (C-1) and (C-2) may be further modified with a compound such as an isocyanate, a phenol resin, or an amine. (Compound (C-3))
一分子中に少なくとも一個のリン原子に結合した水酸基を有する化合物(C-0)としては、例えば、メタリン酸、オルトリン酸、ピロリン酸、三リン酸、四リン酸等の如き十酸化四リン酸を加水分解してできる酸、亜リン酸、二亜リン酸、次亜リン酸等を挙げることができる。更には、(モノ、ジ)メチルホスフェート、(モノ、ジ)エチルホスフェート、(モノ、ジ)ブチルホスフェート、(モノ、ジ)オクチルホスフェート、(モノ、ジ)-2-エチルオクチルホスフェート、、(モノ、ジ)イソデシルホスフェート、モノメチルホスファイト、モノエチルホスフェイト、モノブチルホスファイト、モノオクチルホスファイト、モノ-2-エチルオクチルホスファイト、モノイソデシルホスファイト等の如き、これらのエステル化合物を挙げることができる。
Examples of the compound (C-0) having a hydroxyl group bonded to at least one phosphorus atom in one molecule include tetraphosphoric acid tetraphosphates such as metaphosphoric acid, orthophosphoric acid, pyrophosphoric acid, triphosphoric acid, and tetraphosphoric acid. The acid, phosphorous acid, diphosphorous acid, hypophosphorous acid, etc. which can be hydrolyzed can be mentioned. Furthermore, (mono, di) methyl phosphate, (mono, di) ethyl phosphate, (mono, di) butyl phosphate, (mono, di) octyl phosphate, (mono, di) -2-ethyl octyl phosphate, (mono , Di) isodecyl phosphate, monomethyl phosphite, monoethyl phosphate, monobutyl phosphite, monooctyl phosphite, mono-2-ethyl octyl phosphite, monoisodecyl phosphite, etc. be able to.
エポキシ化合物としては、例えばエチレングリコール、プロピレングリコール、ヘキサンジオール、ネオペンチルグリコール、トリメチロールプロパン、トリエチロールエタン、トリメチロールプロパン、グリセリン、ジグリセリン、ペンタエリスリトール、ソルビトール、スピログリコール、水添ビスフェノールA等の如き脂肪族ポリオールとエピクロルヒドリンとを反応して得られるグリシジルエーテル型エポキシ化合物;
Examples of the epoxy compound include ethylene glycol, propylene glycol, hexanediol, neopentyl glycol, trimethylol propane, triethylol ethane, trimethylol propane, glycerin, diglycerin, pentaerythritol, sorbitol, spiroglycol, hydrogenated bisphenol A and the like. A glycidyl ether type epoxy compound obtained by reacting such an aliphatic polyol with epichlorohydrin;
カテコール、レゾルシノール、ヒドロキノン、ビスフェノール(A,F,S,AD)テトラヒドロキシフェニルメタン等の如き芳香族ポリヒドロキシ化合物のエチレンオキシドもしくはプロピレンオキシド付加体等の如きポリオール類とエピクロルヒドリンとを反応して得られるグリシジルエーテル型エポキシ化合物;ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール等の如きポリエーテルポリオールとエピクロルヒドリンとを反応して得られるグリシジル化合物;
Glycidyl obtained by reacting polyols such as ethylene oxide or propylene oxide adducts of aromatic polyhydroxy compounds such as catechol, resorcinol, hydroquinone, bisphenol (A, F, S, AD) tetrahydroxyphenylmethane and the like with epichlorohydrin Ether type epoxy compounds; glycidyl compounds obtained by reacting a polyether polyol such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like with epichlorohydrin;
プロパントリカルボン酸、ブタンテトラカルボン酸、アジピン酸、フタル酸、イソフタル酸、テトラフタル酸、トリメリット酸の如き脂肪族ないしは芳香族ポリカルボン酸とエピクロルヒドリンとを反応して得られるグリシジルエステル型エポキシ化合物;アニリン、(p、m-)アミノフェノール、ジアミノジフェニルメタン、ビスアミノメチルシクロヘキサン、メタキシリレンジアミン等の如きアミンとエピクロルヒドリンとを反応して得られるグリシジルアミン型エポキシ化合物;
Glycidyl ester type epoxy compounds obtained by reacting aliphatic or aromatic polycarboxylic acids such as propanetricarboxylic acid, butanetetracarboxylic acid, adipic acid, phthalic acid, isophthalic acid, tetraphthalic acid, trimellitic acid and epichlorohydrin; aniline A glycidylamine type epoxy compound obtained by reacting an amine such as (p, m-) aminophenol, diaminodiphenylmethane, bisaminomethylcyclohexane, metaxylylenediamine, and epichlorohydrin;
フェノールノボラックとエピクロルヒドリンとを反応して得られるフェノールノボラック型エポキシ化合物;クレゾールノボラックとエピクロルヒドリンとを反応して得られるクレゾールノボラック型エポキシ化合物;3,4-エポキシ-6-メチルシクロヘキシルメチル-3’,4’-エポキシ-6’-メチルシクロヘキサンカルボキシレート、3,4-エポキシシクロへキシルメチル-3’,4’-シクロヘキサンカルボキシレート、ビス(3,4-エポキシ-6-メチルシクロヘキシルメチルアジペート、ビニルシクロヘキセンジエポキシサイド、ビス(2,3-エポキシシクロペンチル)エーテル、リモネンジオキサイド等の如きシクロ環の二重結合を酸化して得られる環式脂肪族型エポキシ樹脂化合物;
Phenol novolac type epoxy compound obtained by reacting phenol novolak and epichlorohydrin; Cresol novolak type epoxy compound obtained by reacting cresol novolak and epichlorohydrin; 3,4-epoxy-6-methylcyclohexylmethyl-3 ′, 4 '-Epoxy-6'-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3', 4'-cyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyladipate, vinylcyclohexene diepoxy A cycloaliphatic epoxy resin compound obtained by oxidizing a double bond of a cyclo ring such as side, bis (2,3-epoxycyclopentyl) ether, limonene dioxide;
ブタジエン、ヘキサジエン、オクタジエン、ドデカジエン、ポリブタジエン、ポリイソプレン、大豆油等の線状脂肪族の二重結合を酸化して得られる線状脂肪族のエポキシ化合物;更にはトリアジン、ヒダントイン等の如き複素環を含有するエポキシ化合物等の多官能エポキシ化合物を挙げることができる。これらを単独、あるいは混合して用いてよい。
Linear aliphatic epoxy compounds obtained by oxidizing linear aliphatic double bonds such as butadiene, hexadiene, octadiene, dodecadiene, polybutadiene, polyisoprene, and soybean oil; and further heterocyclic rings such as triazine and hydantoin. Mention may be made of polyfunctional epoxy compounds such as epoxy compounds to be contained. These may be used alone or in combination.
なお、カルボン酸をはじめ、イソシアネート、フェノール類、アミン等の化合物によって、更に変性しないならばn-ブチルグリシジルエーテル、アリルグリシジルエーテル、2-エチルヘキシルグリシジルエーテル、グリシジル(メタ)アクリレート、スチレンオキサイド、フェニルグリシジルエーテル、クレジルグリシジルエーテル等の如き一官能のエポキシ化合物を得ることも出来る。
If not further modified by carboxylic acid, isocyanate, phenols, amines, etc., n-butyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, glycidyl (meth) acrylate, styrene oxide, phenyl glycidyl Monofunctional epoxy compounds such as ether and cresyl glycidyl ether can also be obtained.
カルボン酸としては、例えば、ギ酸、酢酸、プロピオン酸、酪酸、イソ酪酸、吉草酸、イソ吉草酸、カプロン酸、エナント酸、カプリル酸、ペラルゴン酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、ピバル酸、メトキシ酢酸、ピルビン酸、グリオキシル酸等の如き脂肪族飽和モノカルボン酸;(メタ)アクリル酸、3,3-ジメチルアクリル酸、クロトン酸、イソクロトン酸、チグリン酸、ビニル酢酸、ペンテン酸、オレイン酸等の如きエチレン性不飽和モノカルボン酸;
Examples of the carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, Aliphatic saturated monocarboxylic acids such as stearic acid, pivalic acid, methoxyacetic acid, pyruvic acid, glyoxylic acid; (meth) acrylic acid, 3,3-dimethylacrylic acid, crotonic acid, isocrotonic acid, tiglic acid, vinylacetic acid, Ethylenically unsaturated monocarboxylic acids such as pentenoic acid and oleic acid;
シュウ酸、マロン酸、メチルマロン酸(無水物)、(無水)コハク酸、ジメチルコハク酸(無水物)、ジグリコール酸、(無水)グルタル酸、2-オキソグルタル酸、ジメチルグルタル酸(無水物)、アジピン酸、3-メチルアジピン酸、3-オキサアジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバチン酸、ジアセチル酒石酸等の如き脂肪族飽和ジカルボン酸及びそれらの無水物;
Oxalic acid, malonic acid, methylmalonic acid (anhydride), (anhydrous) succinic acid, dimethylsuccinic acid (anhydride), diglycolic acid, (anhydrous) glutaric acid, 2-oxoglutaric acid, dimethylglutaric acid (anhydride) Aliphatic saturated dicarboxylic acids such as adipic acid, 3-methyladipic acid, 3-oxaadipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, diacetyltartaric acid and the like;
1-シクロプロパンジカルボン酸、1,1-シクロブタンジカルボン酸、1,2-シクロヘキサンジカルボン酸(無水物)、1,4-シクロヘキサンジカルボン酸、メチル-1,2-シクロヘキサンジカルボン酸(無水物)、1,1-シクロヘキサン二酢酸、ビシクロ[2.2.2]オクタンジカルボン酸(無水物)等の如き脂環族飽和ジカルボン酸及びそれらの無水物;
1-cyclopropanedicarboxylic acid, 1,1-cyclobutanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid (anhydride), 1,4-cyclohexanedicarboxylic acid, methyl-1,2-cyclohexanedicarboxylic acid (anhydride), 1 , 1-cyclohexanediacetic acid, alicyclic saturated dicarboxylic acids such as bicyclo [2.2.2] octanedicarboxylic acid (anhydride) and the like;
(無水)マレイン酸、2,3-ジメチルマレイン酸(無水物)、フマル酸、(無水)イタコン酸、メサコン酸、グルタコン酸、(無水)シトラコン酸、ムコン酸、3-メチレンシクロプロパン-1,2-ジカルボン酸、ビシクロ[2.2.2]オクト-5-エン-2,3-ジカルボン酸(無水物)、4-オクテン-1,8-ジカルボン酸、1-シクロペンテン-1,2-ジカルボン酸、5-ノルボルネン-2,3-ジカルボン酸(無水物)、テトラヒドロフタル酸(無水物)、4-メチルテトラヒドロフタル酸(無水物)、4,5-エポキシ-1,2,3,6-テトラヒドロフタル酸(無水物)等の如きエチレン性不飽和ジカルボン酸及びそれらの無水物;
(Anhydrous) maleic acid, 2,3-dimethylmaleic acid (anhydride), fumaric acid, (anhydrous) itaconic acid, mesaconic acid, glutaconic acid, (anhydrous) citraconic acid, muconic acid, 3-methylenecyclopropane-1, 2-dicarboxylic acid, bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylic acid (anhydride), 4-octene-1,8-dicarboxylic acid, 1-cyclopentene-1,2-dicarboxylic acid Acid, 5-norbornene-2,3-dicarboxylic acid (anhydride), tetrahydrophthalic acid (anhydride), 4-methyltetrahydrophthalic acid (anhydride), 4,5-epoxy-1,2,3,6- Ethylenically unsaturated dicarboxylic acids such as tetrahydrophthalic acid (anhydride) and their anhydrides;
安息香酸、o-トルイル酸、1-ナフトエ酸、アトロパ酸、ケイ皮酸等の如き芳香族モノカルボン酸;(無水)フタル酸、4-メチルフタル酸(無水物)、ホモフタル酸、イソフタル酸、テレフタル酸、カルボキシフェノキシ酢酸、フェニルマロン酸、フェニルマロン酸、フェニレン二酢酸、フェニルコハク酸、ベンジルマロン酸、カルボキシケイ皮酸等の如き芳香族ジカルボン酸及びそれらの無水物;ニコチン酸、イソニコチン酸、2-フランカルボン酸、2-チオフェンカルボン酸等の如き複素環カルボン酸及びそれらの無水物等を挙げることが出来る。
Aromatic monocarboxylic acids such as benzoic acid, o-toluic acid, 1-naphthoic acid, atropaic acid, cinnamic acid; (anhydrous) phthalic acid, 4-methylphthalic acid (anhydride), homophthalic acid, isophthalic acid, terephthalic acid Acid, carboxyphenoxyacetic acid, phenylmalonic acid, phenylmalonic acid, phenylenediacetic acid, phenylsuccinic acid, benzylmalonic acid, carboxycinnamic acid and the like; and nicotinic acid, isonicotinic acid, Examples thereof include heterocyclic carboxylic acids such as 2-furancarboxylic acid and 2-thiophenecarboxylic acid, and anhydrides thereof.
また、グリコール酸、乳酸、グリセリン酸、3-ヒドロキシプロピオン酸、ヒドロキシピルビン酸、1-ヒドロキシ-1-シクロプロパンカルボン酸、ヒドロキシ酪酸、2-ヒドロキシイソ吉草酸、2-ヒドロキシイソ吉草酸、ビス(ヒドロキシメチル)プロピオン酸、コメン酸、2-ヒドロキシカプロン酸、メバロン酸、メコン酸、サリチル酸、3-イソプロピルサリチル酸、2-ヘキサヒドロキシサリチル酸、p-ヒドロキシ安息香酸、2,3-ジヒドロキシ安息香酸、レゾルシル酸、ゲンチシン酸、ホモゲンチシン酸、プロトカテク酸、シキミ酸、バニリン酸、イソバニリン酸、ホモバニリン酸、ヒドロキシ-o-トルイル酸、ヒドロキシ-m-トルイル酸、ヒドロキシ-p-トルイル酸、ヒドロキシフェニル酢酸、マンデル酸、ジヒドロキシマンデル酸、バニリルマンデル酸、2-ヒドロキシオクタン酸、o-オルセリン酸、p-ヒドロキシフェニルピルビン酸、ヒドロクマル酸、メリロット酸、フロレチン酸、2-ヒドロキシノナン酸、カフェイン酸、ヒドロキシケイ皮酸、ヒドロキシヒドロケイ皮酸、シリンガ酸、アトロラクチン酸、トロパ酸、2-ヒドロキシデカン酸、ヘスペリチン酸、フェルラ酸、10-ヒドロキシデカン酸、10-ヒドロキシ-2-デセン酸、ロイヤルジェリー酸、o-チモチン酸、カルバクロチン酸、ヒドロキシ-1-ナフトエ酸、ヒドロキシ-2-ナフトエ酸、ジヒドロキシナフトエ酸、イソボルネオル酢酸、ヒドロキシステアリン酸、フロイオノル酸、ロイコトリエンB4、デオキシコール酸、α-ヒオデキシコール酸、ケノデオキシコール酸、ウルソデオキシコール酸、ヒオコール酸、アザフリン酸の如きオキシモノカルボン酸;
Also, glycolic acid, lactic acid, glyceric acid, 3-hydroxypropionic acid, hydroxypyruvic acid, 1-hydroxy-1-cyclopropanecarboxylic acid, hydroxybutyric acid, 2-hydroxyisovaleric acid, 2-hydroxyisovaleric acid, bis ( Hydroxymethyl) propionic acid, comenic acid, 2-hydroxycaproic acid, mevalonic acid, meconic acid, salicylic acid, 3-isopropylsalicylic acid, 2-hexahydroxysalicylic acid, p-hydroxybenzoic acid, 2,3-dihydroxybenzoic acid, resorcylic acid Gentisic acid, homogentisic acid, protocatechuic acid, shikimic acid, vanillic acid, isovanillic acid, homovanillic acid, hydroxy-o-toluic acid, hydroxy-m-toluic acid, hydroxy-p-toluic acid, hydroxyphenylacetic acid, mandelic acid, The Droxymandelic acid, vanillylmandelic acid, 2-hydroxyoctanoic acid, o-orceric acid, p-hydroxyphenylpyruvic acid, hydrocoumaric acid, mellilotic acid, phloretic acid, 2-hydroxynonanoic acid, caffeic acid, hydroxycinnamic acid, Hydroxyhydrocinnamic acid, syringic acid, atrolactic acid, tropic acid, 2-hydroxydecanoic acid, hesperic acid, ferulic acid, 10-hydroxydecanoic acid, 10-hydroxy-2-decenoic acid, royal jelly acid, o-thymotin Acid, carbacrotinic acid, hydroxy-1-naphthoic acid, hydroxy-2-naphthoic acid, dihydroxynaphthoic acid, isoborneol acetic acid, hydroxystearic acid, furoonolic acid, leukotriene B4, deoxycholic acid, α-hyodexicolic acid, chenodeoxyco Oxymonocarboxylic acids such as oxalic acid, ursodeoxycholic acid, hyocholic acid, azafuric acid;
(無水)タルトロン酸、ジヒドロキシマロン酸、リンゴ酸、酒石酸、オキサロ酢酸、2,3-ジヒドロキシコハク酸、テトラヒドロキシコハク酸、ジヒドロキシフマル酸、シトラマル酸、ガラクタール酸、ジクロタリン酸、2-ヒドロキシ-2-イソプロピルコハク酸、ヒドロキシフタル酸(無水)、ヒドロキシイソフタル酸、2-ヒドロキシテレフタル酸、エチル(2-ヒドロキシ-3-ブテニル)-マロン酸、2-(ヒドロキシメチル)-3-イソブチル-コハク酸、3-ヒドロキシ-5-メチル-4-シクロヘキセン-1,2-ジカルボン酸、4-ヒドロキシ-1,3-ジメチル-1,2-シクロヘキサンジカルボン酸、2,5-ジヒドロキシ-1,4-ベンゼン二酢酸、フロイオン酸、クエン酸等の如きオキシポリカルボン酸及びそれらの無水物を挙げることが出来る。これらを単独、あるいは混合して用いてよい。
(Anhydrous) Tartronic acid, dihydroxymalonic acid, malic acid, tartaric acid, oxaloacetic acid, 2,3-dihydroxysuccinic acid, tetrahydroxysuccinic acid, dihydroxyfumaric acid, citramalic acid, galactaric acid, dicrotalic acid, 2-hydroxy-2- Isopropyl succinic acid, hydroxyphthalic acid (anhydrous), hydroxyisophthalic acid, 2-hydroxyterephthalic acid, ethyl (2-hydroxy-3-butenyl) -malonic acid, 2- (hydroxymethyl) -3-isobutyl-succinic acid, 3 -Hydroxy-5-methyl-4-cyclohexene-1,2-dicarboxylic acid, 4-hydroxy-1,3-dimethyl-1,2-cyclohexanedicarboxylic acid, 2,5-dihydroxy-1,4-benzenediacetic acid, Oxypolycarboxylic acids such as furionic acid and citric acid and It can be mentioned those of anhydride. These may be used alone or in combination.
一分子中に少なくとも一個のリン原子に結合した水酸基を有する化合物と、エポキシ化合物の反応、あるいは、一分子中に少なくとも一個のリン原子に結合した水酸基を有する化合物と、エポキシ化合物とカルボン酸との反応は、無溶剤、あるいは水可溶性溶媒で行い、必要によりアミン化合物のような触媒も使用してよい。
Reaction between a compound having a hydroxyl group bonded to at least one phosphorus atom in one molecule and an epoxy compound, or a compound having a hydroxyl group bonded to at least one phosphorus atom in one molecule, an epoxy compound and a carboxylic acid The reaction is carried out in the absence of a solvent or in a water-soluble solvent, and a catalyst such as an amine compound may be used if necessary.
ここで用いる水混和性有機溶剤としては特に制限はないが、たとえばトルエン、キシレン、ソルベッソ#100、ソルベッソ#150等の芳香族炭化水素系、ヘキサン、ヘプタン、オクタン、デカン等の脂肪族炭化水素系、酢酸メチル、酢酸エチル、酢酸イソプロピル、酢酸ブチル、酢酸アミル、ギ酸エチル、プロピオン酸ブチル等のエステル系の各種有機溶剤が挙げられる。また水混和性有機溶剤としてメタノール、エタノール、プロパノール、ブタノール等のアルコール系、アセトン、メチルエチルケトン等のケトン系、エチレングリコール(モノ,ジ)メチルエーテル、エチレングリコール(モノ,ジ)エチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノイソプロピルエーテル、モノブチルエーテル、ジエチレングリコール(モノ,ジ)メチルエーテル、ジエチレングリコール(モノ,ジ)エチルエーテル、ジエチレングリコールモノイソプロピルエーテル、ジエチレングリコールモノブチルエーテル、トリエチレングリコール(モノ,ジ)メチルエーテル、プロピレングリコール(モノ,ジ)メチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、ジプロピレングリコール(モノ,ジ)メチルエーテル等のグリコールエーテル系の各種有機溶剤が挙げられる。これらの各種有機溶剤及び水は、樹脂との相溶性、塗料化した後の外観などの性能に応じて単独もしくは組み合わせて使用することができる。水混和性有機溶剤は、塗料粘度の調整や塗膜外観の調整等に応じて単独もしくは組み合わせてイオン交換水と混合して使用することができる。また、触媒としては前述の有機アミン化合物及びそれらの無機酸塩または有機酸塩;三フッ化ホウ素、塩化リチウム、塩化スズ、臭化リチウム、臭化スズ等の如きハロゲン化金属;水酸化ナトリウム、水酸化リチウム等の如き金属水酸化物;2-メチルイミダゾール、2-エチル-4-メチルイミダゾール、2-フェイルイミダゾール等の如きイミダゾール類及びそれらの無機物又は有機物等付加物;トリフェニルホスフィン、トリフェニルアンチモン等を挙げることが出来、これらを単独、あるいは混合して用いてよい。
The water-miscible organic solvent used here is not particularly limited. For example, aromatic hydrocarbons such as toluene, xylene, Solvesso # 100 and Solvesso # 150, and aliphatic hydrocarbons such as hexane, heptane, octane and decane. And various ester organic solvents such as methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, amyl acetate, ethyl formate, and butyl propionate. Water-miscible organic solvents include alcohols such as methanol, ethanol, propanol and butanol, ketones such as acetone and methyl ethyl ketone, ethylene glycol (mono, di) methyl ether, ethylene glycol (mono, di) ethyl ether, and ethylene glycol mono Propyl ether, ethylene glycol monoisopropyl ether, monobutyl ether, diethylene glycol (mono, di) methyl ether, diethylene glycol (mono, di) ethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol (mono, di) methyl ether, Propylene glycol (mono, di) methyl ether, propylene glycol monopropyl ether, propylene glycol Over mono butyl ether, dipropylene glycol (mono, di) include various organic solvents glycol ether such as methyl ether. These various organic solvents and water can be used alone or in combination depending on the compatibility with the resin and the performance such as the appearance after coating. The water-miscible organic solvent can be used alone or in combination with ion-exchanged water depending on the adjustment of the paint viscosity or the appearance of the coating film. Examples of the catalyst include the aforementioned organic amine compounds and inorganic acid salts or organic acid salts thereof; metal halides such as boron trifluoride, lithium chloride, tin chloride, lithium bromide, tin bromide; sodium hydroxide, Metal hydroxides such as lithium hydroxide; imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-failimidazole and the like, and adducts thereof such as inorganic or organic substances; triphenylphosphine, triphenyl Antimony etc. can be mentioned, These may be used individually or in mixture.
カルボキシル基を有するポリエステル樹脂(A)とアミノ樹脂(B)の樹脂固形分中の比率は、40/60~80/20の質量比であることが好ましく、より好ましくは45/55~60/40である。カルボキシル基を有するポリエステル樹脂(A)の比率が40より低いと塗膜の加工性が劣るようになり、80より高いと塗膜の硬度や耐水性が不足する傾向がある。リン酸系化合物(C)の樹脂固形分中の比率は、本発明の効果を生ずる範囲であればいかなる範囲でも差し支えないが、カルボキシル基を有するポリエステル樹脂(A)とアミノ樹脂(B)の合計100質量部に対してリン酸系化合物(C)を0.1~10質量部含有することが好ましい。リン酸系化合物(C)の含有比率が、0.1を下回ると塗膜の硬度等が劣り、10を超えると塗膜の光沢や貯蔵性に劣るようになる。
The ratio of the polyester resin (A) having a carboxyl group and the amino resin (B) in the resin solid content is preferably a mass ratio of 40/60 to 80/20, more preferably 45/55 to 60/40. It is. When the ratio of the polyester resin (A) having a carboxyl group is lower than 40, the processability of the coating film becomes inferior, and when it is higher than 80, the hardness and water resistance of the coating film tend to be insufficient. The ratio of the phosphoric acid compound (C) in the resin solid content may be any range as long as it produces the effects of the present invention, but the total of the polyester resin (A) having a carboxyl group and the amino resin (B). It is preferable to contain 0.1 to 10 parts by mass of the phosphoric acid compound (C) with respect to 100 parts by mass. When the content ratio of the phosphoric acid compound (C) is less than 0.1, the hardness of the coating film is inferior, and when it exceeds 10, the gloss and storage properties of the coating film are inferior.
本発明の水性塗料組成物の用途としては、2ピース缶は勿論、特に厳しい絞り加工やネジ切り加工を有する缶(ボトル缶)の上塗り塗料に好適に使用することが出来る。
As an application of the water-based coating composition of the present invention, it can be suitably used as a top coating for cans (bottle cans) having particularly severe drawing and threading, as well as two-piece cans.
更に、本発明の水性塗料組成物を、缶用塗料として用いる場合には、必要に応じて、酸化チタン、シリカなどの顔料、表面活性剤、消泡剤、分散剤等の公知の添加剤を配合することができる。カルボキシル基を有するポリエステル樹脂(A)のアミン中和物と、硬化剤としてのアミノ樹脂(B)は水性媒体中に溶解及び/又は分散した形態で塗料調製に供される。ここには、カルボキシル基を有するポリエステル樹脂(A)と硬化剤としてのアミノ樹脂(B)の何れか、若しくは両方の一部が溶解し、一部が分散したものも含まれる。水性媒体としては、通常イオン交換水と水混和性有機溶剤との混合溶剤が用いられる。水可溶性溶媒としては、前述のものをあげることが出来る。また、カルボキシル基を有するポリエステル樹脂(A)の水溶性を上げるために、塩基による中和を行う必要があるが、中和するのに用いる塩基性化合物としては、(モノ,ジ,トリ)メチルアミン、(モノ,ジ,トリ)エチルアミン、(モノ,ジ,トリ)プロピルアミン等のアルキルアミン;(モノ,ジ)エタノールアミン、(モノ,ジ)イソプロパノールアミン、N-メチルエタノールアミン、N,N-ジメチルエタノールアミン、N,N-ジエチルエタノールアミン、2-アミノ-2-メチルプロパノール、2-(ジメチルアミノ)-2-メチルプロパノール、N-メチルジエタノールアミン等のアルカノールアミン;エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン等の多価アミン等の有機アミン及びアンモニアが挙げられる。ここで、カルボキシル基を有するポリエステル樹脂(A)と、硬化剤としてのアミノ樹脂(B)を有する水性塗料の固形分濃度は、通常20~70質量%、好ましくは30~60質量%である。70質量%を超える場合には高粘度で取扱いが困難となり、20質量%に満たない場合には調製した塗料の粘度が低くなりすぎる傾向がある。
Furthermore, when the aqueous coating composition of the present invention is used as a can coating, known additives such as pigments such as titanium oxide and silica, surfactants, antifoaming agents, and dispersing agents are added as necessary. Can be blended. The amine neutralized product of the polyester resin (A) having a carboxyl group and the amino resin (B) as a curing agent are used for the preparation of a paint in a form dissolved and / or dispersed in an aqueous medium. This includes one in which either or both of the polyester resin (A) having a carboxyl group and the amino resin (B) as a curing agent are dissolved and partly dispersed. As the aqueous medium, a mixed solvent of ion-exchanged water and a water-miscible organic solvent is usually used. Examples of the water-soluble solvent include those mentioned above. In order to increase the water solubility of the polyester resin (A) having a carboxyl group, it is necessary to neutralize with a base. As a basic compound used for neutralization, (mono, di, tri) methyl is used. Alkylamines such as amine, (mono, di, tri) ethylamine, (mono, di, tri) propylamine; (mono, di) ethanolamine, (mono, di) isopropanolamine, N-methylethanolamine, N, N Alkanolamines such as dimethylethanolamine, N, N-diethylethanolamine, 2-amino-2-methylpropanol, 2- (dimethylamino) -2-methylpropanol, N-methyldiethanolamine; ethylenediamine, diethylenetriamine, triethylenetetramine , Polyamines such as tetraethylenepentamine, etc. Organic amines and ammonia. Here, the solid content concentration of the polyester resin (A) having a carboxyl group and the aqueous coating material having the amino resin (B) as a curing agent is usually 20 to 70% by mass, preferably 30 to 60% by mass. When it exceeds 70% by mass, it is difficult to handle due to high viscosity, and when it is less than 20% by mass, the viscosity of the prepared coating tends to be too low.
金属缶は、従来から、飲料、食品類等の包装容器の一種として広く用いられてきている。これらの缶の外面は、美装、防錆、内容物表示等の目的で印刷及び塗装がなされている。缶胴部の外面は高度の絞り加工を施さない缶の場合(2ピース缶等)は、「金属基材+インキ+上塗りクリヤー塗料」で構成されているが、高度の絞り加工を施す缶の場合には、以下の試験片-1,2のようにサイズ塗装が施されることが多い。サイズ塗装に用いるコーティング剤は、金属基材の表面に薄く有機被膜を設けることにより、金属基材とインキもしくは金属基材と上塗りクリヤーとの間に強固な密着性を付与して、後工程で絞り加工性を向上させる役割をもつ透明な塗料である。
Metal cans have been widely used as a kind of packaging containers for beverages, foods and the like. The outer surface of these cans is printed and painted for the purpose of aesthetics, rust prevention, contents display, and the like. The outer surface of the can body is made up of “metal substrate + ink + clear coating” in the case of cans that are not highly drawn (such as two-piece cans). In some cases, size coating is often applied as in test pieces -1 and 2 below. The coating agent used for size coating provides a strong adhesion between the metal substrate and the ink or the metal substrate and the overcoat clear by providing a thin organic film on the surface of the metal substrate. It is a transparent paint that plays a role in improving drawing processability.
(塗装金属缶の層構成)
(1)試験片-1:金属+サイズ塗膜有+上塗りクリヤー塗料
(2)試験片-2:金属+サイズ塗膜有+インキ+上塗りクリヤー塗料
(3)試験片-3:金属+サイズ塗膜無+上塗りクリヤー塗料
(4)試験片-4:金属+サイズ塗膜無し+インキ+上塗りクリヤー塗料 (Layer structure of painted metal cans)
(1) Specimen-1: Metal + Size coating + Topcoat clear coating (2) Specimen-2: Metal + Size coating coating + Ink + Topcoat clear coating (3) Specimen-3: Metal + Size coating Film-free + Topcoat clear paint (4) Specimen-4: Metal + No size coating + Ink + Topcoat clear paint
(1)試験片-1:金属+サイズ塗膜有+上塗りクリヤー塗料
(2)試験片-2:金属+サイズ塗膜有+インキ+上塗りクリヤー塗料
(3)試験片-3:金属+サイズ塗膜無+上塗りクリヤー塗料
(4)試験片-4:金属+サイズ塗膜無し+インキ+上塗りクリヤー塗料 (Layer structure of painted metal cans)
(1) Specimen-1: Metal + Size coating + Topcoat clear coating (2) Specimen-2: Metal + Size coating coating + Ink + Topcoat clear coating (3) Specimen-3: Metal + Size coating Film-free + Topcoat clear paint (4) Specimen-4: Metal + No size coating + Ink + Topcoat clear paint
本発明の水性塗料組成物は、各種基材、例えば金属、プラスチックフィルム、又は金属板にプラスチックフィルムを積層してなるもの等に、ロールコート、コイルコート、スプレー塗装、刷毛塗り等公知の手段により塗装することができる。金属としては電気メッキ錫鋼鈑、ティンフリースチール鋼鈑、アルミニウム板、ステンレス鋼鈑等が挙げられ、プラスチックフィルムとしてはポリエチレンテレフタラート(PET)、ポリブチレンテレフタラート等のプラスチックのフィルムが挙げられる。
The water-based coating composition of the present invention is applied to various substrates such as metal, plastic film, or a metal plate laminated with a plastic film by known means such as roll coating, coil coating, spray coating and brush coating. Can be painted. Examples of the metal include an electroplated tin steel plate, a tin-free steel plate, an aluminum plate, and a stainless steel plate. Examples of the plastic film include a plastic film such as polyethylene terephthalate (PET) and polybutylene terephthalate.
本発明の水性塗料組成物は、アルミニウム板から形成される、特に一方の端が開口している有底円筒状金属の円筒外面に、上記(試験片-1,2,3,4)の組み合わせで塗装される。本発明の水性塗料組成物は、膜厚が1~10μm程度が好ましい。均一に塗装されるためには、上記塗装方法のうちロールコート塗装方法が好適である。該ロールコートの塗装速度は、飲料缶の生産速度を考慮すると、200~400m/min.程度であると推測される。本発明の水性塗料組成物は、常温乾燥しても良いが焼付けにより熱硬化させた方がより性能を発揮できる。焼付けの方法としては、電気オーブン、遠赤外線オーブン、ガスオーブン等が好適に用いられる。焼付けの条件としては、150℃~240℃の温度雰囲気中で20秒~15分程度の焼付けが好適に用いられる。
The water-based coating composition of the present invention is a combination of the above (test specimens-1, 2, 3, 4) formed on an outer surface of a bottomed cylindrical metal formed from an aluminum plate, particularly at one end. Painted with. The aqueous coating composition of the present invention preferably has a film thickness of about 1 to 10 μm. Of these coating methods, the roll coat coating method is suitable for uniform coating. Considering the production speed of beverage cans, the coating speed of the roll coat is 200 to 400 m / min. It is estimated that it is about. The water-based coating composition of the present invention may be dried at room temperature, but it can exhibit more performance when thermally cured by baking. As a baking method, an electric oven, a far-infrared oven, a gas oven or the like is preferably used. As a baking condition, baking for about 20 seconds to 15 minutes in a temperature atmosphere of 150 ° C. to 240 ° C. is preferably used.
以下実施例により本発明を説明するが本発明はこれらに限定されるものではない。尚、各例中の部および%は質量基準を示す。また、樹脂の数平均分子量はGPCポリスチレン換算により求めた。
Hereinafter, the present invention will be described by way of examples, but the present invention is not limited thereto. In addition, the part and% in each example show a mass reference | standard. Moreover, the number average molecular weight of resin was calculated | required by GPC polystyrene conversion.
(合成例1):ポリエステル樹脂A-1の合成
撹拌機、精留塔および温度計を具備した反応釜に、ネオペンチルグリコール439.5重量部、無水フタル酸142.8重量部、イソフタル酸347.5重量部、セバシン酸145.4重量部、アジピン酸49.7重量部を配合し、250℃まで徐々に加熱した後に、250℃に20時間程度保持して脱水しながら、固形分酸価が7になるまでエステル化反応を行った。エステル化後、180℃にて無水トリメリット酸を31.4重量部添加して付加反応を固形分酸価が23になるまで試みた。付加反応終了後、ブチルセロソルブを687.6重量部を仕込み、数平均分子量が4500、固形分酸価23.5、不揮発分60.0%のポリエステル樹脂(A-1)を得た。 (Synthesis Example 1): Synthesis of polyester resin A-1 In a reaction kettle equipped with a stirrer, a rectifying column, and a thermometer, 439.5 parts by weight of neopentyl glycol, 142.8 parts by weight of phthalic anhydride, 347 of isophthalic acid .5 parts by weight, sebacic acid 145.4 parts by weight, adipic acid 49.7 parts by weight, gradually heated to 250 ° C., then held at 250 ° C. for about 20 hours for dehydration, solid acid value The esterification reaction was carried out until 7 was achieved. After esterification, 31.4 parts by weight of trimellitic anhydride was added at 180 ° C., and an addition reaction was attempted until the solid content acid value became 23. After completion of the addition reaction, 687.6 parts by weight of butyl cellosolve was charged to obtain a polyester resin (A-1) having a number average molecular weight of 4500, a solid content acid value of 23.5, and a nonvolatile content of 60.0%.
撹拌機、精留塔および温度計を具備した反応釜に、ネオペンチルグリコール439.5重量部、無水フタル酸142.8重量部、イソフタル酸347.5重量部、セバシン酸145.4重量部、アジピン酸49.7重量部を配合し、250℃まで徐々に加熱した後に、250℃に20時間程度保持して脱水しながら、固形分酸価が7になるまでエステル化反応を行った。エステル化後、180℃にて無水トリメリット酸を31.4重量部添加して付加反応を固形分酸価が23になるまで試みた。付加反応終了後、ブチルセロソルブを687.6重量部を仕込み、数平均分子量が4500、固形分酸価23.5、不揮発分60.0%のポリエステル樹脂(A-1)を得た。 (Synthesis Example 1): Synthesis of polyester resin A-1 In a reaction kettle equipped with a stirrer, a rectifying column, and a thermometer, 439.5 parts by weight of neopentyl glycol, 142.8 parts by weight of phthalic anhydride, 347 of isophthalic acid .5 parts by weight, sebacic acid 145.4 parts by weight, adipic acid 49.7 parts by weight, gradually heated to 250 ° C., then held at 250 ° C. for about 20 hours for dehydration, solid acid value The esterification reaction was carried out until 7 was achieved. After esterification, 31.4 parts by weight of trimellitic anhydride was added at 180 ° C., and an addition reaction was attempted until the solid content acid value became 23. After completion of the addition reaction, 687.6 parts by weight of butyl cellosolve was charged to obtain a polyester resin (A-1) having a number average molecular weight of 4500, a solid content acid value of 23.5, and a nonvolatile content of 60.0%.
(合成例2):ベンゾグアナミン樹脂B-1(高エーテル型)の合成
攪拌機、冷却管、温度計を備えた容量1リットルの四ッ口フラスコに、メタノール640部(20モル)、92%パラホルムアルデヒド130.4部(4モル)、ベンゾグアナミン187部(1モル)、10%水酸化ナトリウム水溶液0.3部を仕込み、70℃まで昇温した。同温度で4時間反応を行った後、30℃まで降温し、62.0%硝酸にてpHを3.0に調整して2時間反応させた。次いで、50%水酸化ナトリウムにてpHを8.0に調整した後、未反応のメタノール、ホルムアルデヒドを加熱減圧下に溜去し、エチレングリコールモノノルマルプロピルエーテルで希釈した。生成物中の塩を加圧濾過にて取り除き、不揮発分80.1%、ガードナー粘度Z2の生成物を得た。 (Synthesis Example 2): Synthesis of benzoguanamine resin B-1 (high ether type) Into a 1-liter four-necked flask equipped with a stirrer, a condenser and a thermometer, 640 parts (20 mol) of methanol, 92% paraformaldehyde 130.4 parts (4 moles), benzoguanamine 187 parts (1 mole), and 10 parts of a 10% aqueous sodium hydroxide solution were charged, and the temperature was raised to 70 ° C. After performing the reaction at the same temperature for 4 hours, the temperature was lowered to 30 ° C., the pH was adjusted to 3.0 with 62.0% nitric acid, and the reaction was performed for 2 hours. Subsequently, after adjusting the pH to 8.0 with 50% sodium hydroxide, unreacted methanol and formaldehyde were distilled off under heating and reduced pressure, and diluted with ethylene glycol mononormal propyl ether. The salt in the product was removed by pressure filtration to obtain a product having a nonvolatile content of 80.1% and a Gardner viscosity Z2.
攪拌機、冷却管、温度計を備えた容量1リットルの四ッ口フラスコに、メタノール640部(20モル)、92%パラホルムアルデヒド130.4部(4モル)、ベンゾグアナミン187部(1モル)、10%水酸化ナトリウム水溶液0.3部を仕込み、70℃まで昇温した。同温度で4時間反応を行った後、30℃まで降温し、62.0%硝酸にてpHを3.0に調整して2時間反応させた。次いで、50%水酸化ナトリウムにてpHを8.0に調整した後、未反応のメタノール、ホルムアルデヒドを加熱減圧下に溜去し、エチレングリコールモノノルマルプロピルエーテルで希釈した。生成物中の塩を加圧濾過にて取り除き、不揮発分80.1%、ガードナー粘度Z2の生成物を得た。 (Synthesis Example 2): Synthesis of benzoguanamine resin B-1 (high ether type) Into a 1-liter four-necked flask equipped with a stirrer, a condenser and a thermometer, 640 parts (20 mol) of methanol, 92% paraformaldehyde 130.4 parts (4 moles), benzoguanamine 187 parts (1 mole), and 10 parts of a 10% aqueous sodium hydroxide solution were charged, and the temperature was raised to 70 ° C. After performing the reaction at the same temperature for 4 hours, the temperature was lowered to 30 ° C., the pH was adjusted to 3.0 with 62.0% nitric acid, and the reaction was performed for 2 hours. Subsequently, after adjusting the pH to 8.0 with 50% sodium hydroxide, unreacted methanol and formaldehyde were distilled off under heating and reduced pressure, and diluted with ethylene glycol mononormal propyl ether. The salt in the product was removed by pressure filtration to obtain a product having a nonvolatile content of 80.1% and a Gardner viscosity Z2.
(合成例3):ベンゾグアナミン樹脂B-2(イミノ型)
92%パラホルムアルデヒドの仕込量を81.5部(2.5モル)とした以外は合成例1と同様の操作を行い、不揮発分80.3%、ガードナー粘度Z4の生成物を得た。 (Synthesis Example 3): Benzoguanamine resin B-2 (imino type)
The same operation as in Synthesis Example 1 was conducted except that the amount of 92% paraformaldehyde was changed to 81.5 parts (2.5 mol) to obtain a product having a nonvolatile content of 80.3% and a Gardner viscosity Z4.
92%パラホルムアルデヒドの仕込量を81.5部(2.5モル)とした以外は合成例1と同様の操作を行い、不揮発分80.3%、ガードナー粘度Z4の生成物を得た。 (Synthesis Example 3): Benzoguanamine resin B-2 (imino type)
The same operation as in Synthesis Example 1 was conducted except that the amount of 92% paraformaldehyde was changed to 81.5 parts (2.5 mol) to obtain a product having a nonvolatile content of 80.3% and a Gardner viscosity Z4.
官能基の数値はベンゾグアナミン1モルに対するモル数を表わす。
官能基: 13C-NMRによる官能基測定の確認装置として、日本電子(株)製のJNM-EX270を用い、試料をジメチルスルフォキシド-d6 に溶かし、室温で、CNOE-プロトンデカップリング条件で行った。 The numerical value of the functional group represents the number of moles relative to 1 mole of benzoguanamine.
Functional group: JNM-EX270 manufactured by JEOL Ltd. was used as a confirmation device for functional group measurement by 13 C-NMR, and the sample was dissolved in dimethyl sulfoxide-d 6 and subjected to CNOE-proton decoupling conditions at room temperature. I went there.
官能基: 13C-NMRによる官能基測定の確認装置として、日本電子(株)製のJNM-EX270を用い、試料をジメチルスルフォキシド-d6 に溶かし、室温で、CNOE-プロトンデカップリング条件で行った。 The numerical value of the functional group represents the number of moles relative to 1 mole of benzoguanamine.
Functional group: JNM-EX270 manufactured by JEOL Ltd. was used as a confirmation device for functional group measurement by 13 C-NMR, and the sample was dissolved in dimethyl sulfoxide-d 6 and subjected to CNOE-proton decoupling conditions at room temperature. I went there.
(合成例4):リン酸系化合物C-1Aの合成
攪拌機、温度計、還流冷却器及び窒素ガス導入管を備えた反応容器に、エピコート1001(JER株式会社製)110.8部とプロピレングリコールモノメチルアセテート101.8部を仕込んで加熱溶解し、75℃に達したら50%リン酸7.6部を1時間かけて連続滴下した。75℃で8時間反応させた後、トリエチルアミン6.1で中和し、酸価15.1mgKOH/g、不揮発分51.6%のリン酸系化合物C-1Aを得た。 (Synthesis Example 4): 110.8 parts of Epicoat 1001 (manufactured by JER Corporation) and propylene glycol were added to a reaction vessel equipped with a synthetic stirrer, a thermometer, a reflux condenser and a nitrogen gas introduction tube of phosphoric acid compound C-1A. 101.8 parts of monomethyl acetate was added and dissolved by heating. When the temperature reached 75 ° C., 7.6 parts of 50% phosphoric acid was continuously added dropwise over 1 hour. After reacting at 75 ° C. for 8 hours, the mixture was neutralized with triethylamine 6.1 to obtain phosphoric acid compound C-1A having an acid value of 15.1 mg KOH / g and a nonvolatile content of 51.6%.
攪拌機、温度計、還流冷却器及び窒素ガス導入管を備えた反応容器に、エピコート1001(JER株式会社製)110.8部とプロピレングリコールモノメチルアセテート101.8部を仕込んで加熱溶解し、75℃に達したら50%リン酸7.6部を1時間かけて連続滴下した。75℃で8時間反応させた後、トリエチルアミン6.1で中和し、酸価15.1mgKOH/g、不揮発分51.6%のリン酸系化合物C-1Aを得た。 (Synthesis Example 4): 110.8 parts of Epicoat 1001 (manufactured by JER Corporation) and propylene glycol were added to a reaction vessel equipped with a synthetic stirrer, a thermometer, a reflux condenser and a nitrogen gas introduction tube of phosphoric acid compound C-1A. 101.8 parts of monomethyl acetate was added and dissolved by heating. When the temperature reached 75 ° C., 7.6 parts of 50% phosphoric acid was continuously added dropwise over 1 hour. After reacting at 75 ° C. for 8 hours, the mixture was neutralized with triethylamine 6.1 to obtain phosphoric acid compound C-1A having an acid value of 15.1 mg KOH / g and a nonvolatile content of 51.6%.
(合成例5):アクリル樹脂A-2の合成
攪拌機、温度計、還流冷却器、窒素ガス導入管及び滴下槽を備えた反応容器にエチレングリコールモノイソプロピルエーテル450部を仕込み120℃まで昇温した。この温度を保持しつつ、滴下槽からアクリル酸エチル87.0部、アクリル酸n-ブチル87.0部、スチレン75.0、2-ヒドロキシエチルメタクリレート30.0部及びアクリル酸21.0部と、過酸化ベンゾイル18.0部からなる混合物を4時間かけて連続滴下した。滴下終了の1時間後に、ジ-t-ブチルパーオキサイド3.0部を添加し、更に2時間の間反応させた。次いでかくして得られた樹脂溶液より減圧下で、375.0部の溶剤を留去せしめ、N,N-ジメチルエタノールアミン20.0部で中和せしめた。引き続いて水200.0質量部で希釈せしめることによって、不揮発分が50.6%で、かつ、酸価が26.5なるアクリル樹脂の水溶液を得た。これをアクリル樹脂A-2と略記する。 (Synthesis Example 5): Synthesis of acrylic resin A-2 A reactor equipped with a stirrer, thermometer, reflux condenser, nitrogen gas introduction tube and dropping tank was charged with 450 parts of ethylene glycol monoisopropyl ether and heated to 120 ° C. . While maintaining this temperature, 87.0 parts of ethyl acrylate, 87.0 parts of n-butyl acrylate, 75.0 parts of styrene, 30.0 parts of 2-hydroxyethyl methacrylate, and 21.0 parts of acrylic acid were added from the dropping tank. A mixture of 18.0 parts of benzoyl peroxide was continuously added dropwise over 4 hours. One hour after the completion of the dropwise addition, 3.0 parts of di-t-butyl peroxide was added and the reaction was continued for another 2 hours. Next, 375.0 parts of the solvent was distilled off from the resin solution thus obtained under reduced pressure, and neutralized with 20.0 parts of N, N-dimethylethanolamine. Subsequently, an aqueous solution of an acrylic resin having a non-volatile content of 50.6% and an acid value of 26.5 was obtained by diluting with 200.0 parts by mass of water. This is abbreviated as acrylic resin A-2.
攪拌機、温度計、還流冷却器、窒素ガス導入管及び滴下槽を備えた反応容器にエチレングリコールモノイソプロピルエーテル450部を仕込み120℃まで昇温した。この温度を保持しつつ、滴下槽からアクリル酸エチル87.0部、アクリル酸n-ブチル87.0部、スチレン75.0、2-ヒドロキシエチルメタクリレート30.0部及びアクリル酸21.0部と、過酸化ベンゾイル18.0部からなる混合物を4時間かけて連続滴下した。滴下終了の1時間後に、ジ-t-ブチルパーオキサイド3.0部を添加し、更に2時間の間反応させた。次いでかくして得られた樹脂溶液より減圧下で、375.0部の溶剤を留去せしめ、N,N-ジメチルエタノールアミン20.0部で中和せしめた。引き続いて水200.0質量部で希釈せしめることによって、不揮発分が50.6%で、かつ、酸価が26.5なるアクリル樹脂の水溶液を得た。これをアクリル樹脂A-2と略記する。 (Synthesis Example 5): Synthesis of acrylic resin A-2 A reactor equipped with a stirrer, thermometer, reflux condenser, nitrogen gas introduction tube and dropping tank was charged with 450 parts of ethylene glycol monoisopropyl ether and heated to 120 ° C. . While maintaining this temperature, 87.0 parts of ethyl acrylate, 87.0 parts of n-butyl acrylate, 75.0 parts of styrene, 30.0 parts of 2-hydroxyethyl methacrylate, and 21.0 parts of acrylic acid were added from the dropping tank. A mixture of 18.0 parts of benzoyl peroxide was continuously added dropwise over 4 hours. One hour after the completion of the dropwise addition, 3.0 parts of di-t-butyl peroxide was added and the reaction was continued for another 2 hours. Next, 375.0 parts of the solvent was distilled off from the resin solution thus obtained under reduced pressure, and neutralized with 20.0 parts of N, N-dimethylethanolamine. Subsequently, an aqueous solution of an acrylic resin having a non-volatile content of 50.6% and an acid value of 26.5 was obtained by diluting with 200.0 parts by mass of water. This is abbreviated as acrylic resin A-2.
(実施例1~5塗料及び比較例1,2塗料の調製)
合成例1で得られたポリエステル樹脂溶液、合成例2,3で得られたアミノ樹脂溶液、合成例4で得られたリン酸系化合物、及び、合成例5で得られたアクリル樹脂とを表2に示した割合で配合し、これにエチレングリコールモノブチルエーテル、水、及びp-トルエンスルホン酸を樹脂固形分に対して0.1%、シリコーン系レベリング剤を樹脂固形分に対して0.3%添加混合して、樹脂固形分40.0%、有機溶剤含有量20.0%のクリア塗料を調製した。 (Preparation of Examples 1 to 5 and Comparative Examples 1 and 2)
The polyester resin solution obtained in Synthesis Example 1, the amino resin solution obtained in Synthesis Examples 2 and 3, the phosphoric acid compound obtained in Synthesis Example 4, and the acrylic resin obtained in Synthesis Example 5 are shown. 2 was blended in the proportions shown in Table 1, and ethylene glycol monobutyl ether, water, and p-toluenesulfonic acid were 0.1% based on the resin solids, and the silicone leveling agent was 0.3% based on the resin solids. % And mixed to prepare a clear paint having a resin solid content of 40.0% and an organic solvent content of 20.0%.
合成例1で得られたポリエステル樹脂溶液、合成例2,3で得られたアミノ樹脂溶液、合成例4で得られたリン酸系化合物、及び、合成例5で得られたアクリル樹脂とを表2に示した割合で配合し、これにエチレングリコールモノブチルエーテル、水、及びp-トルエンスルホン酸を樹脂固形分に対して0.1%、シリコーン系レベリング剤を樹脂固形分に対して0.3%添加混合して、樹脂固形分40.0%、有機溶剤含有量20.0%のクリア塗料を調製した。 (Preparation of Examples 1 to 5 and Comparative Examples 1 and 2)
The polyester resin solution obtained in Synthesis Example 1, the amino resin solution obtained in Synthesis Examples 2 and 3, the phosphoric acid compound obtained in Synthesis Example 4, and the acrylic resin obtained in Synthesis Example 5 are shown. 2 was blended in the proportions shown in Table 1, and ethylene glycol monobutyl ether, water, and p-toluenesulfonic acid were 0.1% based on the resin solids, and the silicone leveling agent was 0.3% based on the resin solids. % And mixed to prepare a clear paint having a resin solid content of 40.0% and an organic solvent content of 20.0%.
(試験片-1:サイズ塗膜有+上塗りクリヤー塗料)
厚さ0.21mmのアルミニウム板上にDIC株式会社製6E-090(サイズコート)を乾燥膜厚が1.5μmとなるように塗装し、素材の最高到達温度200℃で1分間焼付け塗装板を得た。この塗装板上に前期のようにして得られた上塗り塗料をコーターにて乾燥膜厚が約7μmとなるように塗装し、素材到達温度が210℃で2分間焼き付けて上塗りクリヤー塗装板を得た。 (Specimen-1: size paint film + clear clear paint)
A 6E-090 (size coat) manufactured by DIC Corporation was applied to an aluminum plate having a thickness of 0.21 mm so that the dry film thickness was 1.5 μm, and the baked coated plate was applied for 1 minute at a maximum material temperature of 200 ° C. Obtained. The top coat obtained as described above was applied onto this coated plate with a coater so that the dry film thickness was about 7 μm, and the material arrival temperature was baked at 210 ° C. for 2 minutes to obtain a clear top coated plate. .
厚さ0.21mmのアルミニウム板上にDIC株式会社製6E-090(サイズコート)を乾燥膜厚が1.5μmとなるように塗装し、素材の最高到達温度200℃で1分間焼付け塗装板を得た。この塗装板上に前期のようにして得られた上塗り塗料をコーターにて乾燥膜厚が約7μmとなるように塗装し、素材到達温度が210℃で2分間焼き付けて上塗りクリヤー塗装板を得た。 (Specimen-1: size paint film + clear clear paint)
A 6E-090 (size coat) manufactured by DIC Corporation was applied to an aluminum plate having a thickness of 0.21 mm so that the dry film thickness was 1.5 μm, and the baked coated plate was applied for 1 minute at a maximum material temperature of 200 ° C. Obtained. The top coat obtained as described above was applied onto this coated plate with a coater so that the dry film thickness was about 7 μm, and the material arrival temperature was baked at 210 ° C. for 2 minutes to obtain a clear top coated plate. .
(試験片-2:サイズ塗膜有+インキ+上塗りクリヤー塗料)
厚さ0.21mmのアルミニウム板上にDIC株式会社製6E-090(サイズコート)を乾燥膜厚が1.5μmとなるように塗装し、素材の最高到達温度200℃で1分間焼付け塗装板を得た。その上にポリエステル樹脂をビヒクルの主成分とするインキ(DIC株式会社製金属平版インキMTC NS藍)を印刷(未乾燥の膜厚が4μm)し、インキが未乾燥の状態で、各上塗り塗料をコーターにて乾燥膜厚が約7μmとなるように塗装し、素材到達温度が210℃で2分間焼き付けて上塗りクリヤー塗装板を得た。 (Test piece-2: Size paint film + ink + top clear paint)
A 6E-090 (size coat) manufactured by DIC Corporation was applied to an aluminum plate having a thickness of 0.21 mm so that the dry film thickness was 1.5 μm, and the baked coated plate was applied for 1 minute at a maximum material temperature of 200 ° C. Obtained. On top of that, an ink (metal lithographic ink MTC NS indigo made by DIC Corporation) containing polyester resin as a main component of the vehicle is printed (undried film thickness is 4 μm). Coating was performed with a coater so that the dry film thickness was about 7 μm, and the material arrival temperature was baked at 210 ° C. for 2 minutes to obtain a top-coated clear coated plate.
厚さ0.21mmのアルミニウム板上にDIC株式会社製6E-090(サイズコート)を乾燥膜厚が1.5μmとなるように塗装し、素材の最高到達温度200℃で1分間焼付け塗装板を得た。その上にポリエステル樹脂をビヒクルの主成分とするインキ(DIC株式会社製金属平版インキMTC NS藍)を印刷(未乾燥の膜厚が4μm)し、インキが未乾燥の状態で、各上塗り塗料をコーターにて乾燥膜厚が約7μmとなるように塗装し、素材到達温度が210℃で2分間焼き付けて上塗りクリヤー塗装板を得た。 (Test piece-2: Size paint film + ink + top clear paint)
A 6E-090 (size coat) manufactured by DIC Corporation was applied to an aluminum plate having a thickness of 0.21 mm so that the dry film thickness was 1.5 μm, and the baked coated plate was applied for 1 minute at a maximum material temperature of 200 ° C. Obtained. On top of that, an ink (metal lithographic ink MTC NS indigo made by DIC Corporation) containing polyester resin as a main component of the vehicle is printed (undried film thickness is 4 μm). Coating was performed with a coater so that the dry film thickness was about 7 μm, and the material arrival temperature was baked at 210 ° C. for 2 minutes to obtain a top-coated clear coated plate.
(試験片-3:サイズ塗膜無+上塗りクリヤー塗料)
厚さ0.21mmのアルミニウム板状にサイズコーティングを施さない以外は試験片1の場合と同様に試験片-3を得た。 (Specimen-3: No size coating + top clear coating)
Specimen-3 was obtained in the same manner as for Specimen 1 except that the size coating was not applied to an aluminum plate having a thickness of 0.21 mm.
厚さ0.21mmのアルミニウム板状にサイズコーティングを施さない以外は試験片1の場合と同様に試験片-3を得た。 (Specimen-3: No size coating + top clear coating)
Specimen-3 was obtained in the same manner as for Specimen 1 except that the size coating was not applied to an aluminum plate having a thickness of 0.21 mm.
(試験片-4:サイズ塗膜無し+インキ+上塗りクリヤー塗料)
厚さ0.21mmのアルミニウム板状にサイズコーティングを施さない以外は試験片2の場合と同様に試験片-4を得た。 (Test piece-4: No size coating + ink + top clear coating)
Test piece-4 was obtained in the same manner as in the case of test piece 2 except that the size coating was not applied to the aluminum plate having a thickness of 0.21 mm.
厚さ0.21mmのアルミニウム板状にサイズコーティングを施さない以外は試験片2の場合と同様に試験片-4を得た。 (Test piece-4: No size coating + ink + top clear coating)
Test piece-4 was obtained in the same manner as in the case of test piece 2 except that the size coating was not applied to the aluminum plate having a thickness of 0.21 mm.
試験方法を以下に記載する。又、評価結果を表3,4に示す。
The test method is described below. The evaluation results are shown in Tables 3 and 4.
(1.鉛筆硬度試験)
塗装板をJIS-S-6006に規定された高級鉛筆を用いJIS-K-5400に準じて鉛筆硬度を測定した。 (1. Pencil hardness test)
The pencil hardness was measured according to JIS-K-5400 using a high-grade pencil specified in JIS-S-6006 for the coated plate.
塗装板をJIS-S-6006に規定された高級鉛筆を用いJIS-K-5400に準じて鉛筆硬度を測定した。 (1. Pencil hardness test)
The pencil hardness was measured according to JIS-K-5400 using a high-grade pencil specified in JIS-S-6006 for the coated plate.
(2.湯中鉛筆硬度試験)
塗装板を80℃の湯中に浸漬し、30分後に湯中につけたまま、JIS-S-6006に規定された高級鉛筆を用いJIS-K-5400に準じて鉛筆硬度を測定した。 (2. Pencil hardness test in hot water)
The coated plate was immersed in hot water at 80 ° C., and after 30 minutes, the pencil hardness was measured according to JIS-K-5400 using a high-grade pencil specified in JIS-S-6006.
塗装板を80℃の湯中に浸漬し、30分後に湯中につけたまま、JIS-S-6006に規定された高級鉛筆を用いJIS-K-5400に準じて鉛筆硬度を測定した。 (2. Pencil hardness test in hot water)
The coated plate was immersed in hot water at 80 ° C., and after 30 minutes, the pencil hardness was measured according to JIS-K-5400 using a high-grade pencil specified in JIS-S-6006.
(3.加工密着性試験)
ボトル形状加工及びネジ加工を代用するため、試験塗装板を直径約25mm×高さ約17mmのキャップ形状に打抜き加工してからネジ加工したものを、30分間煮沸処理を行い、塗膜の割れと剥離の程度を下記基準により目視で判定した。○以上が実用レベル。
◎:割れ、剥離が全く無い。
○:若干割れ、剥離がある。
△:割れ、剥離がやや多い。
×:割れ、剥離が著しい。 (3. Work adhesion test)
In order to substitute for bottle shape processing and screw processing, the test coating plate was punched into a cap shape with a diameter of about 25 mm and a height of about 17 mm, and then the screw processing was performed for 30 minutes by boiling, The degree of peeling was visually judged according to the following criteria. ○ Above is the practical level.
(Double-circle): There is no crack and peeling at all.
○: There are some cracks and peeling.
Δ: Slightly cracking and peeling
X: Cracking and peeling are remarkable.
ボトル形状加工及びネジ加工を代用するため、試験塗装板を直径約25mm×高さ約17mmのキャップ形状に打抜き加工してからネジ加工したものを、30分間煮沸処理を行い、塗膜の割れと剥離の程度を下記基準により目視で判定した。○以上が実用レベル。
◎:割れ、剥離が全く無い。
○:若干割れ、剥離がある。
△:割れ、剥離がやや多い。
×:割れ、剥離が著しい。 (3. Work adhesion test)
In order to substitute for bottle shape processing and screw processing, the test coating plate was punched into a cap shape with a diameter of about 25 mm and a height of about 17 mm, and then the screw processing was performed for 30 minutes by boiling, The degree of peeling was visually judged according to the following criteria. ○ Above is the practical level.
(Double-circle): There is no crack and peeling at all.
○: There are some cracks and peeling.
Δ: Slightly cracking and peeling
X: Cracking and peeling are remarkable.
(4.耐沸水性試験)
塗装板をそれぞれ沸騰水で30分間煮沸(ボイル)処理した後、塗膜の白化の程度を目視で判定した。○以上が実用レベル。
◎:白化が全くない。
○:若干白化が認められる
△:白化がやや多い。
×:白化が著しい。 (4. Boiling water resistance test)
Each coated plate was boiled with boiling water for 30 minutes, and then the degree of whitening of the coating film was visually determined. ○ Above is the practical level.
A: There is no whitening at all.
○: Some whitening is observed. Δ: Whitening is slightly high.
X: Whitening is remarkable.
塗装板をそれぞれ沸騰水で30分間煮沸(ボイル)処理した後、塗膜の白化の程度を目視で判定した。○以上が実用レベル。
◎:白化が全くない。
○:若干白化が認められる
△:白化がやや多い。
×:白化が著しい。 (4. Boiling water resistance test)
Each coated plate was boiled with boiling water for 30 minutes, and then the degree of whitening of the coating film was visually determined. ○ Above is the practical level.
A: There is no whitening at all.
○: Some whitening is observed. Δ: Whitening is slightly high.
X: Whitening is remarkable.
(5.密着性試験)
塗装板を沸騰水で30分間煮沸(ボイル)処理した後、塗膜にカッターを使用して碁盤目状に1mm間隔で11本の切込みを入れ、セロハンテープを貼着した後、セロハンテープを剥離する際に剥離した碁盤目の数で評価した(剥離した碁盤目の数/100)。 (5. Adhesion test)
After boiling the coating plate with boiling water for 30 minutes (boiling), use a cutter on the coating to make 11 cuts in a grid pattern at intervals of 1 mm, paste the cellophane tape, and peel the cellophane tape. It was evaluated by the number of grids that were peeled off (number of grids peeled / 100).
塗装板を沸騰水で30分間煮沸(ボイル)処理した後、塗膜にカッターを使用して碁盤目状に1mm間隔で11本の切込みを入れ、セロハンテープを貼着した後、セロハンテープを剥離する際に剥離した碁盤目の数で評価した(剥離した碁盤目の数/100)。 (5. Adhesion test)
After boiling the coating plate with boiling water for 30 minutes (boiling), use a cutter on the coating to make 11 cuts in a grid pattern at intervals of 1 mm, paste the cellophane tape, and peel the cellophane tape. It was evaluated by the number of grids that were peeled off (number of grids peeled / 100).
本発明の水性塗料組成物は、比較的穏やかな加工工程を有する2ピース缶はもとより、特に、過酷な加工工程を有するボトル缶への適用と、広く缶用塗料に用いることが出来る。
The aqueous coating composition of the present invention can be applied not only to a two-piece can having a relatively gentle processing step, but also to a bottle can having a severe processing step, and can be widely used for a paint for cans.
Claims (7)
- カルボキシル基を含有するポリエステル樹脂(A)、アミノ樹脂(B)及びリン酸系化合物(C)を含有することを特徴とする水性塗料組成物。 A water-based coating composition comprising a polyester resin (A) containing a carboxyl group, an amino resin (B) and a phosphoric acid compound (C).
- 前記したポリエステル樹脂(A)が、数平均分子量が1000~10000、酸価が10~50mgKOH/gである請求項1に記載の水性塗料組成物。 The water-based coating composition according to claim 1, wherein the polyester resin (A) has a number average molecular weight of 1,000 to 10,000 and an acid value of 10 to 50 mgKOH / g.
- 前記したアミノ樹脂(B)が、数平均分子量が300~1000の、高エーテル型ベンゾグアナミン樹脂である請求項1又は2に記載の水性塗料組成物。 The water-based coating composition according to claim 1 or 2, wherein the amino resin (B) is a high ether type benzoguanamine resin having a number average molecular weight of 300 to 1,000.
- 前記したリン酸系化合物(C)が、一分子中に少なくとも一個のリン原子に結合した水酸基を有する化合物である請求項1~3のいずれかに記載の水性塗料組成物。 The aqueous coating composition according to any one of claims 1 to 3, wherein the phosphoric acid compound (C) is a compound having a hydroxyl group bonded to at least one phosphorus atom in one molecule.
- 前記したリン酸系化合物(C)が、一分子中に少なくとも一個のリン原子に結合した水酸基を有する化合物により変性されたエポキシ化合物である、請求項1~4のいずれかに記載の水性塗料組成物。 The water-based paint composition according to any one of claims 1 to 4, wherein the phosphoric acid compound (C) is an epoxy compound modified with a compound having a hydroxyl group bonded to at least one phosphorus atom in one molecule. object.
- ポリエステル樹脂(A)とアミノ樹脂(B)を、(A)/(B)=40/60~80/20の質量比で含有し、(A)と(B)の合計100質量部に対して、リン酸系化合物(C)を0.1~10質量部含有する請求項1~5のいずれかに記載の水性塗料組成物。 The polyester resin (A) and the amino resin (B) are contained in a mass ratio of (A) / (B) = 40/60 to 80/20, with respect to a total of 100 parts by mass of (A) and (B). The aqueous coating composition according to any one of claims 1 to 5, comprising 0.1 to 10 parts by mass of the phosphoric acid compound (C).
- ボトル缶の上塗り塗料用に使用する請求項1~6のいずれかに記載の水性塗料組成物。 The water-based paint composition according to any one of claims 1 to 6, which is used for a top coat of a bottle can.
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014024976A (en) * | 2012-07-27 | 2014-02-06 | Dic Graphics Corp | Aqueous resin composition |
JP2014118432A (en) * | 2012-12-13 | 2014-06-30 | Universal Seikan Kk | Coating composition for can, bottle can coated with the coating composition and manufacturing method of bottle can |
WO2015033857A1 (en) * | 2013-09-06 | 2015-03-12 | Dic株式会社 | Polyester polyol, polyol preparation for laminating adhesive agent, resin composition, curable resin composition, adhesive agent for laminating use, and back sheet for solar cell |
JP2018070749A (en) * | 2016-10-28 | 2018-05-10 | ユニバーサル製缶株式会社 | Paint composition for can accompanied with processing, method for producing can accompanied with processing, and can accompanied with processing |
JP2019085459A (en) * | 2017-11-02 | 2019-06-06 | 株式会社放電精密加工研究所 | Surface-coated base material that can be used as substitute material of anodized aluminum material, and coating composition for forming top coat layer on the substrate surface |
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02212570A (en) * | 1989-02-10 | 1990-08-23 | Toyo Ink Mfg Co Ltd | Aqueous coating composition |
JPH07242854A (en) * | 1994-03-08 | 1995-09-19 | Dainippon Ink & Chem Inc | Aqueous coating composition |
JPH07331166A (en) * | 1994-06-03 | 1995-12-19 | Toyo Ink Mfg Co Ltd | Water-based coating composition for polyester film-covered deep-drawn can |
JP2000044870A (en) * | 1998-07-31 | 2000-02-15 | Dainippon Ink & Chem Inc | Aqueous coating material resin composition for outer surface of can |
JP2005307040A (en) * | 2004-04-22 | 2005-11-04 | Toyo Ink Mfg Co Ltd | Coating material composition and metal sheet or metal can obtained by using the composition |
JP2006306939A (en) * | 2005-04-26 | 2006-11-09 | Toyo Seikan Kaisha Ltd | Water-base coating composition and coated article |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4638020A (en) * | 1984-11-23 | 1987-01-20 | Ppg Industries, Inc. | Aqueous composition comprising a phosphated epoxy and non-self dispersible resin |
JP2002097345A (en) * | 2000-09-20 | 2002-04-02 | Dainippon Ink & Chem Inc | Resin composition |
-
2010
- 2010-01-18 WO PCT/JP2010/050464 patent/WO2010084833A1/en active Application Filing
- 2010-01-18 JP JP2010528233A patent/JPWO2010084833A1/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02212570A (en) * | 1989-02-10 | 1990-08-23 | Toyo Ink Mfg Co Ltd | Aqueous coating composition |
JPH07242854A (en) * | 1994-03-08 | 1995-09-19 | Dainippon Ink & Chem Inc | Aqueous coating composition |
JPH07331166A (en) * | 1994-06-03 | 1995-12-19 | Toyo Ink Mfg Co Ltd | Water-based coating composition for polyester film-covered deep-drawn can |
JP2000044870A (en) * | 1998-07-31 | 2000-02-15 | Dainippon Ink & Chem Inc | Aqueous coating material resin composition for outer surface of can |
JP2005307040A (en) * | 2004-04-22 | 2005-11-04 | Toyo Ink Mfg Co Ltd | Coating material composition and metal sheet or metal can obtained by using the composition |
JP2006306939A (en) * | 2005-04-26 | 2006-11-09 | Toyo Seikan Kaisha Ltd | Water-base coating composition and coated article |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014024976A (en) * | 2012-07-27 | 2014-02-06 | Dic Graphics Corp | Aqueous resin composition |
JP2014118432A (en) * | 2012-12-13 | 2014-06-30 | Universal Seikan Kk | Coating composition for can, bottle can coated with the coating composition and manufacturing method of bottle can |
WO2015033857A1 (en) * | 2013-09-06 | 2015-03-12 | Dic株式会社 | Polyester polyol, polyol preparation for laminating adhesive agent, resin composition, curable resin composition, adhesive agent for laminating use, and back sheet for solar cell |
CN105579490A (en) * | 2013-09-06 | 2016-05-11 | Dic株式会社 | Polyester polyol, polyol preparation for laminating adhesive agent, resin composition, curable resin composition, adhesive agent for laminating use, and back sheet for solar cell |
JP2018070749A (en) * | 2016-10-28 | 2018-05-10 | ユニバーサル製缶株式会社 | Paint composition for can accompanied with processing, method for producing can accompanied with processing, and can accompanied with processing |
JP7090397B2 (en) | 2016-11-11 | 2022-06-24 | ユニバーサル製缶株式会社 | How to make a can with screws |
JP2019085459A (en) * | 2017-11-02 | 2019-06-06 | 株式会社放電精密加工研究所 | Surface-coated base material that can be used as substitute material of anodized aluminum material, and coating composition for forming top coat layer on the substrate surface |
JP7148237B2 (en) | 2017-11-02 | 2022-10-05 | 株式会社放電精密加工研究所 | A surface-coated substrate that can be used as an alternative material to an alumite material, and a coating composition for forming a topcoat layer on the surface of the substrate |
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